films - esc2015.krakow.pl

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ESC 2015
Krakow, June 8-11, 2015
15th European Student
Colloid Conference
Krakow • June 8-11, 2015
BOOK OF ABSTRACTS
ESC 2015
Sponsorship
Gold
Sponsor
Platinium
Sponsor
2
ESC 2015
Contents
Organizing Committee
4
Conference Programme
5
List of Posters
7
Abstracts
10
Invited lectures
11
Oral presentations
21
Posters
70
List of Conference Participants
114
Authors’ Index
121
3
ESC 2015
Organizing Committee
Katarzyna Kilan (chair)
Marek Piotrowski (webmaster)
Karolina Podgórna (event manager)
Magdalena Włodek
Marta Łapczyńska
Anna Pajor-Świerzy
Aneta Kędra
Tomasz Kruk
Grzegorz Potasiewicz
Zofia Krasińska
Krzysztof Szczepanowicz
Marta Kolasińska-Sojka
Magdalena Elżbieciak-Wodka
Ewelina Jarek
Elżbieta Porębska
Supported by:
Prof. dr hab. Piotr Warszyński
4
ESC 2015
Krakow, June 8-11,Wednesday,
2015 June 10
Monday, June 8
Tuesday, June 9
10.00
ENRIQUE LOPEZ-CABARCOS (Spain)
Entrapment of Enzymes and Drugs within Colloidal
Particles for their Application in Health Sciences
REINHARD MILLER (Germany)
Dynamics of surfactant adsorption layers at
water/oil interfaces
SZCZEPAN ZAPOTOCZNY (Poland)
Micellar multilayer films
ZBIGNIEW ADAMCZYK (Poland)
Protein Adsorption – a True Story
10:30
coffee
coffee
coffee
coffee
11:00
MARIA CHATZIDAKI (Greece)
Formulation and in vitro characterization of W/O
colloidal nanodispersions for medical applications
JOOYOUNG WON (Germany)
β-lactoglobulin adsorption at the water/oil system
at different pH and ionic strength
MOHMED MULLA (United Kingdom)
Preparation of Colloidal Inkjet Inks by Emulsion
Polymerisation
ALEKSANDRA KEZWOŃ (Poland)
The effect of the protein hydrolysis on surface
activity and surface dilational rheology of type I
collagen
11:20
JOANNA SZAFRANIEC (Poland)
Towards Modern Drug Carriers: Nanocapsules
Stabilized by Amphiphilic Copolymers
WEI LIN (Germany)
A thermodynamic study of ligand adsorption to
colloidal surfaces demonstrated by means of
catechols binding to ZnO QDs
MARÍA DEL MAR FERNÁNDEZ MARTÍNEZ-REY
(Spain)
Effect of the pore size of activated carbon
nanoparticles on CDLE (capacitive energy
extraction based on double layer expansion)
KIRILL EMELYANENKO (Russia)
Stability of nanoscale nonionic films atop of
discretely charged electrolyte interface
11:40
ANNALISA SALVATORE (Italy)
Core-Shell Nanoparticles for DNA Delivery Actuated
by Magnetic Fields
EMILY JAMES (United Kingdom)
Droplet dynamics: Oil droplet attachment and
spreading on solid substrates
PALOMA ARENAS-GUERRERO (Spain)
Anomalous birefringence of planar clay particles
GAMON JACINTHE (France)
Quantitative determination of anchoring
molecules on the surface of ZnO particules and
effects on electronical properties
12:00
ROBERTA LIUZZI (Italy)
Microstructured fluids at skin interface: biomedical
applications
TAMAS ONCSIK (Switzerland)
Hofmeister Effects in Colloidal Aggregation in
Aqueous Solutions of Ionic Liquids
12:20
MARTA KUJDA (Poland)
Physicochemical characteristics of albumin dimer
and its monolayers on solid surfaces –
electrokinetic studies
REKA TOTH (France)
Silica-ceria interactions during polishing
12:40
KAROLINA PODGÓRNA (Poland)
Synthesis of polyelectrolyte nanocapsules with iron
oxide nanoparticles for magnetic targeting
BRETT SYMONDS (United Kingdom)
Quantifying the rainfastness of fluorescently
labelled poly(vinyl alcohol) deposits on vicia faba
leaf surfaces via fluorescent microscopy
09:00
13:00
13:20
13:40
BIAO LU (France)
Evaluation of Cytotoxicity of Biorefinery-derived
Amphiphilic Molecules on Multi-scale In-vitro
Models
VIKTORIA OLIYNYK/ANDREY PANKO (Ukraine)
Modification of colloid-chemical and balneological
properties of therapeutical muds with nano- and
microparticles
MARTA ŁAPCZYŃSKA (Poland)
Synthesis of the PCL nanoparticles containing
neuroprotectants from oil-in-water nanoemulsion
by phase inversion emulsification method
SŁAWOMIR DROZDEK (Poland)
Co-encapsulation of CdSexS1-x/ZnS quantum dots
with photosensitizers- colloidal stability and
optical properties
KATARZYNA KUBIAK (Poland)
In situ QCM-D investigation of silver nanoparticle
monolayer formation on polycation modified
surfaces
Thursday, June 11
CHRISTIAN REDEKER (United Kingdom)
Surface-confined interactions of
lipopolysaccharide layers
SEBASTIAN GÖDRICH (Germany)
Nanopatterned charge distributions on
polyetherimide electret-films
MICHAEL MCNALLY (United Kingdom)
Nanoparticle Production by Atomic Vapour
Deposition on a Liquid Jet
MONICA TONELLI (Italy)
Investigation of the structural properties of MgObased eco-sustainable cements
lunch
lunch
IDO COOPERSTEIN (Israel)
UV Curable Oil-in-Water Emulsions for 3D
Functional Printing
VAMSEEKRISHNA ULAGANATHAN (Germany)
Effect of pH and salt concentration on velocity of
rising bubbles in Beta-Lactoglobulin solution
ANNA NIECIKOWSKA (Poland)
Effect of the bubble dimensions and the shape
deformation degrees on its coalescence time at
free water surface
ESC 2015
14:00
lunch
lunch
15:00
CHRISTIAN SCHULZ (The Netherlands)
Author workshop – how to successfully publish
scientific articles
JAN HUPKA (Poland)
Filming of bubbles
JIRI SMILEK (Czech Republic)
Diffusion Techniques as Reactivity Mapping Tool of
Biocolloids
ANNA LATOWSKA (Poland)
Influence of imidazolium ionic liquids structure on
aggregation behavior of triton X-100 nonionic
surfactant
15.30
16:30
16:50
17:10
MOHSEN MOAZZAMI GUDARZI (Switzerland)
Direct Force Measurements Involving Positively
and Negatively Charged Colloidal Particles in the
Presence of Multivalent Cations
SAMUEL SKINNER (Australia)
Revisiting Kynchian Analysis of Gravitational and
Centrifugal Settling for Strongly Flocculated
Suspensions
KIRSTY STARK (United Kingdom)
Metallic Nanoparticles and their interfacial
properties
SAOIRSE DERVIN (Ireland)
Sol-Gel derived nanostructured materials for
thermal insulation applications
coffee
ANTONIO CARCIATI (Italy)
Linear viscoelasticity of human blood
17:50
coffee
18:10
LIEN VERMEIR (Belgium)
Influence of molecular exchange on the enclosed
water volume fraction of W/O/W double emulsions
as determined by low-resolution NMR diffusometry
and T2-relaxometry
TRACEY HO (Australia)
Adhesion between Surfaces in the Presence of
Polyelectrolyte Multilayers made with Seaweed
Polysaccharides
JOANNA MIODUSKA (Poland)
Impact of WO3 on surface topography of titania
photocatalysts
ANNA WAMKE (Poland)
Characterization of Langmuir monolayers formed
by derivatives of fluorinated Polyhedral Oligomeric
Silsesquioxanes
MONIKA ĆWIĘKA (Poland)
Nondestructive Characterization of Lysozyme
Layers on Silica Surface using MP-Surface Plasmon
Resonance and Quartz Crystal Microbalance
MARTA ORCZYK (Poland)
Effect of triterpenoid and steroidal saponins
on DPPC and cholesterol monolayers
ŁUKASZ LAMCH (Poland)
Zinc phthalocyanines locaton in methoxy
poly(ethylene oxide) and poly(L-lactide) block
copolymer micelles – 1H NMR investigation
FOTEINI DELISAVVA (Czech Republic)
Nanoparticle self-assembly in aqueous solutions;
influence of polymer’s molar mass and gemini
surfactants’ spacer length
poster session
poster session
18:50
19:10
19:30
BRIAN VINCENT (United Kingdom)
Aggregation in Dispersions Containing Mixtures of
Particles
SARA SKOGLUND (Sweden)
Effect of Laundry Surfactants on Surface Charge
and Colloidal Stability of Silver Nanoparticles
17:30
18:30
WUGE BRISCOE (United Kingdom)
Surfactant layers and polymer brushes under
confinement and shear
Wieliczka Salt Mine Tour +
conference dinner
6
ESC 2015
List of Posters
1. Adsorption and Interfacial Phenomena
P1_1
P1_2
P1_3
P1_4
P1_5
P1_6
P1_7
P1_8
P1_9
P1_10
P1_11
Emelyanenko K., Emelyanenko A., L. Boinovich
Many-body Van der Waals interactions in nanoscale wetting and free films
Kairaliyeva T., Karbaschi M., Taeibi-Rahni M., Faraji S., Schano K.H., Aidarova S.B. and Miller R.
Irregularities of Drop Formation at a Circular capillary
Księżniak Katarzyna, Pawlos Witold, Hupka Jan
Effect of selected parameters on flotation recovery in KGHM Polska Miedź S.A
Maciejewska Julia, Sadowska Marta, Oćwieja Magdalena , Adamczyk Zbigniew
Nanoparticle monolayers on colloid carrier particles
Mould Elizabeth, Briscoe Wuge H.
Foam formation and stability as controlled by surfactant adsorption at the air-water interface
Radulova Gergana, Danov Krassimir, Kralchevsky Peter, Petkov Jordan and Stoyanov Simeon
Shear rheology of hydrophobin adsorption layers at oil/water interfaces and data interpretation in terms of
a viscoelastic thixotropic model
Setiowati Arima Diah, Saeedi Serveh, Van der Meeren Paul
Improved Heat Stability of Whey Protein Isolate Stabilized Emulsions by Conjugation with Low
Methoxyl Pectin using Dry Heat Treatment
Slastanova Anna, Chen Meng, Robles Eric, Briscoe Wuge H.
Surfactants and polymers at air-water interface: from molecular interactions and interfacial structures to
foaming properties
Ulatowska Justyna
Adsorption of As(III) from aqueous solutions by fly ash agglomerates: Dynamic study
Wojewódka Przemysław, Aranowski Robert, Jungnickel Christian
Asphalt binder - interfacial interactions measurements
Yamaguchi Atsushi and Kobayashi Motoyoshi
Zeta potential of colloidal particles covered with proteins
2. Polyelectrolytes, Lipids and Self-Assembly
P2_1
P2_2
P2_3
P2_4
P2_5
P2_6
Georgieva Gergana, Anachkov Svetoslav, Kralchevsky Peter, Danino Dganit, Abezgauz Ludmila,
Liebewirth Ingo, Koynov Kaloian
Fatty acid induced growth of giant micelles in ternary surfactant solutions
Gorczyca Marcelina, Korchowiec Beata, Korchowiec Jacek, Augustyniak Krzysztof,
Regnouf-de-Vains Jean-Bernard, Rogalska Ewa
Investigation of the interaction between phospholipids and tetra-p-guanidinoethylcalix[4]arene having
antibacterial activity
Ho Tracey, Krasowska Marta, MacWilliams Stephanie, Bremmell Kristen, Stringer Damien N.,
Beattie David A.
In Situ Spectroscopic Study of Polyelectrolyte Multilayer Formation and Hydration under Confinement
Moreno-Cencerrado Alberto,, Tharad Sudarat, Iturri Jagoba, Mittendorfer Margareta,
Promdonkoy Boonhiang, Krittanai Chartchai and Toca-Herrera Jose L.
Interaction cytolytic protein Cyt2Aa2 / lipid bilayer: binding and structural changes
Mzareulishvili N., Kurtanidze M., and Rukhadze M.
Study of Microenvironment of Brij30 Reverse Micelles with Optical Probes
Sokolan Nina, Voron’ko Nikolay, Derkach Svetlana
Properties of gelatin–chitosan polyelectrolyte complexes
7
ESC 2015
P2_7
P2_8
P2_9
Tokarczyk Karolina, Jachimska Barbara
Investigation of interaction between PAMAM dendrimers and SiO 2 surface
Tokarczyk Karolina, Jachimska Barbara
Analysis of the PAMAM dendrimers-BSA complexes adsorption using QCM-D and MP-SPR techniques
Wlodek Magdalena, Kolasinska-Sojka Marta, Warszynski Piotr
POPC/POPE lipid vesicles deposition on polyelectrolyte films
3. Nanostructured Materials
P3_1
P3_2
Joanna Starkie, Dr. Alex Routh
The crystallisation of petroleum diesel and wax anti-settling additives
Wąsik Patryk, Redeker Christian, Trask Richard, Briscoe Wuge H.
Hierarchical surface patterns from evaporative drying of nanofluids
4. Biomaterials and Medical Aspects of Colloids
P4_1
P4_2
P4_3
P4_4
P4_5
P4_6
P4_7
P4_8
P4_9
P4_10
Bartlomiej Kalaska, Kamil Kaminski, Emilia Sokolowska, Monika Kujdowicz, Iwona Gawlik,
Krzysztof Szczubialka, Dariusz Pawlak, Maria Nowakowska, Andrzej Mogielnicki
Effects of Cationically Modified Polysaccharide Antidotes for Unfractionated Heparin on Blood Pressure
in Rats
Jabłczyńska Katarzyna, Sosnowski Tomasz R.
Polysaccharide nanocomposite particles for aerosol therapy
Konczak Lukasz, Panczyk Tomasz
Sidewall Functionalization of Magnetically Triggered Nanocontiner by Colloid Nanoparticles and Amide
Groups. A Molecular Dynamics Study
Piotr Krzywda, Wiktor Kasprzyk, Szczepan Bednarz
Novel fluorescent silicone materials
Manami Nishiya, Takuya Sugimoto, and Motoyoshi Kobayashi
Electrophoretic mobility of latex particles: Effects of divalent counter-ions
Piotrowski Marek, Szczepanowicz Krzysztof, Jantas Danuta, Lasoń Władysław, Warszyński Piotr
Evaluation of neuroprotective action of nanoencapsulated model drugs
Sun Qian and Routh Alexander F.
Metal coated colloidosomes and potential applications
Świątek S, Loch J.I., Lewiński K., Jachimska B.
Studies of the functional layers of β-lactoglobulin as biomolecules carriers
Varga Noémi, Sebők Dániel, Dékány Imre
Controlled release of encapsulated neurotransmitters from core-shell nanoparticles
Wolski Paweł, Pańczyk Tomasz
Molecular dynamics study of Doxorubicin interaction with suspensions of modified carbon nanotubes
5. Thin Films and Functional Coatings
P5_1
P5_2
P5_3
P5_4
P5_5
Ćwięka Monika, Jachimska Barbara
The effect of the solution pH on the lysozyme immobilization at the gold surface
Gaurav Pathak and Dusko Cakara
Spectroscopic Ellipsometry of PEDOT:PSS thin films at solid/liquid and solid/gas interfaces
Janikowska Maria, Korchowiec Beata, Gorczyca Marcelina, Wojszko Kamila, Trojan Sonia,
Henry Max, Rogalska Ewa
Action of selected saponins on biological model membranes
Kruk Tomasz, Pajor-Świerzy Anna, Szyk-Warszyńska Lilianna, Socha Robert, Warszyński Piotr
Functional ultrathin polyelectrolyte coatings formed with reduced graphene oxide and Prussian Blue
nanoparticles as a sensitive tool for H2O2 detection
Kruk Tomasz, Szczepanowicz Krzysztof, Warszyński Piotr
Multifunctional polyelectrolyte ultrathin coatings for biomedicine applications
8
ESC 2015
P5_6
P5_7
P5_8
Świątek S., Jachimska B.
Bovine β-lactoglobulin layers on gold surface: Role of ionic strength
Trojan Sonia, Ustarbowska Małgorzata, Korchowiec Beata, Janikowska Maria, Joly Jean-Pierre,
Rogalska Ewa
The role of chain unsaturation in the formation of organized molecular films of crown ether - modified
phospholipid monolayers
Trojan Sonia, Korchowiec Beata, Joly Jean-Pierre, Korchowiec Jacek, Rogalska Ewa
Interactions of amphiphilic crown ether with metal ions in Langmuir films
6. Modeling of Colloid Systems
P6_1
P6_2
P6_3
Enev Vojtěch, Klučáková Martina, Smilek Jiří, Doskočil Leoš
Methylation of humic acids – the impact on the reactivity, chemical composition and properties of HAs
studied by spectrometric techniques
Krasińska Zofia, Jamróz Dorota
Molecular Dynamics modelling of interaction between heparin and its potential neutralizer
Mikulcová Veronika, Kašpárková Věra, Pohlodek Jiří
Undecane-in-water Emulsions prepared by the Phase Inversion Temperature Method
9
ESC 2015
Abstracts
10
ESC 2015
Invited lectures
Enrique Lopez-Cabarcos
Entrapment of Enzymes and Drugs within Colloidal Particles for
their Application in Health Sciences
Christian Schulz
Author workshop – how to succesfully publish scientific articles
Reinhard Miller
Dynamics of surfactant adsorption layers at water/oil interfaces
Jan Hupka
Filming of bubbles
Szczepan Zapotoczny
Wuge H. Briscoe
Surfactant layers and polymer brushes under confinement and shear
Zbigniew Adamczyk
Brian Vincent
Aggregation in Dispersions Containing Mixtures of Particles
11
ESC 2015
Entrapment of Enzymes and Drugs within Colloidal Particles for their
Application in Health Sciences
E. Lopez Cabarcos
Department of Physical Chemistry II, Faculty of Pharmacy, Complutense University of
Madrid, 28040 Madrid, Spain
* - [email protected]
The use of colloidal particles in medical devices and pharmaceutical technology is just
beginning and its development can be spectacular in the coming years. In this contribution I
will present examples of the potential of colloidal systems as matrices for immobilizing
substances such as enzymes and drugs.
First, I will describe the entrapment of redox enzymes within microgels with the aim
to use them as biological component in biosensors. The polymeric microgels supply an
excellent matrix for the immobilization of enzymes since they provide an appropriate
environment for the enzyme and their porosity can be modified through the amount of
crosslinker used in their synthesis, and this fact is very important for entrapment of enzymes
of with different molecular weight. Furthermore, the composition and the surface of the
microgels can be modified to get rid of substances that produce interference in the enzymatic
response and are present in complex samples such as blood and serum. One important
property of these biosensors is their remarkable stability.
Second, the use of colloidal carriers made of biocompatible polymers is an alternative
for improving the transport of hydrophobic drugs across biological surfaces. In this work we
report the synthesis, characterisation, and possible application as drug-delivery system
magnetically triggered, of hybrid microparticles formed by magnetic nanoparticles embedded
within poly(ε-caprolactone). The magnetism of the microparticles permits their localisation
within the body using Magnetic Resonance Imaging and the biodegradable polymer layer
allows entrapping drugs that can be released when temperature increases.
Keywords: microgels, biosensors, hybrid microparticles, biocompatible polymer, drug
delivery system, magnetic resonance imaging, poly(ε-caprolactone).
12
ESC 2015
Author workshop – how to successfully publish scientific articles
Christian Schulz (Associate Publisher, Elsevier)
This workshop is for early career scientists looking for assistance in identifying, preparing
and submitting research articles to an academic journal. The workshop will provide advice on
best practices, top tips, ethics, the review process and other important considerations.
Are you:

A PhD student interested in publishing your first scientific or medical article?

A young PostDoc who wants to understand why articles are rejected?

A researcher who wishes to know what goes on behind the scenes in scientific
publishing?
Questions addressed at this workshop will include:

What do I need to consider when preparing my article?

How do I write an article for a specific journal?

What happens after I submit my article to a scientific journal?

How does the peer-review process work?

How do I choose a suitable journal?

Which tools are available during the writing process?

Or any other questions you might have!
Visit www.elsevier.com/authors for more information about publishing your article with
Elsevier.
13
ESC 2015
Dynamics of surfactant adsorption layers at water/oil interfaces
J. Won, V. Ulaganathan, T. Kairaliyeva, M. Karbaschi and R. Miller*
Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1,
14424 Potsdam, Germany
The characterization of liquid/liquid interfaces is generally similar to that of liquid surfaces,
with some peculiarities from an experimental as well as theoretical point of view. The work
horse for measuring the interfacial tension and dilational rheology of interfacial layers is the
drop profile analysis tensiometry (Fig. 1). This technique allows studying the formation of
adsorption layers over a rather broad time range and provides also data at very large
adsorption time, which are required for constructing the equilibrium adsorption isotherm.
There are unfortunately some systems which cannot be studies with this profile tensiometry –
systems in which both liquids have the same density. In these cases the only feasible
technique is capillary pressure tensiometry (Fig. 2), which also works under weightlessness
conditions in space.
Using this experimental technique adsorption layers have been studied of various series of
surfactants, of which the cationic surfactants alkyl trimethyl ammonium bromide (CnTAB)
and the sodium alkyl sulphates (SCnS) are in the focus of the presented work here. It will be
shown that at the interface between the aqueous surfactant solution and alkane as the oil phase
the adsorption of the surfactant molecules is in competition to the alkane molecules. For
comparison, also data for the solution/air interface are discussed. It turns out that the interface
between the aqueous solution and an alkane saturated air as the second fluid phase represents
an intermediate situation between the two interfaces water/air and water/alkane (Fig. 3).
Fig. 1 Pendent drop used
for shape analysis
tensiometry
Fig. 2 Spherical drop for
measuring the capillary
pressure
Fig. 3 Interfacial tension isotherms for SDS
measured at the water/air, water/hexane vapor, and
water/hexane interfaces
14
ESC 2015
Filming of bubbles
Jan Hupka
Gdansk University of Technology, Faculty of Chemistry, Department of Chemical
Technology, ul. Gabriela Narutowicza 11/12, 80-233 Gdansk
Key words: oily bubbles, surfactants, flotation, bitumen, precursor film
Fundamental and practical aspects of bubble filming with an oil phase are presented with
respect to flotation of bitumen droplets and the mechanism of bubble generation in porous
media. Positive spreading coefficient is required for bubble filming. It can be easily controlled
by addition of surfactants to the oil phase. The attachment of bitumen to a gas bubble and the
kinetics of bitumen spreading over the bubble surface should be rapid in order to guarantee an
efficient separation process. However, the experimental data have shown that transfer of
viscous bitumen from a quartz surface to an air bubble is relatively slow at room and
moderate temperatures. It was observed, that formation of thin bitumen films (precursor
films) preceded a bulk bitumen layer. The bulk layer spread at the bubble surface with a
velocity of an order of magnitude less than the velocity of the precursor film. Gas bubble
attachment mechanism to bitumen surface, spreading of bitumen on a gas bubble and the
release of bitumen-enveloped bubbles from mineral particles may weigh heavily on process
efficiency in multiple phase systems.
15
ESC 2015
Szczepan Zapotoczny
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland
Layer-by-layer (LbL) electrostatic self-assembly deposition method of oppositely charged
polyelectrolytes, is one of the most intensively investigated technique for fabrication of
ultrathin films. Originally introduced by Decher as “fuzzy nanoassemblies” LbL films exhibit
relatively high homogeneity as polymer chains forming adjacent layers highly interpenetrate.
However, for some possible applications (e.g. energy and/or electron transfer), more
stratified, discrete structures are deserved.
Here a novel approach is described to stratify multilayer polymer films by employing
amphiphilic polyelectrolytes as building blocks. These polyelectrolytes form well-define
micellar structures in aqueous solution with alkyl, aryl and/or perfluoroalkyl cores that are
also stable in the films after deposition. Such structured films with hydrophobic nanodomains
served
as host matrices for photoactive probes enabling studies of photoinduced
electron transfer (PET) and excitation energy transfer
(EET) (fig. 1). The micellar structures of the films was
confirmed using atomic force microscopy and their
stratification was indicated by following EET between
the energy donors and acceptors embedded within the
micellar layers with varying distance using fluorescence
microscopy. Further characterization of the films was
performed by means of spectroscopic ellipsometry and
contact angle measurements.
Fig. 1 Schematic model of photoinduced electron or
energy transfer between appropriate donor and acceptor
molecules embedded in the neighbouring layers of a
micellar LbL film.
Literature:
1. M. Kopeć, W.Niemiec, A. Laschewsky, M. Nowakowska, S. Zapotoczny, 2014,
„Photoinduced Energy and Electron Transfer in Micellar Multilayer Films", J. Phys.
Chem C, 118, 2215.
2. M. Kopeć, Ł. Łapok, A. Laschewsky, S. Zapotoczny, M. Nowakowska, 2014,
"Polyelectrolyte multilayers with perfluorinated phthalocyanine selectively entrapped
inside the perfluorinated nanocompartments", Soft Matter, 10, 1481.
3. M. Kopeć, T. Kruk, S. Zapotoczny, A. Laschewsky, S. Holdcroft, M. Mac, M.
Nowakowska, 2012, „Photoinduced electron transfer in multilayer films composed of
conjugated polyelectrolyte and amphiphilic copolymer hosting electron acceptor
molecules", J. Mat Chem., 22, 140.
4. W. Niemiec, S. Zapotoczny, K. Szczubiałka, A. Laschewsky, M. Nowakowska, 2010,
"Nanoheterogeneous multilayer films with perfluorinated domains fabricated using layerby-layer method", Langmuir, 26, 11915.
Acknowledgements:
Polish Ministry of Science and Higher Education „Ideas Plus” program.
16
ESC 2015
Surfactant layers and polymer brushes under confinement and
shear
Wuge H. Briscoe
School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK
It is very common in technological applications and biological systems that surfaces come to
close proximity or intimate contact. These surfaces are often decorated with polymers and
surfactants (or lipids), thereby tailoring surface properties and facilitating desired surface
interactions. The efficacy of these processes depends intricately on the structural
characteristics of the polymer and surfactant molecules present on the surface.
Using a version of the surface force apparatus, we have measured normal and, in particular,
shear forces between a pair of surfaces bearing two distinct surface structures in aqueous
media: polymer brushes and surfactant bilayers. Their effectiveness in reducing friction will
be critically compared in this talk, in particular the unifying feature of fluid hydration layers
about charged species in aqueous media. The implications of our results to the lubrication
process in biological living systems will also be discussed.
Literature: 1. Chen, M, Briscoe, WH, Armes, S & Klein, J 2009, ‘Lubrication at physiological pressures by
polyzwitterionic brushes’. Science, vol 323, pp. 1698 – 1701 2. Briscoe, WH, Titmuss, S, Tiberg, F, Thomas, R, McGillivray, D & Klein, J 2006, ‘Boundary
lubrication under water’. Nature, vol 444 (7116), pp. 191 - 194
17
ESC 2015
Zbigniew Adamczyk
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,
ul. Niezapominajek 8, 30-239 Cracow, Poland
Protein adsorption studies are often plagued by many misinterpretations and confusions
stemming from the abandonment of basic physics. Therefore, in this lecture, the thesis of a
dominant role of Coulomb electrostatic interactions in protein adsorption phenomena is
formulated. In order to prove this, a combination of theoretical and direct, in situ experimental
methods are implemented. In theoretical modeling emphasis is focused on coarse-grained
methods, exploiting the efficient bead models of protein molecules. Using this approach basic
hydrodynamic properties of protein molecules, such as the diffusion tensor, hydrodynamic
diameters and intrinsic viscosities are calculated using the linear Stokes equation.
Additionally, the surface blocking functions and jamming coverages for such model shapes
are determined using the random sequential adsorption (RSA) modeling. Knowing the
jamming coverage and blocking functions, boundary conditions for bulk transport equations
are formulated. Solutions of these equations for the convection and diffusion-controlled
transport are discussed. The theoretical results are exploited for the interpretation of protein
adsorption kinetics studied by AFM, QCM and in situ electrokinetic methods (streaming
potential, electrophoresis). Application of such hybrid approaches enabled one to
quantitatively determine protein adsorption mechanisms on various substrates including
polymeric microparticles (polystyrene latexes). It is shown that protein adsorption is mainly
governed by the discrete electrostatic interactions among ion pairs with negligible role of
other interaction types. Anomalous adsorption of proteins at surfaces bearing like surface
charges, where the classical, mean-field theories fail, is explained in terms of heterogeneous
charge distributions on protein molecules. By exploiting these experimental data, the validity
of the coarse grained approaches combined with solutions of the continuity equation for
quantitatively predicting protein adsorption kinetics is confirmed.
Acknowledgements: This work was financially supported by the Research Grants: POIG 01.01.0212-028/ 09-00 and the NCN Grant UMO-2012/07/B/ST4/00559.
18
ESC 2015
Aggregation in Dispersions Containing Mixtures of Particles
Professor Brian Vincent
University of Bristol, School of Chemistry, Bristol, BS8 1TS, UK
Many colloidal systems industrially consist of mixtures of particles. This introduces new
concepts, and indeed even new types of interparticle forces, compared to dispersions of single
particles. Over the years my group in Bristol has studied different kinds of mixed particle
systems, mainly from the dispersion stability standpoint. This seminar will include a mixture
of earlier and more recent studies in this area, and will attempt to draw together some of the
observations we have made. For binary mixtures of two particle types a recurring theme will
be that the overall stability of the system to aggregation depends on two main factors: the
ratio of the particle sizes, and the ratio of the particle concentrations.
Three types of system will be considered. The first is the classical case of mixtures of
particles of opposite charge. Here the primary driving force for (hetero-) aggregation is longrange electrostatic attraction (at least at low ionic strengths). Where the particles are of similar
size then fractal hetero-aggregate structures are obtained, with fractal dimensions generally
lower than for homo-aggregates [1]. For systems where the particle size ratio is much greater
than one, then one may consider this as a system where the smaller particles “adsorb” onto the
larger, oppositely-charged particles [2-4]. The particle concentration ratio then controls
whether one obtains particle bridging aggregates or complete coverage of the large particles
by the small ones, preventing further aggregation.
Similar considerations apply when the nature of the attractive force is changed to that between
two sets of particles, each carrying a different adsorbed (or preferably grafted) polymer layer,
but where the equivalent homopolymers (in solution) form coacervate mixtures. A good
example here is mixtures of poly(acrylic acid) [PAA] or poly(methacrylic acid) [PMMA], and
poly(ethylene oxide) [PEO] in water at low pH (below about pH 4.5). These polymers form
coacervates as a result of strong H-boding between the ether oxygen of the PEO chains and
19
ESC 2015
the hydrogen of the carboxylic acid groups in the PAA or PMAA chains. At high pH no such
H-bonding can occur, because of ionisation of the carboxylic acid groups; then two polymers
phase separate into two phases, each rich in one of the polymers, rather than coacervate. Here
I will discuss the interactions between two sets of acrylate particles, one having grafted PEO
chains, and the other having grafted PMMA chains [5]. The main technique used in this work
has been controlled stress rheology [6].
The third mixed-particle system, which was more recently explored in my group, is rather
different. Here the main driving force for particle aggregation is the depletion attraction
caused by the addition of non-adsorbing (i.e. free) polymer is solution. Many studies of single
particles plus free polymer systems have been explored, but we were the first (I believe) to
study mixtures of two particles, plus free polymer. The depletion interaction is usually
relatively weak, and leads to reversible aggregation, and colloidal phase separation, rather
than the classical aggregation behaviour observed in systems with stronger interparticle
attraction forces. The phase behaviour in single particle systems is relatively well-understood,
so it was of interest to explore the phase behaviour in mixtures of binary particles, plus free
polymer. Of particular interest was the case where the two particles are of different sizes, one
much larger then the radius of gyration of the free polymer and one where the particle size
was similar to it [7,8].
Literature:
1. Snoswell, Rogers, Howe and Vincent, Langmuir, 2005 21 11439
2. Tadros, Vincent & Young, Faraday Disc. Chem. Soc., 1978 74 337
3. Luckham, Tadros & Vincent, Colloids Surfaces, 1983 6 101
4. Harley, Thompson & Vincent, Colloids & Surfaces, 1992 62 163
5. Cawdery, Milling & Vincent, Colloid Surfaces, 1994 272 1273
6. Starck & Vincent, Langmuir 2006 22 5294
7. Zhou, van Duijneveldt & Vincent, Langmuir 2010 26 9397
8. Zhou, van Duijneveldt & Vincent, Phys. Chem. Chem. Phys, 2011 13 11
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ESC 2015
Oral presentations
21
ESC 2015
Formulation and in vitro characterization of W/O colloidal
nanodispersions for medical applications
Chatzidaki D. Maria1,2*, Damien Amadei3, Vassiliki Papadimitriou1, Julien Monteil3,
Fernando Leal-Calderon3, Frédéric Carrière4, Xenakis Aristotelis1,2.
1
Institute of Biology Medicinal Chemistry & Biotechnology, National Hellenic Research
Foundation, Athens, Greece
2
MTM, Faculty of Science and Engineering, Örebro University, Sweden
3
Laboratoire Chimie et Biologie des Membranes et des Nanoobjets, Univ. Bordeaux, France
4
Laboratoire d’Enzymology Interfacial and Physiology de la Lipolysis CNRS-Aix-Marseille
Université Marseille, France
For the last decades, there has been a significant increase of interest of medical industries for
W/O nanodispersions. More specifically, their unique ability to form nanostructures and
effectively encapsulate bioactive molecules, make them attractive biomaterials. In this
respect, W/O emulsions and microemulsions were successfully formulated using
biocompatible components and a relatively low percentage of emulsifiers1. Hydrophilic
bioactive molecules such as hydroxytyrosol (HT)2, an antioxidant of Extra Virgin Olive Oil
(EVOO) was effectively encapsulated. Structural characterisation of the systems in terms of
viscosity, Dynamic Light Scattering (DLS) and Electron Paramagnetic Resonance (EPR)
spectroscopy was measured. Moreover, the bioactive molecules’ release was qualitatively
observed by measuring the scavenging activity of HT towards galvinoxyl stable free radical3.
Following, a “two step” in vitro digestion model4 was introduced in order to investigate the
behavior of the systems in the absence and presence of HT under gastrointestinal conditions
and their potential interactions with gastric and pancreatic lipases.
Finally, in order to check the inhibition effect of HT on colon cancer, cell line BRAF V600E
mutant was treated with the proposed microemulsions used as effective vehicles of HT.
Literature:
1. Amadei, D.; Chatzidaki, M. D.; Devienne, J.; Monteil, J.; Cansell, M.; Xenakis, A.; Leal-Calderon,
F. 2014. Low shear-rate process to obtain transparent W/O fine emulsions as functional foods.
Food Res. Int., 62, 533-540.
2. Fernandez-Bolanos, J. G.; Lopez, O.; Fernandez-Bolanos, J.; Rodriguez-Gutierrez, G. 2008.
Hydroxytyrosol and derivatives: isolation, synthesis, and biological properties. Curr. Org. Chem.,
12 (6), 442-463.
3. Papadimitriou, V.; Sotiroudis, T. G.; Xenakis, A.; Sofikiti, N.; Stavyiannoudaki, V.; Chaniotakis,
N. A. 2006. Oxidative stability and radical scavenging activity of extra virgin olive oils: an electron
paramagnetic resonance spectroscopy study. Anal. Chim. Acta, 573-574, 453-8.
4. Fernandez, S.; Chevrier, S.; Ritter, N.; Mahler, B.; Demarne, F.; Carrière, F.; Jannin, V. 2009. In
vitro gastrointestinal lipolysis of four formulations of piroxicam and cinnarizine with the self
emulsifying excipients Labrasol® and Gelucire® 44/14. Pharm. Res., 26 (8), 1901-1910.
22
ESC 2015
Towards Modern Drug Carriers: Nanocapsules Stabilized by
Amphiphilic Copolymers
Szafraniec Joanna1*, Janik Małgorzata1, Gumieniczek Elżbieta1, Zapotoczny Szczepan1
1
The development of the techniques of preparation of nanocontainers has attracted particular
attention in recent years. Numbers of works have been directed towards controlled release
strategies to achieve high efficiency of encapsulation by minimizing the degradation and
prolonging time of release. This approach is particularly important in pharmaceutical
applications, especially concerning liphophilic active substances. Since the reservoir systems
are expected to have desirable properties it is important to choose appropriate material for
their preparation.
In this work we present studies on surfactant-free technique of preparation of nanocapsules on
liquid cores. Emulsion droplets were stabilized by amphiphilic graft polymers that anchored
the hydrophobic side chains in the oil droplets. Formation of such nanocapsules was
confirmed by dynamic light scattering measurements as well as electron microscopies (SEM
and cryo-TEM). Obtained capsules shown long-term stability which was further improved by
formation of multilayer shells via “layer-by-layer” technique relying on consecutively
alternating adsorption of oppositely charged polyelectrolytes. Moreover, they were able to
effectively encapsulate hydrophobic fluorescence probes which enable application in the field
of nanodelivery systems.1
Literature:
1. Szafraniec Joanna, Janik Małgorzata, Odrobińska Joanna, Zapotoczny Szczepan, 2015.
Nanocapsules Templated on Liquid Cores Stabilized by Graft Amphiphilic Polyelectrolytes.
Nanoscale. DOI: 10.1039/C5NR00064E.
Acknowledgements:
J. S. acknowledges the financial support from the project Interdisciplinary PhD Studies "Molecular
sciences for medicine" (co-financed by the European Social Fund within the Human Capital
Operational Programme).
23
ESC 2015
Core-Shell Nanoparticles for DNA Delivery Actuated by Magnetic
Fields
Annalisa Salvatore*, Debora Berti, Massimo Bonini, Piero Baglioni
Department of Chemistry and CSGI, University of Florence, via della Lastruccia 3, 50019
Sesto Fiorentino, Italy
One of the major areas of research in nanomedicine is the design of drug delivery systems
with remotely controllable release of the drug. Despite the enormous progress in the field, this
aspect still poses a challenge, especially in terms of selectivity and possible harmful
interactions with biological components other than the target. We report an innovative
approach for the controlled release of DNA, based on clusters of core–shell magnetic
nanoparticles [1].The coating of magnetic nanoparticles with an external inert shell, such as
gold, has been proposed in order to add further properties (enhance biocompatibility,
protection of the magnetic core against oxidation) to the nanoparticles, without modifying
their superparamagnetic behaviour. Moreover, gold provides an optimized and wellestablished platform for chemical functionalization, through the attachment of thiolated
biomolecules, such as DNA. Another possible strategy is to connect DNA by click-chemistry
methods.
The versatility of DNA as a block molecule for nanotechnologies, lies in the unique
recognition selectivity, modularity, molecular recognition properties towards biological
targets, thermal responsitivity, which can be coupled to the optical, thermal, electric
properties of inorganic nanomaterials.
We have accomplished the conjugation of Au@Fe3O4 with a thiolated single-stranded
oligonucleotide, whose pairing with a half-complementary strand in solution induces
clusterization. The application of a low frequency (6 KHz) alternating magnetic field induces
DNA melting with the release of the single strand that induces clusterization. The release and
delivery of the staple is based on the hyperthermic heating of clusters of DNA coated
magnetic NPs [2].
The possibility of steering and localizing the magnetic nanoparticles, and magnetically
actuating the DNA release discloses new perspectives in the field of nucleic-acid based
therapy.
Literature:
1. M. Bonini, D. Berti, P. Baglioni, Nanostructures for magnetically triggered release of drugs and
biomolecules, CURRENT OPINION IN COLLOID & INTERFACE SCIENCE, 2013, 18, 5, 459467.
2. M. Banchelli, S. Nappini, C. Montis, M. Bonini, P. Canton, D. Berti and P. Baglioni, Magnetic
nanoparticle clusters as actuators of ssDNA release, Phys. Chem. Chem. Phys., 2014,16, 1002310031
24
ESC 2015
Microstructured fluids at skin interface: biomedical applications
Liuzzi Roberta1,2*, Carciati Antonio1,2, Caserta Sergio1,2, Guido Stefano1,2
1
Department of Chemical, Materials and Production Engineering, University of Naples
“Federico II”, P.zzle Tecchio 80, 80125 Naples
2
CEINGE- Advanced Biotechnologies, Via Sergio Pansini 5, 80131 Naples
In the last years, multiphase fluids, such as emulsions, have been investigated as optimal
dermal or transdermal vehicles for drug permeation into the skin. Several cosmetic and
pharmaceutical products are based on emulsions. Surfactants can be added to reduce
interfacial tension of the droplets and to improve the stability of the final products 1. The
morphology of these multiphase fluids can strongly influence the capacity of the dispersed
phases, typically containing the active principles, to penetrate and to interact with skin layers.
Emulsion morphology can be affected by the process flow, or even by the stress induced
during the application of the product. For example the rubbing of a lotion can lead very high
shear stresses on the fluid, causing drop deformation and break-up2. On the other hand, skin is
a very complex structure, that acts as barrier against the penetration of external compounds3
(Fig1). The comprehension of the effective interaction mechanisms between multiphase fluids
and skin by which these formulations work, is today argument of notable interest and not
totally clear. The aim of this work is to propose innovative methodologies to investigate the
penetration of different compounds thorough skin biopsies or model systems by time-lapse
confocal microscopy and images analysis. Confocal laser scanning microscopy can be a
valuable tool for the investigation of the dynamic evolution of the transport process.
Localization of a permeating molecule is possible by using a fluorescent tracers specific of
one of the emulsion components. Our study can provide information useful for a fine tuning
of drug posology and formulation, in order to optimize delivery efficiency for different
applications.
Fig. 1 Autofluorescence of skin samples: arm (a-c), frontal site (b)
Literature:
1. M. J. Lawrence and G. D. Rees. 2000. Microemulsion-based media as novel drug delivery systems.
Advanced drug delivery reviews 45 (1), 89-121.
2. S. Caserta,S. Reynaud,M. Simeone, S. Guido. 2007. Drop deformation in sheared polymer blends.
Journal of Rheology 51. 761-774.
3. K. Moser, K. Kriwet, A. Naik, Y. N. Kalia and R. H. Guy. 2001. Passive skin penetration
enhancement and its quantification in vitro. European journal of pharmaceutics and
Biopharmaceutics 52 (2), 103-112.
25
ESC 2015
Physicochemical characteristics of albumin dimer and its
monolayers on solid surfaces – electrokinetic studies
Marta Kujda1*, Zbigniew Adamczyk1
1
Adsorption of globular proteins on solid surfaces has significance in biochemistry,
biotechnology and bioengineering for preparing biosensors, biomaterials and immunological
assays. In these processes, various albumins are often used. Human serum albumin (HSA) is a
monomer protein, which is present at a high concentration in the blood. It plays an important
role as a carrier of fatty acids, hormones, vitamins and drugs. The use of albumin as a carrier
for drugs has been systematically studied. However, the administered HSA is readily
eliminated from blood circulation under pathological conditions. In order to solve this issue it
was suggested to increase a molecular size of HSA and prepare synthetic cross-linked dimeric
form. Therefore, an original objective of this work was the synthesis, thorough
physicochemical characteristics and determination of ligand binding properties of albumin
dimer using electrokinetic methods. The physicochemical characteristics of the monomer and
the synthesized albumin dimer such as diffusion coefficient, hydrodynamic diameter,
electrophoretic mobility and zeta potential have been determined as a function of pH and
ionic strength using the dynamic light scattering (DLS) and laser Doppler velocimetry (LDV)
methods. However, despite essential significance, adsorption of these proteins at solid
surfaces has not been studied in a systematic way. Protein adsorption was carried out for the
range of ionic strength 10-2 to 0.15 M NaCl at pH 3.5. It was determined that maximum
coverage of albumins increases as a function of ionic strength. The study of desorption
process confirmed the stability of monolayers in various conditions of pH. Therefore, in the
next stage, monolayers of albumin dimer on negatively charged mica surface were prepared
and characterized using the in situ streaming potential method. These stable albumin
monolayers were used to perform studies on ligand (such as ions, antioxidants) bindings
properties using the precise electrokinetic method. This technique has great advantages in
comparison to standard binding assays (ex. ELISA test). The obtained results revealed unique
physicochemical properties of HSA dimer and its monolayers and can be used in numerous
practical applications in drug and biomaterials design.
Acknowledgements: This work was supported financially by the Polish National Science Centre,
grant no. PRO-2012/07/N/ST5/02219, Smoluchowski Scholarship from KNOW Leading National
Research Centre and project Doctus.
26
ESC 2015
Synthesis of polyelectrolyte nanocapsules with iron oxide
nanoparticles for magnetic targeting
1
1
2
2
1
1
K.Podgórna , K.Szczepanowicz , A.Karabasz , M.Bzowska , J.Korecki , M.Bielańska ,
1
P.Warszyński
1
2
Faculty of Biochemistry, Biophysics, and Biotechnology of the Jagiellonian Uniwersity,
Gronostajowa 7, 30-387 Krakow, Poland
Magnetic vehicles became highly promising for delivery of therapeutic actives as they
can be targeted to selected pathologically changed tissues/cells through the application of a
magnetic field gradient. That should not only significantly decrease deleterious side effects,
but also may drastically enhance therapy efficiency. Various types of carries were proposed
for targeted drug release. One of them, are polyelectrolyte nanocapsules, prepared by layer by
layer technique. It is a convenient method to form multilayer coatings on colloidal cores by
sequential adsorption of charged species like polyelectrolytes, nanoparticles (e.g. magnetic
nanoparticles), proteins, organic molecules.
The aim of this work was preparation and characterization of magnetically responsive,
loaded nanocapsules based on a liquid core encapsulation by polyelectrolyte (PE) multilayer
adsorption. Nanocapsules were prepared by LBL method using biocompatible
polyelectrolytes (Poly L-lysine and Poly Glutamic acid), with low-energy
microemulsification. Two approaches were proposed for incorporation of magnetic particles
with different sizes within nanocapsules. Iron oxide nanoparticles were encapsulated in the
liquid core or they were embedded into the polyelectrolyte multilayer shell. Moreover, the
model drug (β carotene) was successfully encapsulated in liquid core. Size of obtained
magnetic capsules were investigated using Dynamic Light Scattering and Nanoparticles
Tracking Analysis. Moreover morphology of magnetic carriers were investigated by CryoScanning Electron Microscopy. Toxicity test of synthesized magnetic nanocapsules were
performed. Additionally, magnetic properties of synthesized nanocapsules were examined
using Mossbauer Spectroscopy. This magnetically responsive drug nano delivery system may
be a promising platform for future targeted therapies or other biomedical applications.
27
ESC 2015
Evaluation of Cytotoxicity of Biorefinery-derived Amphiphilic
Molecules on Multi-scale In-vitro Models
Lu Biao1*, Miao Yong2, Chagnault Vincent2, Grand Eric2, Wadouachi Anne2, Postel Denis2,
Egles Christophe1, Pezron Isabelle3, Vayssade Muriel1
1
Sorbonne Universités, Université deTechnologie de Compiègne, BMBI UMR CNRS 7388,
France
2
Université de Picardie Jules Verne, LG2A CNRS FRE 3517, France
3
Sorbonne Universités, Université deTechnologie de Compiègne, EA TIMR 4297, France
Nowadays, a wide variety of new molecules can be synthesized from plants [1,2]. Among
them, the family of glyco-derived molecules, which are considered as alternatives to chemical
surfactants, due to their relatively high biodegradability and biocompatibility, exhibit
interesting properties both in terms of their self-assembly and their ability to induce biological
responses.
In this study, we have screened synthesized glycolipids according to their solubility in
aqueous phase. Four pre-selected molecules, with a C8 chain linked to a glucose or maltose
head through an amide functional group, either under the form of carbamoyl (carbohydrate
scaffold bearing the carbonyl) or alkylcarboxamide (the alkyl chain bearing the carbonyl),
were then dissolved in water for surface tension measurements. To evaluate the cytotoxicity
of these molecules on cells and tissues, 3 in-vitro models were established: i) Monolayer
model, L929 cells were seeded in a culture plate to form a single cell layer; ii) 3D cell culture
model, L929 cells were embedded into collagen gel; iii) Commercialized HSE (Human Skin
Equivalent), differentiated human keratinocytes were cultured at air-liquid interface.
Results show that the synthesized glycolipids, Glu1amideC8, Glu6amideC8, Glu6amideC8’
and Mal1amideC8 can reduce the surface tension of water solution to the same level as
Tween 20 and Hecameg do. In the meantime, Glu1amideC8, Glu6amideC8’ and
Mal1amideC8 present less cytotoxicity effects on L929 cells both in the monolayer model and
the 3D model than Tween 20 and Hecameg. All synthesized molecules have no obvious
influence on cell metabolic activity in HSE. It indicates their potential of being used for
biological related products.
This work was performed, in partnership with the SAS PIVERT, within the frame of the
French Institute for the Energy Transition (Institut pour la Transition Energétique (ITE)
P.I.V.E.R.T. (www.institut-pivert.com) selected as an Investment for the Future
(“Investissements d’Avenir”). This work was supported, as part of the Investments for the
Future, by the French Government under the reference ANR-001.
Literature:
1. Krister Holmberg, Natural surfactants, Current Opinion in Colloid & Interface Science, 2001, 6(2),
p. 148-159.
2. Valery M. Dembitsky, Astonishing diversity of natural surfactants: 1. Glycosides of fatty acids and
alcohols, Lipids, 2004, 39(10), p. 933-953.
Acknowledgements:
Acknowledgements to the Chinese Scholarship Council for the financial support of Biao Lu PhD
grant.
28
ESC 2015
Modification of colloid-chemical and balneological properties of
therapeutical muds with nano- and microparticles
V.O. Oliynyk 1*, A.V. Panko1, O.M. Nikipelova2
1
2
F.D.Ovcharenko Institute of biocolloid chemistry
Ukrainian Research Institute of Medical Rehabilitation and Balneology
An influence of modification additives on the basis of montmorillonite and calcium carbonate
[1, 2] containing nano- and microparticles on colloid-chemical and balneological properties of
peloids (therapeutical muds) was investigated with rheological, SEM, XRD, chemical and
medico-biological methods. It was showed that such additives allow increasing therapeutical
mud medicobiological activity in 2-3 times in established conditions of their modification
influence on peloids. It was established that besides of modificators’ adsorption, ionexchanging characteristics and ability to isothermal or nanochemical recondensation in
laminar or convective mixing mode, their positive influence on therapeutical mud properties
is specified with processes of their interaction with peloid microorganisms. They promote
slow-down of nanoparticle growth process caused by isothermal Van der Waals
recondensation.
Literature:
1. Panko A.V., Ablets E.V., Kovzun I.G., Protsenko I.T., Ulberg Z.R., Nikipelova E.M. 2014.
Biocolloid nanoparticle influence of CaCO3 on medicoendoecological peloid properties. CERECO2014: Proceedings of the Conference: P.152-158
2. Olejnik V.A., Panko A.V., Nikipelova E.M., Alekseenko N.A., Kovzun I.G. 2012. Influence of
nanomaterials on biological activity of marine pelagic sediments (peloids). Proc. of the
International Conference Nanomaterials: Applications and Properties. Vol. 1, № 2: 02NNBM16
(3pp).
29
ESC 2015
Synthesis of the PCL nanoparticles containing neuroprotectants
from oil-in-water nanoemulsion by phase inversion emulsification
method
Łapczyńska M.1*, Piotrowski M.1, Jantas D.2, Szczepanowicz K. 1, Warszyński P.1
1
2
Department of Experimental Neuroendocrinology Polish Academy of Sciences,
Smętna 12, 31-343 Cracow, Poland
Alzheimer’s and Parkinson’s are called diseases of civilization and are strongly related
with rapidly ageing of population. Prevention and treatment of stroke and neurodegenerative
diseases are major and unresolved problems of contemporary medicine. Despite of the
progress in understanding of molecular mechanisms of neuronal injury and preventing them,
only few neuroprotective substances are used in the clinic. However, their efficiency in the
treatment is not satisfactory. One of the major limitations is an inefficient delivery of
neuroprotective drugs by the blood-brain barrier (BBB) to the affected part of the brain.
Therefore, the main aim of the research is to develop a new strategy of delivery of
neuroprotectants by the nanocarriers, which are able to cross BBB without imposing side
effect on its normal function.
In the present work we were focused on synthesis of PCL (polycaprolactone)
nanoparticles containing active neuroprotectants (Polydatin and/or Resveratrol) as well as
model drugs (Cumarin-6 and/or Clozapine). This neuroprotectant loaded PCL nanocarriers
were prepared from oil-in-water nanoemulsion by phase inversion emulsification method. All
nanocarriers were characterized by size, size distribution, zeta potential and imaged by SEM.
Biotest of the synthsized nanosystems and their stability in the simulated body fluid (SBF)
was also determined.
Acknowledgements: This study was supported by the Norwegian Financial Mechanism grant PolNor/199523/64/2013 NanoNeucar and M. Smoluchowski scholarship, KNOW.
30
ESC 2015
Diffusion Techniques as Reactivity Mapping Tool of Biocolloids
Smilek Jiří1*, Sedláček Petr1, Klučáková Martina1
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova
464/118, 61200 Brno, Czech Republic
1
One of the most important gaps in the knowledge of biocolloids or biopolymers is the study
on their reactivity. Simple universal reactivity mapping tool for these compounds is needed.
Major gaps in knowledge of biocolloids are still found in their reactivity and barrier properties
in natural dynamic systems. To overcome the problem with study on reactivity, new universal
reactivity-mapping tool is required.
The original combination of simple diffusion experiments of suitable diffusion probe with the
advantages of hydrogel porous media (simple preparation of hydrogels, the diffusion is
undisturbed by convection, etc.) provides very valuable information about the reactivity of
biocolloids. The transport and barrier properties of these compounds are studied by diffusion
of simple organic dyes through hydrogel material where different biocolloids are
homogenously distributed. The reactivity and barrier properties of biocolloids are compared
by determination of fundamental diffusion parameters such as effective diffusion coefficient,
sorption capacity, lag time (the time needed for penetration of chosen organic dye through
hydrogel porous barrier) or concentration of organic dye on the interface hydrogel-solution.
The barrier and transport properties were studied by both non-stationary and stationary
diffusion experiments in the diffusion cell. The linear polysaccharide agarose was used for
preparation of porous hydrogel media in both cases. The influence of changes in physicalchemical properties of the system can be studied very easily (pH, ionic strength, temperature,
concentration of active substances, modification of humic acids, etc.). Hydrogels contain the
majority of water and the system used for study on reactivity of biocolloids is dynamic,
because of mentioned facts, conditions of studied biocolloids in laboratory are closed to real
biocolloids environment. Developed methods together with classical sorption experiments
could be the universal tool for study on reactivity of various natural compounds. The
universality of developed methods was tested also on systems with natural biopolymers
(chitosan, sodium alginate, hyaluronic acid), supramolecular compounds (humic acids)1,2. The
influence of basic physical-chemical conditions of the systems containing natural substances
can be studied easily at laboratory conditions and this is one of the greatest advantages of
developed methods.
Literature:
1. Sedláček Petr, Smilek Jiří, Klučáková Martina. 2013. How the interactions with humic acids affect
the mobility of ionic dyes in hydrogels – Results from diffusion cells. Reactive and Functional
Polymers: 1500-1509.
2. Sedláček Petr, Smilek Jiří, Klučáková Martina. 2014. How the interactions with humic acids affect
the mobility of ionic dyes in hydrogels – 2. Non-stationary diffusion experiments. Reactive and
Functional Polymers: 41-50.
Acknowledgements:
This work was supported by the project “Materials Research Centre at FCH BUT - Sustainability and
Development” No. LO1211 of the Ministry of Education, Youth and Sports of the Czech Republic.
31
ESC 2015
Direct Force Measurements Involving Positively and Negatively
Charged Colloidal Particles in the Presence of Multivalent
Cations
Moazzami Gudarzi Mohsen1*, Maroni Plinio1, Borkovec Michal1
1
Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva,
Switzerland
Classical theory of DLVO is able to present an accurate prediction of the interactions among
colloidal particles in simple monovalent salts, especially at low ionic strength. However, it
fails to capture the forces involve at short distances. The presence of these short range nonDLVO interactions becomes more pronounce in the presence of multivalent ions. These
forces could have different origin, magnitude and range depending on the surface properties
and interacting medium.
Interactions between positively and negatively charged latex particles in the aqueous solution
of rod-like oligoamine were investigated using colloidal probe technique. Our technique
allows us to attach individual particles to the cantilever in situ in fluid cell and measure the
colloidal forces between two particles in both symmetric and asymmetric fashions (Fig. 1).
Oligoamine cations strongly adsorb to negative interface, even overcharge the interface
whereas they repel from the positively charged interface. DLVO theory can quantitatively
predict the interaction between the surfaces, but at large distances (>6nm). Additional
attractive forces exist at short distances among both positive and negative interfaces. These
non-DLVO forces decay exponentially with average decay length of 1nm and 0.3nm for
negatively and positively charged particles, respectively. Analysing the interactions in
asymmetric system showed that the non-DLVO forces can be modelled with decay length of
0.5nm. The magnitude of these forces is between the non-DLVO forces in symmetric cases.
Apart from the origin of these forces, these results fairly indicate there is not a noticeable
synergistic or antagonistic effect as dissimilar interfaces interact together compare to when
they interact in symmetric mode.
Fig. 1 Surface forces can be measured among the dissimilar particles in symmetric (A-A, B-B) and asymmetric
(A-B) fashions using multi-particle colloidal probe technique.
32
ESC 2015
Revisiting Kynchian Analysis of Gravitational and Centrifugal
Settling for Strongly Flocculated Suspensions
Skinner Samuel1*, Stickland Anthony1, Usher Shane1, Scales Peter1
1
Particulate Fluids Processing Centre, The University of Melbourne
Solid-liquid separation involving strongly flocculated suspensions is important in a large
range of industrial applications, including mineral processing and wastewater treatment and
disposal. Development of theoretical descriptions of solid-liquid separation, or dewatering,
has allowed modelling of different dewatering behaviour and optimisation of dewatering
device design. Kynch (1952) developed a dewatering theory for interpreting experimental
gravitational settling results at high particle concentrations but it failed to account for
compression of the settled material1. Buscall and White (1987) introduced a fundamentally
rigorous dewatering theory for colloidal suspensions able to account for this material
compressibility2. The theory uses two key parameters; the extent of dewatering or
compressive yield stress, Py(ɸ), and the rate of dewatering or hindered settling function, R(ɸ).
R(ɸ) is a material property dependent on the solids volume fraction, ɸ, that quantifies the
interphase drag or hydrodynamic force on colloidal suspensions. This can be applied to a
solid moving through liquid during settling or liquid moving through solids in the case of
cake consolidation. There are existing methods for determining R(ɸ) from gravitational
settling tests3 and centrifugal settling tests4 that have been shown to accurately model
dewatering behaviour. The work of Usher et al. (2013) assumes certain aspects of centrifugal
sedimentation behaviour that only approximate model predictions. A more rigorous analysis
using the method of characteristics is conducted in this analysis. This study extends the work
of Lester et al. (2005) by applying the same methodology to settling under a centrifugal force.
The model suspensions used in this study were wastewater treatment sludges, which are
dewatered industrially using a wide variety of operations from basic sedimentation to highspeed centrifugation. R(ɸ) values were extracted for these materials over a large range of
volume fractions. These results enable more rigorously valid characterisation of material
dewaterability from batch gravitational and centrifugal settling tests, thus providing useful
information for suspension processing.
Literature:
1. Kynch, George1, 1952. A theory of sedimentation. Transactions of the Faraday Society 48: 166176.
2. Buscall, Richard1, White, Lee2. 1987. The consolidation of concentrated suspensions. Part 1. The
theory of sedimentation. Journal of the Chemical Society. Faraday Transactions 1: Physical
Chemistry in Condensed Phases 83(3): 873-891
3. Lester, Daniel1, Usher, Shane2, Scales, Peter3. 2005. Estimation of the hindered settling function
R(ɸ) from batch-settling tests. AIChE Journal 51(4): 1158-1168.
4. Usher, Shane1, Studer, Lindsay2, Wall, Rachael3, Scales, Peter4. 2013. Characterisation of
dewaterability from equilibrium and transient cenrifugation test data. Chemical Engineering
Science 93: 277-291
33
ESC 2015
Linear viscoelasticity of human blood
Carciati Antonio1, 2*, Tomaiuolo Giovanna1, 2, Caserta Sergio1, 2, Guido Stefano1, 2
1
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale,
Università di Napoli Federico II
2
CEINGE Biotecnologie avanzate, Napoli
Rheology of soft-colloid suspensions such as human blood are extremely relevant from both a
scientific point of view and for clinic. Human blood can be seen as a colloidal system, in
which red blood cells (RBCs) are the suspended particles and plasma is the liquid. From the
rheological pint of view, in fact, blood is a complex fluid with non-Newtonian characteristics.
It consists primarily of deformable red blood cells2 which tend to aggregate reversibly in
microstructures, called “rouleaux”, which resemble stacks of coins (Fig 1); this tendency is a
major contributor to the viscoelastic flow behavior of blood. An increasing amount of clinical
and experimental data underlines the importance of the flow behavior of blood, the latter
being a major determinant of proper tissue perfusion1.
A
B
10 µm
Fig. 1 Typical rouleaux structures at volume fraction of 8% (A) and 16% (B).
In order to provide valuable information about blood microstructure, linear viscoelastic tests are
necessary. Currently few results are available in the literature and only a recent investigation by
passive microrheology3 has measured blood viscoelastic moduli, but the application of this
technique to a heterogeneous material such as blood is questionable.
Here, we report on an extensive rheological characterization of human blood both under steady
and oscillatory state. In particular, we present the first systematic set of oscillatory shear
measurements by conventional bulk rheology in order to evaluate storage and loss moduli of
whole human blood. The rheological behavior of human blood was characterized both in
physiological conditions and in RBC aggregating media. The latter ones were obtained by the
addition of a polymer and by increasing the hematocrit above the normal physiological levels.
Literature:
1. Baskurt OK, Meiselman HJ. 2003. Blood rheology and hemodynamics. In: Seminars in thrombosis
and hemostasis. New York: Stratton Intercontinental Medical Book orporation, c1974-. 435-450.
2. Tomaiuolo G, Simeone M, Martinelli V, Rotoli B, Guido S. 2009. Red blood cell deformation in
microconfined flow. Soft Matter. 5(19): 3736-3740.
3. Campo-Deaño L, Dullens RP, Aarts DG, Pinho FT, Oliveira MS. 2013. Viscoelasticity of blood
and viscoelastic blood analogues for use in polydymethylsiloxane in vitro models of the circulatory
system. Biomicrofluidics. 7(3): 034102.
34
ESC 2015
Influence of molecular exchange on the enclosed water volume
fraction of W/O/W double emulsions as determined by
low-resolution NMR diffusometry and T2-relaxometry
Vermeir Lien1*, Balcaen Mathieu1, Sabatino Paolo2, Dewettinck Koen3, Van der Meeren Paul
1
Particle and Interfacial Technology Group
2
NMR and Structure Analysis Unit
3
Laboratory of Food Technology and Engineering
123
Ghent University, Belgium
Oil in water (O/W) emulsions are widely used in various fields, ranging from foods to
pharmaceuticals. During the last years, the incorporation of water within the emulsified oil
phase has received an ever increasing interest. First of all, these so-called water in oil in water
(W1/O/W2) emulsions enable the formulation of light foods as part of the oily dispersed phase
is replaced by water. In addition, this technology enables to separate an internal water phase
(Water1) from an external water phase (Water2) by the oily phase, which opens perspectives
for encapsulation of otherwise incompatible water-soluble components.
Low-resolution T2-relaxometry and pfg-NMR diffusometry can be applied for determination
of the enclosed water volume fraction of W/O/W emulsions. Whereas pfg-NMR diffusometry
enables the discrimination between internal and external water based on differences in
diffusion behavior, the T2-relaxometry method is based on the relaxation behavior differences
of the internal and external water upon addition of an external water-soluble paramagnetic
probe, such as manganese dichloride. As compared to most alternative techniques, low
resolution NMR does not require the physical separation of both water phases. In addition,
both low resolution NMR techniques do not require any tracer addition during multiple
emulsion preparation, and hence can also be applied on existing formulations. Whereas T2
relaxation is faster and less affected by NMR parameters, pfg-NMR has the advantage that it
does not require any sample pretreatment.
The exchange kinetics seemed to play a crucial role in both NMR methods. More specifically,
water exchange effects on the enclosed water volume fraction as estimated by pfg-NMR
diffusometry became more noticeable with increasing NMR diffusion delay (in the seconds
range), whereas Mn2+ exchange mediated effects on the estimated enclosed water volume
fraction obtained by T2-relaxometry became more pronounced with increasing storage time
(in the days range). In terms of Mn2+ repartitioning kinetics (Mn2+-doped), double emulsions
with different fat phases behaved differently, as could be observed from the behavior of the
slow mode relaxation time as a function of storage time. However, an increased solid fat
content did not guarantee slower exchange kinetics. These experiments also demonstrate the
applicability of both methods to investigate exchange kinetics in emulsion systems [1].
Literature:
1. Vermeir Lien, Balcaen Mathieu, Sabatino Paolo, Dewettinck K. and Van der Meeren Paul (2014).
Influence of molecular exchange on the enclosed water volume fraction of W/O/W double
emulsions as determined by low-resolution NMR diffusometry and T2-relaxometry. Colloids and
Surfaces A, 456, 129-138.
35
ESC 2015
Impact of WO3 on surface topography of titania photocatalysts
Mioduska Joanna*, Anna Zielińska-Jurek, Hupka Jan
Gdansk University of Technology, Faculty of Chemistry,
Department of Chemical Technology
Titanium dioxide is promising photocatalyst for purification of water and air.
The most significant limitations in its use result from wide band gap (around 3.2 eV
for anatase), making it active in UV light. In order to extend light absorption to the visible
range of solar radiation, titanium dioxide has to be modified and/or doped.
In the presented work, titania was modified with tungsten trioxide (WO3). WO3 has its
valence and conduction bands correspondingly lower than those of titanium dioxide.
The combination of these two semiconductors results in obtaining a composite with lower
energy gap, hence with the activity shifted toward visible region. Absorbance spectrum versus
wavelength of modified and pure titania is presented in Fig. 1.
The surface morphology plays an important role in the photocatalytic activity
of semiconductor nanoparticles. The use of scanning electron microscope was the preliminary
examination of the photocatalyst topography, in order to evaluate, changes of modified
or catalyst doped samples. Besides SEM images, the samples were subsequently characterized
using XRD, which allowed to determine the dominated crystal phase.
Fig. 1 Absorbance spectrum versus wavelength of modified and pure titania
36
ESC 2015
Characterization of Langmuir monolayers formed by derivatives
of fluorinated Polyhedral Oligomeric Silsesquioxanes
Anna Wamke1*, Marta Piechocka1, Katarzyna Dopierała1, Krystyna Prochaska1,
Hieronim F. Maciejewski2, Aneta D. Petelska3
1
Institute of Chemical Technology and Engineering, Poznan University of Technology,
Berdychowo 4, 60-965 Poznań, Poland
2
Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań, Poland
3
Institute of Chemistry, University of Bialystok, Ciolkowskiego 1K, 15-245 Bialystok, Poland
Previous studies have shown that fully condensed polyhedral oligomeric silsesquioxanes
(POSS) were able to form stable insoluble monolayers at the A/W interface [1]. The chemistry of
this class of amphiphilic materials has emerged as a new field of modern nanotechnology. POSS
derivatives consisting of a thermally robust inorganic SiO core with flexible organic functional
corona, represent hybrid organic-inorganic materials with unique physico-chemical properties.
Interfacial properties of POSS play a key role in future applications. However, there are very few
reports which describe the Langmuir monolayers form by POSS at the interface. Some derivatives
of fully condensed fluorinated POSS have been used in the development of high performance
materials as well as in medical applications [2].
In this study, the monolayer behavior at the A/W interface for six derivatives of fully
condensed fluorinated POSS were presented. The differences between chemical structure of
POSS compounds analysed results from various ratio of unreactive (fluorinated, F) and reactive
(trimethoxysilane, TMS) substituents added to the inorganic core of their molecules. One of the
goal of this study was observing the hydrolysis and condensation processes of TMS substituents
in POSS molecules forming a monolayer at the A/W interface.
The interfacial properties were analysed by using computer–controlled KSV NIMA
Langmuir film balance system (KN 0033) with KSV NIMA Surface Potential Sensor (SPOT) and
a Brewster Angle Microscopy (BAM) (KSV NIMA MicroBAM). The Polarization modulation
Infrared Reflection Absorption Spectrometer (KSV NIMA PM-IRRAS) was used to study the
effectivity of the hydrolysis and condensation reactions of TMS groups present in POSS
molecules.
The results obtained showed that derivatives of fully condensed fluorinated POSS
compounds formed liquid stable monolayers at the A/W interface which compressibility strongly
depends on the type of substituents present in POSS molecules. Moreover it was found that the
effectivity of hydrolysis and condensation reactions of TMS groups is strongly affected by the pH
values of subphase.
Literature:
1. K. Dopierała, A. Wamke, M. Dudkiewicz, H.F. Maciejewski, K. Prochaska, 2014. Interfacial
Properties of fully condensed functional POSS. A Langmuir Monolayer Study. J PHYS CHEM C
118: 24548-24555.
2. S.T. Iacono, A.J. Peloquin, D.W. Smith, J.M. Mabry Chapter 6 in Applications of Polyhedral
Oligomeric Silsesquioxanes, Volumen 3 J. G. Matisons, C. Hartmann-Thompson, Dordrecht,
Heidelberg, London, New York: Springer Science+Business Media B.V., 2011.
Acknowledgements:
This work was financially supported by Polish National Science Center, Grand No. UMO2012/05/B/ST02200. The authors are grateful for the opportunity to perform research on KSV NIMA
PM-IRRAS purchased within EU Project number POPW.01.03.00-20-004/1.
37
ESC 2015
Nondestructive Characterization of Lysozyme Layers on Silica
Surface using MP-Surface Plasmon Resonance and Quartz
Crystal Microbalance
Ćwięka Monika*, Jachimska Barbara
Lysozyme has a very important function in the immune system, as it exhibits strong
antibacterial activity against gram-positive bacteria. This phenomenon has found practical
applications in medicine, the pharmaceutical industry and the food processing industry. For
this reason, the understanding of how the protein interacts with inorganic material surfaces is
of major interest in both fundamental research and applications such as biotechnology.
However, despite intense studies, the mechanism and the structural determinants of the
protein/surface interactions are still not fully understood.
The development of new research techniques makes it possible to study adsorption
with increasing accuracy: from simple measurements of adsorption kinetics at high protein
concentrations to detecting even a single protein molecule adsorbed on a surface. The
adsorption of lysozyme (LSZ) at a silica surface has been chosen as a model system. We have
analysed the LYZ adsorption using Quartz Crystal Microbalance with Dissipation (QCM-D)
and Multi-Parametric Surface Plasmon Resonance (MP-SPR) methods. A combination of
these complementary techniques has provided crucial information on the mechanisms behind
the protein-material interactions, LSZ structural changes and biomolecular rearrangements.
We have found that the pH strongly affects the effectiveness of LSZ adsorption onto the
surface and leads to orientation changes of protein on the surface. The highest adsorption
value was attained near the protein’s Iso-electric Point. The data clearly indicates that
electrostatic interactions are a driving force for LSZ adsorption.
Furthermore, from the combination of the QCM-D and MP-SPR data with the
assumption that the excess sensed mass measured in QCM-D compared to the MP-SPR mass
is due to trapped water, we have estimated the hydration of LSZ layer on the surface of silica.
Acknowledgements:
This work was supported by Grant NCN OPUS4 2012/07/B/ST5/00767.
38
ESC 2015
β-lactoglobulin adsorption at the water/oil system
at different pH and ionic strength
Jooyoung Won1,*, Jürgen Krägel1, Georgi Gochev1,2 and Reinhard Miller1
1
2
Max Planck Institute of Colloids and Interfaces, D-14424 Potsdam/Golm, Germany
Institute of Physical Chemistry, Bulgarian Academy of Sciences, 1113, Sofia, Bulgaria
Proteins, in general, adsorb at liquid interfaces and are well-known as efficient stabilizers of
foams and emulsions [1,2]. β-lactoglobulin (BLG) is one of the most widely studied ones due
to its major industrial applications particularly in food processing.
Oscillating drop tensiometry was applied to study adsorbed protein interfacial layers at
water/oil interfaces. In this work, the influence of different pH and ionic strength on the
dynamics of BLG water/tetradecane interface has been investigated. Dynamic interfacial
tension () and interfacial dilational elastic modulus (E’) of BLG solutions at three different
pH values of 3, 5 and 7 and at three different ionic strength are measured by Profile Analysis
Tensiometer (PAT-1, SINTERFACE Technologies, Berlin). Furthermore, interfacial tension
and dilational rheology of mixed solutions of BLG and with the anionic surfactant SDS
(sodium dodecyl sulphate) of varying protein/surfactant concentrations have been also
studied.
The presented results of the adsorption isotherm and the dilational visco-elasticity under
equilibrium and dynamic conditions is based on measurements of the dynamic interfacial
pressure and its response to sinusoidal drop area variations.
Literature:
1. Eric Dickinson and Yanda B.Galazka. 1991. Emulsion stabilization by ionic and covalent
complexes of β-lactoglobulin with polysaccharides. Food Hydrocolloids,5,281-296.
2. Georgi Gochev, Inga Retzlaff, Dotchi R. Exerowa and Reinhard Miller. 2014. Electrostatic
stabilization of foam films from β-lactoglobulin solutions. Colloids and Surfaces A, 460, 272–279.
39
ESC 2015
A thermodynamic study of ligand adsorption to colloidal surfaces
demonstrated by means of catechols binding to ZnO QDs
Wei Lin,1* Johannes Walter,1 Alexandra Burger,2 Harald Maid,2 Andreas Hirsch,2
Wolfgang Peukert,1 Doris Segets1
1
Institute of Particle Technology, 2Institute of Organic Chemistry,
Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany
Although being of major importance for various particle-based applications, the characterization
of liquid-borne colloidal surfaces in solution especially with respect to functionalization and
ligand exchange reaction is still an open and highly challenging question. Therefore, a general
strategy to study the thermodynamics of ligand adsorption to colloidal surfaces was established by
means of catechol (Ethyl 3,4-dihydroxybenzoate, CAT) binding to ZnO quantum dots (QDs).1
First, isothermal titration calorimetry (ITC) was used to extract all relevant thermodynamic
parameters, namely association constant, enthalpy, entropy and free energy of the ligand binding.
To confirm the characterization of ligand binding by measuring the heat of adsorption, the free
energy was cross-validated by mass-based adsorption isotherms. To close the mass balance,
analytical ultracentrifugation (AUC) was applied to detect the amount of free, unbound catechol
in solution. Then, Raman spectroscopy and nuclear magnetic resonance spectroscopy (NMR)
were performed to quantify the replaced amount of acetate with CAT (65%) and to distinguish
bound (chemisorbed) and unbound (physisorbed) CAT. Finally, based on a collection of all our
results, the full picture of ligand binding to the ZnO colloid is obtained as illustrated in Fig. 1.
HO
0.25 0.5 0.75 1.0
ML ML ML ML
O
HO
O
ZnO in EtOH
HO
-
-
O
-
O
O
-
O
H 3C
O
O
O O
O
O
O H 3C
O
-
-
O
-
O
O
O
O
O
O
O
O
HO
R
O
-
O
-
O
R
O
O
O
O
O
HO
OH
O
O
O
CH3
O
OH
free acetate bound acetate
HO
HO
O
O
R
CH3
O
OH
R
HO
OH
R
HO
R
R
HO
R
O
HO
HO
O
O
R
R
-
O
O
O
O HO
O HO
O
O
O
O
H3 C
O
O
R
-
R
O
O
O
O
O
R
HO
R
O O
OH
OH
CH3
CH3
O
O
O
R
HO
O
R
R
O O
R
O
CH3
-
O
O
-
O
O
O
OH
O
O
O
-
O
R
CH3
-
O
O
CH3
O
O
O
-
HO
HO
HO
O
H3 C
O
O
R
O
O
H 3C
O
CH3
O
O
H 3C
-
O
CH3
R
O
R
free CAT physisorbed CAT chemisorbed CAT
Fig. 1 Full picture of ligand exchange reaction and particle-ligand structure for ZnO quantum dots and CAT.
As all our results are in good agreement with each other and highly complementary, it is sufficient
to get the full picture of ligand binding in various particle-ligand interfacial systems even if only
parts of our approach can be applied. We believe that the general applicability of our
methodologies will provide strong encouragement for similar studies in the field of colloids and
thus paves the way to a knowledge-based interface design.
Literature:
1. Lin W., Walter J., Burger A. Maid H., Hirsch A., Peukert W., Segets D., 2015. A thermodynamic
study of ligand adsorption to colloidal surfaces demonstrated by means of catechols binding to
ZnO quantum dots. Chem. Mater., 27: 358−369.
40
ESC 2015
Droplet dynamics: Oil droplet attachment and spreading on solid
substrates
James Emily,1* Vaccaro Mauro2, Graydon Andrew2, Brooker Anju2, Jamadagni Sumanth3,
Biggs Simon4, Cayre Olivier1, Hunter Timothy1, and Harbottle David1
1
Institute of Particle Science and Engineering, University of Leeds, Leeds, UK
Procter & Gamble Ltd, Whitley Road, Newcastle, Tyne and Wear, UK
3
Procter & Gamble, Corporate R&D, Modeling and Simulation, West Chester, USA
4
Faculty of Engineering, Architecture and Information Technology, The University of
Queensland, Brisbane, Australia
2
The interaction between liquid droplets and solid substrates is ubiquitous in many commercial and
industrial applications. Often the application governs the nature of the liquid-solid interaction with
the droplet adhesion and ability to coat a substrate controlled by physical, chemical and
environmental conditions.
In the current research, short-time droplet spreading dynamics have been studied by measuring
the droplet contact diameter as a function of spreading time on a solid substrate in air. The droplet
spreading dynamics are shown to confirm two spreading regimes; i) inertial regime (r ∝ t0.5)
immediately after droplet-solid contact; and ii) viscous regime confirming Tanners law (r ∝ t0.1).
A series of silicone-based oils (poly (dimethyl siloxane) or PDMS) all bearing a methyl terminal
group but of different viscosities (10 – 10000 cSt) were initially studied. Normalization of the
spreading time by the oil viscosity resulted in a master curve that represents the viscous spreading
dynamics of these PDMS oils, see Figure 1. The effect of droplet impact velocity was also
assessed by varying the release height (6 cm and 3 cm) of the PDMS oil droplet. While both
heights result in a single master curve as a function of PDMS oil viscosity, there are differences
between the two master curves in the inertial regime and the long-time viscous regime. Reasoning
for the long-time deviation is currently being investigated.
Finally, the study considered the effect of PDMS oil terminal group by comparing the methylterminated oils against amino-terminated counterparts of similar viscosities and droplet spreading
dynamics in water. Multiple master curves for the different terminal groups and the varying
droplet height enable greater understanding of the droplet spreading dynamics and the governing
parameters which promote rapid droplet spreading.
b)
6
5
5
4
4
Diameter (mm)
Diameter (mm)
a)
6
3
2
10 cSt
50 cSt
500 cSt
1000 cSt
10000 cSt
1
0.01
0.1
1
Time (s)
10
3
2
10 cSt
50 cSt
500 cSt
1000 cSt
10000 cSt
1
1E-3
0.01
0.1
1
10
100
Time/Viscosity (Pa)
Fig. 1 a) Time dependent droplet spreading as a function of oil viscosity, b) normalization by the oil viscosity.
41
ESC 2015
Hofmeister Effects in Colloidal Aggregation in Aqueous Solutions
of Ionic Liquids
Oncsik Tamas*, Szilagyi Istvan, Trefalt Gregor, Borkovec Michal
Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva,
Switzerland
Specific ion effects are important for many scientific phenomena such as properties of
electrolyte solutions (e.g. viscosity, surface tension), protein behavior, colloid aggregation,
etc. There is an extensive literature about ion-specific aggregation of different type of
particles according to the Hofmeister series. However, most of them have dealt with simple
electrolytes. In this project we used ionic liquids (ILs) as coagulating agents, systematically
varying their constituents. The colloidal particles used were polystyrene latex particles
functionalized with charge-determining sulfate and amidine groups. The diameters of the
particles were 530 nm and 220 nm, respectively. Time-resolved dynamic light scattering
(DLS) and electrophoresis were used for the characterization. While with DLS we determined
the absolute aggregation rates and the corresponding critical coagulation concentrations
(CCC) which separates the slow and fast aggregation regimes, electrophoresis was used to
determine the charge state of the particles in different conditions. We tried to correlate the
suspension stability to the Hofmeister effect. We have also investigated the effect of increased
cation hydrophobicity. Depending on the type of salt, screening, neutralization, overcharging
can be observed at the concentration range investigated which is in good agreement with
previous results1. In some systems even restabilization can be seen. Based on our
measurements we placed the IL cations and anions into the well-known Hofmeister series.
Fig. 1 Aggregation and charging behavior of SL530 particles in the presence of ILs containing cations of
different hydrophobicity
Literature:
1. Szilagyi Istvan, Szabo Tamas, Desert Anthony, Trefalt Gregor, Oncsik Tamas, Borkovec Michal
2014. Particle aggregation mechanisms in ionic liquids, Phys. Chem. Chem. Phys. 16, 9515-9524
42
ESC 2015
Silica-ceria interactions during polishing
Réka Toth1,2 *, Grégory Lefèvre1, Philippe Barboux1, David Carrière3, Lauriane D'Alençon2,
Thierry Le Mercier2, Valérie Buissette2
1
2
RMD, Institut de Recherche de Chimie Paris, CNRS - France
Solvay, Centre de Recherche et Innovation de Paris Aubervilliers – France
3
Laboratoire LIONS, CEA Saclay - France
Chemical mechanical polishing is widely used in microelectronics industry. Polishing
consists in applying a slurry of colloidal particles onto a solid surface called substrate,
through a pressure applied with a rotating polymeric pad. Polishing is not simply a grinding
or abrasion problem, since in some case a substrate may be polished by softer powders. The
understanding of particle-substrate interactions is important to improve industrial polishing
performances in the future. For example, we have studied the interaction between the
substrate and the particles during a polishing experiment of SiO2 with CeO2.
Mechanical contact, hydrodynamic behaviour of the colloidal suspension, interaction
between particles and substrate, or adsorption effects between particle and dissolved species
are all important parameters to consider for polishing. Indeed, studies show the importance of
surface charge on polishing rate [1], and a proposed mechanism is that silica is torn away
from the substrate by the ceria particles sticking onto it [2].
To verify this hypothesis we followed the properties of the colloidal ceria particles
during a model polishing experiment. The evolution of the zeta potential of the particles
indicates that silica progressively covers their surface. This is in agreement with Energy
Dispersive X-ray analysis, which shows the presence of a silica layer deposited onto the
particles after polishing. These samples have been compared with model mixtures of ceria and
silica by small angle X-ray scattering (SAXS) that follows the ceria-silica interaction. Finally,
Infrared spectroscopy performed on the particles has shown that this silica layer results of the
peeling of the substrate, also confirmed by an AFM study on the substrate after polishing.
Fig. 1: Schematic illustration of a typical polishing tool.
Literature:
1. Lee M. Cook, 1990, Chemical processes in glass polishing, J. Non-Crystalline Solids 120:152-171
2. Tetsuya Hoshino, Yasushi Kurata, Yuuki Terasaki, Kenzo Susa, 2001, J. Non-Crystalline Solids
283:129-136
43
ESC 2015
Quantifying the rainfastness of fluorescently labelled
poly(vinyl alcohol) deposits on vicia faba leaf surfaces via
fluorescent microscopy
Brett Symonds1*, Niall Thomson2, Chris Lindsay2, Vitaliy Khutoryanskiy1
1
Reading School of Pharmacy, University of Reading, Whiteknights, PO Box 224, Reading,
RG6 6AD
2
Formulation Technology Group, Jealott’s Hill International Research Centre, Bracknell,
RG42 6EY
The world faces the significant challenge of securing a sustainable supply of food for a
growing population. This challenge must be met with less arable land per person and with
fewer resources. It is estimated that by 2050 the world’s population will reach 9 billion and
the United Nations Food and Agricultural Organisation estimates that the 2006-7 world
agricultural output must increase by 60% in order to meet projected demand.1 In some
situations up to 90% of the sprayed product may not reach the target site.2 This reduced
efficiency has been accredited to poor penetration through the plant cuticle, photolytic,
hydrolytic, microbial degradation and wash-off due to rain.3 There is evidence that, among
other substances, polymers are useful rainfastness agents.4
A laboratory scale method for characterising rainfastness is reported, as well as a larger scale
experiment using artificial rain to validate the method. A series of poly(vinyl alcohol) (PVA)
samples were fluorescently labelled with 5-(4,6-dichlorotriazinyl) aminofluorescein (5DTAF). Using fluorescent microscopy and ImageJ image analysis a method was developed to
follow how deposits of these polymer samples washed off of vicia faba (field/broad bean)
leaves (Fig. 1). This quantification of rainfastness is of great interest in the area of
agrochemical formulation. Characterising molecular weight of the polymers proved that those
PVA deposits of higher molecular weight were more rainfast than those of lower molecular
weight.
Fig. 1 An exemplary wash-off profile of a labelled deposit of PVA with corresponding pictures where the area of
coverage in the pictures is quantified with ImageJ and plotted.
44
ESC 2015
Literature:
1. FAO Statistical Yearbook 2013. (United Nations, 2013). At
<http://www.fao.org/docrep/018/i3107e/i3107e00.htm>
2. Pimentel, D. Amounts of pesticides reaching target pests: Environmental impacts and ethics. J.
Agric. Environ. Ethics 8, 17–29 (1995).
3. Wang, C. J. & Liu, Z. Q. Foliar uptake of pesticides—Present status and future challenge. Pestic.
Biochem. Physiol. 87, 1–8 (2007).
4. Gaskin, R. E. & Steele, K. D. A comparison of sticker adjuvants for their effects on retention and
rainfastening of fungicide sprays. New Zeal. Plant Prot. Soc. 342, 339–342 (2009).
Acknowledgements:
We acknowledge the BBSRC (CASE Studentship: BB/J0124401/1) and Syngenta for funding the
doctorate project. We also acknowledge the Chemical Analysis Facility (CAF) at the University of
Reading for use of NMR, WAXS and DSC equipment. Finally, we acknowledge our colleagues at the
University of Reading and Syngenta for their useful input, in particular Anne Stalker for providing
plants as well as Jill Foundling for help with microscopy, both of Syngenta.
45
ESC 2015
UV Curable Oil-in-Water Emulsions for 3D Functional Printing
Cooperstein Ido, Prof Magdassi Shlomo
Casali Center for Applied Chemistry, Institute of Chemistry and Center for Nanoscience
and Nanothechnology, The Hebrew University of Jerusalem, Jerusalem, Israel
In recent years the technology and materials for 3D printing was highly advanced and enable
printing of high resolution 3D structures. Additive manufacturing, or three dimensional
printing, is implemented in a variety of fields such as rapid prototyping and scaffolds for
medical applications. The 3D structures are formed with various monomers or polymeric
precursors and additives, while currently the main function of the printed object is the
structure itself. The goal of our research is to fabricate 3D porous structures containing
continuous functional matrix within the pores. These structures are fabricated by printing a
newly developed oil-in-water emulsion ink composed of curable acrylic monomers mixture as
the "oil" droplets, dispersed in water phase. The printing is performed by the digital light
process (DLP) method, in which the structure is formed by localized polymerization of
monomers. At the first stage, the UV light initiates curing of the monomer droplets, while at
the second stage, the continuous water phase evaporates and interconnected voids are formed.
Currently we focus on impregnating these voids within the printed structures with silver
nanoparticles that after a simple room temperature sintering process forms a conductive,
continues silver matrix within a solid polymer.
A
B
C
Fig. 1: Images of electric circuit printed from the curable emulsion (A) Image of the clean porous 3D
structure (B) Image of the porous structure after inserting Ag in DB dispersion, sintering and connecting
to 1.5V and LED, (C) UHR-SEM cross-section image of the printed structure with embedded Ag NPs.
Literature:
1. Cooperstein, I., M. Layani, and S. Magdassi. 2015. 3D printing of porous structures by UV-curable
O/W emulsion for fabrication of conductive objects. J. Mater. Chem. C, 3, 2040-2044.
46
ESC 2015
Effect of pH and salt concentration on velocity of rising bubbles
in Beta-Lactoglobulin solution
V.Ulaganathan1,*, G.Gochev1, M.Krzan2, S.S.Dukhin3, C.Gehin-Delval4 and R.Miller1
1
Max-Planck-Institut für Kolloid- und Grenzflächenforschung, 14424 Potsdam, Germany
Jerzy Haber Institute of Catalysis and Surface Chemistry, PAN, 30-239 Cracow, Poland
3
New Jersey Institute of Technology, University Heights, Newark, NJ 07102, USA
4
Nestlé Research Centre, Vers-Chez-Les-Blanc, 1000 Lausanne 26, Switzerland
2
The rising velocity profile of air bubbles in surfactant solutions is a sensitive measure for the
formation of a dynamic adsorption layer (DAL) at the bubble surface. Due to a certain surface
coverage by adsorbed surfactants the bubble surface becomes partly or completely immobilized
depending on the bulk concentration which retards the bubble’s rising velocity [1]. The adsorption
of ionic surfactants is affected by salt concentration due to presence of counter ions [2], which
eventually affects the rising bubble velocity [3]. In case of proteins the presence of salt and pH in
the solution would influence its molecular conformation and its adsorption properties [4].
Therefore, the present study gives an insight into the effect of solution conditions on the
f
-lactoglobulin.
Fig.1 Local velocity profiles of bubbles of 1.5 mm diameter (approx.) rising in 5x10 -7 mol/l
solution in 10mM of citric phosphate buffer at different pH.
-lactoglobulin
Literature:
1. S.S. Dukhin, R. Miller, G. Loglio, Physico-chemical hydrodynamics of rising bubble, in: D.
Möbius, R. Miller (Eds). 1998. Drops and Bubbles in Interfacial Research, New York, Elsevier,
367-432.
2. P. Warszyński, W. Barzyk, K. Lunkenheimer, H. Fruhner. 1998. Surface Tension and Surface
Potential of Na n-Dodecyl Sulfate at the Air−Solution Interface: Model and Experiment, J. Phys.
Chem. B. 102, 10948–10957.
3. M. Krzan, K. Malysa. 2012. Influence of electrolyte presence on bubble motion in solutions of
sodium n-alkylsulphates, (C8, C10, C12), 48, 49–62.
4. K. Engelhardt, M. Lexis, G. Gochev, C. Konnerth, R. Miller, N. Willenbacher, et al. 2013. pH
Effects on the Molecular Structure of β-Lactoglobulin Modified Air–Water Interfaces and Its
Impact on Foam Rheology, Langmuir. 29, 11646–11655.
Acknowledgement:
Nestle Research Centre, Lausanne, Switzerland for PhD grant (VU).
47
ESC 2015
Effect of the bubble dimensions and the shape deformation
degrees on its coalescence time at free water surface
Niecikowska Anna1*, Wiertel Agata1, Zawała Jan1, Małysa Kazimierz1
1
Degree of the bubble shape deformations during collisions with liquid/air interfaces
affects dimensions of the thin liquid films formed at free liquid surface and therefore plays an
important role in kinetics of the bubble coalescence. Depending on the bubble size and actual
deformation degree, the kinetics of drainage and stability of the intervening liquid film, separating
the interacting surfaces, can be quite different. When the bubble collides with free water surface
the outcome of collision depends on mutual rates of the competitive processes: (i) transfer of the
kinetic energy, associated with the bubble motion, into the surface energy, and (ii) drainage of the
separating liquid film to so-called critical thickness of rupture (hcr). The differences in kinetics of
these two simultaneous processes determine if bubble bursts or bounces prior to its rupture.
This paper presents the results of investigations on effect of the air bubble size and the
shape deformation degree on its coalescence time at free surface of distilled water. The
phenomena occurring during collisions and bouncing of the bubbles of radii 0.50 - 0.88 mm were
monitored using high-speed video recordings. The movies recorded were analysed frame-byframe to determine the bubble shape deformations and its local velocity variations during the
consecutive collisions. The bubble coalescence time (tc) was determined as the time interval from
the moment of the bubble 1st collision till its rupture. It was found that the tc values varied from ca.
25 to ca. 80 ms, when the bubble diameter was changed from 0.50 to 0.88 mm, respectively.
Prolongation of the tc was a consequence of larger number of the bubble bouncing from the water
surface prior to the rupture. Results of the experiments showed that the degree of bubble shape
deformation decreases with the subsequent collision number, due to dissipation of the kinetic
energy associated with the bubble motion and lower impact velocity of each consecutive strike
(see Fig. 1). The same effect was observed for all ranges of the bubble sizes studied. Kinetics of
the bubble coalescence is therefore determined by variations in radius of the intervening liquid
film (Rf), which is lower for smaller bubble deformation degrees.
Fig. 1 Photos and simulations of the bubble deformations at the consecutive collisions
Acknowledgements:
Financial support from National Research Center (NCN grant No. 2013/09/D/ST4/03785) is
acknowledged with gratitude.
48
ESC 2015
Influence of imidazolium ionic liquids structure on aggregation
behavior of triton X-100 nonionic surfactant
Anna Latowska*, Justyna Łuczak, Jan Hupka
Department of Chemical Technology, Chemical Faculty, Gdańsk University of Technology,
ul. Narutowicza 11/12, 80-952 Gdańsk, Poland
Physical and chemical properties of ionic liquids (ILs) have attracted much attention
in respect to their applications in organic synthesis, separation processes, electrochemistry, as well
as nanomaterials preparation. Particularly important is ILs negligible volatility, which prevents air
pollution, thereby makes them an alternative to volatile organic solvents. Moreover,
by modification of the cation structure and selection of the anion type, the properties of ILs may
be controlled and designed for selective applications [1, 2].
ILs have also gained an interest in colloid and surface chemistry due to their surface and
interface properties which enable to promote self-assembly of amphiphiles. Up to date only few
ILs were confirmed to support micellization of amphiphiles, however data on examined systems
are scarce and not classified yet. Moreover it was found that aggregation in ILs occurs less readily
than in water, due to solute-solvent interactions, different from those in aqueous systems [3].
Here we demonstrate an influence of ILs structure on micelle formation of Triton X-100
nonionic surtactant at 25oC. A group of imidazolium ionic liquids containing from two to eight
carbon atoms in the alkyl chain of the imidazolium cation and four different anions, namely
tetrafluoroborate, [BF4], hexafluorophosphate, [PF6], bis(trifluoromethanesulfonyl)imide, [Tf2N]
and trifluoromethanesulfonate, [TfO] anions were investigated for supporting surfactant
aggregation. The presence of aggregates in IL/Triton X-100 solutions was examined by means of
surface tension measurements as well as dynamic light scattering. It was observed that shortening
of the hydrocarbon substituent in the imidazolium cation as well as selection of the anion with
smaller size and less diffuse nature, strongly facilitates micelle formation. Therefore, aggregation
behavior was confirmed in ionic liquids composed of two to six carbon atoms in IL imidazolium
cation and with [BF4] and [PF6] anions. In given experimental conditions solvents composed of
eight carbon atoms in cation alkyl substituents, [Tf2N] and [TfO] anions did not support surfactant
aggregation. The presence of micelles in ionic liquids was confirmed by dynamic light scattering
measurements. The results revealed that the micellar diameter strictly depends on surfactant
concentration and increases significantly with increase of the surfactant content.
1. Greaves, T.L. and C.J. Drummond, Solvent nanostructure, the solvophobic effect and amphiphile
self-assembly in ionic liquids. Chemical Society Reviews, 2013. 42(3): p. 1096-1120.
2. Łuczak, J., A. Latowska, and J. Hupka, Micelle formation of Tween 20 nonionic surfactant in
imidazolium ionic liquids. Colloids and Surfaces A: Physicochemical and Engineering Aspects,
2015. 471(0): p. 26-37.
3. Inoue, T. and H. Yamakawa, Micelle formation of nonionic surfactants in a room temperature
ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate: Surfactant chain length dependence of
the critical micelle concentration. Journal of Colloid and Interface Science, 2011. 356(2): p. 798802.
49
ESC 2015
Effect of Laundry Surfactants on Surface Charge and Colloidal
Stability of Silver Nanoparticles
Sara Skoglund1*, Troy Lowe1, Jonas Hedberg1, Eva Blomberg1, Inger Odnevall Wallinder1,
Susanna Wold2 and Maria Lundin3
1
KTH Royal Institute of Technology, School of Chemical Science and Engineering, Surface
and Corrosion Science, SE-100 44 Stockholm, Sweden
2
KTH Royal Institute of Technology, School of Chemical Science and Engineering, Applied
Physical Chemistry, SE-100 44 Stockholm, Sweden
3
§Chemistry, Materials and Surfaces, SP Technical Research Institute of Sweden, Box 5607,
SE-114 86 Stockholm, Sweden
The stability of silver nanoparticles (Ag NPs) potentially released from clothing during a
laundry cycle and their interactions with laundry-relevant surfactants [anionic (LAS), cationic
(DTAC), and nonionic (Berol)] have been investigated. Surface interactions between Ag NPs
and surfactants influence their speciation and stability. In the absence of surfactants as well as
in the presence of LAS, the negatively charged Ag NPs were stable in solution for more than
1 day. At low DTAC concentrations (≤1 mM), DTAC−Ag NP interactions resulted in charge
neutralization and formation of agglomerates. The surface charge of the particles became
positive at higher concentrations due to a bilayer type formation of DTAC that prevents from
agglomeration due to repulsive electrostatic forces between the positively charged colloids.
The adsorption of Berol was enhanced when above its critical micelle concentration (cmc).
This resulted in a zeta potential close to zero and subsequent agglomeration. Extended DLVO
theory calculations were in compliance with observed findings. The stability of the Ag NPs
was shown to depend on the charge and concentration of the adsorbed surfactants. Such
knowledge is important as it may influence the subsequent transport of Ag NPs through
different chemical transients and thus their potential bioavailability and toxicity.
Fig 1: Particle size distribution measurements based on volume density of Ag NPs in aqueous solutions of pH
10 with different concentrations of DTAC, showing larger agglomerates in 1 mM DTAC than in the other
DTAC concentrations (left). This correlates well with zeta potential measurements, showing a charge
neutralization at 1 mM DTAC (right), making it more prone to agglomerate
50
ESC 2015
Metallic Nanoparticles and their interfacial properties
Stark Kirsty1*, Cayre Olivier1, Biggs Simon2
1
Institute of Particle Science Engineering, School of Chemical and Process Engineering,
University of Leeds
2
Faculty of Engineering, Architecture & Information Technology,
The University of Queensland
Particle stabilised emulsion systems have received a renewed interest over the past few years
due to their differing properties compared to conventional surfactant stabilised emulsions.
Nanometer sized particles are able to stabilise emulsion droplets as small as a few
micrometers in diameter. Nanoparticles have been shown to adsorb strongly to oil-water
interfaces.
In this work we describe a nanoparticle system, where the polymeric stabilisers for the
particle themselves facilitates the particle adsorption at liquid-liquid and liquid-air interfaces.
In particular, we will show the use of metallic nanoparticles to stabilise hexadecane in water
emulsions.
Polymer-stabilised nanoparticles were synthesised via a one-pot method, whereby metal ions
are reduced in the presence of the polymer. Studies have been conducted which demonstrate
the drastic influence of the ratio between polymer and metal particles on the interfacial
tension measurements. Additionally metallic nanoparticles provide functionality, such as the
potential for acting as catalysts and therefore efforts to maximise the emulsion droplet surface
loading of nanoparticles have been made. We present here some initial studies to show the
effect of oil to water volume ratio and particle concentration on both the characteristics of the
emulsions produced and the interfacial rheology of corresponding 2D interfaces. Comparisons
are also drawn between the adsorption on corresponding 2D polymer surfaces.
Figure 1: a) TEM micrograph of polymer stabilised metal nanoparticles, b) cryoTEM micrograph of nanoparticle
stabilised oil droplet
51
ESC 2015
Sol-Gel derived nanostructured materials for thermal insulation
applications
Dervin Saoirse*, Pillai Suresh
Institute of Technology Sligo, Nanotechnology research group, Department of Environmental
Science, Ash lane, Sligo, Ireland
Sol gel technology facilitates effortless control of the composition, properties, and nanoarchitecture of nanosystems, depicting this process as an advantageous approach for the
synthesis of nanostructures, such as aerogels. Aerogels are highly porous nanostructured solid
frameworks of gel, isolated in tact from the gels liquid component, formed as a result of the
agglomeration of solid nano-sized particles dispersed within a homogenous precursor.
Figure 1 Aerogel formation via sol-gel technology
At present, buildings account for approximately 40% of Europe’s energy consumption, with
almost half of this energy required for heating and cooling purposes alone. Such poor energy
ratings advocate a demand for novel, effective thermal insulation materials. The current
research therefore proposes to employ aerogel powders as an insulation material, in the form
of a paint additive. Aerogels express remarkable features including ultralow density and
thermal conductivity, yielding an ideal material for thermal insulation applications. Added to
a paint, the aerogel powders will act as an additional layer of insulation, creating an energy
efficient building. Thus this study aims to optimise the sol-gel process in order to produce an
aerogel with abundant, nanometre scale pores (≥90% air), high surface area (>600m 2/g) and
ultra-low thermal conductivity and further enhance the mechanical strength, of the
occasionally brittle, nanostructured aerogels via the incorporation of graphene into the aerogel
sol. The synthesis of graphene reinforced aerogels, and the characterisation of the
nanostructures using XRD, Raman and FESEM will be discussed.
Literature:
1. EU Directive 2010/31/EU of the European Parliament and of the Council of 19 May 2010, Energy
performance of buildings
2. Xie, T ; He, Y.L. Hu, Z.J. (2013), Theoretical study on thermal conductivities of silica aerogel
composite insulating material, International Journal of Heat Transfer, 58, 540-542.
3. Baetens, Ruben, Bjørn Petter Jelle, and Arild Gustavsen. Aerogel insulation for building
applications: a state-of-the-art review. Energy and Buildings 43.4 (2011): 761-769
Acknowledgements:
The authors would like to acknowledge Science Foundation Ireland (SFI) for financial support to carry
out the research.
52
ESC 2015
Adhesion between Surfaces in the Presence of Polyelectrolyte
Multilayers made with Seaweed Polysaccharides
Tracey Ho 1*, Marta Krasowska 1, Kristen Bremmell 2, Damien N. Stringer 3,
David A. Beattie 1
1
Ian Wark Research Institute, University of South Australia, Mawson Lakes, Adelaide, SA
5095, Australia
2
School of Pharmacy and Medical Science, University of South Australia, City East Campus,
North Terrace, Adelaide, SA 5000
3
Marinova Pty Ltd, 249 Kennedy Drive, Cambridge, TAS 7170, Australia
A drive towards creating biologically relevant functional surface coatings has led to the
emergence of polysaccharide-based polyelectrolyte multilayers (PEM) for applications in
biomimetic lubrication. These polysaccharide-based PEM surface coatings are formed easily
through the Layer-by-Layer (LbL) assembly technique. In this study, we focus on the
formation and properties of polysaccharide-based PEM consisting of alternating layers of
polyanionic fucoidan and polycationic chitosan. Whereas chitosan is a well-studied
component of polysaccharide PEMs, fucoidan, a sulfated polysaccharide extracted from
seaweed, is relatively little studied in PEM formation. Two pharmaceutical-grade fucoidan
samples, extracted from two different species of seaweed, were studied in this work. The two
fucoidans exhibit variation in sugar monomer composition and in molecular weight.
The formation of the fucoidan/chitosan PEM was investigated by zeta potential
measurements, quartz crystal microbalance with dissipation monitoring (QCM-D), and
spectroscopic ellipsometry. Their behaviour in controlling surface forces and adhesion
between two silica surfaces was investigated using colloid probe atomic force microscopy
(CP AFM). Surface forces upon approach of surfaces, and magnitude of adhesion upon
retraction of surfaces, were determined layer-by-layer, as the multilayer built up. Differences
were observed dependent upon the identity of the outer layer (chitosan or fucoidan), and also
dependent on the identity of the fucoidan polymer. The implications of these observations on
the use of such PEM coatings as adhesion modifiers will be discussed.
53
ESC 2015
Effect of triterpenoid and steroidal saponinson DPPC and
cholesterol monolayers
Orczyk Marta1*, Kamil Wojciechowski1
1
Warsaw University of Technology, Faculty of Chemistry
* [email protected]
Saponins are a family of glycoside type biosurfactants, produced by plants, microorganisms
as well as some marine organisms. These natural biologically active substances present a
number of interesting properties. In spite of numerous potential applications of saponins there
is still lack of viable and detailed information confirming the effectiveness and mechanism of
their interaction with biological membranes. The most probable hypothesis explaining the
effect of saponins on biological membranes is based on formation of complexes with
membrane lipids, especially cholesterol. Nevertheless, the exact mechanism of action of
saponins on biological membranes has not yet been fully elucidated. Hence the necessity for
carrying out such research.
Fig. Possible application of saponins
In this study, we compare the activity of four different saponins, i.e., glycyrrhizic acid, αhederin, hederacoside C and digitonin on model Langmuir monolayers. The study was
conducted on monolayers composed of a single lipid (DPPC) and of its mixtures with
cholesterol. In order to study the resistance of the monolayers against saponins, a combination
of surface pressure relaxation and surface dilational rheology were employed. In an attempt to
observe the morphology changes and phase transitions of the single and mixed monolayers
exposed to different saponins, fluorescence microscopy was additionally employed. All
studied saponins are capable of penetrating the DPPC and DPPC/cholesterol monolayers.
However, clearly the most pronounced increase in surface preasure in Gibbs layers as well as
in the saponin-penetrated monolayers were observed for α-hederin and digitonin.
Acknowledgements:
This work was financially supported by the Polish National Science Centre, grant no. DEC2011/03/B/ST4/00780.
54
ESC 2015
Zinc phthalocyanines locaton in methoxy poly(ethylene oxide) and
poly(L-lactide) block copolymer micelles – 1H NMR investigation
Łukasz Lamch1*, Rafał Latajka1, Kazimiera A. Wilk1
1
Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw
University of Technology, WybrzezeWyspianskiego 27, 50-370 Wroclaw, Poland
Polymeric nanostructures, including polymeric micelles, have attracted much attention as
delivery vehicles in photodynamic therapy (PDT), owing to their abiliy to selectively
accumulate the desired photosensitizers molecules within the tumor tissue with vestigial or no
uptake by nontarget cells and necessarily without the loss of their activity. Phthalocyanines
are important group of photosensitizers for PDT, due to excellent photochemical properties,
i.e. exceptional stability and high light absorption coefficient with maximum in the red/near
IR region. The location of the solubilizate, depending upon the chemical structure of block
copolymer and cargo, is fundamental for improving photosensitizers’ properties after
encapsulation and interiactions with biological systems [1].
In our study we report preparation and characterization of polymeric micelles of methoxy
poly(ethylene oxide)-b-poly(L-lactide) loaded with three different zinc phthalocyanines (zinc
phthalocyanine (ZnPc) as well as its tetrasulfonic acid (ZnPc-sulfo4) and perfluorinated
(ZnPcF16) derivatives). The size distribution (i.e. the hydrodynamic diameter), the
morphology of the polymeric micelles and the concentration of the entrapped photosensitizer
was determined by DLS, AFM and UV–Vis spectroscopy, respectively. The studied
nanocarriers exibited good physical stability, high drug loading efficiency and appropiate size
(less than about 150 nm). The structure of polymeric micelles and the location of cargo were
analyzed utilizing nuclear magnetic resonance of protons (1H NMR). Spectra, performed in
different solvents, showed that poly(L-lactide) chains formed polymeric micelles solidelike
core in water. We proved that ZnPc-sulfo4 and ZnPcF16 interacts with poly(ethylene oxide)
chains of block copolymer and water molecules, despite their different hydrophobicity.
Polymeric micelles, loaded with ZnPc, were confirmed not to exhibit any interactions
between cargo and miclles corona. According to our results ZnPc was found to locate in the
polymeric micelles core, while both ZnPcF16 and ZnPc-sulfo4 – in polymeric micelles corona.
Literature:
1. Łukasz Lamch, Urszula Bazylińska, Julita Kulbacka, Jadwiga Pietkiewicz, Katarzyna BieżuńskaKusiak, Kazimiera A. Wilk. Polymeric micelles for enhanced Photofrin® delivery, cytotoxicity and
pro-apoptotic activity in human breast and ovarian cancer cells. Photodiagn Photodyn Therapy 11
(2014) 570—585
Acknowledgements:
This work was supported by Wroclaw Research Center EIT+ under the project ‘Biotechnologies and
advanced medical technologies’ – BioMed (POIG 01.01.02-02-003/08-00) financed from the
European Regional Development Fund Operational Programme Innovative Economy 1.1.2, and was
also financed by a statutory activity subsidy from the Polish Ministry of Science and Higher Education
for the Faculty of Chemistry of Wrocław University of Technology.
55
ESC 2015
Nanoparticle self-assembly in aqueous solutions; influence of
polymer’s molar mass and gemini surfactants’ spacer length.
Fotini Delisavva*, Karel Prochazka, Mariusz Uchman
Department of Physical and Macromolecular Chemistry; Faculty of Science, Charles
University in Prague, Hlavova 8, 12840 Prague 2, Czech Republic
*
- [email protected]
Nanoparticle self-assemly has been under thorough investigation for decades due to numerous
potential applications in cosmetics, detergent products and medicine1. In this study, we focus
on the coassembly of a series of gemini surfactants2, of the type alkendiyl-α,ωbis(dimethylalkylammonium bromide) with varying length of the spacer group3 (12-s-12, s=
2, 3, 4, 6, 8, 10, 12), mixed with block copolymer polyelectrolyte poly(ethylene oxide)-bpoly(methacrylic acid)4 of different unit lengths, PEO705-PMAA476 and PEO681-PMAA188 in
aqueous solutions. The complex nanoparticles were characterized using dynamic, static and
electrophoretic light scattering, small angle x-ray scattering, atomic force microscopy and
cryo-transmision electron microscopy. Thermodynamic and kinetic aspect of the systems was
investigated using isothermal titration calorimetry. It was found that the properties of the
particles can be tailored by changing the spacer group of gemini surfactants, as well as the
length of polyelectrolyte block.
Literature:
1. Yuchun Han, Yilin Wang. 2010. Aggregation behavior of gemini surfactants and their interactions
with macromolecules in aqueous solution. Physical Chemistry Chemical Physics 13: 1939-1956.
2. Roul Zana. 2002. Dimeric (gemini) surfactants: effect of the spacer group on the association
behavior in aqueous solution. Journal of Colloid and Interface Science 248: 203-220.
3. Yuchun Han, Wentao Wang, Yongqiang Tang, Shusheng Zhang, Zhibo Li, Yilin Wang. 2013.
Coassembly of poly(ethylene glycol)-block-poly(glutamate sodium) and gemini surfactants with
different spacer lengths. Langmuir 29: 9316-9323.
4. Mariusz Uchman, Miroslav Stepanek, Sylvain Prevost, Borislav Angelov, Jan Bednar, MarieSousai Appavou, Michael Gradzielski, Karel Prochazka. 2012. Coassembly of poly(ethylene
oxide)-block-poly(methacrylic acid) and N-dodecylpyridinium chloride in aqueous solutions
leading to ordered micellar assemblies within copolymer aggregates. Macromolecules 45: 64716480.
Acknowledgements:
The authors acknowledge the financial support from the Ministry of Education of the Czech Republic
(long-term Research Project No. MSM0021620857) and the Grant Agency of the Czech Republic
(Grants No. P208/12/P236, P106/12/0143 and P106/13-02938S).
56
ESC 2015
Preparation of Colloidal Inkjet Inks by Emulsion Polymerisation
Mohmed Mulla*, Huai Nyin Yow, Olivier Cayre, and Simon Biggs
University of Leeds
Nanoparticles are widely used in ink formulations as they offer some very desirable
advantages, including a long shelf life due to the high stability of the dispersions, and
controllable jetting behaviour. The aim of this project is to produce high solids content, sub
100 nm monodisperse latex particles to be used as model inkjet inks. Highly concentrated (up
to 45 wt% solids content) stable PMMA latex particle dispersions have been prepared via
emulsion polymerisation. More specifically a chain transfer agent has been utilised to enhance
particle nucleation efficiency, aiding the preparation of polymer particles with a narrow
weight distribution and increased monodispersity. Our initial work has found that high
nanolatex concentration can be achieved with a relatively low emulsifier concentration,
without sacrificing the colloidal stability of the dispersions. Waterborne nanoparticles around
50 nm have been obtained with a 45 wt % solids content. These dispersions do not require any
lengthy processing to perform rheological experiments in regions where the particle
suspensions show clear shear thinning behaviour.
In this study, we systematically study the effect of the emulsifier, initiator and chain transfer
agent concentration on final particle size and polydispersity of the synthesised particles. We
also determine the depletion flocculation behavior, upon addition of free polymer to these
systems. In addition we also study the stability, deposition and jetting behavior of the
prepared dispersions at various particle concentrations, in ethylene glycol as a co-solvent and
at various concentrations of non-adsorbing polymer (to induce depletion flocculation).
57
ESC 2015
Effect of the pore size of activated carbon nanoparticles on CDLE
(capacitive energy extraction based on double layer expansion)
M.M. Fernández*, G.R. Iglesias, S. Ahualli , M.L. Jiménez, A.V. Delgado 1
1
Department of Applied Physics, School of Science, University of Granada, 18071 Granada,
Spain
The Capacitive energy extraction based on Double Layer Expansion (CDLE) is the name of a new
method devised for extracting energy from the exchange of fresh and salty water in porous
electrodes (1, 2). It is based on the change of the capacitance of electrical double layers at the
electrode/solution interface when the concentration of the bulk electrolyte solution is modified.
Fig. 1 shows the typical evolution of the cell voltage when 20 and 500 mM NaCl solutions are
exchanged.
Potential (mV)
450
400
350
300
SALT
FRESH WATER
WATER
0
100
200
Time (s)
300
400
Fig. 1 Cell voltage evolution when salt and fresh water solutions are exchanged through activated carbon
electrodes.
In this contribution we test different pore size carbons electrodes as supporting surfaces for the
exchange and energy harvesting process (3). We found that, despite of the huge accumulated
charge in small pore size electrodes, larger pore electrodes determines the ease with which the
ions can diffuse inside and therefore, improve the performing of CDLE cycles. Moreover, we
could optimise the extracted power of larger pore size electrodes by some parameters as charging
voltage, cycle time, charging and discharging resistance and distance between electrodes. All this
improvements have lead to a power of 6 mW/m 2. This can be considered a promising result for
Capmix techniques
Literature:
1. R. E. Pattle. Production Of Electric Power By Mixing Fresh And Salt Water In The Hydroelectric
Pile. Nature, 174(4431):660–660, 1954.
2. D. Brogioli. Extracting renewable energy from a salinity difference using a capacitor. Phys. Rev.
Lett., 103(5):058501, July 2009.
3. Guillermo R. Iglesias, María M. Fernández, Silvia Ahualli, María L. Jiménez, Oleksander P.
Kozynchenko, and Ángel V. Delgado. Materials selection for optimum energy production by
double layer expansion methods. Journal of Power Sources, 261:371-377, 2014.
Acknowledgements:
This work was partially supported by PE2012-0694 (Junta de Andalucía, Spain) and FIS2013-4766663-1-R (MINECO, Spain) .
58
ESC 2015
Anomalous birefringence of planar clay particles
Paloma Arenas-Guerrero1*, Guillermo Iglesias1, Ángel V. Delgado1, María L. Jiménez1
1
Department of Applied Physics, University of Granada, Spain
Upon application of an external electric field, non-spherical nanoparticles in suspension can
orient giving rise to a macroscopic optical anisotropy known as electric birefringence. Although
the foundations of this phenomenon have been long-established [1], the process is hitherto not
fully understood and many materials with interesting properties have been reported to exhibit
anomalous birefringent behaviours that are still under discussion [2,3,4].
One of these materials is sodium montmorillonite (NaMt) [4,5], a plate-like clay which shows a
sign reversal of the birefringence, i.e., a shift in the axis of alignment of the particles. This
suggests that NaMt particles possess at least 2 different dipole moments, one along the symmetry
axis and one along the surface. However, the mechanism of formation and physical properties of
such dipoles are still to be satisfactorily elucidated.
Fig. 1 Field-dependence of the birefringence of a sample of NaMt (0.01 g/l, 0.3 mM NaCl) for several values of
the frequency of the applied field. The response goes from negative to positive when the frequency is raised.
With this motivation we have carried out a thorough analysis of the electric birefringence of
NaMt particles in aqueous suspension. Thus, the dynamic response of the system, the field
strength dependence and the spectral behaviour of this material have been studied under different
experimental conditions of pH and ionic strength in order to further understand the anomalous
birefringent phenomenology of the clay.
Literature:
1. E. Frederiq, C. Houssier. Electric Dichroism and Electric Birefringence. Clarendon: Oxford
(1973).
2. H. Hoffmann, D. Gräbner. Adv. in Colloid and Interface Science 216, 20–35 (2015).
3. F. Mantegazza, M. Caggioni, M. L. Jiménez, T. Bellini. Nature Physics 1, 103-106 (2005).
4. D. Shah, C. Thompson. Hart. J. Phys. Chem., 67 (6), 1170-1178 (1963).
5. K. Yamaoka, R. Sasai. J. Colloidal and Interface Sci., 209 (2), 408-420 (1999).
Acknowledgements: This work was partially supported by PE2012-0694 (Junta de Andalucía, Spain),
FIS2013-47666-C3-1-R (MINECO, Spain) and the FPU 2014 Program (MEC, Spain).
59
ESC 2015
Co-encapsulation of CdSexS1-x/ZnS quantum dots with
photosensitizers- colloidal stability and optical properties
Drozdek Sławomir1*, Janusz Szeremeta2, Marcin Nyk2,
Marek Samoć2, Kazimiera A. Wilk1
1
Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw
University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
2
Advanced Materials Engineering and Modelling Group, Faculty of Chemistry, Wroclaw
University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
Polymeric nanoparticles are promising nanocarriers which have attracted much attention as a
delivery system in many biomedical applications due to improved permeation, specific cell
targeting and long circulation in blood. Co-encapsulated therapeutic and diagnostic
compounds in polymeric nanoparticles can be protected from the biological environment also
their bioavailability and biodistribution can be enhanced [1].
In our studies we report a new approach to fabricate theranostic nanocapsules prepared via
solvent/emulsification method. The hydrophobic quantum dots CdSexS1-x/ZnS (QDs) with
photosensitizer (zinc phthalocyanine ZnPc or aluminum phthalocyanine AlPc) were
encapsulated in biocompatible polymeric nanocapsules intended for energy transfer between
QDs as donors and photosensitizer molecules as acceptors. Pluronic P123 was applied as the
polymer component; Cremophor EL® as the nonionic surfactant and silicone oil as the oil
phase. Dynamic light scattering (DLS), transmission electron microscopy (TEM) and atomic
force microscopy (AFM) investigations conﬁrmed the particle diameter below 250 nm and
polydispersity of ca. 0.1-0.3. UV-vis spectroscopy was applied to determine encapsulation
efficiencies of ZnPc and AlPc (which were about 60% and 50%, respectively). The studied
nanocarriers demonstrated good kinetic stability, which was verified by backscattered profiles
obtained by the turbidimetric technique. The presence of energy transfer was proved by
evaluation of fluorescence lifetimes of QDs/ZnPc and QDs/AlPc-loaded nanocapsules using
time-correlated single-photon counting (TCSPC). The nanocarriers showed strong one- and
two-photon-induced luminescence, the latter upon excitation in the NIR biological optical
transmission window spectral range. Furthermore, we confirmed that the co-encapsulation of
QDs with ZnPc or AlPc in physically stable polymeric nanocapsules increases their solubility
in aqueous solution and moderates their chemical and physical status in the nanocarriers oil
microenvironment e.g., enhanced photostability. Our results suggest that this simple hybrid
system possesses the essential features required for both energy transfer and potential
application in PDT.
Literature:
1. Bazylińska Urszula, Drozdek Sławomir, Nyk Marcin, Kulbacka Julita, Samoć Marek, Wilk
Kazimiera. 2014. Core/Shell quantum dots encapsulated in biocompatible oil-core nanocarriers as
two-photon fluorescent markers for bioimaging. Langmuir 30: 14931−14943
Acknowledgements:
Support for this work by the National Science Center (Poland) under Grant No. 2012/05/B/ST4/00095
is gratefully acknowledged.
60
ESC 2015
In situ QCM-D investigation of silver nanoparticle monolayer
formation on polycation modified surfaces
Katarzyna Kubiak*, Zbigniew Adamczyk, Magdalena Oćwieja
* [email protected]
Silver nanoparticles and their monolayers deposited on solid surfaces find
a wide spectrum of applications as antibacterial coatings, catalysis materials, antireflection
coatings or filters and conductive inks [1]. Because of that, silver particles play an important
role in nanoscience and nanomedicine.
The Quartz Crystal Microbalance (QCM) offer an exceptional opportunity to
investigate in situ kinetics of silver nanoparticles deposition by controlling a mass of particles
adsorbed on a surface of a sensor.
In this work silver particle monolayers at polyelectrolyte modified surfaces were
investigated. The deposition kinetics of silver nanoparticles on Au/SiO2/PAH substrate was
studied under in situ conditions by using the QCM method and the ex situ SEM imaging.
Because of low dissipation, the Sauerbrey’s equation was used for calculating the mass per
unit area (coverage). Measurements were done for various bulk suspension concentrations,
flow rates and ionic strengths. It was shown that particle deposition for the low coverage
regime is governed by the bulk mass transfer step that results in a linear increase of the
coverage with the time. A comparison of QCM and SEM results showed that the hydration of
the silver monolayers was negligible. This allowed one to derive a universal kinetic equation
that describes the mass transfer rates in the cell as a function of the bulk concentration, flow
rate and diffusion coefficient. Measurements were also performed for longer times and for
various ionic strengths where the deposition kinetics and the maximum coverage of particles
were determined. The experimental data confirmed a significant increase in the maximum
coverage with ionic strength, This was interpreted as due to the decreasing range of the
electrostatic interactions among deposited particles. These results were adequately interpreted
in terms of the extended random sequential adsorption (eRSA) model. Additionally, it was
shown that the QCM data matched the ex situ SEM results indicating that the monolayer
hydration was also negligible for higher coverage range. These results derived for the model
silver nanoparticle system can be exploited as reference data for the interpretation of protein
adsorption kinetics where the dry mass is needed in order to assess the extent of hydration.
Literature:
1. M. Oćwieja, Z. Adamczyk, K. Kubiak, J. Colloid Interface Sci. 2012, 376, 1.
Acknowledgment: This work has been supported by the EU Human Capital Operation Program,
Polish Project No. POKL.04.0101-00-434/08-00 and Malopolskie Centrum Przedsiebiorczosci
“Doctus” project.
61
ESC 2015
Nanoparticle Production by Atomic Vapour Deposition on a
Liquid Jet
Michael J. McNally1*, Gediminas Galinis1, Hanieh Yazdanfar1, Mumin M. Koc1,
Oliver Youle1, Ruth L. Chantry2, Klaus von Haeften1
1
2
University of Leicester, UK
SuperSTEM, STFC Daresbury Campus
Synthesis of metal nanoparticles in liquids encompasses powerful empirical methods for
production of a variety of shapes, structures and compounds relevant to emerging applications
in medicine, sensing, catalysis and energy harvesting [1]. Chemical synthesis techniques
generate individual metal atoms or ions well dispersed in a solvent by chemical reduction. In
order to realise this reaction step, certain boundary conditions must be met, such as reagent
solubility and the presence of additives or impurities. These requirements complicate
synthesis and, in effect, mean that individual synthesis protocols are unique and specific to a
particular metal and shape [2]. Here we demonstrate an intuitively simpler route, the
introduction of metal atoms directly into a liquid solvent, in a procedure suitable for almost
any combination of metals and liquids.
A straightforward method for generating atomic metal vapours is evaporation in vacuum.
Subsequent deposition into solution has, to date, been limited to deposition into solvents with
low vapour pressure such as ionic liquids [3] and dense organic oils [4]. Using a liquid microjet to inject solvent into vacuum, we have been able to deposit silver atoms directly into liquid
ethanol, producing stable nanoparticles (Fig. 1). An immediate advantage of this method is
that all particles produced are ligand free, with active surfaces accessible for enhanced
catalytic performance [5]. By depositing metal atoms into a solution of pre-existing
nanoparticles, or by simultaneous deposition of multiple materials, hybrid particles could be
produced in one step, and continuously, enabling the large-scale synthesis of nanomaterials
such as TiO2 decorated with gold for the photocatalytic splitting of water [6].
Fig. 1 Schematic of liquid jet production process: Metal atoms are evaporated from a target material, arriving as
individual, well dispersed atoms in the liquid jet (a), where they nucleate (b), and then grow into larger
nanoparticles (c).
62
ESC 2015
Literature:
1. Lohse, S. E. & Murphy, C. J., 2012, Applications of colloidal inorganic nanoparticles: From
medicine to energy. J. Am. Chem. Soc. 134: 15607-15620
2. Xia, Y., Xiong, Y., Lim, B. & Skrabalak, S. E., 2009, Shape-controlled synthesis of metal
nanocrystals: Simple chemistry meets complex physics? Angew. Chemie - Int. Ed. 48: 60-103
3. Torimoto, T. et al., 2006, Sputter deposition onto ionic liquids: Simple and clean synthesis of
highly dispersed ultra-fine metal nanoparticles. Appl. Phys. Lett. 89: 243117
4. Wender, H. & Gonçalves, R. V., 2011, Sputtering onto liquids: from thin films to nanoparticles. J.
Phys. Chem. C. 115: 16362-16367
5. Li, D. et al., 2011, Surfactant removal for colloidal nanoparticles from solution synthesis: The
effect on catalytic performance. ACS Catal. 2: 1358-1362
6. Linic, S., Christopher, P. & Ingram, D. B., 2011, Plasmonic-metal nanostructures for efficient
conversion of solar to chemical energy. Nat. Mater. 10: 911-921
63
ESC 2015
The effect of the protein hydrolysis on surface activity and surface
dilational rheology of type I collagen
Kezwoń Aleksandra1*, Frączyk Tomasz2, Chromińska Ilona1, Wojciechowski Kamil1
1
Department of Microbioanalytics, Warsaw University of Technology, Warsaw, Poland.
2
Department of Biophysics, The Institute of Biochemistry and Biophysics
Polish Academy of Sciences, Warsaw, Poland.
Collagen is the most abundant protein in vertebrates, constituting about 30% of all proteins in
tissues of a human body [1]. It can be found in skin, tendons, cartilages, bones, teeth and even
blood vessel walls [2]. There are currently about 28 known types of collagen differing in
amino acid composition, structure, length, biological role and abundance [1]. For the purpose
of the present research, the surface tension and surface dilational rheology for the native,
temperature- and pH-modified, as well as enzymatically hydrolyzed collagen (type I) were
measured using Axisymmetric Drop Shape Analysis method. Both the enzyme concentration
and incubation time were optimized for enzymatic hydrolysis using a collagen-specific
collagenase from Clostridium histolyticum, CHC, at 37°C.
Unmodified collagen is weakly surface active, but its layers formed by spontaneous
adsorption at the water/air surface display exceptional dilational rheology parameters. At high
oscillation frequency limit (0.1 Hz) the layers are predominantly elastic, with the storage
modulus, E’ = 36 mN/m for collagen concentration of 5 · 10−6 M [3]. Our results suggest that
even simple modifications (temperature, pH, enzymatic hydrolysis) of collagen can enhance
the collagen’s surface properties, especially in terms of the surface dilational elasticity
modulus, E’, which can reach values as high as 69 mN/m. The best results were achieved for
collagen only slightly hydrolysed, which encourages us to further extend our research in this
direction.
Literature:
1. Karl E. Kadler, Clair Baldock, Jordi Bella, Raymond P. Boot-Handford. 2007. Collagens at a
glance. J Cell Sci 120: 1955-1958.
2. Joseph M. Wallace, Qishui Chen, Ming Fang, Blake Erickson, Bradford G. Orr, Mark M. Banaszak
Holl. 2010. Type I collagen exists as a distribution of nanoscale morphologies in teeth, bones, and
tendons. Langmuir 26: 7349–7354.
3. Aleksandra Kezwoń, Kamil Wojciechowski. 2014. Effect of temperature on surface tension and
surface dilational rheology of type I collagen. Colloids and Surfaces A: Physicochem Eng Aspects
460: 168-175.
64
ESC 2015
Stability of nanoscale nonionic films atop of discretely charged
electrolyte interface
Emelyanenko K.1*, Emelyanenko A.1, Boinovich L.1
1
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of
Sciences, Moscow, Russia
Understanding the polarization effects and the electrostatic forces arising due to the presence
of ionized molecules or charged nanoparticles in the vicinity of interfaces is of considerable
interest both in science and technology. During last decades the theoretical analysis of this
problem was given in numerous papers, taking into account uniform and nonuniform smeared
charge distribution as well as discrete charges. The case of charges located inside ionic liquid
or aqueous electrolyte solution with nonpolar wetting film on the top may be of great interest,
on one hand, for studying the stability of such films. On the other hand, the interface charging
can be effectively used in nanotechnological applications, for example in controlling the
thickness of nonpolar and nonionic coatings. Note that for such systems the real charges are
dressed by a cloud of counterions and coions, that is, the polarization effects and the
electrostatic forces are significantly screened in all contacting media.
In this presentation we consider the surface forces arising in thin wetting film of nonpolar
liquid due to discrete charges embedded inside the aqueous solution at its interface with
nonionic wetting film. The polarization of contacting media by the discrete charges will be
treated by the image charge method. It will be shown that the arising polarization effects lead
to the appearance of additional contribution to the disjoining pressure in the film associated
with image charge forces. The analytical solution for disordered ensemble of charges at
water/oil interface will be presented for the cases of diluted and concentrated solutions [1]. It
will be shown that for particular systems the image-charge component of the disjoining
pressure can dominate over the other types of surface forces.
Literature
1. Emelyanenko K.A. Emelyanenko A.M., Boinovich L.B. (2015) Image-charge forces in thin
interlayers due to surface charges in electrolyte. Physical Review E 91, 032402 (8 pages). DOI:
10.1103/PhysRevE.91.032402.
Acknowledgements
This study was financially supported by the Program for fundamental studies of Presidium of the
Russian Academy of Sciences, and by the President of the Russian Federation (grant for the support
of leading scientific schools of the Russian Federation, project no. NSh-2181.2014.3).
65
ESC 2015
Quantitative determination of anchoring molecules on the surface
of ZnO particules and effects on electronical properties
J. Gamon1,2,*, P. Barboux1, D. Giaume1, T. Le Mercier2
1
Institut de Recherche de Chimie Paris (IRCP), CNRS 11 rue Pierre et Marie Curie, 75005
Paris, France
2
Solvay, Research and Innovation Center of Paris (RIC Paris) 52 rue de la Haie-Coq, 93306
Aubervilliers, France
* [email protected]
Improving electrical conductivity in thin film semiconductor devices such as solar cells,
thermoelectric modules, or in display applications for instance, remains a key point for better
performances. As polycrystalline films have the favor of the industry for their lower
fabrication cost, the limitation of the current is most of the time attributed to charge scattering
at the grain boundaries due to high energy barriers at the interface between grains.(1)
This work focuses on the understanding of intergranular electrical conductivity in the view of
improving thin film semiconductor performances deposited via a soft chemistry deposition
routes. In this goal, ZnO:Al was chosen as a model for our investigations as it is a reference
material in many semiconductor applications (sensors, solar cells, Transparent Conducting
Oxides)(2).
Many studies have already demonstrated the role of adsorbed species onto ZnO thin films and
nanostructures surfaces to improve sensor selectivity or charge transfer in dye sensitized solar
cells for instance (3).
With this in mind, we have performed liquid phase adsorption studies of organic molecules
onto ZnO particles through conductimetry and IR. Intergap molecular surface states were
identified thanks to electrochemical impedance spectroscopy (Mott Schottky measurements).
Conductivity on pressed powders was studied as a function of the applied pressure to show
the effect of the grain boundaries and of the powder compaction.
This study allows a quantitative determination of molecules at the surface of particles.
Literature:
1. Greuter F, Blatter G. Electrical properties of grain boundaries in polycrystalline compound
semiconductors. Semicond Sci Technol. 1990;5(2):111.
2. Klaus Ellmer, Andreas Klein, Bernd Rech. Transparent Conductive Zinc Oxide. Springer Series in
Material Science. 2008.
3. Galoppini E. Linkers for anchoring sensitizers to semiconductor nanoparticles. Coord Chem Rev.
2004 juillet;248(13–14):1283–97.
66
ESC 2015
Surface-confined interactions of lipopolysaccharide layers
Christian Redeker1*, Richard Stevenson1, M. Carmen Galan1, Wuge H. Briscoe1
1
Reflectivity
Gram-negative bacteria are widespread microbes and examples include key pathogenic
species such as Escherichia coli and Salmonella. They are characterised by the distinct
structure of their outer membrane, which is mainly comprised of bacterica-specific
lipopolysaccharides (LPS). In contrast to zwitterionic human lipids, LPS is negatively
charged. Hence, the membrane can act as a bacteria-specific target for cationic antibacterial
0
agents.
Electrostatic
and
hydrophobic
10
++
interactions between the peptides and membrane
-1
components can lead to disturbance of the
10
membrane order, weakening the protective and
-2
regulatory functions of the bacterial membrane.
10
LPS and mixed phospholipid-LPS layers have
-3
10
been used as model membranes to study the
1
interactions between peptides and bacterial
-4
2
10
membranes [1]. However, the effect of the LPS
polysaccharide chain length, its composition in
3
-5
10
the mixed model membrane, and presence of
4
divalent cations on the membrane structure and
-6
10
interactions have not been systematically
5
studied. This study investigates the influence on
-7
-1
10
Q (Å )
the structure and interactions of surface-confined
LPS layers as a function of LPS carbohydrate
0.1
0.2
0.3
0.4
0.5
0.6
chain length, calcium cation concentration and
Fig.1 BM28 XRR curves from LPS liposomes
++
adsorption with ~10 mM Ca : 1) On
surface properties using X-ray reflectometry
negatively charged bare mica; RT; 2) On bare
(XRR) [2] and the surface force apparatus (SFA)
mica at 52 °C; 3) On positively charged PEI[3]. Preliminary XRR results show the formation
coated mica; 52 °C; 4) Rinsed with 20 mM Ca++
of LPS (Rd mutant) bilayers on three surfaces of
subsequent to 3); 5) On hydrophobic STAI
different physicochemical properties (bare mica,
coated mica, 52 °C.
STAI-coated mica, polyethyleneimine (PEI)
coated mica) (Fig. 1) in the presence of calcium cations and elevated temperatures (45 °C).
We will further investigage the effect of a number antimicriobial peptides on the membrane
structure.
Literature:
1. Wasim Abuillan et al. 2013. Physical interactions of fish protamine and antisepsis peptide drugs
with bacterial membrane revealed by combiantion of specular x-ray reflectivity and grazingincidence x-ray fluorescence. Physical Review E. 88:012705.
2. Wuge H. Briscoe et al. 2012. Synchrotron XRR study of soft nanofilms at the mica-water
interface. Soft Mater. 8:5055
3. Wuge H. Briscoe et al. 2006. Boundary lubrication under water. Nature. 444:191
Acknowledgements: C.R. is supported by Douglas Everett fund.
67
ESC 2015
Nanopatterned charge distributions on polyetherimide electretfilms
Gödrich Sebastian1*, Bartz Christian2, Schmidt Hans-Werner2, Papastavrou Georg1
1
2
Physical Chemistry II, University of Bayreuth, 95447 Bayreuth, Germany
Macromolecular Chemistry I, University of Bayreuth, 95447 Bayreuth, Germany
Electrets are dielectric materials with quasi-permanent polarization due to external charging.
In particular, polymer electrets are widely used in various applications such as microphones,
electret-filters, and xerography. A promising class of such polymer electret materials are
polyetherimides (PEI). This class of aromatic polymers shows a good thermal stability and
has been characterized extensively in the recent years, in particular with respect to its
macroscopic charge storage properties [1, 2]. For applications, the charge stability with
respect to environmental influences, such as temperature and humidity is essential.
Here, we investigate by in-situ techniques the surface-potential decay of Ultem® 1000 PEIfilms with defined charge distribution in the nm-range at elevated temperatures and ambient
conditions. Charge is injected into the polymer films by an atomic force microscopy (AFM)
contact-charging approach (Fig. 1, a). Afterwards, the generated charge pattern is read-out by
Kelvin probe force microscopy (KPFM)-imaging (Fig. 1, b) during in-situ tempering of the
sample. Thereby, the temperature-induced surface-potential decay can be analyzed as a
function of time. Comparable in-situ studies have been carried out so far primarily with
respect to the influence of humidity.[3] Here, we compare the results obtained by scanning
probe techniques for local charge distributions with those by macroscopic techniques for
homogeneously charged Ultem® 1000 PEI-films and find good agreement. Electret films
with nano-structured charge distributions are predestined for applications in electret fieldeffect transistors, energy harvesting MEMS, or high-density data storage.
Fig. 1 a) Charge patterns are generated in an Ultem® 1000 PEI film by applying voltage pulses between a
conductive AFM-tip and a conductive substrate serving as a counter-electrode. b) Surface-potential
measurement by KPFM-imaging showing a charge pattern (3 lines) prepared with the aforementioned charging
technique.
Literature:
1. Erhard D. P., Giesa R., Altstädt V., Schmidt H.-W., 2010, J. Appl. Polym. Sci., 115, 1247.
2. Erhard D. P., Lovera D., Giesa R., Altstädt V., Schmidt H. W., 2010, J. Polym. Sci. B: Polym.
Phys., 48, 990.
3. Knorr N., Rosselli S., Nelles G., 2010, J. Appl. Phys., 107, 054106.
68
ESC 2015
Investigation of the structural properties of MgO-based
eco-sustainable cements
Tonelli Monica1*, Francesca Ridi1, Emiliano Fratini1, Piero Baglioni1, Silvia Borsacchi2,
Francesca Martini2, Marco Geppi2,3
Department of Chemistry “Ugo Schiff” & CSGI, University of Florence, Sesto F.no (FI) 50019,
Italy
2
Istituto di Chimica dei Composti Organo Metallici del Consiglio Nazionale delle Ricerche CNR,
U.O.S di Pisa, Pisa 56124, Italy
3
Department of Chemistry and Industrial Chemistry, University of Pisa, Pisa 56124, Italy
1
Cement is the binder at the base of one of the most important building materials, the concrete.
Because of the large amounts involved in the global consumption, its production process is responsible
for ingent quantities of CO2 emitted [1]. Nowadays, worldwide interest is becoming more and more
focused in developing an eco-compatible cement and formulations based on reactive periclase (MgO)
constitute one of the most promising emerging technologies [2]. In the presence of water,
MgO/silicate mixtures hydrate and form a binder phase, M-S-H (magnesium silicate hydrate), a
colloidal gel analogue to calcium silicate hydrate, C-S-H, present in traditional cements. A systematic
study defining the relationship among composition, structure and properties of these binders is still
lacking, but this knowledge is essential to optimize the properties of building materials and to
modulate their perfomances to specific applications [3]. In this regard, the effect of mixing traditional
cement and MgO-based eco-sustainable cement was evaluated. In this work, we considered the effect
of changing percentages of Portland cement. The kinetics of hydration of the pastes prepared were
monitored, as they give access to crucial informations for practical applications. Concurrently, pastes
were characterized starting from molecular level up to the micro/macroscopic scale. The results show
that both C-S-H and M-S-H gel phases have been obtained and the identification of the two binders
confirm the idea that it could be possible to combine the ecological features of MgO-based cement
with traditional cements.
Fig. 1 Schematic illustration of the eco-sustainability of the MgO-based cement.
Literature:
1. Ellis M. Gartner and Donald E. Macphee. 2011. A physico-chemical basis for novel cementitious
binders. Cement and Concrete Research 41: 736-749.
2. Stuart M Evans and Nikolas Vlasopoulos. 2010. Novacem: Carbon Negative Cement and the
Green Cement Bond.
3. Francesca Ridi, Emiliano Fratini, Piero Baglioni. 2011. Cement: a two thousand year old nanocolloid. Journal of Colloid and Interface Science 357: 255-264.
Acknowledgements: CSGI and FIR2013 (Project RBFR132WSM) for financial support.
69
ESC 2015
Posters
70
ESC 2015
P1_1
Many-body Van der Waals interactions in nanoscale wetting and
free films
Emelyanenko K.1*, Emelyanenko A.1, Boinovich L.1
1
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of
Sciences, Moscow, Russia
Van der Waals forces result from electrodynamic interactions between the bodies separated
by a thin interlayer. They bear a universal character, acting between the bodies with any
chemical nature and represent one of the strongest type of interactions at small separations.
Two main distinct approaches are used for the calculation of these forces. The microscopic
approach was developed by Hamaker on the basis of London theory for interactions between
separate atoms. In the macroscopic theory, formulated by Dzyaloshinsky, Lifshitz and
Pitaevsky, the interaction between two bodies is considered as a result of interaction between
fluctuating electromagnetic fields.
Both abovementioned approaches are valid within definite restrictions, which do not allow
their application for calculation of forces between nanosize particles or for the analysis of
surface forces in very thin, a few molecular diameter films. However the accounting for the
many-body interactions in the frame of microscopic approach allows one to treat the van der
Waals interactions in abovementioned systems adequately. To realize this approach we have
adopted the coupled oscillating dipoles method. In this method the van der Waals interactions
between two bodies or in thin films are calculated by direct summation of two-atom, threeatom, four-atom, etc. interactions. In our work we applied this approach to compute the van
der Waals forces in free [1] and wetting films. We have analyzed the peculiarities of surface
forces in very thin films and incomplete monolayers, where the macroscopic theory is not
applicable. Other problem addressed in our study was related to the influence of finite size of
substrate on the stability of wetting films.
Literature
1. Emelyanenko K.A. Emelyanenko A.M., Boinovich L.B. (2012) Calculation of van der Waals
Interaction Energy in Free Liquid Films Accounting for Many-body Contributions. Chemistry
Letters, 41, 1253-1255.
Acknowledgements
This study was financially supported by the Program for fundamental studies of Presidium of the
Russian Academy of Sciences, and by the President of the Russian Federation (grant for the support
of leading scientific schools of the Russian Federation, project no. NSh-2181.2014.3).
71
ESC 2015
P1_2
Irregularities of Drop Formation at a Circular capillary
T. Kairaliyeva1,2*, M. Karbaschi1, M. Taeibi-Rahni1,3, S. Faraji1, K.H. Schano4,
S.B. Aidarova2 and R. Miller1
1
Max Planck Institute of Colloids and Interfaces, 14424 Potsdam/Golm, Germany
2
Kazakh National Technical University after K.I.Satpayev, Almaty, Kazakhstan
3
Sharif University of Technology, Teheran, Iran
4
Gamma-Service, Berlin, Germany
A wide range of important phenomena in fluid dynamics contains multiphase flows and thus
such flows are of great importance to many scientists and engineers. Even though there has
been a great deal of research conducted in this area of fluid mechanics, the complete
dynamics of such flows are not yet fully understood due to their complex interphase coupling,
whereby different phases may strongly affect one another. Fluid interfaces are omnipresent in
most modern technologies and their quantitative characterization is essential for the optimum
use of such technologies. It turned out over the recent years that non-equilibrium properties
are very essential and the interactions between physico-chemical interfacial properties and
hydrodynamics make interfacial dynamics considerably complicated. In particular, processes
like emulsification, foaming, or coating require the understanding of very dynamic properties.
The quantitative understanding of the mutual dynamical bulk-interface interactions is the
main challenge in studying the stability of many systems (like foams and emulsions). Thus,
the properties of the adsorbed layers depend on rather complex mutual bulk-interface
interrelations [1].
The drop volume method is a frequently used technique to measure the surface tension of
liquids and the interfacial tension between two immiscible liquids. Its application is limited to
a certain interval of drop formation time. At smaller drop formation times, less than say 20 s
for capillaries of about 1 mm in diameter, a remarkable hydrodynamic effect on the drop
formation can be observed. At still smaller drop times, irregularities can be observed which
appear to be of chaotic nature. More careful studies showed that these chaotic irregularities
are regular in nature and are highly reproducible. The aim of the present studies is to
investigate the nature of these irregularities, under certain conditions showing bifurcation [2].
In our work we used a specially designed instrument - Drop Detachment Analyzer (DDA).
This instrument can show us how the formation time of single drops at a circular tip of a
capillary tube are measured with high precision. During the work we expect that drop
formation time (DFT) to be linear with time, but in experiments non-linear effects have been
observed. The first objective was to find out what causes these non-linearities and second one
to check the effects of surface tension and viscosity on these phenomena. We used pure water,
different water-ethanol and water-glycerol mixtures.
Literature:
1. M. Taeibi Rahni, M. Karbaschi, and R. Miller, “Computational Methods for Complex Liquid-Fluid
Interfaces”, To be soon published in the series “Progress in Colloid and Interface Science”, CRC
Press, Taylor & Francis Group, in press
2. V.B. Fainerman, R. Miller, “Hydrodynamic effects in measurements with the drop volume
technique at small drop times. 2. Drop time and drop volume bifurcations”, Colloids and Surfaces, A:
Physicochemical and Engineering Aspects 97 (1995) 255-262.
72
ESC 2015
P1_3
Effect of selected parameters on flotation recovery
in KGHM Polska Miedź S.A.
Księżniak Katarzyna1*, Pawlos Witold2, Hupka Jan1
1
Gdansk University of Technology, Faculty of Chemistry, Department of Chemical
Technology
2
KGHM Polska Miedź S.A. - Divisions of Concentrators (O/ZWR)
The operations of Division of Concentrators KGHM Polska Miedź S.A. are comprised
of three ore enrichment plants, located in the vicinity of mines but having separate
organization structures. Ore processing facilities play special role in the production of copper
concentrate.
Our laboratory research data pertain to flotation efficiency of feeds with different
densities and at varying rotor speeds. The material used in the experiments originated from
preliminary flotation feed from the second technological line of ZWR Polkowice Region.
Froth flotation is one of the most important process in the field of mineral processing. The
success of flotation widely depends on proper selection of flotation reagents: collector and
frother. The mixture of ethyl and isobutyl sodium xanthates was used as collector. Flotation
was carried out in single fractional operations. The feed was add before process, reagents
were added in one portion and subsequently started flotation. The concentrate was collected in
each experiment at intervals of 7 minutes. The concentrate and tailings were dried, weighed
and then analysed for the content of copper.
In the investigation feed and remaining products were subjected to Cu content [%]
analysis, grain composition and Cu content determination in given grain classes. The flotation
efficiency measured as shows a linear increase of the recovery with an increase of feed
density and rotor speed.
Fig. 1 Flotation recovery (%) as a function of
flotation pulp density for three different
impeller rotational speed
Fig. 2 Cu concentration (%) (copper content in
concentarte) as a function of impeller
rotational speed for three different flotation
pulp denisty
73
ESC 2015
P1_4
Nanoparticle monolayers on colloid carrier particles
Maciejewska Julia*, Sadowska Marta, Oćwieja Magdalena , Adamczyk Zbigniew
Adsorption of colloid particles and proteins on larger micro-particles is an interesting
phenomenon from the basic science point of view. Elucidation of the adsorption mechanisms
is important for many practical processes, e.g., microcapsule formulations used for controlled
drug delivery. However, despite a vital significance, there are few systematic works in the
literature devoted to this subject. Therefore, the aim of this work was to quantitatively
evaluate nanoparticle deposition mechanisms on spherically shaped interfaces under diffusion
controlled transport conditions. Our system consisted of negative charged polystyrene latex
particles (820 nm in diameter) used as colloid carriers and positively charged amidine latex
nanoparticles (98 nm in diameter) or hematite nanoparticles (90 nm in diameter). Adsorption
of nanoparticles was studied by using the in situ LDV and the concentration depletion
methods involving AFM and SEM imaging (see Fig.1). This allowed one to determine the
electrophoretic mobility of larger negative latex particles as a function of the nanoparticle
coverage. Also the influence of ionic strength on the maximum coverage of particles was
systematically studied. These dependencies were quantitatively interpreted in terms of the 3D
electrokinetic model previously used for planar interfaces. In this way a robust method was
developed enabling one to determine the coverage of nanoparticles and protein on latex
carriers under in situ conditions. These calibration experiments obtained for monodisperse
amidine latex particles were also exploited for the interpretation of hematite nanoparticle
deposition from polydisperse suspensions.
a)
b)
Fig. 1 SEM micrograph: a) positively charged amidine latex nanoparticles b) positively charged hematite
nanoparticles, both adsorbed on negatively sulfonate polystyrene latex particles
Acknowledgements: This work is financially supported by the PRELUDIUM 2013/11/N/ST4/00981
and OPUS 2012/07/B/ST4/00559.
74
ESC 2015
P1_5
Foam formation and stability as controlled by surfactant
adsorption at the air-water interface
Mould Elizabeth1*, Briscoe Wuge H.1
1
University of Bristol
Foams are ubiquitous in our everyday lives, widespread in cosmetics, detergency and food
products. An aqueous foam can be defined as a dispersion of gas in a liquid phase, generally
stabilized by the adsorption of surfactants at the air-water interface.1 This project aims to
examine thin-film stability as controlled by surfactant adsorption,2 studying the relationship
between surfactant structure and the properties of the resulting foam following gas dispersion,
with the synergistic effects of surfactant mixtures also considered. Different analytical
techniques have been used including tensiometry, foam analysis, and conductivity to measure
various physical parameters such as surface tension, the critical micelle concentration, and
foamability and decay parameters. Following the quantification of various physical
parameters these were linked to the macroscopic structure of the foam.
Air
Water
Surfactant
Air
Literature:
1. Prud’homme Robert, Khan Saad. 1996, Foams: Theory, Measurements and Applications, Marcel
Dekker, Volume 57: 1-285.
2. Karakashev Stoyan, Manev Emil. 2014. Hydrodynamics of thin liquid films: Retrospective and
perspectives, Advances in Colloid and Interface Science.
Acknowledgements:
The project is supported by an EPSRC Impact Acceleration grant. E.M. would like to thank the
Briscoe research group for their guidance and support.
75
ESC 2015
P1_6
Shear rheology of hydrophobin adsorption layers at oil/water
interfaces and data interpretation in terms of a viscoelastic
thixotropic model
Radulova Gergana*1, Danov Krassimir1, Kralchevsky Peter1,
Petkov Jordan2 and Stoyanov Simeon3,4
1
Department of Chemical Engineering, Faculty of Chemistry & Pharmacy, Sofia University,
1164 Sofia, Bulgaria
2
Unilever Research & Development, Port Sunlight, Wirral, Merseyside CH63 3JW, U.K.
3
Unilever Research & Development, 3133AT Vlaardingen, The Netherlands
4
Laboratory of Physical Chemistry & Colloid Science, Wageningen University, 6703 HB
Wageningen, Netherlands
We investigated the surface shear rheology of class II HFBII hydrophobin layers at the
oil/water interface. Experiments in two different dynamic regimes, fixed rate of strain and
oscillations, have been carried out with a rotational rheometer. The rheological data obtained
in both regimes comply with the same viscoelastic thixotropic model, which is used to
determine the surface shear elasticity and viscosity, Esh and sh. Their values for HFBII at
oil/water interfaces are somewhat lower than those at the air/water interface. Moreover, Esh
and sh depend on the nature of oil, being smaller for hexadecane in comparison with
soybean-oil. It is remarkable that Esh is independent of the rate of strain in the whole
investigated range of shear rates. For oil/water interfaces, Esh and sh determined for HFBII
layers are considerably greater than for other proteins, like lysozyme and -casein. It is
confirmed that the hydrophobin forms the most rigid surface layers among all investigated
proteins not only for the air/water, but also for the oil/water interface. The wide applicability
of the used viscoelastic thixotropic model is confirmed by analyzing data for adsorption
layers at oil/water interfaces from lysozyme and -casein – both native and cross-linked by
enzyme, as well as for films from asphaltene. This model turns out to be a versatile tool for
determining the surface shear elasticity and viscosity, Esh and sh, from experimental data for
the surface storage and loss moduli, G' and G".
Fig. 1. (left) Plots of the shear stress sh vs. time t – data obtained in fixed-rate-of-strain regime. (right) Mean
shear elasticity Esh vs. the rate-of-strain amplitude a , calculated from the experimental G' and G".
76
ESC 2015
P1_7
Improved Heat Stability of Whey Protein Isolate Stabilized
Emulsions by Conjugation with Low Methoxyl Pectin using
Dry Heat Treatment
Setiowati Arima Diah*, Saeedi Serveh, Van der Meeren Paul
Particle and Interfacial Technology Group, Ghent University
Whey Protein Isolate (WPI) is known to have excellent emulsifying properties. However,
WPI is also known to be very susceptible to heat denaturation. On the other hand, heat
processing is commonly encountered in industry for improving the safety and shelf life of
foods. As heat induced denaturation of whey proteins will lead to the alteration of their
functional properties, heating of whey protein stabilized emulsions can alter
theircharacteristics, such as the consistency, which may betransformed from liquid to highly
viscous fluid and, in the worst case, to a gel.Previous research has shown that combining the
hydrophobic properties of proteins and the hydrophilic properties of polysaccharides can help
improving the functional properties and heat stability of whey proteins. This can be achieved
through conjugation of protein and polysaccharide. In this research,the heat stability of oil in
water emulsions(10% w/w) stabilized by 0.5 % conjugates of WPI-Low Methoxyl (LM)
Pectin with ratio of 2:1(WPI:LM Pectin) was compared to the stability of emulsions stabilized
by 0.5% WPI and by 0.5% mixture of WPI and LM Pectin. The emulsions were prepared by
microfluidisation at a driving air pressure of 4 bars, at a pH value of 6.5 and 5, and with a
NaCl concentration of 30 mM.
WPI tended to have lower emulsifying properties at pH 5, i.e. around its isoelectric point,
which is thought to be due to a lack of electrostatic repulsion. On the other hand,
electrophoretic mobility measurements indicated that conjugation shifted the isoelectric point
to a lower pH value, which caused the conjugates to be able to maintain their functionality at
the native protein’s isoelectric point. Particle size distribution results indeed showed that the
conjugates displayed much better emulsifying properties at pH 5.
WPI stabilized emulsions displayeda poor stability towards heat irrespective of pH and ionic
strength at temperatures above 80°C. On the other hand, emulsions stabilized by conjugates of
WPI and LM Pectin exhibited excellent heat stability. Upon heating at 80oC up to 20 minutes,
oil droplet size measurement showed that there was almost no change in the particle size
distribution of the conjugate-stabilized emulsions after heating. Viscosity measurements
showeda similar trend: whereas the consistency of emulsions stabilized by WPI ranged from a
highly viscous to a gel-like structure after heating, heat treated emulsions stabilized by
conjugates did not show any change in consistency and had flow behavior indexvalues close
to Newtonian fluid (n=1). This pronounced heat stabilizingeffect of LM Pectin,however, was
not observed in emulsions stabilized by a mixture of WPI and LM Pectin. Therefore, the
conjugation between WPI and LM Pectin seems to play an important role for the improved
emulsifying and heat stabilizing propertiesof the emulsion.
Overall, our experiments indicated that conjugation of WPI and LM Pectin by dry heat
treatment could largely improve the functional properties of the protein, whereby not only the
pH sensitivity, but also the heat-sensitivity of WPI-stabilized emulsions could be significantly
improved.
77
ESC 2015
P1_8
Surfactants and polymers at air-water interface: from molecular
interactions and interfacial structures to foaming properties
Slastanova Anna1*, Chen Meng2, Robles Eric3, Briscoe Wuge H.1
1
Procter & Gamble Beijing Innovation Centre
3
Procter & Gamble Newcastle Innovation Centre
2
Liquid foams are a class of soft matter defined as a dispersion of gas bubbles in a surfactant
solution. The stability of a foam is influenced by the layer of surfactant/polymer complexes at the
air-water interface. Understanding the structure and properties of this interfacial layer is therefore
of fundamental importance and relevance to a variety of practical applications, e.g. consumer
products and oil industries. In recent years, studies using surface-sensitive experimental
techniques such as X-ray and neutron reflectivity have considerably advanced our understanding
on interfacial behaviours of these mixtures1. However, the correlation is yet to be fully established
between polymer structural parameters (e.g. polymer architecture, charge density, molecular
weight and hydrophobicity) and the complex polymer/surfactant interfacial behaviour. Two
neutral comb co-polymers (arbitralily named Polymers A & B) with a hydrophilic PEG backbone
and differing lengths and densities of hydrophobic PVAc grafts were studied using surface
tensiometry, foam analysis, and X-ray reflectivity. Such comb co-polymers can be thought of as a
very sparsely grafted polymer brush, with interesting interfacial properties and effective roles in
stabilising foams and removing grease. Our initial XRR results (Fig. 1) at the solid-liquid
interface of Polymers A & B indicate their strong interactions with lipid multilayers, and suggest
promising detergency properties.
a)
b)
Fig. 1 a) X-ray reflectivity results of Polymers A and B with a DOPC lipid multilayer obtained at ESRF BM28;
b) Proposed mechanism of detergency mediated by the polymer, whereby lipid multilayers are disrupted and
removed in larger blocks of lipids rather than layer by layer.
Literature:
1. Taylor DJ., Thomas RK., Penfold J. 2007. Polymer/surfactant interactions at the air/water interface.
Advances in Colloid Interface Science 132: 69-110.
Acknowledgements:
The project is jointly funded by EPSRC Case Award and Procter & Gamble (P&G). The polymers are
kindly donated by P&G. Advice and support from Dr Meng Chen and Dr Eric Robles at P&G Beijing
and Newcastle Innovation Centres, repectively, are gratefully acknowledged.
78
ESC 2015
P1_9
Adsorption of As(III) from aqueous solutions by fly ash
agglomerates: Dynamic study
Justyna Ulatowska*
Wroclaw University of Technology, Faculty of Chemistry, Division of Chemical Engineering,
Norwida 4/6, 50-373 Wrocław, Poland
Many efforts have been made to remove As(III) from water and wastewater using various
adsorbents [1]. Fly ash is a powdery material generated from the combustion of coal in power
plants and has a pozzolanic property and therefore it is valuable and desirable material. In
many different branches of industry, fly ash is converted into more convenient compressed
form of granules, pellets or briquettes [2]. Granulated fly ash has been used as a sorbent for
heavy metal ions such as As(III), Cu(II) or Cd(II) [2,3].
The purpose of this study was to investigate the possibility of the utilization of fly ash as
a low cost adsorbent. Dynamic tests were carried out in terms of breakthrough curves of
lab-scale fixed bed column at different parameters: flow rate, size of fly ash agglomerates and
the amount of sorbent. Adsorption dynamic of As(III) was studied in a 0.025 m length and
0.015 m ID glass column, bed with fly ash agglomerates of size from 2.5 to 5.0 mm (20 g).
The liquid flow rate was 1.66 mL/min, initial As(III) concentration was 1000 mg/L and
experiments were performed at room temperature (about 25±1 oC).
The adsorption dynamic was described by Thomas and Yoon-Nelson models, and the
experimental data fitted well with Yoon-Nelson model. The external mass transfer and the
pore diffusion coefficient could be estimated using theoretical correlations [4]. It was shown
that the mass transfer process is controlled by the film mass transport in liquid.
The test results indicated that fly ash agglomerates could be used as a cheap adsorbent for the
removal of As(III) from aqueous solutions.
Literature:
1. Mohan Dinesh i Pittman Charles. 2007. Arsenic removal from water/wastewater using adsorbents –
A critical review. Journal of Hazardous Materials 142: 1-53.
2. Polowczyk Izabela, Bastrzyk Anna, Koźlecki Tomasz, Sawiński Wojciech, Rudnicki Piotr,
Sokołowski Adam i Sadowski Zygmunt. 2010. Use of fly ash agglomerates for removal of arsenic.
Environmental Geochemistry and Health 32: 361-366.
3. Aguilar-Carrillo Javier, Garrido Fernando, Barrios Laura i Garcia-Gonzalez Maria Teresa. 2006.
Sorption of As, Cd and Tl as influenced by industrial by–products applied to an acidic soil:
Equilibrium and kinetics experiments. Chemosphere 65: 2377–2387.
4. Karau Andreas, Benken C., Thömmes Jörg i Kula Maria Regina. 1997. The influence of particle
size distribution and operating conditions on the adsorption performance in fluidized bed.
Biotechnology and Bioengineering 55: 54-64.
Acknowledgements: The work was financed by a statutory activity subsidy from the Polish Ministry
of Science and Higher Education for the Faculty of Chemistry of Wrocław University of Technology.
79
ESC 2015
P1_10
Asphalt binder – aggregate interfacial interactions measurements
Przemysław Wojewódka*, Robert Aranowski, Christian Jungnickel
Adhesion between asphalt and aggregates is the most crucial parameter for pavement
durability. Insufficient adhesion results in stripping process of asphalt binder from the surface
of the aggregate, what can lead to damage of the pavement. In this regards, estimation of the
adhesion forces in the simple and quick way is very important.
In this paper, we present method developed for asphalt-aggregate contact angle direct
measurements in a wide range of temperature. Contact angles at the mineral-binder-air
interface were measured using a high temperature contact angle goniometer by a sessile drop
technique, which allows quick estimation of adhesion agent and aggregate type impact on
asphalt mixes durability. Developed method was verified by two other techniques – EU
Standard Test Method 12697 and by calculation contact angles with Young-Dupré equation.
The surface tensions values were obtained by the contact angle measurements between
samples and probe liquids with well-known surface tension. Research was performed with
granite and limestone aggregates and with the road binder paving grade 35/50 (range of
needle penetration @25°C).
80
ESC 2015
P1_11
Zeta potential of colloidal particles covered with proteins
Atsushi YAMAGUCHI1 and Motoyoshi KOBAYASHI2*
1
Graduate School of Life and Environmental Sciences, University of Tsukuba, Japan
2
Faculty of Life and Environmental Sciences, University of Tsukuba, Japan
Colloidal particles covered with proteins are found in many applications in pharmacy,
cosmetic, food, and so on. In these applications, predicting and controlling the interfacial
properties of protein-covered particles are important. In the present study, we measured
adsorption mass of lysozymes on silica particles (diameter 302 nm) and zeta potentials of
silica particles covered with lysozymes. Moreover, zeta potentials of silica particles with
lysozymes were analyzed by using 3D model with zeta potentials of lysozymes and silica
particles experimentally determined.
In 10 mM KCl, zeta potentials of lysozymes are 31 mV at pH 5 and 16 mV at pH 7, and
those of silica particles are -10 mV at pH 5 and -41 mV at pH 7. Adsorption mass at pH 7 is
larger than that at pH 5 (Fig.1). This is because, at pH 7, the electric repulsive force between
lysozymes is weak and the electric attractive force between a lysozyme and a silica particle is
strong. All the lysozymes are adsorbed on silica particles till the adsorption mass reaches near
the maximum value.
Zeta potentials of bare silica particles are negative (Fig.2). Then they gradually get close to
0 mV by adsorption of lysozymes. Further adsorption of lysozymes causes charge reversal of
silica particles. Calculated zeta potentials by 3D model are in good agreement with
experimental ones at low adsorption mass. Especially 3D model successfully describes the
isoelectric point at both pH. When the adsorption amount of lysozymes is high, on the other
hand, calculated values underestimate experimental ones. We suppose this discrepancy is
caused by the change of deprotonation amount of lysozymes and silica particles upon
adsorption.
30
completely adsorb
20
10 mM KCl, pH 7
0.02
Zeta potential (mV)
Adsorption mass (g/g)
0.025
10 mM KCl, pH 5
0.015
0.01
10
0
-10
-20
pH 5, Experiment
pH 7, Experiment
pH 5, 3D model
pH 7, 3D model
-30
0.005
-40
-50
0
0
0.005
0.01
0.015
0.02
Added lysozyme /mass of silica (g/g)
0.025
Fig.1 Adsorption mass of lysozymes on silica
particles at 10 mM KCl. Symobols are experimental
values (○: pH 5, □: pH 7). The full line represents
the adsorption mass if all the added lysozymes are
completely adsorbed on silica particles.
0
0.005
0.01
0.015
0.02
0.025
Added lysozyme /mass of silica (g/g)
Fig.2 Zeta potentials of silica particles covered
with lysozymes at 10 mM KCl. Symobols are
experimental values (○: pH 5, □: pH 7). Lines
represent the culculated values with 3D model
from zeta potentials of lysozymes and silica
particles.
81
ESC 2015
P2_1
Fatty acid induced growth of giant micelles in ternary surfactant
solutions
Georgieva Gergana1*, Anachkov Svetoslav1, Kralchevsky Peter1,
Danino Dganit2, Abezgauz Ludmila2, Liebewirth Ingo3, Koynov Kaloian3
1
Dpt. Chemical and Pharmaceutical Engineering, Sofia University, Sofia, Bulgaria
2
Dpt. Biotechnology and Food Engineering, Technion - IIT, Haifa, Israel
3
Max Planck Institute for Polymer Research, Mainz, Germany
Synergistic growth of rodlike micelles was recently reported in binary mixed solutions of
anionic (SLES, sodium laurylethersulfate) and zwitterionic (CAPB, cocamidopropyl betaine)
surfactants at relatively low concentrations1. In our study, the composition in terms of SLES and
CAPB was selected to be near the maximal micelle size of the binary system and we added a third
component – fatty acid: caprylic (HC8) and lauric (HC12). For a given fatty acid concentration,
the viscosity of the micellar solution exhibits a sharp and high maximum, which is higher for the
short-chain fatty acid. Experiments with polarized light and NMR revealed that these viscous
solutions are isotropic, rather than liquid-crystalline. Cryo-TEM experiments of the ternary
micellar solution with lauric acid demonstrated a complex phase behavior: wormlike micelles to
the left of the peak; giant interweaved wormlike micelles at the peak, and wormlike micelles
transforming into disclike aggregates to the right of the peak. Such coexistence of worm-like and
disclike aggregates is possible in view of the theory on micellar growth 2. In the case of HC8,
cryo-TEM imaging revealed that giant interweaved wormlike micelles form in the vicinity of the
peak in viscosity. The observed resonance growth of giant micelles could be explained by a fine
balance of packing constraints, which significantly depend on fatty acid concentration.
HC8 in 70 mM CAPB + 30 mM SLES-1EO
o
25 C
30000
Viscosity (mPa.s)
27900
20000
10000
0
0
10
20
30
HC8 concentration (mM)
Fig. 1 Dependence of viscosity on fatty acid concentration (left) and a cryo-TEM image at the peak (right).
Literature:
1. Christov Nikolay1, Denkov Nikolai2, Kralchevsky Peter3, Ananthapadmanabhan Kavssery4, Lips
Alex5. 2004. Synergistic sphere-to-rod micelle transition in mixed solutions of sodium dodecyl
sulfate and cocoamidopropyl betaine. Langmuir 20: 565-571.
2. Anachkov Svetoslav1, Kralchevsky Peter2, Danov Krassimir3, Georgieva Gergana4,
Ananthapadmanabhan Kavssery5. 2014. Disclike vs. cylindrical micelles: Generalized model of
micelle growth and data interpretation. J. Colloid Interface Sci. 416: 258-273.
82
ESC 2015
P2_2
Investigation of the interaction between phospholipids and tetrap-guanidinoethylcalix[4]arene having antibacterial activity
Gorczyca Marcelina1*, Korchowiec Beata1, Korchowiec Jacek1, Augustyniak Krzysztof1,
Regnouf-de-Vains Jean-Bernard2, Rogalska Ewa2
1
2
Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow, Poland
Structure et Réactivité des Systèmes Moléculaires Complexes, BP 239, CNRS/Université de
Lorraine, 54506 Vandoeuvre-lès-Nancy cedex, France
* – [email protected]
Calixarenes, a class of macrocyclic oligomers, have shown antibacterial activity. In this
regard, we demonstrated recently that different calixarene derivatives modify the properties
of model membranes [1-2]. In the present work the behavior of tetra-pguanidinoethylcalix[4]arene (CX) and its monomer p-guanidinoethylphenol (mCX) in
a membrane environment was studied. CX was synthesized as an antibacterial agent. Indeed,
this derivative is active against different Gram-positive and Gram-negative bacteria and does
not show cell toxicity [3]. Interestingly, the antibacterial activity of mCX is much weaker
compared to CX. Here, all atom molecular dynamics simulations (MD) and surface pressure
measurments were employed to better understand the mechanism of the the interaction of CX
and mCX with lipid membranes. A zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine
(DMPC) and a negatively charged 1,2-dimyristoyl-sn-glycero-3-phospho-L-serine (DMPS)
were used as models of eukaryotic and bacterial cell membranes, respectively. All MD
simulations were performed using NAMD2 package and CHARMM27 force field.
The simulations were carried out under a constant number of particles (N), constant
temperature (T), constant normal pressure (pN), and constant surface tens
N
ensemble. The results obtained show that the two guanidinoethyl derivatives have different
impact on model lipid membranes. It was demonstrated that CX and mCX concentrate near
the anionic DMPS monolayer. Moreover, in contrast to the p-guanidinoethylphenol,
calixarene penetrates the hydrophobic part of the phospholipid film. In the case of the
zwitterionic DMPC, no significant effect of CX and mCX on the properties of phospholipd
film was observed. The overall results indicate that charge-charge and apolar interactions
between CX and lipids are responsible for the reorganization of model membranes.
Literature:
1. Korchowiec B., Gorczyca M., Ben Salem A., Regnouf de Vains J.-B., Rogalska E., Colloids Surf.
B 2013, 103, 217-222.
2. Korchowiec B., Korchowiec J., Gorczyca M., Regnouf de Vains J.-B., Rogalska E.,
J. Phys. Chem. B 2015, 119(7), 2990-3000.
3. Mourer M., Duval R. E., Finance C., Regnouf de Vains J.-B., Bioorg. Med. Chem. Lett. 2006, 16,
2960-2963.
Acknowledgements: This work was supported by the Polish National Science Centre, project No.
2012/07/B/ST5/00890. M. G. acknowledges the financial support from the project Interdisciplinary
PhD Studies “Molecular sciences for medicine” (co-financed by the European Social Fund within the
Human Capital Operational Programme).
83
ESC 2015
P2_3
In Situ Spectroscopic Study of Polyelectrolyte Multilayer
Formation and Hydration under Confinement
Tracey Ho1*, Marta Krasowska1, Stephanie MacWilliams1, Kristen Bremmell2,
Damien N. Stringer3, David A. Beattie1
1
Ian Wark Research Institute, University of South Australia, Mawson Lakes, Adelaide, SA
5095, Australia
2
School of Pharmacy and Medical Science, University of South Australia, City East Campus,
North Terrace, Adelaide, SA 5000
3
Marinova Pty Ltd, 249 Kennedy Drive, Cambridge, TAS 7170, Australia
The formation of fucoidan/chitosan-based polyelectrolyte multilayers (PEMs) has been
studied with in situ FTIR spectroscopy. Attenuated total reflectance (ATR) FTIR
spectroscopy has been used to follow the sequential build-up of the multilayer, with peaks
characteristic of each polymer being seen to increase in intensity with each additional
adsorption stage. In addition, spectral processing allowed for the extraction of spectra from
individual adsorbed layers of the build-up, and these were then used to provide unambiguous
determination of the adsorbed mass of the PEM at each stage of formation.
The nature of the hydration water within the polyelectrolyte multilayer has also been studied
with FTIR spectroscopy, specifically in situ synchrotron FTIR microscopy. Measurements
were made with the polymer film confined between two solid surfaces, to remove bulk water
from the area probed by the infrared evanescent wave. The acquired spectra have enabled the
hydrogen bonding environment of the polymer film hydration water to be determined. The
implications of the altered water environment in the multilayer are discussed within the
context of potential application of the multilayer film as a lubricant.
84
ESC 2015
P2_4
Interaction cytolytic protein Cyt2Aa2 / lipid bilayer:
binding and structural changes
Alberto Moreno-Cencerrado1 Sudarat Tharad2, Jagoba Iturri1, Margareta Mittendorfer3,
Boonhiang Promdonkoy3, Chartchai Krittanai2 and Jose L. Toca-Herrera1
1
Institute for Biophysics, Department of Nanobiotechnology, University of Natural Resources
and Life Sciences Vienna (BOKU), Vienna 1190, Austria
2
Institute of Molecular Biosciences, Mahidol University, Salaya Campus, Nakhonpathom
73170, Thailand
3
National Center for Genetic Engineering and Biotechnology, National Science and
Technology Development Agency, Pathumthani 12120, Thailand.
Cyt2Aa2, a cytolytic protein produced by the Bacillus Thuringiensis Gram-positive soil
bacterium known by its insecticide and antimicrobial properties,[1] shows capability to bind
and form a protein complex with a synthetic lipid membrane without the requirement of a
receptor.[2] However, the binding mechanism by which the interaction of Cyt2Aa2 to lipid
bilayers occurs is still unclear.
In this work, quartz crystal microbalance with dissipation (QCM-D) and atomic force
microscopy (AFM) techniques were employed for real time characterization of the interaction
of Cyt2Aa2 onto hybrid cholesterol/lipid surface-supported bilayers. This allowed not only
for a qualitative (i.e. binding kinetics, mechanical properties) but also for a quantitative
characterization (Cyt2Aa2 deposited mass) of the process, which turned to be critically
dependent on the protein concentration employed. Thus, at low concentrations (10 μg/ml)
Cyt2Aa2 binds slowly on the lipid bilayer forming a compliance protein/lipid layer with
aggregates. On the contrary, at higher protein concentrations (100 μg/ml) the binding is much
faster, and the complex formed is more rigid. Such a structure is also featured by the
appearance of randomly distributed holes. These results suggests that the protein/lipid bilayer
binding mechanism seems to be carpet-like at low protein concentrations and pore forminglike at high protein concentrations.
Keywords: cytolytic protein, (cholesterol-)lipid bilayer, binding mechanism, atomic force
microscopy, quartz crystal microbalance with dissipation
Literature:
1. Hofte, H. et al. Microbiol. Rev. 1989, 53, 242-255.
2. Suktham, K. et al. Toxicon 2013, 74, 130-137
85
ESC 2015
P2_5
Study of Microenvironment of Brij30 Reverse Micelles
with Optical Probes
N.Mzareulishvili1, M.Kurtanidze2 and M.Rukhadze3
1
Iv.Javakhishvili Tbilisi State University, I.Chavchavadze ave 3, 0179, Tbilisi
Reverse micelles became very popular in different areas of life sciences [1]. Reverse
micelles are used as artificial model of biomembranes due to resemblance of their
structure. Nonionic surfactants provide milder environment for encapsulation of enzymes
and proteins inside the water nanocages of reverse micelles. Investigation of reverse
micelles through the UV-visible absorption spectra of optical probes provides important
information about nature of water in water droplets of reverse micelles [2].
The microenvironment of reverse micelles of polyoxyethylene(4)lauryl ether(Brij 30) was
investigated by UV-visible spectroscopy on the basis of methyl orange(MO) and onitroaniline as molecular probes.
The influence of both additives of water and water solutions of some kosmotropic and
chaotropic salts on the association degree of methyl orange with reverse micelles was
studied. Association degrees of MO with Brij30 reverse micelles were calculated by
absorption data of MO at wavelengths of 408 and 416 nm in 0.13 M Brij30 solution in
hexane at different water/surfactant ratio (W). The existence of three types of water is
revealed by dependence of methyl orange absorption maxima versus water content in the
nanocages of reverse micelles. Different influence of kosmotropic and chaotropic anions
on the formation of free water in water core of reverse micelle was observed, viz. the
formation of free water in water core of reverse micelle begins at different W in the
presence of perchlorate and iodide as compared with acetate and fluoride ions.
The influence of both additives of water and water solutions of some salts on the binding
of o-nitroaniline (o-NA) to the reverse micelles of Brij-30 was determined by UV-visible
spectroscopy. Binding constants of o-NA with Brij30 reverse micelles were calculated by
absorption data of o-NA at wavelengths of 376 and 400 nm in hexane (0.0 M and 0.23 M
Brij30). Concentrations of free and bound o-NA were determined by solution of equation
systems at intermediate concentrations of Brij30 [3]. Different influence of kosmotropic
and chaotropic anions on binding constant Kb was revealed, viz. the values of binding
constants in the presence of chaotropic anions are higher than those in the presence of
kosmotropic ions.
Literature:
1. P.M. Wiggins, Water in Complex environments such as living systems, Physica A. 314(2002)
485-491.
2. Qi L. and Ma J. Investigation of the Microenvironment in Nonionic Reverse Micelles Using
Methyl Orange and Methylene Blue as Absorption Probes. Journal of colloid and interface
science. 197 (1998) , 36 - 42.
3. R.D. Falcone, J.J. Silber, M.A. Biasutti, N.M. Correa, Binding of o-Nitroaniline to Nonaqueous
AOT Reverse Micelles, Organic Chemistry in Argentina, ARKIVOC, vii, (2011) 369-379.
86
ESC 2015
P2_6
Properties of gelatin–chitosan polyelectrolyte complexes
Nina Sokolan1*, Nikolay Voron’ko1, Svetlana Derkach1
1
Murmansk State Technical University
The most frequently used stabilizers in the food industry are proteins and gelatin is the most
popular among them. This compound is the product of the hydrolytic degradation of fibrillar
collagen proteins and retains many important properties of collagen. However, the
composition of proteins (which provide the high rate of adsorption) with polysaccharides
(which are responsible for the steric factor of stabilization and increase in the viscosity of a
continuous phase) are currently considered as the most perspective stabilizers.
The protein/polysaccharide interaction can be realized by two modes: the formation of
covalent bonds between functional groups of macromolecules or electrostatic (non-covalent)
interactions. Electrostatic interactions lead to the formation of polyelectrolyte complexes. It is
worth mentioning that the complexes have a unique ability for reversible changes in their
phase state according to variations in ambient factors (pH, ionic strength, temperature etc.).
Therefore, they are treated as so-called smart or intelligent polymer systems.
In the presented work the interaction of gelatin and cationic polysaccharide chitosan with
stoichiometric (bio)polyelectrolyte complexes formation inside of the aqueous phase which
has pH less than isoelectric point of gelatin has been studied by capillary viscosimetry, UV
spectroscopy (Fig. 1) and dispersion of light scattering methods. The aqueous dispersions of
complexes show increase in the particle size of dispersed phase and accordingly the relative
viscosity compared with sols of the individual components – gelatin and polysaccharide.
A
234 237
3.0
2.5
224
2.0
1.5
3 4 5
1.0
2
1
6
0.5
0.0
180
200
220
240
260
280
300
320
340 360
l, nm
Fig. 1 UV-spectra for
gelatin (1) gelatin-chitosan (2 - 5) and chitosan (6) sols
at different concentration of chitosan and pH 3.7
The models and mechanism of (bio)polyelectrolyte complexes formation are discussed to be
due to the electrostatic interactions between the positive charged amino groups of chitosan
and negative charged amino acids residues (glutamic Glu and aspartic Asp acids) of gelatin.
The properties of gelatin–chitosan complexes as food emulsion stabilizers have been
investigated.
Acknowledgements:
This work was supported by the Russian Foundation for Basic Research (project № 14-08-98811
r_Sever_a).
87
ESC 2015
P2_7
Investigation of interaction between PAMAM dendrimers and
SiO2 surface
Tokarczyk Karolina*, Jachimska Barbara
Dendrimers are a new class of macromolecules increasingly used in a wide range of
scientific research. Over the past decade, much research has been focused on the application
of dendrimers both in biomedical fields (drug delivery, gene delivery, cancer-targeting
therapy, diagnosis) and catalytic research (solar energy conversion, artificial photosynthesis
and hydrogenation of olefins and aromatic compounds). There is particular interest with
properties such as globular shape and defined size resulting from low dispersities of these
macromolecules with regular and highly branched three-dimensional architectures.
The experimental studies of 6th-generation poly (amidoamine) G6 PAMAM
dendrimers have been carried out using various techniques such as quartz crystal
microbalance (QCM-D) and surface plasmon resonance (MP-SPR). QCM-D and MP-SPR are
powerful methods that enable highly sensitive, qualitative, real-time, label-free, and
noninvasive detection of adsorbed macromolecules. These measurements allowed the
determination of the kinetics of adsorption of PAMAM from aqueous solution on a SiO2coated surface. We found that the thickness of the PAMAM films depends strongly on the pH
of the solution which influences swelling of the PAMAM films. These results supply
compelling experimental evidence for significant swelling of G6 PAMAM dendrimer upon its
protonation at the solid/solution interface. This phenomenon is a consequence of spatial
relocation of the dendrimer amide groups due to the interactions of the positively charged
amines with the oppositely charged condensed counter-ions and the penetrating water
molecules.
Literature:
1. Jachimska Barbara, Łapczyńska Marta, Zapotoczny Szczepan. 2013. Reversible Swelling Process
of Sixth-Generation Poly(amido amine) Dendrimers Molecule As Determined by Quartz Crystal
Microbalance Technique. J. Phys. Chem. C 117: 1136
Acknowledgements:
88
ESC 2015
P2_8
Analysis of the PAMAM dendrimers-BSA complexes adsorption
using QCM-D and MP-SPR techniques
Tokarczyk Karolina*, Jachimska Barbara
Dendrimers are fascinating hyperbranched polymers, which are multifunctional, welldefined and nano-sized compounds. Due to their unique properties and specific structure they
have been considered to be one of the most promising groups which could revolutionise
medicine. At present, dendrimers are very popular in many areas of research: drug delivery,
gene delivery, cancer-targeting therapy and diagnosis. Thus, control over the interactions
between these macromolecules and blood plasma media is a key parameter in the design of
advanced materials.
In our present work we analyse interactions between 6th-generation polyamidoamine,
PAMAM, dendrimers and bovine serum albumin (BSA). BSA albumin has been selected as it
belongs to the dominant group of mammalian blood plasma proteins, namely albumin. BSA is
characterised by: a relatively high molecular weight, three-domain structure and an
asymmetric charge distribution. BSA is able to adopt different conformations, which are
modified by changes in pH or ionic strength. The physicochemical properties of G6
PAMAM-BSA complexes have been investigated using different techniques such as surface
plasmon resonance (MP-SPR) and quartz crystal microbalance (QCM-D). These are powerful
methods that enable highly sensitive, qualitative, real-time, label-free and noninvasive
detection of macromolecular interactions. These measurements allow the determination of the
kinetics of adsorption of PAMAM-BSA from aqueous solution on a SiO2-coated surface. It
was found that the thickness of the PAMAM-BSA films depends strongly on the pH of the
solution. Comparison of the results obtained from MP-SPR and QCM-D makes it possible to
estimate the water content of the film. These results are essential for designing an alternative
scheme for drug and gene delivery.
Literature:
1. Jachimska Barbara, Łapczyńska Marta, Zapotoczny Szczepan. 2013. Reversible Swelling Process
of Sixth-Generation Poly(amido amine) Dendrimers Molecule As Determined by Quartz Crystal
Microbalance Technique. J. Phys. Chem. C 117: 1136
Acknowledgements:
This work was supported by Grant NCN OPUS4 2012/07/B/ST5/00767
89
ESC 2015
P2_9
POPC/POPE lipid vesicles deposition on polyelectrolyte films
Wlodek Magdalena1*, Kolasinska-Sojka Marta1, Warszynski Piotr1
1
Polyelectrolyte – supported lipid bilayers (SLB) are interesting systems for various
biomimetic applications such as cell-membrane models, biosensors and drug delivery carriers.
Understanding of the mechanism of supported lipid bilayers formation after exposure of small
lipid vesicles to a soft support is still a scientific challenge.
In this work, by combining the quartz crystal microbalance with dissipation (QCM-D) and
atomic force microscopy (AFM), we have investigated the formation of SLB on
polyelectrolyte multilayers as a function of buffer’s pH and an addition of NaCl as well as the
type of the underlying cushion.
The vesicles used were mixtures of zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3phosphocholine (POPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine
(POPE) in phosphate buffer with or without NaCl addition. Three various pH values of buffer
were also investigated. Polyelectrolyte cushions applied as a support for lipid bilayer were
constructed by the layer by layer deposition of pairs of polycations (PEI, PDADMAC, PLL)
and polyanions (PSS, PGA) on quartz or silicon surface, with different number of layers.
Surface structure and properties of the solid substrates were characterized with ellipsometry to
find thickness and swelling properties and their roughness was determined using AFM.
We found that pathway of adsorption and deposition of lipid vesicles depended on pH and
addition of NaCl in buffer solution. The kinetics of SLB formation and the quality of already
formed lipid bilayer depended on the type of support used, i.e., type of cushion, the amount of
water entrapped within polyelectrolyte multilayer.
Acknowledgements:
The work presented was financed by the National Science Centre, Contract No. DEC2011/01/DST5/04913 and COST Action CM1101.
90
ESC 2015
P3_1
The crystallisation of petroleum diesel and wax anti-settling
additives
Joanna Starkie1*, Dr. Alex Routh1
1
University of Cambridge
Crystallisation of long chain n-alkanes from petroleum diesel causes engine problems at low
temperatures. Cold flow additives have been developed to counteract these problems. One
example are wax anti-setting additives (WASAs), which are used to limit the sedimentation of
wax crystals by reducing the crystal size and improving the stability of the wax crystals
suspensions. In comparison with other additives, the mechanism of WASAs action has
received very little attention in the scientific literature and current knowledge is mainly
sourced from industry and reported in patents.1
Initial work has been conducted to produce a model diesel system using long chain n-alkanes
that crystalise at room temperature to study the effect of cold flow additives and WASAs.
Figure 1 showes the effect of cold flow additives and WASAs on this model diesel system.
Fig. 2: a) shows large wax crystal plates formed without the presence of cold flow additives. b) shows smaller
needle-like wax crystals formed in the presence of cold flow additives and WASAs.
Literature:
1. Marie Emmanuelle, Chevalier Yves, Brunel Sylvain, Eydoux Franck, Germanaud Laurent and
Flores Philippe 2004, Journal of Colloid and Interface Science, 269: 117-125.
Acknowledgements:
We thank Prof. Pete Dowding, Prof. Ken Lewtas for their help with this project. This work was
supported by Infineum Ltd. and the Cambridge Trusts.
91
ESC 2015
P3_2
Hierarchical surface patterns from evaporative drying of
nanofluids
Wąsik Patryk1,2,*, Redeker Christian2, Trask Richard3, Briscoe Wuge H.2
1
Bristol Centre for Functional Nanomaterials, University of Bristol, Bristol, BS8 1FD, UK
2
3
Advanced Composites Centre for Innovation and Science, Bristol, BS8 1TR, UK
Nature articulates language of shapes fluently and delivers complex structures on all length
scales with ease via self-assembly. A simple, yet versatile method used in nanotechnology to
obtain surface patterns of hierarchical nanostructures is Evaporation Controlled SelfAssembly (ECSA). During the ECSA process, particles inside a droplet are organized into a
variety of structures guided by the inter-particle forces and evaporation-induced flows of the
solvent. It can be harnessed to produce a plethora of surface patterns by manipulating
parameters such as particle concentration, size and shape, evaporation rate, addition of
polymers, and surface chemistry of the substrate.
Recently, the possibility of creating sophisticated residual patterns using a novel ECSA
process has been demonstrated [1]. In this process, upon evaporation, ZnO nanorods in a
droplet undergo chemical and morphological transformations via a dissolution and nonequilibrium recrystallization process (Fig. 1a), producing a self-assembled 3D network
structures made of ultra-long (up to 1.5 cm) Zn(OH)2 fibres (Figs. 1 b-c). It has been shown
that, by further annealing, the 3D networks undergo further transformation to porous
structures made of ZnO nanocrystals (Fig. 1d).
In nanotechnology, we aspire to study and understand the mechanisms that control the
formation of surface patterns with intriguing geometry to create sophisticated hierarchical
nanostructures with tailored functionalities. Here we would like to present results on how size
and shape of ZnO nanoparticles, types of solvent mixtures, incorporation of other
nanoparticles and active compounds, as well as different substrates govern the structure and
composition of residual surface patterns created by the use of this novel ECSA process.
Fig. 1 a) ZnO nanorods in a nanofluid droplet undergo transformation into Zn(OH) 2 residual surface patterns
during the evaporation, b)-c); d) porous network of ZnO, produced by annealing Zn(OH) 2 network at 550 °C [1].
Literature:
1. Wu Hua et al. 2014. Self-assembly in an evaporating nanofluid droplet: rapid transformation of
nanorods into 3D fibre network structures. Soft Matter 10: 5243-5248.
Acknowledgements:
This project is funded by The Engineering and Physical Sciences Research Council (EPSRC) through
the Bristol Centre for Functional Nanomaterials (BCFN).
92
ESC 2015
P4_1
Effects of Cationically Modified Polysaccharide Antidotes for
Unfractionated Heparin on Blood Pressure in Rats
Bartlomiej Kalaska1, Kamil Kaminski2, Emilia Sokolowska1, Monika Kujdowicz2,
Iwona Gawlik2* Krzysztof Szczubialka2, Dariusz Pawlak1, Maria Nowakowska2,
Andrzej Mogielnicki1
1
Department of Pharmacodynamics, Medical University of Bialystok, Mickiewicza 2C,
Bialystok, Poland
2
Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, Poland
Introduction: Unfractionated heparin (UFH) as one of the most popular anticoagulants requires
safer antidote than currently used protamine. Derivatives of polysaccharides are proven to be
effective antidotes for UFH. They could replace protamine because of their better
biocompatibility and lower immunogenicity. One of protamine adverse effects that is particularly
dangerous is blood pressure decrease
Methods: Polymers were synthesized by substitution of Dextran (Dex) and γ-cyclodextrin (GCD)
with glycidyltrimethylammonium chloride (GTMAC) or N-acrylamidopropyl-N,N,Ntrimethylammonium chloride (APTMAC). Dex was cationically modified also by grafting
poly(allylamine hydrochloride) (PAH) using the radical polymerization process. The amino
groups in the resulting graft polymer (Dex40-PAH) were then substituted with arginine to obtain
Dex40-PAH-Arg polymer possessing two types of cationic groups. The structure of the polymers
was confirmed using 1H NMR, FT-IR and the elemental analysis, and proper compounds were
chosen for animal testing. MBP course was measured in rats over one hour after administration of
chosen GTMAC derivatives of sugar polymers. Maximum doses: Dex40-GTMAC2 (12.5 mg·kg1), Dex40-GTMAC3 (22.5 mg·kg1), Dex6-GTMAC (28.8 mg·kg-1), GCD-GTMAC2 (32.4
mg·kg-1) and protamine as reference agent (3 and 9 mg·kg-1). Course of mean blood pressure
(MBP) was also registered for 60 min after iv administration of UFH (300 U∙kg-1 followed by the
administration of the investigated polymer or protamine. The statistical analysis was performed
using the U Mann Whitney test.
Results: The obtained polymers were animal tested for UHF reversal effect, early toxicity and
effects on mean blood pressure. Studied agents reversed antithrombotic effect of UFH. Majority
of polysaccharides derivatives we obtained have no statistically significant effect on blood
pressure compared to vehicle. Some of the polymers caused severe hypotonia and animal studies
were interrupted.
Conclusion: The novel polymers have very promising properties and can potentially substitute
protamine as the UFH antidote.
Literature:
1. Kaminski K, Plonka M, Ciejka J, Szczubialka K, Nowakowska M, Lorkowska B, Korbut R, Lach
R (2011) Cationic derivatives of dextran and hydroxypropylcellulose as novel potential heparin
antagonists. J Med Chem 54: 6586-6596.
Acknowledgement: The study was supported by National Science Centre Grant No. DEC2011/03/B/NZ7/00755. BK was supported by funds from Leading National Research Center in
Bialystok (31/KNOW/2013). KK and IG was supported by National Science Centre Grant No. UMO2013/09/D/ST5/03864. KK, KS, and MN acknowledge the financial support of the
Foundation for Polish Science Team Programme co-financed by the EU European Regional
Development Fund, PolyMed, TEAM/2008-2/6.
93
ESC 2015
P4_2
Polysaccharide nanocomposite particles for aerosol therapy
Jabłczyńska Katarzyna*, Sosnowski Tomasz R.
Faculty of Chemical and Process Engineering, Warsaw University of Technology
The work is focused on analysis of particles produced by spray drying from a precursor
containing biocompatible and biodegradable polysaccharide nanoparticles, which can be
carriers for active substances used in inhalation therapy. Suspensions of nanoparticles which
had been synthesized from dextran and carboxymethylcellulose were dried in Büchi B-290
spray dryer. The effect of process variables and type of precursor on the morphology and
powder characteristic was determined. Powder particles size and morphology examination
was carried out by means of scanning electron microscopy. Polisaccharide powders were
aerolized with commercially available dry powder inhaler and the size distributions of
resulting aerosol particles were measured using a diffraction spectrometer (Malvern).
The obtained results indicate that adjustment of the drying conditions allow the preparation
of the nanostructured modified polysaccharide powder particles with the characteristics
making them suitable for inhalation as drug carriers.
a
b
Fig. 1 a) Drying of nanosuspension droplet in different process conditions; b) SEM micrograph of powder
obtained by spray drying of suspension of nanoparticles from modified dextran.
Literature:
1. Jabłczyńska Katarzyna, Janczewska Magdalena, Kulikowska Aleksandra, Sosnowski Tomasz R.
2015. Preparation and Characterization of Biocompatible Polymer Particles as Potential
Nanocarriers for Inhalation Therapy. Int. J. Polymer Sci., 2015:1-8.
Acknowledgements:
The work is financed by National Science Centre, Poland, Project No. 2014/13/N/ST8/01667. The
study is related to the activity of the European network action COST MP1106 “Smart and green
interfaces - from single bubbles and drops to industrial, environmental and biomedical applications”
94
ESC 2015
P4_3
Sidewall Functionalization of Magnetically Triggered
Nanocontiner by Colloid Nanoparticles and Amide Groups.
A Molecular Dynamics Study
Konczak Lukasz1*, Panczyk Tomasz1
1
This work discusses two approaches for controlling of capping and uncapping the inner cavity
of the magnetically triggered nanocontiner1,2, that is magnetic nanoparticles covalently linked
to carbon nanotube tips (Figure 1). The first approach is the noncovalent functionalization of
nanotube sidewalls based on adsorption of charged fine colloid nanoparticles. The second
approach is covalent functionalization of the nanotubes sidewalls by incorporation of polar
amide groups. Single and triple walled carbon nanotubes were analysed as well as the
presence of cisplatin molecules encapsulated in the nanotubes inner cavities. Both approaches
might result in obtaining the preferred energetic balance that is less stable uncapped state and
relatively low activation barrier for spontaneous transition from the uncapped to the capped
state. However, adsorption of fine colloids turned out to be too weak to make the whole
system stable for a long time. On the other hand, covalent attachment of polar amide
functional group leads to the required energetic balance of the nanocontiner.
Fig. 1 Covalent and noncovalent functionalization of carbon nanotube.
Literature:
1. Panczyk T., Jagusiak A., Pastorin G., Ang W. H., Narkiewicz-Michalek J., 2013. Molecular
Dynamics Study of Cisplatin Release from Carbon Nanotubes Capped by Magnetic Nanoparticles.
J. Phys. Chem. C: 117, 17327–17336.
2. Panczyk T., Da Ros T., Pastorin G., Jagusiak A., Narkiewicz-Michalek J., 2014. Role of
Intermolecular Interactions in Assemblies of Nanocontainers Composed of Carbon Nanotubes and
Magnetic Nanoparticles: A Molecular Dynamics Study. J. Phys. Chem. C: 118, 1353–1363.
Acknowledgements:
This work was supported by Polish National Science Center grant UMO-2012/07/E/ST4/00763.
95
ESC 2015
P4_4
Novel fluorescent silicone materials
Krzywda Piotr1*, Kasprzyk Wiktor1, Bednarz Szczepan1
1
Cracow University of Technology, Faculty of Chemical Engineering and Technology,
Department of Biotechnology and Physical Chemistry,
Warszawska 24 St. 31-155 Krakow, Poland
Fluorescence is one of the most frequently used phenomena in many fields of science.
Nowadays, we are looking for original dyes that may contribute to the development of various
fluorescence techniques and expand the area of their applications. Novel group of fluorescent
dyes are the compounds obtained through low-temperature pyrolysis of citric acid in the
presence of α,β-diamines, α,β-aminoalcohols or α,β-aminothiols. These compounds are very
promising because of their non-toxic and biocompatible nature, relatively high fluorescence
quantum yields and chemical inertness. It is also possible to apply them in the synthesis of
fluorescent polymeric materials [1].
The main aim of this research was to develop a methodology for the synthesis of
transparent and flexible silicone materials with fluorescent properties. The first step was the
incorporation of α,β-diamine moieties into chemical structure of silicone polymer. Thus, N[3-(Trimethoxysilyl)propyl]ethylenediamine was used as a source of α,β-diamine groups. The
next step involved surface condensation of these groups with citric. Latter step produced
fluorescent derivative of 2-pyridone (i.e. 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7carboxylic acid) chemically bonded to the silicone chain.
The obtained fluorescent flexible silicon materials were characterized according to
their FT-IR spectra, wetting and hydrolytic properties. Their possible application as silicone
material’s markers was confirmed by the fluorescence stability tests under various
environmental conditions. Furthermore, it was found, that obtained fluorescent polymers can
be used for the detection of iron ions, chromates and vitamin C.
A
B
Fig. 1. Transparent silicone material with fluorescent properties;
A- under daylight, B- under UV light 365 nm.
Literature:
1. Kasprzyk Wiktor, Bednarz Szczepan, Bogdał Dariusz. 2013. Luminescence phenomena of
biodegradable photoluminescent poly(diol citrates). ChemComm 49, 57, p. 6445-6447
Acknowledgements:
The authors gratefully acknowledge the support for this work from the European Union through the
European Social Funds (contract no. UDA-POKL.04.01.01-00-029/10-00) and (contract no.
UDAPOKL. 04.01.02-00-217/11-00).
96
ESC 2015
P4_5
Electrophoretic mobility of latex particles:
Effects of divalent counter-ions
Manami Nishiya1, Takuya Sugimoto1, and Motoyoshi Kobayashi2*
1
2
Faculty of Life and Environmental Sciences, University of Tsukuba, Japan
0
Electrophoretic mobility (10-8 m2 V-1 s-1)
Electrophoretic mobility (10-8 m2 V-1 s-1)
We measured electrophoretic mobility (EPM) of carboxyl latex particles in mixed
solutions of KCl and CaCl2. Experiments were carried out as functions of the solution pH, the
mixed molar ratio of Ca2+ to K+ (X= [Ca2+] / [K+]), and the ionic strength. Experimental EPM
was analyzed by using 1-pKH with or without Ca2+ association model, diffuse double layer
model, and the Ohshima equation including the relaxation effect or the Smoluchowski
equation neglecting the relaxation effect for calculating theoretical EPM value. Figure 1
shows the EPM of carboxyl latex particles at the ionic strength I=10 mM as a function of the
solution pH. In Fig. 1, symbols are experimental values, lines are theoretically calculated.
While the lines in Fig. 1 (a) are drawn by neglecting Ca2+ association, lines in Fig. 1 (b) are
obtained taking account of Ca2+ association. The magnitude of the EPM is large at high pH
due to deprotonation of carboxyl groups on the particle. At high pH, as the ratio X increases,
the absolute value of the experimental EPM decreases. In contrast, at low pH, EPMs are on a
single curve irrespective of the ratio X; the charging behavior is controlled by ionic strength at
low pH even in the presence of Ca2+. The theoretical EPMs calculated by using 1-pKH without
Ca2+ association model demonstrated the same tendency of the experimental ones (Fig. 1 (a)).
Thus, effects of double layer are significant in mixed solutions containing Ca2+. At high pH,
however, the magnitude of the theoretical EPMs without Ca2+ association is larger than the
experimental ones. On the other hand, the theoretical EPMs calculated by using 1-pKH model
with Ca2+ association quantitatively agree with the experimental ones (Fig. 1 (b)). Therefore,
the modeling of the binding of Ca2+ with deprotonated carboxyl groups is crucial for the
evaluation of charging behavior of the particle. That is, the binding of Ca2+ reduces the net
surface charge.
(a) 10 mM
without Ca2+ association
-1
-2
-3
-4
-5
-6
-7
○ X=0.5
● X=0.1
△ X=0.01
■ X=0
-8
-9
-10
2
4
6
8
pH
10
12
0
(b) 10 mM
with Ca2+ association
-1
-2
-3
-4
-5
-6
-7
○ X=0.5
● X=0.1
△ X=0.01
■ X=0
-8
-9
-10
2
4
6
8
10
12
pH
Fig.1 The relationship between electrophoretic mobility of carboxyl latex particles and pH at ionic
strength I =10 mM. Symbols are experimental values. Solid and dashed lines are theoretical values
calculated by the Ohshima equation and the Smoluchowski equation, respectively. Mixed molar ratios
X= [Ca2+] / [K+] are 0, 0.01, 0.1, and 0.5 from lower to upper lines. Calculated values are obtained (a)
without Ca2+ association and (b) with Ca2+ association.
97
ESC 2015
P4_6
Evaluation of neuroprotective action of nanoencapsulated
model drugs
Piotrowski Marek1,*, Szczepanowicz Krzysztof1, Jantas Danuta2,
Lasoń Władysław2, Warszyński Piotr1
1
2
Institute of Pharmacology, PAS, Krakow, Poland
The purpose of the present study was to evaluate the neuroprotective action of
nanoencapsulated inhibitors of intracellular biochemical cascades leading to neuronal cell
death. Core-shell nanocapsules were synthesized using nanoemulsification and the layer-bylayer technique. The average size of synthesized nanocapsules was around 80 – 100 nm and
the concentration was in the rage of 1010 - 1011 particles/ml. Their zeta potential values ranged
from less than -30 mV for the ones with external polyanion layers through -4 mV for the
PEG-ylated layers to more than 30 mV for the polycation layers. Nanocapsules were
colloidally stable for the period not shorter than 30 days. Biocompatibility of synthesized
nanocarriers was evaluated in the SH-SY5Y human neuroblastoma cell line using
biochemical cell viability/toxicity assays (MTT, LDH). The results obtained showed that
synthesized nanocapsules coated with poly-aminoacids (PLL, PGA) were non-toxic to SHSY5Y human neuroblastoma cells, therefore they were used as nanocarriers for selected
neuroprotective substances (MDL 28170, undecylenic acid, cyclosporine A and curcumin).
Moreover, studies with fluorescently labeled polyelectrolytes demonstrated approximately
20% cellular uptake of synthetized nanocapsules. Further studies showed that
nanoencapsulated forms of neuroprotectants were biocompatible and protected SH-SY5Y
cells in a model of cell death induced by cell-damaging agents (H2O2, staurosporine,
doxorubicin) in lower concentrations than those of the same drug added directly to the culture
medium. These data suggest that designed nanocapsules might serve as a novel solution for
the delivery of hydrophobic neuroprotective agents.
Acknowledgements:
This PhD thesis was completed thanks to the financial support from the project Interdisciplinary PhD
Studies "Molecular sciences for medicine" (co-financed by the European Social Fund within the
Human Capital Operational Programme). The research leading to these results has also received
funding from the Polish-Norwegian Research Programme operated by the National Centre for
Research and Development under the Norwegian Financial Mechanism 2009-2014 in the frame of
Project Contract Pol-Nor/199523/64/2013 NanoNeucar.
98
ESC 2015
P4_7
Metal coated colloidosomes and potential applications
Qian Sun1,2*and Alexander F. Routh1,2
1
Department of Chemical Engineering and Biotechnology, Pembroke Street, Cambridge CB2
3RA, United Kingdom
2
BP Institute, University of Cambridge, Madingley Road, Cambridge CB3 0EZ,
United Kingdom
Polymer shell colloidosomes can be used in a wide variety of industries, such as food,
bioreactors and medicine. In our group we make them by emulsifying an aqueous latex
dispersion in sunflower oil. The latex particles migrate to the oil-water interface and are
locked in place, typically by heating. Fig 1 shows a SEM image of a colloidosome where the
surface is quite smooth.
Fig. 1 SEM image of a colloidosome
To expand applications of the colloidosomes, we aim to place on metal shell around the
outside. Recently, we used sodium citrate (Na3Citrate) in the core and gold chloride (HAuCl4)
in the wash solution, to successfully make gold coated colloidosomes. Fig 2 shows SEM
images of the capsules. The colloidosomes are fully covered with gold particles. The next step
is to explore applications. For example targeted cell delivery will necessitate binding a guide
protein to the colloidosome shell.
Fig. 2 SEM image colloidosomes coated with gold particles
Acknowledgements:
The authors thank Richard Langford (Department of Physics, University of Cambridge) for his
assistance with use of the scanning electron microscope.
99
ESC 2015
P4_8
Studies of the functional layers of β-lactoglobulin
as biomolecules carriers
S. Świątek1*, J.I. Loch2, K. Lewiński2, B. Jachimska1
1J.
Haber Institute of Catalysis and Surface Chemistry, PAS, Niezapominajek 8,
30-239 Cracow, Poland,
2Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Cracow, Poland
*[email protected]
Bovine β-lactoglobulin (LGB) is a globular protein with weakly understood
physiological function, however it has been proven that LGB can transport hydrophobic
compounds: retinol, vitamin D3 or fatty acids, therefore this protein can be potentially
used as a carrier of biomolecules [1]. Previous studies showed that interactions of LGB
with ligands strongly depends on pH of the solution and is related to the Tanford
transition [2]. The main binding site of LGB is located inside the β-barrel and the second
one on the protein surface [3].
Studies of the effectiveness of forming LGB complex with one of the anasthetic
drug - tetracaine (TCA) was undertaken. Both the natural ligands of LGB like fatty acids
and TCA are linear molecules of similar size, therefore this ligand with biomedical
properties was chosen to perform preliminary studies of its interaction with LGB.
Physicochemical properties of LGB and LGB-TCA complex were characterized. The zeta
potential and isoelectric point (i.e.p) of the protein were determined by utilizing
electrophoretic mobility with capillary electrophoresis technique. UV-vis spectra for
LGB, TCA and its complex were recorded. The adsorption capacity of LGB was studied
using quartz crystal microbalance with dissipation energy monitoring technique (QCMD).
Correlation between the adsorption capacity (mass and thickness of layers) of
LGB and pH or ionic strength of the solution was evaluated and the optimized conditions
for ligand-LGB binding were investigated. Performed experiments revealed that
characterization of the layers formed on the QCM sensor may play an important role in
studies of future protein-hydrophobic ligand interactions.
Literature:
5. Kontopidis George, Holt Carl, Sawyer Lindsay, 2004. Invited Review: β-Lactoglobulin:
Binding Properties, Structure and Function. Journal of Dairy Science 87: 785-796.
6. Bin Y. Qin, Maria C. Bewley, Lawrence K. Creamer, Heather M. Baker, Edward N.
Baker, Geoffrey B. Jameson, 1998. Structural Basis of the Tanford Transition of
Bovine β-Lactoglobulin. Biochemistry 37: 14014-4023.
7. Ming-Chi Yang, Hong-Hsiang Guan, Ming-Yih Liu, Yih-Hung Lin, Jinn-Moon Yang,
Wen-Liang Chen, Chun-Jung Chen, Simon J. T. Mao, 2008. Crystal structure of a
secondary vitamin D3 binding site of milk β-lactoglobulin. Proteins 71: 1197-1210.
Acknowledgements:
100
ESC 2015
P4_9
Controlled release of encapsulated neurotransmitters from coreshell nanoparticles
Noémi Varga1*, Dániel Sebők1, Imre Dékány1
1
Institution MTA-SZTE Supramolecular and Nanostructured Materials Research Group,
University of Szeged, Department of Medical Chemistry, Faculty of Medicine, H-6720,
Dóm tér 8, Szeged, Hungary
Novel, carrier-systems with the desired properties in nanoscale may promote the drug
delivery into the brain which give possibility to treat the neurological disorders (Alzheimer,
Parkinson disease). For this purpose we have synthetized one-layered core-shell
nanocomposites for delivery of neurotransmitters, like the kynurenic acid (KYNA) and the
dopamine hydrochloride (DOPA). Bovine serum albumin (BSA) and poly-L-lactide-coglycolic acid (PLGA) were used as carrier systems. A polyelectrolyte layer was formed on the
core/dopant surfaces. The composites were characterized by dynamic light scattering (DLS),
fluorescence measurements and transmission electron microscopy (TEM). The changes in the
structure during the formation of the core-shell nanocomposites were investigated by infrared, CD spectroscopy and small angle X-ray scattering (SAXS). The in vitro release properties of
drug molecules were investigated by a vertical diffusion cell (Franz cell) at 25 and 37.5°C.
The interaction between the carrier and the drug are reversible based on the release studies.
The application of kinetic models suggest possibility to describe the release kinetic. The
properties of the core-shell nanocomposites (size, zeta potential, structural parameters, etc.)
suggest that these core-shell nanoparticles are applicable in future in the controlled delivery of
therapeutic agents [1,2].
Fig. 1 Schematic picture of the formation of the core-shell nanoparticles (not to scale)
Literature:
1. Noémi Varga, Mária Benkő, Dániel Sebők, Imre Dékány, 2014. BSA/polyelectrolyte core–shell
nanoparticles for controlled release of encapsulated ibuprofen. Colloids and Surfaces B:
Biointerfaces 123: 616–622.
2. Noémi Varga, Mária Benkő, Dániel Sebők, Gabriella Bohus, László Janovák and Imre Dékány,
2015. Mesoporous silica core-shell composite functionalized with polyelectrolytes for drug
delivery. http://dx.doi.org/10.1016/j.micromeso.2015.02.008
Acknowledgements: We thank the ECIS and COST for their financial support.
101
ESC 2015
P4_10
Molecular dynamics study of Doxorubicin interaction with
suspensions of modified carbon nanotubes
Paweł Wolski1*, Tomasz Pańczyk1
1
Doxorubicin (DOX) is a member of anthractcline class of chemotherapeutic agents used for
the treatment of many common human cancers1. Congo red (CR) is a diazo dye revealing the
ability of formnig ordered amyloid-like organization of protein aggregates and is used in
testing amyloid proteins2. We performed extensive molecular dynamics simulation of DOX
interaction with CNT covered by CR molecules. We studied serveral combinations of systems
parameters in order to assess how the density of CR and DOX affects the structure and
stability of DOX-CR-CNT conjugates at various pH and ionic strength conditions. We found
that in case of CNT with chirality (10,0) the CR molecules tend to form ribbon-like micellar
structures attached to the nanotubes surfaces. At pH>5 DOX molecules incorporate into the
micelar structure of CR and avoid adsorption on the CNT surfaces. At more acidic pH, when
the CR switches into its protonated form, the DOX molecules are removed from the CR
micele due to enhanced intermolecular interactions between CR molecules and locate in the
bulk. Fig. 1 shows the radial distribution functions for distances between carbon nanotubes
and DOX molecules as well as CR -DOX. It is clearly seen that upon lowering pH the release
of DOX from the CNT-CR conjugates ocurrs. That phenomenon can be utilized in realisation
of pH controlled drug release process.
a
b
Fig. 1 Radial distribution functions (rdf) a - between carbon nanotubes and DOX, b – between CR and DOX.
Literature:
1. R.B. Weiss;1992; The anthracyclines: will we ever find a better doxorubicin?; Semin.
Oncol;19(6):670-86.
2. M. Skowronek et all;Self-assembly of Congo Red-A theoretical and experimental approach to
identify its supramolecular organization in water and salt solutions; Biopolymers;46:267-81.
Acknowledgement
This work was supported by Polish National Science Center (NCN) grant UMO-2012/07/E/ST4/00763
102
ESC 2015
P5_1
The effect of the solution pH on the lysozyme immobilization
at the gold surface
Ćwięka Monika*, Jachimska Barbara
Lysozyme is a small enzyme that exhibits strong antibacterial activity against grampositive micro-organisms. This phenomenon has found practical applications in medicine, the
pharmaceutical industry and the food processing industry. For this reason, the understanding
of how the protein interacts with inorganic surfaces, and how its orientation is governed by
the properties of the surface, is of major interest in both fundamental research and in
biomedical applications.
The development of new research techniques makes it possible to study adsorption
with increasing accuracy: from simple measurements of adsorption kinetics at high protein
concentrations to detecting even a single protein molecule adsorbed on a surface. Quartz
Crystal Microbalance with Dissipation of Energy (QCM-D) and Multi-Parametric Surface
Plasmon Resonance (MP-SPR) are powerful techniques that enable highly sensitive,
qualitative, real-time, label-free, and non-invasive detection of adsorbed proteins.
A combination of these methods has provided significant information on the mechanisms
responsible for the protein surface interactions, structural changes and biomolecular
rearrangements. Using MP-SPR measurements one can determine mechanisms of LSZ
adsorption, e.g., the reversibility and orientation of molecules at interfaces. Furthermore, from
the combination of the QCM-D and MP-SPR data with the assumption that the excess sensed
mass measured in QCM-D compared to the MP-SPR mass is due to trapped water, we have
estimated the hydration of LSZ layer on the surface of gold.
Acknowledgements:
103
ESC 2015
P5_2
Spectroscopic Ellipsometry of PEDOT:PSS thin films at
solid/liquid and solid/gas interfaces
Gaurav Pathak* and Dusko Cakara
Centre for Micro and Nano Sciences and Technology,
University of Rijeka, 51000, Rijeka, Croatia.
We report the results of the in-situ spectroscopic ellipsometry study of poly (3,4ethylenediosythiophene): poly(styrene sulfonate) (PEDOT:PSS) films spin-coated on silicon,
in the visible range of spectrum. When in contact with different ambient media, these films
undergo swelling which is clearly evidenced in the spectroscopic ellipsometric data. The
Lorentz-Drude model of the dielectric function, in combination with the stratified layer
optical model, can be well fitted to the measured ellipsometric data, whereby a very good
agreement is found between the fitted film thickness and the value directly measured by
means of the atomic force microscopy. On the other hand, once the film thickness is
independently determined from the AFM measurement, the real and imaginary parts of the
complex refractive index as function of wavelength (i.e. the dielectric function), can be
obtained from the ellipsometric data by mathematical inversion. The dielectric functions
obtained in that manner are found to be comparable with the dielectric functions obtained by
fitting the Lorentz-Drude model, which leads to the conclusion that this model is indeed
applicable for the description of the dielectric behavior of PEDOT:PSS films.
104
ESC 2015
P5_3
Action of selected saponins on biological model membranes
Janikowska Maria1,2*, Korchowiec Beata1, Gorczyca Marcelina1, Wojszko Kamila1,
Trojan Sonia1, Henry Max3, Rogalska Ewa3
1
2
Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Krakow, Poland
Faculty of Physics, Astronomy, and Applied Computer Science, Jagiellonian University, ul.
S. Lojasiewicza 11, 30-348 Krakow, Poland
3
CNRS, University of Lorraine, BP 239, 54506 Nancy-Vandoeuvre, France
Saponins, naturally occurring plant secondary metabolites are known for their biological
and pharmacological activity [1]. This activity is strongly related to the amphiphilic character
of saponins that allows them to aggregate in aqueous solution and interact with membrane
components [2]. In our work, Langmuir monolayer techniques combined with polarization
modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and Brewster angle
microscopy were used to study the interaction of selected saponins with lipid model
membranes. Two structurally different saponins were used: digitonin and commercial Merck
Saponin. The membranes of different composition, to be precise, cholesterol, 1,2-dipalmitoylsn-glycero-3-phosphocholine and 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol)
were formed at the air/water and air/saponin solution interfaces. Saponin-lipid interaction was
characterized by changes in surface pressure, surface potential, surface morphology and PMIRRAS signal. Both saponins interact with model membranes and change the physical state of
membranes by perturbing the lipid acyl chain orientation. The changes in membrane fluidity
were more significant upon the interaction with Saponin. A higher affinity of saponins for
cholesterol than phosphatidylglycerols was observed. Moreover, our results indicate that
digitonin interacts strongly with cholesterol and solubilize the cholesterol monolayer at higher
surface pressures. It was shown, that digitonin easily penetrate to the cholesterol monolayer
and forms a hydrogen bond with the hydroxyl groups. These findings might be very useful in
further understanding of the saponin action at the membrane interface, and the mechanism of
membrane lysis.
Literature:
1. Böttger S., Hofmann K., Melzig M. F., 2012. Saponins can perturb biologic membranes and reduce
the surface tension of aqueous solutions. A correlation? Bioorganic & Medicinal Chemistry (2012)
20, 2822-2828.
2. Podolak I., Galanty A., Sobolewska D., 2010. Saponins as cytotoxic agents: a review.
Phytochemistry Reviews (2010) 9, 425-474.
Acknowledgements:
Marcelina Gorczyca acknowledges the financial support from an Interdisciplinary PhD Studies project
entitled “Molecular Sciences for Medicine” co-financed by the European Social Fund within the
Human Capital Operational Programme.
105
ESC 2015
P5_4
Functional ultrathin polyelectrolyte coatings formed with reduced
graphene oxide and Prussian Blue nanoparticles as a sensitive tool
for H2O2 detection
Kruk Tomasz*, Pajor-Świerzy Anna, Szyk-Warszyńska Lilianna, Socha Robert,
Warszyński Piotr
Graphene - a new material consisting of single layer of sp 2 – bonded carbon atoms with
unique two-dimensional (2D) nanostructure of a honeycomb lattice attracts attention of many
specialists from various branches of science. Since its discovery in 2004 [1], graphene has
emerged as the “material of the future” due to its unique nanostructure, electrical, thermal and
mechanical properties.
Sequential adsorption of charged nanoobjects, as polyelectrolytes, nanoparticles (known
also as the “Layer by layer” (LbL) deposition method) [2] is considered as one of the most
promising techniques of surface modification and formation of highly tailored functional thin
films for the wide range of possible applications. As graphene is a hydrophobic material, it can
not be directly used for construction of multilayer films with the LbL method. Therefore, we have
proposed to use suspension of graphene oxide ((GO) – negatively charge – anionic layer) for
formation of such films and its subsequent reduction to the reduced graphene oxide (rGO). For
formation of thin, multilayer graphene films using the Layer-by-Layer (LbL) method we
deposited polyelectrolytes, Prussian Blue (PB) nanoparticles and graphene oxide (GO) from their
solutions. We compared several reduction methods to turn GO into reduced graphene oxide. We
noticed that the thermal reduction of GO above the temperature 180 0C is the most effective
process leading to formation of sp2-bonded carbon atoms.The examination of XPS spectra
indicated that after the reduction the ratio of the sp2 carbon increased to c.a. 80 at.%. The structure
and properties of the films before and after reduction were investigated using Ellipsometry
Spectroscopy, ATR-FTIR Spectroscopy, AFM and SEM. The electric conductivity of films after
the reduction was analyzed by the four point surface conductivity measurements, whereas cyclic
voltamperometry was used to determine the electroactive properties of multilayer films.
We showed that using the proposed method it is possible to obtain ultrathin conductive
films on quartz and polyimide (PI) plates. In addition the modified GO – positively charge were
used as polycation to improve surface conductivity. We noticed that in the presence of rGO sheets
the intensity of the redox current of PB embedded in the multilayer films markedly increased due
to enhancement of electron transport to the polyimide electrode surface. In the presence of
hydrogen peroxide characteristic peaks from reduction of H2O2 to OH- ions and oxidation to O2
molecules appeared. Formation of such thin films on PI allows creating flexible electrodes, which
can find applications in biomedicine as disposable, electroactive sensors.
Literature:
1. Novoselov K.S., Geim A.K., Morozov S.V., Jiang D., Zhang Y., Dubonos S.V., Grigorieva I.V.,
Firsov A.A., 2004, Science, 306 666-669.
2. Decher G., Schlenoff J., 2011, Multilayer Thin Films Sequential Assembly of Nanocomposite
Materials, , ISBN 978-3-527-31648-9 - Wiley-VCH, Weinheim.
106
ESC 2015
P5_5
Multifunctional polyelectrolyte ultrathin coatings for biomedicine
applications
Kruk Tomasz*, Szczepanowicz Krzysztof, Warszyński Piotr
The formation of bacterial slime or of biofilms at the surface of biomaterials e.g.
diagnostic devices and a variety of biomedical implants, represents a major medical problems
leading, if untreated to chronic microbial infection. One of the most significant problem is the
process of biofouling, i.e. the unwanted adsorption of proteins, occurring on the surfaces
exposed to solutions containing biological material. Therefore, the development of the
“antifouling” coatings protecting against non-specific protein adsorption, bacteria and fungi
colonization are an important area of research within a broader field of biointerface science.
Immobilization of neutral hydrophilic polymers (e.g. poly(ethylene glycol)) (PEG) at surfaces
is one of the accepted methods to reduce non-specific adsorption of proteins. On the other
hand, silver or copper nanoparticles containing materials and coatings with antimicrobial
activity find applications: in medicine to reduce infections.
The Layer-by-Layer technique of electrostatic self-assembly of charged nanoobjects
has been demonstrated to be a versatile technique for the formation of multilayer thin films.
The method is based on the sequential adsorption of the oppositely charged species on solid
surfaces [1]. „LbL” method, which is considered as one of the most promising techniques of
surface modification can be used for formation of those coatings
The goal of this work was to build up anti adhesive films able to cover any type of
surface and containing PEG. This type of films is expected to reduce/eliminate the nonspecific adsorption of proteins at surface as well as the bacterial colonization of implanted
materials. Synthesized copolymers of poly(glutamic acid) or poly(L-lysine) with grafted PEG
chains with various grafting ratio and various chain lengths, were used for that modification
by formation of the external layer of films. The biofouling process was investigated by
studying the adsorption of different proteins: HSA, fibrinogen as well as proteins from
Human serum using QCM. Apart from polyelectrolytes, negatively charged silver or copper
nanoparticles were used for the multilayers construction that led to the formation of
nanocomposite films. It was found that nanocomposite films have antimicrobial properties.
Literature:
1. Decher G., Schlenoff J., 2011, Multilayer Thin Films Sequential Assembly of Nanocomposite
Materials, ISBN 978-3-527-31648-9 - Wiley-VCH, Weinheim.
Acknowledgements: The work was financed by NCN project UMO 2012/07/N/ST5/00173.
107
ESC 2015
P5_6
Bovine β-lactoglobulin layers on gold surface:
Role of ionic strength
S. Świątek*, B. Jachimska
J. Haber Institute of Catalysis and Surface Chemistry, PAS, Niezapominajek 8,
30-239 Cracow, Poland,
*[email protected]
Bovine β-lacoglobulin (LGB) is a protein with unknown physiological function
belonging to lipocalin family. LGB is probably involved in transport of hydrophobic
compounds and can be potentially used as a carrier protein for biomolecules [1].
The main goal of presented research was to evaluate effectiveness adsorption of
the
β-lactoglobulin on the gold surface at different conditions concerning changes in pH and
ionic strength of the solution. Dynamic Light Scattering (DLS) Malvern Nano ZS method
was used to analyze physicochemical properties of LGB and to determine the size of the
particles. The zeta potential and isoelectric point (pI) of the protein were determined by
utilizing electrophoretic mobility with capillary electrophoresis technique. The
adsorption of protein onto gold surface was studied with quartz crystal microbalance
(QCM-D).
Obtained results revealed that electrophoretic mobility strongly depends on both
pH and ionic strengths of the protein solution. The value of pI was determined to 4.8.
The electophoretic mobility measurements allowed to calculate the zeta potential. For
all LGB isoforms zeta potential was negative in pH>5 and positive at acidic pH.
Experiments performed using QCM-D method showed that adsorption capacity of LGB
on the gold surface highly correlates to pH and ionic strength of the solution. All LGB
layers were identified as molecular layers with low viscoelasticity, as indicated by a low
value of dissipation energy (D<1·10-6). The adsorption data could be well described by
the Sauerbrey model that correlates observed changes in resonance frequency with
mass and thickness of adsorbed LGB layers.
Understanding the mechanism of LGB adsorption process has an important
issues for establishing the optimal conditions for immobilization of this protein on
adsorption surface, for designing bioconjugates for in vivo and in vitro applications and
to examine LGB molecular affinity to soluble ligands.
Literature:
8. Kontopidis George, Holt Carl, Sawyer Lindsay, 2004. Invited Review: β-Lactoglobulin:
Binding Properties, Structure and Function. Journal of Dairy Science 87: 785-796.
Acknowledgements:
108
ESC 2015
P5_7
The role of chain unsaturation in the formation of organized
molecular films of crown ether - modified phospholipid
monolayers
Trojan Sonia1*, Ustarbowska Małgorzata2, Korchowiec Beata2, Janikowska Maria1,
Joly Jean-Pierre3, Rogalska Ewa3
1
Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University,
ul. R. Ingardena 3, 30-060 Cracow, Poland
2
Department of Physical Chemistry, Faculty of Chemistry, Jagiellonian University,
3
Structure et Réactivité des Systémes Moléculaires Complex, BP 239, CNRS/Université
de Lorraine, 54506 Vandoeuvre-lés-Nancy cedex, France
The nature of phospholipids, their structural diversity, and content in the bilayer
determine the properties of biological membrane [1]. Crown ethers are used as well as
membrane forming amphiphiles and due to their ionophoretic properties, as model ion
channels [2].
In this work, the interaction between the synthetic crown ether and
phosphatidylcholines (PCs) having different number of unsaturated chains were studied.
Three phosphatidylcholines were chosen, namely 1,2-dipalmitoyl-sn-glycero-3phosphocholine (DPPC), 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and
1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). PCs monolayers formed at the air/water
interface were used as simple models of biological membranes allowing to investigate the
effect of hydrocarbon chain unsaturation on the membrane activity of crown ether. To this
aim, the properties of mixed monolayers were studied using the Langmuir film technique, as
well as Brewster angle microscopy. The miscibility of phosphatidylcholines and crown ether
was studied using surface pressure and surface potential measurements. The polarizationmodulation infrared reflection-absorption spectroscopy (PM-IRRAS) was used to gain more
information on the intra- and intermolecular interactions in the mixed PCs/crown ether films.
The obtained results indicate that both the degree of hydrocarbon chain unsaturation of PCs
and the amount of crown ether influence the interfacial properties of the mixed monolayers. It
was showed, that the crown ether derivative is miscible with PCs and can be easily
incorporated into lipid membranes.
Literature:
1. Karp, G.. 2004. Cell and Molecular Biology: Concepts and Experiments, 4th ed.. Wiley & Sons:
New York. Chapter 4.
2. Cazacu A., Tong C., Van der Lee A., Fyles T. M., Barboiu M.. 2006. J. Am. Chem. Soc., 128.
p.9541-9548.
Acknowledgements: This work was supported by the Polish National Science Centre, project No.
2014/13/B/ST4/04995.
109
ESC 2015
P5_8
Interactions of amphiphilic crown ether with metal ions
in Langmuir films
Trojan Sonia1*, Korchowiec Beata2, Joly Jean-Pierre3, Korchowiec Jacek1, Rogalska Ewa3
1
Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University,
2
Department of Physical Chemistry, Faculty of Chemistry, Jagiellonian University,
3
Structure et Réactivité des Systémes Moléculaires Complex, BP 239, CNRS/Université
de Lorraine, 54506 Vandoeuvre-lés-Nancy cedex, France
Crown ethers are macrocyclic organic compounds which can be easily modified. Lariat
ethers are a class of membrane-active crown ethers containing hydrocarbon chains attached to
the ether crown. Crown ethers are intensively studied due to their complexation
[1, 2], ionophoretic and channel forming properties [3].
The aim of this work was to investigate the ability of newly synthesized lariat crown ethers
to selective complexation of metal cations. The properties of monomolecular films formed by
crown ether were investigated using Langmuir film techniques. In our research the model
amphiphilic monolayer, corresponding to the single layer of cell membrane was prepared.
Monolayers were formed on the water subphase and on salt solutions containing Cu 2+, Zn2+
and Ni2+ cations. In the case of salt solutions, the compression isotherms were recorded in
order to investigate the influence of cation concentration on the complex formation. Moreover
the studies using polarization modulation infrared reflection-absorption spectroscopy were
carried out. The morphology of monolayers was investigated using Brewster angle
microscopy. The interaction between cation and crown ether compounds were analysed using
the DFT method. Molecular modeling was performed to obtain the conformational details of
the formed complexes.
Literature:
1. Plehnert R., Schrӧter J. A., Tschierske C.. 1998. Langmuir, 14. p.5245-5249.
2. Corvis Y., Korchowiec B., Korchowiec J., Badis M., Mironiuk-Puchalska E., Fokt I., Priebe W.,
Rogalska E.. 2008. J. Phys. Chem. B, 112. p.10953-10963.
3. Cazacu A., Tong C., Van der Lee A., Fyles T. M., Barboiu M.. 2006. J. Am. Chem. Soc., 128.
p.9541-9548.
Acknowledgements:
The research was partially financed by the European Commission within Erasmus program.
This research was supported in part by PL-Grid Infrastructure.
110
ESC 2015
P6_1
Methylation of humic acids – the impact on the reactivity,
chemical composition and properties of HAs studied by
spectrometric techniques
Enev Vojtěch1, 2*, Klučáková Martina1, 2, Smilek Jiří1, 2, Doskočil Leoš1, 2
1
2
Institute of Physical and Applied Chemistry
Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova 118,
Brno, 612 00, Czech Republic
The aim of this work was study chemical composition, chemical properties and reactivity of
methylated standard humic acid (mHA) and its native form. Humic acid (standard sample of
humic acid – International Humic Substances Society – Leonardite HA 1S104H) was
modified by methylation. All samples of Leonardite HAs were characterized by elemental
analysis (EA), total organic carbon analysis (TOC), ultraviolet-visible spectroscopy (UV/Vis),
Fourier transform infrared spectroscopy (FTIR), steady-state fluorescence spectroscopy and
nuclear magnetic resonance (13C NMR). The elemental composition was determined by
a CHNS/O Microanalyser Flash 1112 Carlo Erba. Oxygen content was calculated by
difference: O % = 100 – (C + H + N + S) %, and data obtained were corrected for moisture
and ash content. Absorption coefficients (EET/EBz, E250/E365 and E465/E665) of Leonardite HAs
were calculated from the absorbance values. Infrared spectroscopy is a useful technique in
characterization of structure, functional groups and formation modes of HAs. For the
fluorescence experiments the final concentration of the HAs was adjusted to 10 mg∙L–1. The
pH-value of the samples was adjusted to seven using a standard phosphate buffer.
Fluorescence mono-dimensional spectra and total luminescence spectra (TLS) of HAs were
obtained using steady-state fluorescence spectroscopy. All fluorescence spectra were
performed on a Horiba Scientific Fluorolog. Total luminescence spectra (TLS) were obtained
in the form of excitation/emission matrix (EEM) by scanning the wavelength emission over
the range of 300–600 nm, also the excitation wavelength was in 5 nm steps from 240 to
550 nm. The EEM spectrum of ultrapure water (Mili-Q) was obtained, and it was subtracted
from the EEMs of all samples examined to decrease the influence from the 1st- and 2nd-order
Raman scattering. Fluorescence index (Milori index and HIX) of HAs was calculated from
the area of the emission spectra. The fluorescence intensity (IF) values (in CPS) of samples
were corrected using method of Lakowicz1. 13C NMR spectra of Leonardite HAs were
obtained with a Bruker Avance III NMR spectrometer at an observation frequency of 125.8
MHz for 13C. The approximate number of scans was 25.000. Aromaticity (fa), hydrophilicity
and hydrophobicity ratio (Hfi/Hfo) and biological activity (BiA) of HAs were calculated from
the area of the NMR spectra.
Literature:
1. Lakowicz, J. R., 2006. Principles of Fluorescence Spectroscopy, 3rd edition, Springer, Baltimore,
Maryland.
Acknowledgements: This work has been supported by Ministry of Education, Youth and Sports,
Project LO1211.
111
ESC 2015
P6_2
Molecular Dynamics modelling of interaction between heparin
and its potential neutralizer
Krasińska Zofia1*, Jamróz Dorota2
1
2
Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
Heparin belongs to the group of glycosaminoglycans. Molecules of this biopolymer are
characterized by high density of negative charge. That property determines anticoagulant
activity of heparin and in consequence its application in medicine. However, long presence of
its molecules in cardiovascular system, leads to many side effects, such as dangerous
haemorrhages. In order to avoid that, neutralization of heparin is needed. Currently,
protamine, which is polypeptide with high content of arginine, is used for this purpose.
Unfortunately, application of this substance carries the risk of life-threatening complications
like those connected with anaphylaxis. Therefore, search for a new antidote for heparin,
effective and safe at the same time, are conducted.
This work presents study of a new potential heparin neutralizer, which is based on
a polyallylamine hydrochloride (PAH) polymer, modified by grafting arginine. Molecular
dynamics simulations of interaction between those polymers were performed in both aqueous
and physiological solution. It has been proved that the new compound has ability to
effectively bind heparin due to its strong interaction with the positively charged arginine
chain. Dihedrals distribution analysis of different parts of both molecules allowed to obtain
information about conformational changes of both polymers, resulting from their association.
This information, together with radial distribution function analysis, brings insight into
interaction between both polymers at the molecular level. That determines their binding ratio
in physiological solution.
Literature:
1. Kamiński, K., Kałaska, B., Koczurkiewicz, P., Michalik, M., Szczubiałka, K., Mogielnicki, A.,
Buczko, W., Nowakowska, M., 2014, New arginine substituted derivative of poly(allylamine
hydrochloride) for heparin reversal., Med. Chem. Commun., 5:489-495
112
ESC 2015
P6_3
Undecane-in-water Emulsions prepared by the Phase Inversion
Temperature Method
Mikulcová Veronika1*, Kašpárková Věra1,2, Pohlodek Jiří1
1
Department of Fat, Surfactant and Cosmetics Technology, Faculty of Technology, Tomas
Bata University in Zlín, nám. T. G. Masaryka 5555, 760 01 Zlín, Czech Republic
2
Centre of Polymer Systems, Tomas Bata University in Zlin, T.G.M. Sq. 5555, 760 01 Zlin,
Czech Republic
There has been a growing interest in the development and preparation of emulsions by using
low energy methods. In the current study, the phase inversion temperature (PIT) method was
used to prepare n-undecane/water nanoemulsions in the presence of two pairs of non-ionic
surfactants (Brij 30/Brij 56 and Brij 30/Brij 98). The PIT values were determined by
conductivity measurements and photon correlation spectroscopy (PCS) temperature trend and
applied for the preparation of the nanoemulsions. The influences of HLB value, surfactant
type and concentration on the PIT values were investigated. The effect of oil-to-water ratio
and HLB value on the size and distribution of emulsion droplets was also studied. The
stability of emulsions at different storage temperatures (4 °C, 25 °C and 35 °C) was evaluated
by visual observation and from the changes of particle size measured during the storage by
PCS. The phase inversion temperature method was also compared to another low energy
approach, emulsion phase inversion (EIP) method. The results show that the PIT value
changes with the all above mentioned operational parameters. Conductivity measurements
reveal linear correlation between PIT and HLB. PIT value is also influenced by surfactant
concentration – lower surfactant concentration leads to the higher values of PIT. Therefore, it
is evident that during emulsification using PIT, the samples with the lower surfactant
concentrations need larger energy input to be heated near the PIT and subsequently to be
rapidly cooled down to produce small particles. Regarding size of the emulsion droplets,
prepared samples can be classified as the nanoemulsions, as their particles were smaller than
200 nm. The best stability was obsered for emulsions stored at the temperature of 4 °C.
Acknowledgements:
This work was performed with support of internal grant of TBU in Zlin IGA/FT/2015/002 financed
from funds of specific academic research.
113
ESC 2015
List of Conference Participants
Adamczyk Zbigniew
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239
Cracow, Poland
[email protected]
Arenas-Guerrero Paloma
Department of Applied Physics, University of Granada, Spain.
[email protected]
Augustyniak Krzysztof
[email protected]
Briscoe Wuge
[email protected]
Carciati Antonio
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università di Napoli Federico II
CEINGE Biotecnologie avanzate, Napoli
[email protected]
Chatzidaki Maria
Institute of Biology Medicinal Chemistry & Biotechnology, National Hellenic Research Foundation, Athens, Greece
MTM,
Faculty of Science and Engineering, Örebro University, Sweden
[email protected]
Cooperstein Ido
Casali Center for Applied Chemistry, Institute of Chemistry and Center for Nanoscience and Nanothechnology, The
Hebrew University of Jerusalem, Jerusalem, Israel
[email protected]
Ćwięka Monika
Cracow, Poland
[email protected]
Delisavva Fotini
Department of Physical and Macromolecular Chemistry; Faculty of Science, Charles University in Prague, Hlavova
8, 12840 Prague 2, Czech Republic
[email protected]
Saoirse Dervin
Institute of Technology Sligo, Nanotechnology research group, Department of Environmental Science, Ash lane,
Sligo, Ireland
[email protected]
Drozdek Sławomir
Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw University of Technology,
Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
[email protected]
Emelyanenko Kirill
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia
[email protected]
114
ESC 2015
Enev Vojtěch
Institute of Physical and Applied Chemistry
Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova 118, Brno, 612 00,
Czech Republic
[email protected]
Fernández Maria del Mar
Department of Applied Physics, School of Science, University of Granada, 18071 Granada, Spain
[email protected]
Gamon Jacinthe
Institut de Recherche de Chimie Paris (IRCP), CNRS 11 rue Pierre et Marie Curie, 75005 Paris, France
Solvay Research and Innovation Center of Paris (RIC Paris) 52 rue de la Haie-Coq, 93306 Aubervilliers, France
[email protected]
Gawlik Iwona
Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, Poland
[email protected]
Gergana Georgieva
Dpt. Chemical and Pharmaceutical Engineering, Sofia University, Sofia, Bulgaria
[email protected]
Gödrich Sebastian
Physical Chemistry II, University of Bayreuth, 95447 Bayreuth, Germany
[email protected]
Gorczyca Marcelina
[email protected]
Ho Tracey
Ian Wark Research Institute, University of South Australia, Mawson Lakes, Adelaide, SA 5095, Australia
[email protected]
Hupka Jan
Gdansk University of Technology, Faculty of Chemistry, Department of Chemical Technology, ul. Gabriela
Narutowicza 11/12, 80-233 Gdansk
[email protected]
Jabłczyńska Katarzyna
Faculty of Chemical and Process Engineering, Warsaw University of Technology
[email protected]
James Emily
Institute of Particle Science and Engineering, University of Leeds, Leeds, UK
[email protected]
Janikowska Maria
Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Krakow, Poland
Faculty of Physics, Astronomy, and Applied Computer Science, Jagiellonian University, ul. S. Lojasiewicza 11, 30348 Krakow, Poland
[email protected]
Kairaliyeva Talmira
Max Planck Institute of Colloids and Interfaces, 14424 Potsdam/Golm, Germany
Kazakh National Technical University after K.I.Satpayev, Almaty, Kazakhstan
[email protected]
Kezwoń Aleksandra
Department of Microbioanalytics, Warsaw University of Technology, Warsaw, Poland.
[email protected]
Konczak Łukasz
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences ul. Niezapominajek 8, 30-239
Cracow, Poland
[email protected]
115
ESC 2015
Krasińska Zofia
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences ul. Niezapominajek 8, 30-239
Cracow, Poland
[email protected]
Kruk Tomasz
Cracow, Poland
[email protected]
Krzywda Piotr
Cracow University of Technology, Faculty of Chemical Engineering and Technology, Department of Biotechnology
and Physical Chemistry, Warszawska 24 St. 31-155 Krakow, Poland
[email protected]
Księżniak Katarzyna
Gdansk University of Technology, Faculty of Chemistry, Department of Chemical Technology
[email protected]
Kubiak Katarzyna
Cracow, Poland
[email protected]
Kujda Marta
Cracow, Poland
[email protected]
Lamch Łukasz
Department of Organic and Pharmaceutical Technology, Faculty of Chemistry, Wroclaw University of Technology,
WybrzezeWyspianskiego 27, 50-370 Wroclaw, Poland
[email protected]
Latowska Anna
[email protected]
Lin Wei
Institute of Particle Technology,
Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany
[email protected]
Liuzzi Roberta
Department of Chemical, Materials and Production Engineering, University of Naples “Federico II”, P.zzle Tecchio
80, 80125 Naples
CEINGE- Advanced Biotechnologies, Via Sergio Pansini 5, 80131 Naples.
[email protected]
Lopez Cabarcos
Enrique Department of Physical Chemistry II, Faculty of Pharmacy, Complutense University of Madrid, 28040
Madrid, Spain
[email protected]
Lu Biao
Sorbonne Universités, Université deTechnologie de Compiègne, BMBI UMR CNRS 7388, France
[email protected]
Łapczyńska Marta
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezpaminajek 8, 30-239
Cracow, Poland
[email protected]
116
ESC 2015
Maciejewska Julia
Cracow, Poland
[email protected]
McNally Michael
University of Leicester, UK
[email protected]
Mikulcova Veronika
Department of Fat, Surfactant and Cosmetics Technology, Faculty of Technology, Tomas Bata University in Zlín,
nám. T. G. Masaryka 5555, 760 01 Zlín, Czech Republic
[email protected]
Miller Reinhard
[email protected]
Mioduska Joanna
Gdansk University of Technology, Faculty of Chemistry, Department of Chemical Technology
[email protected]
Moazzami Gudarzi Mohsen
Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva, Switzerland
[email protected]
Moreno-Cencerrado Alberto
Institute for Biophysics, Department of Nanobiotechnology, University of Natural Resources and Life Sciences
Vienna (BOKU), Vienna 1190, Austria.
[email protected]
Mould Elizabeth
[email protected]
Mulla Mohmed
University of Leeds
[email protected]
Mzareulishvili Natia
Iv.Javakhishvili Tbilisi State University, I.Chavchavadze ave 3, 0179, Tbilisi
[email protected]
Niecikowska Anna
Cracow, Poland
[email protected]
Nishiya Manami
[email protected]
Oliynyk Viktoria
F.D.Ovcharenko Institute of biocolloid chemistry
[email protected]
Oncsik Tamas
Department of Inorganic and Analytical Chemistry, University of Geneva, Geneva, Switzerland
[email protected]
Orczyk Marta
Warsaw University of Technology, Faculty of Chemistry
[email protected]
Ottoboni Sara
Strathclyde University, Glasgow, United Kingdom
[email protected]
117
ESC 2015
Pathak Gaurav
Centre for Micro and Nano Sciences and Technology, University of Rijeka, 51000, Rijeka, Croatia.
[email protected]
Piotrowski Marek
Cracow, Poland
[email protected]
Podgórna Karolina
Cracow, Poland
[email protected]
Radulova Gergana
Department of Chemical Engineering, Faculty of Chemistry & Pharmacy, Sofia University, 1164 Sofia, Bulgaria
[email protected]
Redeker Christian
[email protected]
Salvatore Annalisa
Department of Chemistry and CSGI, University of Florence, via della Lastruccia 3, 50019 Sesto Fiorentino, Italy
[email protected]
Schulz Christian
Associate Publisher, Elsevier, Amsterdam, The Netherlands
Setiowati Arima Diah
Particle and Interfacial Technology Group, Ghent University
[email protected]
Skinner Samuel
Particulate Fluids Processing Centre, The University of Melbourne
[email protected]
Skoglund Sara
KTH Royal Institute of Technology, School of Chemical Science and Engineering, Surface and Corrosion Science,
SE-100 44 Stockholm, Sweden
[email protected]
Slastanova Anna
[email protected]
Smilek Jiri
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 464/118, 61200 Brno,
Czech Republic
[email protected]
Sokolan Nina
Murmansk State Technical University
[email protected]
Stark Kirsty
Institute of Particle Science Engineering, School of Chemical and Process Engineering, University of Leeds
[email protected]
Starkie Joanna
University of Cambridge
[email protected]
Sun Qian
Department of Chemical Engineering and Biotechnology, Pembroke Street, Cambridge CB2 3RA, United Kingdom
BP Institute, University of Cambridge, Madingley Road, Cambridge CB3 0EZ, United Kingdom
[email protected]
118
ESC 2015
Symonds Brett
Reading School of Pharmacy, University of Reading, Whiteknights, PO Box 224, Reading, RG6 6AD
[email protected]
Szafraniec Joanna
[email protected]
Świątek Sylwia
Cracow, Poland,
Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Cracow, Poland
[email protected]
Tokarczyk Karolina
Cracow, Poland
[email protected]
Tonelli Monica
Department of Chemistry “Ugo Schiff” & CSGI, University of Florence, Sesto F.no (FI) 50019, Italy
[email protected]
Toth Reka
RMD, Institut de Recherche de Chimie Paris, CNRS - France
Solvay, Centre de Recherche et Innovation de Paris Aubervilliers – France
[email protected]
Trojan Sonia
Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060
Cracow, Poland
[email protected]
Ulaganathan Vamseekrishna
[email protected]
Ulatowska Justyna
Wroclaw University of Technology, Faculty of Chemistry, Division of Chemical Engineering, Norwida 4/6, 50-373
Wrocław, Poland
[email protected]
Varga Noémi
Institution MTA-SZTE Supramolecular and Nanostructured Materials Research Group, University of Szeged,
Department of Medical Chemistry, Faculty of Medicine, H-6720, Dóm tér 8, Szeged, Hungary
[email protected]
Vermeir Lien
Particle and Interfacial Technology Group Ghent University, Belgium
[email protected]
Vincent Brian
University of Bristol, School of Chemistry, Bristol, BS8 1TS, UK
[email protected]
Wamke Anna
Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, 60-965
Poznań, Poland
[email protected]
Warszyński Piotr
Cracow, Poland
[email protected]
119
ESC 2015
Włodek Magdalena
Cracow, Poland
[email protected]
Wojewódka Przemysław
Department of Chemical Technology, Chemical Faculty, Gdańsk University of Technology, ul. Narutowicza 11/12,
80-952 Gdańsk, Poland
[email protected]
Wolski Paweł
Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy of Sciences, ul. Niezapominajek 8, 30-239
Cracow, Poland
[email protected]
Won Jooyoung
Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, 14424 Potsdam, Germany
[email protected]
Yamaguchi Atsushi
[email protected]
Zapotoczny Szczepan
[email protected]
120
ESC 2015
Authors’ Index
Abazović N., 36
Abezgauz L., 82
Adamczyk Z., 18, 26, 61, 74
Ahualli S., 58
Aidarova S.B., 72
Amadei D., 22
Anachkov S., 82
Aranowski R., 80
Arenas-Guerrero P., 59
Aristotelis X., 22
Augustyniak K., 83
Baglioni P., 24, 69
Balcaen M., 35
Barboux P., 43, 66
Bartz C., 68
Beattie D.A., 53, 84
Bednarz S., 96
Berti D., 24
Bielańska M., 27
Biggs S., 41, 51, 57
Blomberg E., 50
Boinovich L., 65, 71
Bonini M., 24
Borkovec M., 32, 42
Borsacchi S., 69
Bremmell K., 53, 84
Briscoe W., 17, 67, 75, 78, 92
Brooker A., 41
Buissette V., 43
Burger A., 40
Bzowska M., 27
Cakara D., 104
Carciati A. 25, 34
Carević M., 36
Carmen Galan M., 67
Carrière D., 43
Carrière F., 22
Caserta S., 25, 34
Cayre O., 41, 51, 57
Chagnault V., 28
Chantry R.L., 62
Chatzidaki M., 22
Chen M., 78
Chromińska I., 64
Čomor M., 36
Cooperstein I., 46
Ćwięka M., 38, 103
D'Alençon L., 43
Danino D., 82
Danov K., 76
Dékány I., 101
Delgado A.V., 58, 59
Delisavva F., 56
Derkach S., 87
Dervin S., 52
Dewettinck K., 35
Dopierała K., 37
Doskočil L., 111
Drozdek S., 60
Dukhin S.S., 47
Egles C., 28
Emelyanenko A., 65, 71
Emelyanenko K., 65, 71
Enev V., 111
Faraji S., 72
Fernández M.M., 58
Fratini E., 69
Frączyk T., 64
Galinis G., 62
Gamon J., 66
Gawlik I., 93
Gehin-Delval C., 47
Geppi M., 69
Gergana G., 82
Giaume D., 66
Gochev G., 39, 47
Gödrich S., 68
Gorczyca M., 83, 105
Grand E., 28
Graydon A., 41
Guido S., 25, 34
Gumieniczek E., 23
Haeften K.von, 62
Harbottle D., 41
Hedberg J., 50
Hirsch A., 40
Ho T., 53, 84
Hunter T., 41
Hupka J., 15, 36, 49, 73
Iglesias G.R., 58, 59
Iturri J., 85
Jabłczyńska K., 94
Jachimska B., 38, 88, 89, 100, 103, 108
Jamadagni S., 41
James E., 41
Jamróz D., 112
Janik M., 23
Janikowska M., 105, 109
Jantas D., 30, 98
Jiménez M.L., 58, 59
Joly J.-P., 109, 110
Jungnickel C., 80
Kairaliyeva T., 14, 72
Kalaska B., 93
Kaminski K., 93
Karabasz A., 27
Karbaschi M., 14, 72
Kašpárková V., 113
Kasprzyk W., 96
Kezwoń A., 64
Khutoryanskiy V., 44
Klučáková M. 31, 111
121
ESC 2015
Kobayashi M., 81, 97
Koc M.M., 62
Kolasińska-Sojka M., 90
Konczak Ł., 95
Korchowiec B., 83, 105 109, 110
Korchowiec J., 83, 110
Korecki J., 27
Koynov K., 82
Krägel J., 39
Kralchevsky P., 76, 82
Krasińska Z., 112
Krasowska M., 53, 84
Krittanai C., 85
Kruk T., 106, 107
Krzan M., 47
Krzywda P., 96
Księżniak K., 73
Kubiak K., 61
Kujda M., 26
Kujdowicz M., 93
Kuljanin-Jakovljević J., 36
Kurtanidze M., 86
Lamch Ł., 55
Lasoń W., 98
Latajka R., 55
Latowska A., 49
Leal-Calderon F., 22
Lefèvre G., 43
Lewiński K., 100
Liebewirth I., 82
Lin W., 40
Lindsay C., 44
Liuzzi R., 25
Loch J.I., 100
Lopez-Cabarcos E., 12
Lowe T., 50
Lu B., 28
Lundin M., 50
Łapczyńska M., 30
Łuczak J., 49
Maciejewska J., 74
Maciejewski H.F., 37
MacWilliams S., 84
Magdassi S., 46
Maid H., 40
Małysa K., 48
Maroni P., 32
Martini F., 69
Max H., 105
McNally M.J., 62
Mercier T., 43, 66
Miao Y., 28
Mikulcová V., 113
Miller R., 14, 39, 47, 72
Mioduska J., 36
Mittendorfer M., 85
Moazzami G.M., 32
Mogielnicki A., 93
Monteil J., 22
Moreno-Cencerrado A., 85
Mould E., 75
Mulla M., 57
Mzareulishvili N., 86
Niecikowska A., 48
Nikipelova O.M., 29
Nishiya M., 97
Nowakowska M., 93
Nyk M., 60
Oćwieja M., 61, 74
Oliynyk V.O., 29
Oncsik T., 42
Orczyk M., 54
Pajor-Świerzy A., 106
Panczyk T., 95, 102
Panko A.V., 29
Papadimitriou V., 22
Papastavrou G., 68
Pathak G., 104
Pawlak D., 93
Pawlos W., 73
Petelska A.D., 37
Petkov J., 76
Peukert W., 40
Pezron I., 28
Piechocka M., 37
Pillai S., 52
Piotrowski M., 30, 98
Podgórna K., 27
Pohlodek J., 113
Postel D., 28
Prochaska K., 37
Prochazka K., 56
Promdonkoy B., 85
Radoičić M., 36
Radulova G., 76
Redeker C., 67, 92
Regnouf-de-Vains J.-B., 83
Ridi F., 69
Robles E., 78
Rogalska E., 83, 105, 109, 110
Routh A., 91, 99
Rukhadze M., 86
Sabatino P., 35
Sadowska M., 74
Saeedi S., 77
Salvatore A., 24
Samoć M., 60
Scales P., 33
Schano K.H., 72
Schmidt H.W., 68
Schulz C. 13
Sebők D., 101
Sedláček P., 31
Segets D., 40
Setiowati A.D., 77
Skinner S., 33
Skoglund S., 50
Slastanova A., 78
Smilek J., 31, 111
Socha R., 106
122
ESC 2015
Sokolan N., 87
Sokolowska E., 93
Sosnowski T.R., 94
Stark K., 51
Starkie J., 91
Stevenson R., 67
Stickland, A., 33
Stoyanov S., 76
Stringer D.N., 53, 84
Sugimoto T., 97
Sun Q., 99
Symonds B., 44
Szafraniec J., 23
Szczepanowicz K., 27, 30, 98, 107
Szczubialka K., 93
Szeremeta J., 60
Szilagyi I., 42
Szyk-Warszyńska L., 106
Świątek S., 100, 108
Taeibi-Rahni M., 72
Tharad S., 85
Thomson N., 44
Toca-Herrera J.L., 85
Tokarczyk K., 88, 89
Tomaiuolo G., 34
Tonelli M., 69
Toth R., 43
Trask R., 92
Trefalt G., 42
Trojan S., 105, 109, 110
Uchman M., 56
Ulaganathan V., 14, 47
Ulatowska J., 79
Usher S., 33
Ustarbowska M., 109
Vaccaro M., 41
Van der Meeren P., 35, 77
Varga N., 101
Vayssade M., 28
Vermeir L., 35
Vincent B., 19
Voron’ko N., 87
Vranješ M., 36
Wadouachi A., 28
Wallinder I.O., 50
Walter J., 40
Wamke A., 37
Warszyński P., 27, 30, 90, 98, 106, 107
Wąsik P., 92
Wiertel A., 48
Wilk K.A., 55, 60
Włodek M., 90
Wojciechowski K., 54, 64
Wojewódka P., 80
Wojszko K., 105
Wold S., 50
Wolski P., 102
Won J., 14, 39
Yamaguchi A., 81
Yazdanfar H., 62
Youle O., 62
Yow H.N., 57
Zapotoczny S., 16, 23
Zawała J., 48
Zielińska-Jurek A., 36
123

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