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Advances in Polymer Science
Editorial Board:
A. Abe · A C. Albertsson · K. Dušek · W.H. de Jeu
H H. Kausch · S. Kobayashi · K S. Lee · L. Leibler
T.E. Long · I. Manners · M. Möller · E.M. Terentjev
M. Vicent · B. Voit · G. Wegner · U. Wiesner
Advances in Polymer Science
Recently Published and Forthcoming Volumes
Modern Techniquesfor Nano-
and Microreactors/-reactions
Volume Editor: Caruso, F.
Vol. 229, 2010
Complex Macromolecular Systems II
Volume Editors: Müller, A.H.E.,
Schmidt, H W.
Vol. 228, 2010
Complex Macromolecular Systems I
Volume Editors: Müller, A.H.E.,
Schmidt, H W.
Vol. 227, 2010
Shape-Memory Polymers
Volume Editor: Lendlein, A.
Vol. 226, 2010
Polymer Libraries
Volume Editors: Meier, M.A.R., Webster, D.C.
Vol. 225, 2010
Polymer Membranes/Biomembranes
Volume Editors: Meier, W.P., Knoll, W.
Vol. 224, 2010
Organic Electronics
Volume Editors: Meller, G., Grasser, T.
Vol. 223, 2010
Inclusion Polymers
Volume Editor: Wenz, G.
Vol. 222, 2009
Advanced Computer Simulation
Approaches for Soft Matter Sciences III
Volume Editors: Holm, C., Kremer, K.
Vol. 221, 2009
Self-Assembled Nanomaterials II
Nanotubes
Volume Editor: Shimizu, T.
Vol. 220, 2008
Self-Assembled Nanomaterials I
Nanofibers
Volume Editor: Shimizu, T.
Vol. 219, 2008
Interfacial Processes and Molecular
Aggregation of Surfactants
Volume Editor: Narayanan, R.
Vol. 218, 2008
New Frontiers in Polymer Synthesis
Volume Editor: Kobayashi, S.
Vol. 217, 2008
Polymers for Fuel Cells II
Volume Editor: Scherer, G.G.
Vol. 216, 2008
Polymers for Fuel Cells I
Volume Editor: Scherer, G.G.
Vol. 215, 2008
Photoresponsive Polymers II
Volume Editors: Marder, S.R., Lee, K S.
Vol. 214, 2008
Photoresponsive Polymers I
Volume Editors: Marder, S.R., Lee, K S.
Vol. 213, 2008
Polyfluorenes
Volume Editors: Scherf, U., Neher, D.
Vol. 212, 2008
Chromatography for Sustainable Polymeric
Materials
Renewable, Degradable and Recyclable
Volume Editors: Albertsson, A C.,
Hakkarainen, M.
Vol. 211, 2008
Wax Crystal Control · Nanocomposites
Stimuli-Responsive Polymers
Vol. 210, 2008
Functional Materials and Biomaterials
Vol. 209, 2007
Phase-Separated Interpenetrating Polymer
Networks
Authors: Lipatov, Y.S., Alekseeva, T.
Vol. 208, 2007
Hydrogen Bonded Polymers
Volume Editor: Binder, W.
Vol. 207, 2007
Modern Techniques
for Nano- and
Microreactors/-reactions
Volume Editor: Frank Caruso
With contributions by
K. Ariga · G. Battaglia · S.L. Biswal · F. Caruso · J.P. Hill
Q. Ji · A.P.R. Johnston · G.C. Kini · K. Landfester
H. Lomas · M. Massignani · A.D. Price · G.K. Such
C.K. Weiss · M.S. Wong
123
Editor
Frank Caruso
Department of Chemical and Biomolecular Engineering
The University of Melbourne
Victoria 3010, Australia
fcaruso@unimelb.edu.au
ISSN 0065-3195 e-ISSN 1436-5030
ISBN 978-3-642-12872-1 e-ISBN 978-3-642-12873-8
DOI 10.1007/978-3-642-12873-8
Springer Heidelberg Dordrecht London New York
Library of Congress Control Number: 2010930620
c
Springer-Verlag Berlin Heidelberg 2010
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is
concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting,
reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication
or parts thereof is permitted only under the provisions of the German Copyright Law of September 9,
1965, in its current version, and permission for use must always be obtained from Springer. Violations
are liable to prosecution under the German Copyright Law.
The use of general descriptive names, registered names, trademarks, etc. in this publication does not
imply, even in the absence of a specific statement, that such names are exempt from the relevant protective
laws and regulations and therefore free for general use.
Cover design: WMXDesign GmbH, Heidelberg
Printed on acid-free paper
Springer is part of Springer Science+Business Media (www.springer.com)
Volume Editor
Frank Caruso
Department of Chemical and Biomolecular Engineering
The University of Melbourne
Victoria 3010, Australia
fcaruso@unimelb.edu.au
Editorial Board
Prof. Akihiro Abe
Professor Emeritus
Tokyo Institute of Technology
6-27-12 Hiyoshi-Honcho, Kohoku-ku
Yokohama 223-0062, Japan
aabe34@xc4.so-net.ne.jp
Prof. A C. Albertsson
Department of Polymer Technology
The Royal Institute of Technology
10044 Stockholm, Sweden
aila@polymer.kth.se
Prof. Karel Dušek
Institute of Macromolecular Chemistry
Czech Academy of Sciences
of the Czech Republic
Heyrovský Sq. 2
16206 Prague 6, Czech Republic
dusek@imc.cas.cz
Prof.Dr.WimH.deJeu
Polymer Science and Engineering
University of Massachusetts
120 Governors Drive
Amherst MA 01003, USA
dejeu@mail.pse.umass.edu
Prof. Hans-Henning Kausch
Ecole Polytechnique Fédérale de Lausanne
SciencedeBase
Station 6
1015 Lausanne, Switzerland
kausch.cully@bluewin.ch
Prof. Shiro Kobayashi
R & D Center for Bio-based Materials
Kyoto Institute of Technology
Matsugasaki, Sakyo-ku
Kyoto 606-8585, Japan
kobayash@kit.ac.jp
Prof. Kwang-Sup Lee
Department of Advanced Materials
Hannam University
561-6 Jeonmin-Dong
Yuseong-Gu 305-811
Daejeon, South Korea
kslee@hnu.kr
Prof.L.Leibler
Matière Molle et Chimie
Ecole Supérieure de Physique
et Chimie Industrielles (ESPCI)
10 rue Vauquelin
75231 Paris Cedex 05, France
ludwik.leibler@espci.fr
vi Editorial Board
Prof. Timothy E. Long
Department of Chemistry
and Research Institute
Virginia Tech
2110 Hahn Hall (0344)
Blacksburg, VA 24061, USA
telong@vt.edu
Prof. Ian Manners
School of Chemistry
University of Bristol
Cantock’s Close
BS8 1TS Bristol, UK
ian.manners@bristol.ac.uk
Prof. Martin Möller
Deutsches Wollforschungsinstitut
an der RWTH Aachen e.V.
Pauwelsstraße 8
52056 Aachen, Germany
moeller@dwi.rwth-aachen.de
Prof.E.M.Terentjev
Cavendish Laboratory
Madingley Road
Cambridge CB 3 OHE, UK
emt1000@cam.ac.uk
Maria Jesus Vicent, PhD
Centro de Investigacion Principe Felipe
Medicinal Chemistry Unit
Polymer Therapeutics Laboratory
Av. Autopista del Saler, 16
46012 Valencia, Spain
mjvicent@cipf.es
Prof. Brigitte Voit
Institut für Polymerforschung Dresden
Hohe Straße 6
01069 Dresden, Germany
voit@ipfdd.de
Prof. Gerhard Wegner
Max-Planck-Institut
für Polymerforschung
Ackermannweg 10
55128 Mainz, Germany
wegner@mpip-mainz.mpg.de
Prof. Ulrich Wiesner
Materials Science & Engineering
Cornell University
329 Bard Hall
Ithaca, NY 14853, USA
ubw1@cornell.edu
Advances in Polymer Sciences
Also Available Electronically
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and Materials Science. If a library does not opt for the whole package, the book
series may be bought on a subscription basis. Also, all back volumes are available
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and the abstract of each article by going to the SpringerLink homepage, clicking
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Advances in Polymer Science.
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at springer.com using the search function by typing in Advances in Polymer
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viii Advances in Polymer Sciences Also Available Electronically
Aims and Scope
The series Advances in Polymer Science presents critical reviews of the present
and future trends in polymer and biopolymer science including chemistry, physical
chemistry, physics and material science. It is addressed to all scientists at universi-
ties and in industry who wish to keep abreast of advances in the topics covered.
Review articles for the topical volumes are invited by the volume editors. As a
rule, single contributions are also specially commissioned. The editors and pub-
lishers will, however, always be pleased to receive suggestions and supplementary
information. Papers are accepted for Advances in Polymer Science in English.
In references Advances in Polymer Sciences is abbreviated as Adv Polym Sci and
is cited as a journal.
Special volumes are edited by well known guest editors who invite reputed authors
for the review articles in their volumes.
Impact Factor in 2009: 4.600; Section “Polymer Science”: Rank 4 of 73
Preface
Encapsulation technologies are widely used in medicine and pharmaceutics,
agriculture and cosmetic industries for the development of a wide range of
controlled-release delivery systems. Thin films, and particulates such as liposomes,
emulsions and capsules, are used for the sustained release of drugs, pesticides,
fragrances and other substances. Advanced variants of these systems have also been
used to perform various confined nano-/microreactions to mimic cellular processes.
The impetus for this stems from the fact that many biological processes are com-
partmentalized within cells through the localization of proteins and other molecules,
and such confinement controls the complex processes. Although the synthetic coun-
terparts are still far from the complexity of living systems, they hold promise for
advancing studies into the synthesis, encapsulation (confinement), reactions and
delivery of (bio)molecules.
This volume provides an overview of a number of extensively used techniques
to encapsulate a host of different materials, ranging from confined polymeriza-
tion to self-assembly. The encapsulation vehicles formed include thin multi-strata
films, emulsions, polymersomes, nanoparticle-based hollow spheres and polymer
capsules. The potential applications of these systems for encapsulation and their use
as microreactors to perform a host of complex reactions are discussed, and examples
showing the diversity of properties that can be controlled in these systems are given.
In Chapter 1, Landfester and Weiss outline details of miniemulsion polymer-
ization for the encapsulation of a range of materials such as dyes, pigments,
fragrances, photo-initiators, drugs, nanoparticles and biomolecules (DNA) in poly-
meric nanoparticles. The preparation of nanoparticles with new properties is also
presented.
Chapter 2, by Ariga, Ji and Hill, presents recent developments on the application
of the layer-by-layer technique for encapsulating enzymes. Encapsulation strategies
are demonstrated for enzymes in both thin film and particle formats to generate
complex enzyme architectures for microreactions. The integration of such systems
into advanced biodevices such as microchannels, field effect transistors and flow
injection amperometric sensors is also presented.
In Chapter 3, Kini, Biswal and Wong discuss recent developments in synthetic
routes and properties of hollow spheres formed from nanoparticles. It is shown that
arranging nanoparticles into hollow spheres through self-assembly produces particle
ix
Preface
systems with new properties that can be exploited for encapsulation, storage and
controlled release, making them potentially useful in medical therapy, catalysis and
encapsulation applications.
In Chapter 4, Massignani, Lomas and Battaglia review the fabrication processes
used to form polymersomes, membrane-enclosed structures that are formed through
self-assembly of amphiphilic copolymers. The resulting molecular properties, meth-
ods to control their size, loading strategies and applications of polymersomes are
also detailed.
Chapter 5, by Price, Johnston, Such and Caruso, focuses on recent progress in the
design of layer-by-layer capsule reactors. Fundamentals that underpin the assembly
of such capsules are presented, followed by the assembly parameters that affect
the retention of components within the resultant capsules. Prominent examples of
layer-by-layer assembled microreactors and potential applications of such systems
in biomedicine and micro-encapsulated catalysis are also discussed.
The collection of chapters in this volume will be of interest to a multidisciplinary
audience working at the interface of chemistry, biology, physics, materials science
and engineering. This volume is also aimed at encouraging scientists and engi-
neers who wish to diversify their research in encapsulation and nano-/microreactor
systems.
Finally, I would like to thank all of the contributors for taking valuable time
from their busy schedules to write stimulating and informative chapters, and to the
Springer team for assistance in publishing this volume in their leading book series
“Advances in Polymer Science.”
Melbourne, Frank Caruso
June 2010
x
[...]... Polymerization 4.3 Polymer Precipitation on Preformed Nanodroplets K Landfester ( ) and C.K Weiss Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany e-mail: landfester@mpip-mainz.mpg.de 3 5 6 13 16 16 19 28 29 30 37 2 K Landfester and C.K Weiss 5 Controlled Release of Components from Nanocapsules ... Katharina Landfester and Clemens K Weiss 1 Enzyme-Encapsulated Layer-by-Layer Assemblies: Current Status and Challenges Toward Ultimate Nanodevices 51 Katsuhiko Ariga, Qingmin Ji, and Jonathan P Hill Non-Layer-by-Layer Assembly and Encapsulation Uses of Nanoparticle-Shelled Hollow Spheres 89 Gautam C Kini, Sibani L Biswal, and Michael S Wong... -Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride 1 Introduction Today, polymeric nanoparticles and nanocapsules with different encapsulated species are of great interest for a number of applications such as functional coatings, inks, adhesives, nutrition, or cosmetics, but also more and more for pharmaceutical and biomedical applications For the preparation of nanoparticles from radically polymerized monomers, the... polymerization: in non-aqueous miniemulsions for polyamide nanopar- • • • • • • • • ticles [12], and in aqueous phase for polybutylcyanoacrylate (PBCA) nanoparticles [13] Cationic polymerization for poly-p-methoxystyrene particles [14, 15] Catalytic polymerization for polyolefin [16, 17] or polyketone particles [18] Ring opening metathesis polymerization for polynorbonene nanoparticles [19, 20] Step-growth... Fig 6 Uptake data for unfunctionalized and MePEG-functionalized PBCA nanoparticles in different cells, HeLa and Jurkat cells [35, 36] Intracellular distribution of the particles is independent of the cell line and the particles’ surface characteristics The particles are distributed evenly throughout the cells and are additionally localized within the cells by confocal microscopy and transmission electron... could be switched forwards and back using UV light or visible light The two-ring form does not interfere with the emission of the BODIPY dye, whereas the three-ring structure of CMTE efficiently quenches the fluorescence of the excited BODIPY dye The switching efficiency is dependent on the distances between BODIPY and CMTE Hence, at higher concentrations, the distance decreases and therefore the energy... assemble SAXS before polymerization SAXS after polymerization 10000 10000 1000 1000 Intensity Intensity 3.46 nm 1.73 nm 1.73 nm 1.45 nm nm 1.15 nm 3.21 nm 3.21 100 3.94 nm 3 94 1.95 nm nm 1.26 nm 1.58 nm 1.58 100 0,0 10 0,5 1,0 –1 S / nm 1,5 0,0 0,5 1,0 1,5 S / nm–1 Fig 10 The formation of nano-onions by using inert inner shell lanthanide complexes; detection by TEM and XRD [71] 16 K Landfester and C.K Weiss... high for an efficient dispersion in order to generate a miniemulsion In this case, the so-called co-sonication process can be used which is suitable for, e.g., organic pigments or magnetite (see Fig 11b) In the following section, several examples are presented to illustrate the principle, the limitations, and the possibilities for the formation of homogenous hybrid nanoparticles 3.1 Organic Pigments and. .. therefore suitable for the miniemulsification process Using NMP [114, 115] or reversible addition–fragmentation chain transfer (RAFT) [119,120,127], agents with ammonium groups for the ion exchange allowed the attachment of initiators on the clay surface for controlled radical polymerizations (NMP, RAFT) Samakande et al investigated the kinetics of RAFT-mediated living polymerization of styrene [120] and. .. magnetite in polystyrene nanoparticles The formation of uniform nanoparticles with high amounts of magnetite can be obtained most successfully by the three-step process involving the co-sonication procedure (see Fig 14) [135, 136] In the first step, magnetite (10 nm) nanoparticles are formed by precipitation from a ferrous and ferric chloride solution 24 K Landfester and C.K Weiss Osmotic pressure agent Monomer . G. Wegner · U. Wiesner Advances in Polymer Science Recently Published and Forthcoming Volumes Modern Techniques for Nano- and Microreactors/-reactions Volume Editor: Caruso, F. Vol. 229, 2010 Complex. Preformed Nanodroplets 37 K. Landfester ( )andC.K.Weiss Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany e-mail: landfester@mpip-mainz.mpg.de 2 K. Landfester and. medicine and pharmaceutics, agriculture and cosmetic industries for the development of a wide range of controlled-release delivery systems. Thin films, and particulates such as liposomes, emulsions and