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Published on 15 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782626664-FP001
Bio-inspired Polymers
View Online
RSC Polymer Chemistry Series
Editor-in-Chief:
Professor Ben Zhong Tang, The Hong Kong University of Science and
Technology, Hong Kong, China
Series Editors:
Professor Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada
Professor Stephen Craig, Duke University, USA
Professor Jianhua Dong, National Natural Science Foundation of China,
China
Professor Toshio Masuda, Shanghai University, China
Professor Christoph Weder, University of Fribourg, Switzerland
Titles in the Series:

1: Renewable Resources for Functional Polymers and Biomaterials
2: Molecular Design and Applications of Photofunctional
Polymers and Materials
3: Functional Polymers for Nanomedicine
4: Fundamentals of Controlled/Living Radical Polymerization
5: Healable Polymer Systems
6: Thiol-X Chemistries in Polymer and Materials Science
7: Natural Rubber Materials: Volume 1: Blends and IPNs
8: Natural Rubber Materials: Volume 2: Composites and
Nanocomposites
9: Conjugated Polymers: A Practical Guide to Synthesis
10: Polymeric Materials with Antimicrobial Activity: From Synthesis to
Applications
11: Phosphorus-Based Polymers: From Synthesis to Applications
12: Poly(lactic acid) Science and Technology: Processing, Properties,
Additives and Applications
13: Cationic Polymers in Regenerative Medicine
14: Electrospinning: Principles, Practice and Possibilities
15: Glycopolymer Code: Synthesis of Glycopolymers and their
Applications
16: Hyperbranched Polymers: Macromolecules in-between Deterministic
Linear Chains and Dendrimer Structures
17: Polymer Photovoltaics: Materials, Physics, and Device Engineering
18: Electrical Memory Materials and Devices
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19: Nitroxide Mediated Polymerization: From Fundamentals to Applications

in Materials Science
20: Polymers for Personal Care Products and Cosmetics
21: Semiconducting Polymers: Controlled Synthesis and Microstructure
22: Bio-inspired Polymers
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Published on 15 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782626664-FP001 View Online
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Edited by
Nico Bruns
University of Fribourg, Fribourg, Switzerland
Email: nico.bruns@unifr.ch
and
Andreas F. M. Kilbinger
University of Fribourg, Fribourg, Switzerland
Email: andreas.kilbinger@unifr.ch
RSC Polymer Chemistry Series No. 22
Print ISBN: 978-1-78262-413-4

PDF eISBN: 978-1-78262-666-4
EPUB eISBN: 978-1-78262-923-8
ISSN: 2044-0790
A catalogue record for this book is available from the British Library
r The Royal Society of Chemistry 2017
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Preface
Life on earth has been evolving for the last 3–4 billion years, in which time it
has developed a level of complexity that is most challenging to understand.
With major breakthroughs in physics and chemistry in the last century, it is
the advances in biological sciences that are gaining momentum in this
century. The insights gained into the inner workings of the living world have
always inspired scientists from bordering disciplines to copy or mimic
nature in abiotic systems. Engineers have long been inspired by the
macroscopic living world and have developed bio-inspired technologies
ranging from Velcro to wing design for aeroplanes to advanced robotics. Bio-
inspiration and biomimetics often go hand-in-hand. While the latter term
describes the direct replication of biological working principles in man-
made systems, bio-inspiration usually refers to a more general translation of
molecular, microscopic, and macroscopic structures and functionalities
from living systems into synthetic ones. On the molecular, and especially on
the macromolecular level, research into bio-inspired structures has been
growing exponentially over the last twenty years and has led to some major
scientific and technological breakthroughs, such as self-cleaning surfaces,
adhesives that provide strong bonding in wet conditions, adaptive and self-
reporting materials and synthetic tools for the preparation of sequence-
controlled polymers. Today, research into bio-inspired polymers is being
carried out at many research institutes worldwide. In fact, several of the co-
authors of this book are collaborating in a National Center of Competence in
Research (NCCR), a research instrument of the Swiss National Science
Foundation (SNSF), working on Bio-Inspired Materials. The number of
textbooks addressing this advanced topic, however, are few, and either cover
bio-inspired chemistry in a broad sense, or bio-inspired materials with a
strong focus on inorganic materials and hybrid materials. Nevertheless, a
vast body of literature deals with soft bio-inspired materials based on

Edited by Nico Bruns and Andreas F. M. Kilbinger
Published by the Royal Society of Chemistry, www.rsc.org
vii
View Online
viii Preface
synthetic and natural polymers. The different aspects of bio-inspiration in

polymer science are fairly varied even within the constraints of a book
focusing ‘‘only’’ on bio-inspired polymers. We therefore believed that com-
piling a book co-authored by some of the leading authorities in biologically
inspired polymers would be a worthwhile endeavour. This book aims to

provide an essential overview of the field.
We have thematically grouped the 17 chapters of our book into three
sections. The first section deals with polymers based on biological building
blocks. The first chapter in this section, written by Börner, ten Brummelhuis,
and co-authors, gives an overview of the techniques available in the ‘‘post-
click area’’ to synthesize peptide and protein polymer conjugates.
Hartmann’s Chapter 2 on glycopolymers similarly addresses pathways to
obtain sugar carrying homo- and block copolymers, as well as their appli-
cations in biotechnology and biomedicine.
The second section covers bio-inspired and biomimetic polymeric structures.
The chapter by Lutz and co-authors focuses on the fundamental problem of
controlling the primary structure of synthetic polymers inspired by nature’s
sequence-controlled macromolecules. The team of Berda describe the fold-
ing of individual polymer chains into single-chain nanoparticles, in analogy
to nature’s folding of protein chains. Kilbinger and co-authors review several
different ways of obtaining polymeric tubular structures, inspired by tubes in
nature that exist on many different length scales. Polymeric membranes are
addressed in the chapter by Meier, Palivan, and co-authors. Such mem-
branes take their inspiration from natural cell membranes, but offer in-
creased mechanical stability while allowing the incorporation of functional
biomolecules such as proteins. As a result, they allow the preparation of
robust nanoreactors and nanocontainers, as well as advanced water purifi-
cation membranes. Polymeric ionic liquids with micelle-like topologies are
presented by Mülhaupt and co-authors. Here, micellar assemblies of am-
phiphiles are used as an inspiration to go beyond what is observed in nature,
i.e. polymeric unimolecular micelles. The chapter by Studart, Burgert, and
co-authors represents the last in this section on bio-inspired polymeric
structures. Here, plants serve as the inspiration for the creation of new
composite materials with gradual variations of their mechanical properties.
Improved composites with superior tolerance of peak stresses and better
load distribution can be obtained by mimicking nature.
The third and last section of our book deals with polymeric materials with
bio-inspired functionality. The opening chapter by Waite gives a biological
perspective of how mussels adhere to interfaces and emphasizes the im-
portance of first understanding the biology before new, truly bio-inspired
materials can be achieved. The second chapter in this section, written by Lee,
describes the synthetic achievements of mussel glue-inspired polymers, and
depicts the polymer chemist’s approach to mimic the mussel adhesion de-
scribed by Waite in the previous chapter. Bruns and co-authors present a
chapter on self-reporting polymeric materials with mechanochromic prop-
erties. Such materials mimic nature’s ability to report, repair, and improve
View Online
Preface ix
materials exposed to mechanical stress. Inspired by the stiffness change of the

sea cucumber dermis, Weder and Moatsou review the general design prin-
ciples to achieve materials that can mimic this naturally observed behavior.
Approaches to mimic natural skeleton muscles using synthetic polymers are
reviewed by Naficy, Spinks, and Baughman in the chapter on bio-inspired

polymer artificial muscles. Cameron’s chapter on materials for tissue engin-
eering and 3D cell culture reviews common methods used to prepare porous
three dimensional scaffold materials and how to improve attachment and
proliferation of various cell types. Colonialization of surfaces by cells is crucial
for cell culture materials. However, if the cells are harmful bacteria, this effect
is not wanted. Thus, living organisms have developed ways to stop bacterial
colonialization on their surfaces. These antimicrobial properties can be
mimicked with synthetic polymers, as highlighted by Tiller and coworkers.
The chapter on superwettability of polymer surfaces reported by Jiang and co-
authors reviews approaches to mimic structured surfaces common in nature
such as those of the Lotus leaf, as found on the leg of the water strider or on
the surface of certain water collecting cacti. The final chapter of this section
(and last chapter in our book) by Vignolini, Steiner, and co-authors deals with
the mimicking of structural colour using biopolymers. Some of the most
brilliant colours observed in nature, for example on the wings of certain
butterflies, the surface of some plants, or the armour of certain beetles, are
caused by periodically organised biopolymers and their interference with
visible light. This last chapter describes this phenomenon and reviews current
approaches to mimic this behavior.
It is to be expected that in a book on bio-inspired polymers certain chapters
will appear ‘‘more bio-inspired’’ than others to some readers at a first glance.
The reason for this is, in our opinion, simply the degree to which certain ideas
from nature have been incorporated into our daily lives or research activities
already. As we increase our understanding of the underlying biology of
nature’s ‘‘box of tricks’’, our view of bio-inspiration will continuously change
as well. It is therefore difficult to determine a ‘‘degree of bio-inspiration’’ and
we therefore prefer to see this book as a current snapshot of research activities
on bio-inspired polymers. We hope that the book itself serves as inspiration
for our readers to develop novel materials with advanced properties that ad-
dress the numerous challenges and opportunities that polymer chemistry and
material sciences are going to face in the future.
We would like to thank all of our authors for contributing such high
quality chapters on the topics of their expertise. We would also like to thank
the editorial staff at the Royal Society of Chemistry for their support in
realizing this book project. Finally, we would like to greatly acknowledge the
financial support of the Swiss National Science Foundation through its
NCCR Bio-Inspired Materials and the many chapter contributions of our
NCCR colleagues.
Nico Bruns and Andreas Kilbinger

Fribourg
Contents
Chapter 1 Synthetic Aspects of Peptide– and Protein–Polymer

Conjugates in the Post-click Era 1
Maria Meißler, Sebastian Wieczorek, Niels ten Brummelhuis
and Hans G. Börner
1.1 Introduction 1
1.2 General Concepts for Bioconjugation 3
1.3 Chemical Synthesis of Peptide– and
Protein–Polymer Conjugates 6
1.3.1 Coupling with Amines 6
1.3.2 Coupling with Thiols 7
1.3.3 Chemical Ligation by Oxime/Hydrazone
Formation 9
1.3.4 Staudinger Ligation 11
1.3.5 Azide–Alkyne Cycloaddition 13
1.3.6 Diels–Alder (DA) Cycloaddition Reactions 15
1.3.7 Chemistry with 1,2,4-Triazoline-3,5-diones
(TAD) 17
1.4 Chemoenzymatic Approaches 19
1.4.1 Transglutaminase (TGase) Catalyzed
Ligation 19
1.4.2 Sortase (Srt)-mediated Ligation 20
1.4.3 Enzyme-induced Functional Group
Modifications 20
1.5 Biotransformations 21
1.6 Conclusions and Future Perspectives 23
References 24

xi
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xii Contents
Chapter 2 Glycopolymers 31
Laura Hartmann and Kira Neuhaus
2.1 Introduction 31
2.2 Synthesis of Glycopolymers 32

2.2.1 Synthesis of Glycopolymers via
Glycomonomers 35
2.2.2 Synthesis of Glycopolymers via
Post-polymerization Strategies 40
2.2.3 Synthesis of Glyco- and Block Copolymers 43
2.3 Analyzing Glycopolymers 53
2.3.1 Multivalent Binding of Glycopolymers 53
2.3.2 Binding Studies of Glycopolymers Targeting
Lectins 55
2.4 Biomedical and Biotechnological Applications
of Glycopolymers 58
2.5 Conclusions 60
Acknowledgements 62
References 62
Chapter 3 Synthesis of Non-natural Polymers with Controlled

Primary Structures 66
Abdelaziz Al Ouahabi, Raj Kumar Roy and Jean-François Lutz
3.1 Introduction 66
3.2 Sequence-controlled Polymers Prepared by
Chain-growth Polymerization 68
3.2.1 Anionic Polymerization 68
3.2.2 Cationic Polymerization 70
3.2.3 Controlled Radical Polymerization 72
3.2.4 Ring-opening Polymerization 77
3.2.5 Ring-opening Metathesis Polymerization 78
Step-growth Polymerization 79
3.3.1 Acyclic Diene Metathesis Polymerization 79
3.3.2 Click Step-growth Polymerization 81
3.3.3 Other Step-growth Approaches 81
3.3.4 Multicomponent Reactions 83
Multi-step-growth Polymerization 86
3.4.1 Conventional Iterative Synthesis 86
3.4.2 Protecting-group-free Iterative Synthesis 87
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Contents xiii
3.4.3 Successive Radical Insertion 91

3.4.4 Convergent and Divergent Strategies 92
3.5 Use of Templates and Catalytic Molecular Machines 94
3.5.1 Template-assisted Sequence-controlled
Polymerization 94
3.5.2 Rotaxane-based Catalytic Machines 96
3.6 Outlook 96
References 98
Chapter 4 Single-chain Nanoparticles 107

Justin P. Cole, Christopher K. Lyon and Erik B. Berda
4.1 Introduction 107

4.2 Synthesis of SCNPs 108
4.2.1 Covalent Cross-linking Reactions 116
4.2.2 Dynamic Covalent Chemistry 118
4.2.3 Non-covalent Chemistry 120
4.2.4 Multiple Intra-chain Interactions 121
4.2.5 Outlook 123
4.3 Characterization of SCNPs 123
4.3.1 Size Exclusion Chromatography 123
4.3.2 Light Scattering 124
4.3.3 Viscometry 124
4.3.4 NMR Spectroscopy 125
4.3.5 Characterizing the Morphology of SCNPs 126
4.4 Potential Applications 130
4.4.1 Catalysis 131
4.4.2 Nano-medicine 132
4.4.3 Chemical Sensors 133
4.4.4 Self-assembly 133
4.5 Summary and Outlook 135
Acknowledgements 135
References 135
Chapter 5 Polymeric Tubular Structures 141

Samantha Doninelli, Michael Badoux and
Andreas F. M. Kilbinger
5.1 Introduction – Bio-inspiration 141

5.2 Tubes Based on Single Polymer Chains 143
5.2.1 Polyaramides 143
5.2.2 Phenylene Helices 150
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xiv Contents
5.2.3Other Helical Polymers 159

5.2.4Helical Polymers with Host–Guest
Interactions 167
5.3 Engineered Polymer Nanotubes 171
5.3.1 Block Copolymer Self-assembly 171

5.3.2 DNA Origami 185
5.3.3 Metal-organic Nanotubes (MONTs) 189
5.3.4 Templated Synthesis of Polymeric Tubes 198
5.3.5 Other Methods to Form Polymeric Tubes 209
5.4 Summary 209
References 210
Chapter 6 Bio-inspired Polymer Membranes 221

Viktoria Mikhalevich, Christina Zelmer, Anja Car,
Cornelia Palivan and Wolfgang Meier

6.2 Properties of Copolymers that Form Bio-inspired
Membranes 223
6.3 Bio-inspired Polymersomes (3D Membranes) 224
6.3.1 Biomolecule Surface-functionalized Vesicles 225
6.3.2 Reconstitution of Membrane Proteins into
Polymer Membranes 229
6.3.3 Bio-inspired Block Copolymer/Lipid
Hybrid Vesicles 232
6.3.4 Protein-polymer Nanoreactors 233
6.4 Bio-inspired Planar Polymer Membranes
(2D Membranes) 235
6.4.1 Monolayer at the Water–Air Interface and
Free-standing Membranes 236
6.4.2 Solid Supported Membranes 236
6.4.3 Combination of 2D Membranes with
Biomolecules 240
6.4.4 Hybrid Polymer–Lipid Membranes 241
6.5 Immobilized Vesicles 244
6.6 Applications of Bio-inspired Polymer Membranes 246
6.6.1 Polymersomes 246
6.6.2 Planar Membranes 249
6.7 Conclusions and Perspectives 250
Abbreviations 250
References 252
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Contents xv
Chapter 7 Polymeric Ionic Liquids with Micelle-like Topologies and

Functions 259
Benjamin Kerscher, Fabian Schüler, Anna-Katharina Evers
and Rolf Mülhaupt

7.2 From Supramolecular Assemblies to Micelle-like
Macromolecules 260
7.3 Nanostructured and Micelle-like Polymeric Ionic
Liquids 265
7.4 Compartmentalized Onion-like Polymeric Ionic
Liquids 270
7.5 Conclusions 278
References 280
Chapter 8 Biological and Bio-inspired Heterogeneous Composites:

From Resilient Palm Trees to Stretchable Electronics 286
Markus Rüggeberg, André R. Studart and Ingo Burgert

8.2 The Natural Building Blocks of Plants 288
8.3 Palms as Role Models for Biological Heterogeneous
Composites 289
8.3.1 Hierarchical Structure and Mechanics
of Palms 290
8.3.2 Controlled Local Composition and
Reinforcement Orientation 291
8.4 Bio-inspired Heterogeneous Composites 292
8.4.1 The Synthetic Building Blocks 293
8.4.2 Controlled Local Composition 293
8.4.3 Controlled Reinforcement Orientation 294
8.4.4 Functional Devices Based on Bio-inspired
Heterogeneous Composites 297
8.5 Discussion 299
8.6 Remaining Challenges and Outlook 302
References 302
Chapter 9 Translating Mussel Adhesion: Four Uncertainties about

the Interface 305
J. Herbert Waite

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xvi Contents
9.2 Are Interfacial Films Cleared Away? 306

9.3 Do Mussels Displace Surface Water? 309
9.4 Is the pH of Adhesive Deposition the Same as
Seawater pH? 313
9.5 Is Interfacial Redox the Same as Seawater Redox? 316

9.6 Summary 319
References 320
Chapter 10 Mussel Adhesive-inspired Polymers 322

Bruce P. Lee

10.2 Catechol Side Chain Chemistry 323
10.2.1 Reversible Catechol Interactions 323
10.2.2 Oxidation-induced Covalent Crosslinking 325
10.2.3 Chemical Modification of Catechol 327
10.3 Preparation of Catechol Functionalized Polymers 329
10.3.1 Catechol Side Chain Protection 329
10.3.2 Direct Functionalization of Catechol 331
10.3.3 Polymerization of Catechol-modified
Monomers 332
10.3.4 Catechol-functionalized Initiator 333
10.4 Application of Catechol Functionalized Polymers 334
10.4.1 Biomedical Adhesives 334
10.4.2 Drug Delivery 338
10.4.3 Coatings for Reducing Biofouling 338
10.4.4 Delivery of Therapeutic Cells 341
10.4.5 Hydrogel Actuators 341
10.4.6 Smart Adhesives 342
10.5 Future Outlook 344
10.6 Summary 344
References 345
Chapter 11 Self-reporting Polymeric Materials with Mechanochromic

Properties 354
Jose V. Araujo, Omar Rifaie-Graham, Edward A. Apebende
and Nico Bruns

11.2 Learning from Nature 355
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Contents xvii
11.3 Mechano-responsiveness 358

11.3.1 Mechanical Input and Methods to
Measure Mechanically-induced Changes
in Polymers 359
11.3.2 Mechano-responsiveness at the Molecular

Level 361
11.3.3 Mechano-responsiveness at the
Supramolecular Level 369
11.3.4 Mechanobiochemistry 377
11.3.5 Mechano-responsiveness at the
Microscopic Level 385
11.4 Conclusions and Future Perspectives 393
References 395
Chapter 12 Mechanically Adaptive Nanocomposites Inspired by Sea

Cucumbers 402
Dafni Moatsou and Christoph Weder

12.2 Mechanical Morphing of the Sea Cucumber
Dermis 403
12.3 Water-responsive Sea Cucumber-mimicking
Nanocomposites 406
12.3.1 Stress Transfer in Mechanically Adaptive
Materials 411
12.4 Mechanically Adaptive Sea Cucumber Mimics with
Specific Responsiveness 413
12.4.1 pH-responsive Composites 413
12.4.2 Light-responsive Composites 414
12.5 Application of Mechanically Adaptive
Nanocomposites in Cortical Implants 415
12.6 Mechanically Adaptive Nanocomposites with
Other Functions 417
12.6.1 Healable Materials 417
12.6.2 Shape Memory 418
12.6.3 Actuators 420
12.7 Related Examples of Mechanically Adaptive
Materials 421
12.8 Summary and Outlook 422
References 423
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xviii Contents
Chapter 13 Bio-inspired Polymer Artificial Muscles 429

Sina Naficy, Geoffrey M. Spinks and Ray H. Baughman

13.2 Natural Muscle 431

13.3 Types of Polymer Artificial Muscles 434
13.3.1 Polymer Coil Muscles 436
13.3.2 Dielectric Elastomer Actuators (DEAs) 444
13.3.3 Bending Type Polymer Artificial Muscles 448
13.4 Bio-inspired Applications for Polymer Artificial
Muscles 452
13.5 Conclusions 454
References 455
Chapter 14 Materials for Tissue Engineering and 3D Cell Culture 460

Caitlin R. Langford and Neil R. Cameron

14.2 Electrospinning 461
14.3 Thermally Induced Phase Separation 466
14.4 Emulsion Templated Porous Polymers (PolyHIPEs) 471
14.5 Breath Figure Method 476
References 480
Chapter 15 Antimicrobial Polymers and Surfaces – Natural Mimics or

Surpassing Nature? 490
Christian Krumm and Joerg C. Tiller

15.2 Classification of Antimicrobial Polymers 492
15.2.1 Considerations on the Comparability of
Biological Testing of Antimicrobial
Polymers 493
15.2.2 Biocide-releasing Polymers 494
15.2.3 Polymeric Biocides 495
15.2.4 Biocidal Polymers 497
15.3 Antimicrobial Surfaces 509
15.4 Anti-fouling Polymers 511
References 514
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Contents xix
Chapter 16 Superwettability of Polymer Surfaces 523

Xi Yao, Jie Ju and Lei Jiang

16.2 Self-cleaning Polymer Surfaces 525

16.2.1 Polymer Surfaces in Air 525
16.2.2 Polymer Surfaces under Water 528
16.3 Special Adhesion 530
16.3.1 Cell-adhesion 530
16.3.2 Liquid-adhesion 532
16.3.3 Air-adhesion 532
16.4 Oil/water Separation 532
16.4.1 Oil/water Separation based on
Superhydrophobic Materials 533
16.4.2 Oil/water Separation based on
Superhydrophilic Materials 534
16.5 Liquid Collection and Transport 535
16.5.1 Spider-silk-inspired Fog Collection System 535
16.5.2 Cactus-inspired Fog Collection System 538
16.5.3 Water Strider Legs and Extended Systems 540
16.5.4 Water Transport on SLIPS and Organogels 543
16.6 Superwetting Polymers in Functional
Nanochannels and Nanopores 546
16.6.1 Superwetting Polymers in Nanochannels
to Control Ion Transport 546
16.6.2 Superwetting Polymers in Nanochannels
for Energy Conversion 549
16.7 Concluding Remarks 551
References 551
Chapter 17 Bio-mimetic Structural Colour using Biopolymers 555

Rox Middleton, Ullrich Steiner and Silvia Vignolini

17.2 Helicoidal Structures and their Optical Response 556
17.2.1 An Intuitive Explanation of the Optical
Effect 556
17.2.2 Mathematical Description 558
17.2.3 Examples 562
17.3 Helicoidal Structures in Nature 562
17.3.1 Cellulose-based Helicoidal Structures for
Structural Colour 564
17.3.2 Chitin-based Helicoidal Structures for
Structural Colour 566
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xx Contents
17.4 Liquid Crystals as Helicoidal Structures 568

17.5 Helicoidal Architectures in Biomimetic Photonics 570
17.5.1 Artificial Helicoidal Cellulose Films 571
17.5.2 Cellulose as a Template – Extending
Functionality 575
17.5.3 Sensors 576
17.5.4 Hydrogels and Cellulose Derivatives 576
17.5.5 Chitin 578
References 580
Subject Index 586

Published on 15 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782626664-00001
CHAPTER 1
Synthetic Aspects of Peptide–

and Protein–Polymer
Conjugates in the Post-click Era
MARIA MEIßLER, SEBASTIAN WIECZOREK,
NIELS TEN BRUMMELHUIS* AND HANS G. BÖRNER*
Laboratory for Organic Synthesis of Functional Systems, Department

of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2,
D-12489 Berlin, Germany
*Email: niels.ten.brummelhuis@hu-berlin.de; h.boerner@hu-berlin.de
1.1 Introduction
The synthesis of peptide– and protein–polymer conjugates offers the possi-
bility to integrate properties of biological macromolecules into synthetic
systems, thereby obtaining hybrid materials with unique functions.1–9
The synthetic polymers within these structures provide a versatile range
of properties,4 whereas the peptide or protein domain introduces highly
specific functions, ranging from enzymatic activity10 to specific interaction
capabilities or recognition,11 and to disease modifying activities
(Figure 1.1).12 The multidisciplinary field of creating bioconjugates gives
access to a variety of materials for application in materials science, bio-
technology, or pharmacology, where the bioconjugates act at the interface
between biology and synthetic materials.6–9

1
View Online
2 Chapter 1
Figure 1.1 Description of the versatile properties of a biomacromolecule (PDB: 1HGU)13

and a synthetic polymer. The combination of both structures into one
hybrid material offers a wide range of functions, which enables their
application in materials science, biotechnology, or pharmacology.1–9
First attempts to combine synthetic polymers with biomacromolecules

emerged in the early 1950s, when initial reports concerning the synthesis of
peptide–polymer conjugates were published by Jatzkewitz.14,15 About 20 years
later, Abuchowski, Davis, and coworkers described the attachment of a linear
poly(ethylene oxide) (PEO) to bovine serum albumin (BSA) and bovine liver
catalase.16,17 Particularly noteworthy was that the extensive modification of
these proteins with a synthetic polymer block did not inhibit the functionality
of the biological macromolecules while simultaneously reducing their im-
munogenicity and increasing blood circulation times.16,17 This widely used
strategy of incorporating PEO onto proteins or peptides with the objective
of improving the properties of biomacromolecules is termed ‘‘PEGylation’’,
referring to poly(ethylene glycol) or PEG.18 Due to polymer modification,
the stability of the resulting protein–polymer conjugates toward proteolytic
digestion and antibody interactions can often be decreased significantly.19,20
This enhancement in stability and solubility of the modified proteins rep-
resents an important improvement for in vivo applications, such as in
pharmaceutical research and the development of protein-based drugs.5,21
Ever since these pioneering works showed the potential of PEGylation, and
the combination of proteins or peptides with synthetic polymers in general,
many research groups have started to investigate peptide–polymer conjugates
as a new class of hybrid materials.1,5,18,21
Controlled techniques to connect the building blocks from the synthetic
and the biological worlds are indispensable for the preparation of
View Online
Synthetic Aspects of Peptide– and Protein–Polymer Conjugates in the Post-click Era 3

22
well-defined peptide– and protein–polymer conjugates. In 2001, Sharpless,
Kolb, and Finn introduced the concept of ‘‘click’’ chemistry, which describes
the most important criteria to attach two molecules to each other in a highly
selective and efficient manner.23 A reaction defined under this term has to
result in very high yields and easily isolable products, while generating only
non-hazardous side products that can easily be removed afterwards. Besides
the copper(I)-catalyzed cycloaddition (CuAAC) between alkynes and azides
described independently by Sharpless24 and Meldal,25 a wide range of
ligation strategies have since been found to fulfill the criteria of ‘‘click’’
reactions.23 Of these (in addition to CuAAC), the strain-promoted azide–
alkyne cycloaddition (SPAAC), Staudinger ligation, oxime formation,
Michael-type additions and other thiol-ene reactions are among the most
frequently cited representatives.26 The advent of various highly efficient
reactions has also proved advantageous for the preparation of peptide– and
protein–polymer conjugates; these synthetic strategies offer versatile
opportunities in the fields of materials science and biomedicine, where they
are being applied widely.26,27
In conjunction with the emerging ‘‘click’’ reactions in this century, sci-
entists have focused on the development of innovative strategies to design
more complex structures.6–9 The rich world of chemical ligation tools, which
have traditionally been used for protein modification, has extensively been
reviewed.1,4,5,10,12,28–32 This book chapter will mainly provide an overview of
the last decade’s progress over the preparation of functional bioconjugates,
also referred to as ‘‘post-click’’ methods.8 After a brief survey of various well-
established and widely used ligation techniques, we will focus on novel types
of chemistry as well as chemoenzymatic approaches and biotransformations
to create functional bioconjugates using enzymatically catalyzed reactions.
Finally, recent advances in this field will be described to provide insight into
potential future directions for the preparation of functional peptide– and
protein–polymer conjugates.
1.2 General Concepts for Bioconjugation

The most widely used method to prepare bioconjugates is based on a con-
vergent strategy – the so-called ‘‘grafting to’’ approach (Figure 1.2a).22,29 In
order to obtain well-defined structures, the peptide or protein, which con-
tains one or more reactive groups, is reacted with a polymer bearing com-
plementary reactive groups. The ‘‘grafting to’’ approach is applied most since
the independent synthesis and characterization of both components prior to
the ligation enables a facile structural and chemical analysis of the resulting
bioconjugates. Some of the disadvantages compared to other methods (vide
infra) are that two macromolecules need to be coupled, which is often slow
and/or inefficient due to the hindered accessibility of the reactive groups.
Additionally, such reactions can only be performed using relatively low
concentrations, and separation of the starting materials from the product is
often difficult. Therefore, highly efficient coupling reactions are required.28
View Online
4 Chapter 1
Figure 1.2 Synthetic strategies for synthesis of peptide– and protein–polymer conju-
gates (PDB: 3V03).34 The ‘‘grafting to’’ approach, where a polymer bearing
reactive groups is attached to a biomacromolecule (a); the ‘‘grafting from’’
strategy, where an initiating moiety is introduced to a peptide or protein,
enabling the polymerization from the specific site of the biomacro-
molecule (b); and the ‘‘grafting through’’ method, which exploits the
(co)polymerization of macromonomers containing a peptide or protein
domain (c).7
However, the synthesis and characterization of both components in-

dependently enables a facilitated structural and chemical analysis of the
resulting bioconjugates.
A range of different reactions for convergent ligation have been developed
so far.6–9 On the one hand, different amino acid side chains within the
peptides and proteins can be addressed using various ligation strategies.
Thiol groups of cysteine residues and primary amine groups at the
N–terminus or on lysine side chains are the most common sites for attach-
ment to polymers.33 On the other hand, more appropriate functional groups
can be introduced to improve the coupling efficiency and to enable site-
specific conjugation, e.g. phosphine or azide residues for Staudinger ligation,
aldehydes for oxime formation, or strained cyclooctynes for SPAAC.26
In the ‘‘grafting from’’ approach a moiety with the ability to initiate
or mediate polymerization is introduced in the biomacromolecule
(Figure 1.2b).22,31,35–40 This divergent strategy often relies on controlled
radical polymerization techniques, since these are highly tolerant to the
presence of functional groups which are frequently found in peptides and
proteins.31 Furthermore, protein denaturation, resulting in loss of function,
is unacceptable, making polymerization in aqueous media under mild
View Online
conditions desirable. Controlled radical polymerization techniques such

as atom transfer radical polymerization (ATRP),36,41 reversible addition-
fragmentation chain transfer (RAFT),42–45 or nitroxide-mediated polymer-
ization (NMP),46 are compatible with aqueous solvents and avoid adverse
side reactions.
One of the first examples following the ‘‘grafting from’’ approach was
the preparation of a protein–polymer conjugate composed of BSA and
poly(N–isopropylacrylamide) (PNIPAM).47 The modification of the protein
with a maleimide-functionalized chain transfer agent (CTA) enabled
the RAFT polymerization of NIPAM, resulting in a thermoresponsive
bioconjugate.
The ‘‘grafting through’’ approach implies the incorporation of a poly-
merizable group into the biomacromolecule, allowing for copolymerization
with synthetic monomer units. This results in a bioconjugate product with a
comb-like structure, where a certain number of the polymer side chains
contain peptide or protein moieties (Figure 1.2c).22,31 Compared to the
concept of ‘‘grafting to’’, the strategy avoids side reactions and low coupling
efficiencies due to the attachment of peptides or proteins to monomers
before the polymerization process, at which stage purification is easier.31 By
comparison, the ‘‘grafting through’’ method is less modular than the
‘‘grafting to’’ strategy. In the ‘‘grafting to’’ approach, theoretically, any peptide
containing a suitable reactive group can be coupled to a well-defined pre-
cursor polymer to produce different products with, e.g., different degrees of
functionalization or with different peptides, etc. For the ‘‘grafting through’’
method, optimized polymerization conditions have to be found for each new
monomer and the average length will not be precisely reproducible.
The first application using the ‘‘grafting through’’ approach was the syn-
thesis of a thermoresponsive antibody–polymer conjugate described in
1987.48 A more recent example deals with the incorporation of fibrinogen in
a protein–polymer conjugate. Pluronic F127 was end-group-modified with an
acrylate moiety on one side, while the other was coupled to fibrinogen.49
The acrylate moiety was used for UV-activated free-radical polymerization.
Since many of the fibrinogen molecules were functionalized with multiple
Pluronic F127 moieties, polymerization triggered cross-linking, yielding a
thermoresponsive hydrogel.
Beyond these three main concepts, the inverse bioconjugation approach
offers another strategy to connect peptides or proteins with synthetic poly-
mers. Using a solid support, which is preloaded with a polymer block, the
biological molecule can be assembled in a stepwise fashion through solid-
phase synthesis. Mutter and coworkers first showed the attachment of PEO
to a poly(styrene) resin via a benzyl ether linker.50 This concept was finally
developed further by Bayer and Rapp leading to a commercially available
PAP resin, which is widely applied in solid-phase peptide synthesis.51 In
a similar approach, Lutz, Börner, and coworkers demonstrated the prepar-
ation of cleavable and non-cleavable soluble polystyrene supports by ATRP
for the liquid-phase synthesis of peptide–polymer conjugates.52
View Online
6 Chapter 1
1.3 Chemical Synthesis of Peptide– and Protein–

Polymer Conjugates
The number of applications for peptide– and protein–polymer conjugates is
constantly increasing. While classical synthetic reactions take advantage of

naturally occurring amino acid side chains for coupling reactions with
polymers, many innovative strategies are based on methods to attach syn-
thetic polymers selectively, and with high efficiency, to improve yields and
purity of the conjugation products.6–9 The following sections will give an
overview of the most commonly used techniques, sorted according to the
different reactive functional groups. Novel bioconjugation approaches will
be discussed in detail.
1.3.1 Coupling with Amines

Exploiting primary amines is attractive since amines are among the most
reactive functional groups present in peptides and proteins, and are found
in relatively high abundance at the surface of globular proteins.53 Various
ligation strategies to attach polymers to them have been established.31 Most
common is the modification of a synthetic macromolecule with an activated
carboxylic acid group in order to address the peptide or protein N–terminus
or a lysine side chain, if available.33 Typically, polymeric derivatives of
N–hydroxysuccinimide (NHS)54 are used (Figure 1.3a). This reaction allows for
the coupling of lysine residues in an almost quantitative manner, resulting
in a stable amide linkage. For example, the NHS end group modification
of PNIPAM derived from RAFT polymerization enabled the ligation to a
cyclic peptide.55 The resulting thermoresponsive peptide–polymer conjugate
possesses the ability to form channels within phospholipid membranes.
However, the applicability of NHS-esters is limited due to their suscepti-
bility to nucleophilic addition reactions, resulting in hydrolytic instability in
Figure 1.3 Bioconjugation of synthetic polymers by targeting primary amines

within biomacromolecules resulting in amide bond formation at the
N–terminus or the lysine side chain: (a) N–hydroxysuccinimidyl (NHS)
activated ester,54 (b) pentafluorophenyl-activated ester.56
View Online

Figure 1.4 Diethyl squarate end-group functionalized PEO used for the squaric
ester-mediated PEGylation of BSA58 (PDB: 3V03).34
aqueous media. To avoid low coupling efficiencies, the integration of pen-

tafluorophenyl-activated carboxylic acid groups into synthetic polymers and
their behavior in bioconjugation have been investigated (Figure 1.3b).56 An
appropriate modification of a collagen-like peptide was used for the site-
selective conjugation of a stimulus-responsive poly(diethylene methyl ether
methacrylate).57 Coupling of two such bioconjugates resulted in the for-
mation of triblock copolymer which showed triple-helix formation and
thermoresponsiveness.
Frey and coworkers presented the squaric acid mediated PEGylation of
proteins.58 Amine bearing PEO was end-group functionalized with squaric
acid diethyl ester, using one of the reactive groups in the squaric acid
moiety. The other was still available for the efficient functionalization of
lysine residues in proteins like BSA (Figure 1.4).
Despite the efficient coupling reactions available for the functionalization
of amines, their high abundance in peptides or proteins prevents selective
bioconjugate formation, since a single-site modification is often not pos-
sible. Furthermore, the multiple and unspecific conjugation of synthetic
polymers can result in loss of function and reduced enzymatic activity, and
can potentially even induce toxicity.33 For these reasons, it is often desirable
to apply more specific and directed coupling strategies, e.g. using reactions
in which one of the components is rarely found in peptides and proteins.
1.3.2 Coupling with Thiols

Cysteine residues are frequently addressed in biological molecules because
they are rather rare in peptides and proteins. If accessible thiols are present,
they can therefore allow for a site-specific polymer ligation, yielding
well-defined bioconjugates.59 Classically, thioether formation by Michael
View Online
8 Chapter 1
Figure 1.5 Bioconjugation of synthetic polymers by targeting thiols (cysteine resi-

dues): (a) Michael addition between thiols and maleimides,60 and (b)
thiol-ene reaction.62
addition of the thiol to a suitable electron-deficient alkene in the polymer

blocks is used. The Michael addition reaction between thiols and mal-
eimides constitutes the most well-known reaction, and is widely used to
prepare bioconjugates of peptides and proteins (Figure 1.5a).60
For example, the aminolysis of the chain transfer agent end group of
PNIPAM prepared by RAFT exposed thiol end groups, which can be reacted
with 1,8-bis-maleimidodiethyleneglycol. Ligation of bovine serum albumin
and ovalbumin to the maleimide-terminated polymer yielded protein–
polymer conjugates.61
Due to its electrophilic properties, maleimides are susceptible to the
addition of other nucleophiles besides thiols, such as primary amines.
Under physiological conditions, the reaction between a thiol group and a
maleimide proceeds more rapidly than with an amine, as is desired.63
However, slight changes in the pH to alkaline conditions can already re-
sult in a shift towards more side reactions with e.g. lysine side chains or the
N–terminus of the biomacromolecule.64 Beyond that, higher pH-values can
even effect the hydrolysis of the maleimide group to an open maleamic acid
form, which is no longer reactive towards thiols.65 After the formation of the
thiol-maleimide product, the ring-opening can effect the stabilization of the
resulting conjugate, which prevents a possible thiol exchange.66
These limitations can be avoided by using the free-radical addition of a
thiol to a double bond (Figure 1.5b), which is referred to as a thiol-ene re-
action62 and can also proceed as a ‘‘click’’ reaction.23 Initially, radical for-
mation can be induced by heat or light.67,68 The generated thiyl radical
enters the addition reaction with the vinyl group, resulting in a carbon-
centered radical. Subsequently, the desired thioether product is generated by
hydrogen abstraction from other thiols, yielding further thiyl radicals. To
achieve bioconjugates for in vivo applications, a photoinitiator is often
added to generate radicals, since this procedure allows for the use of mild,
relatively long wavelength (4300 nm) UV irradiation and can be performed in
aqueous media under physiologic conditions.69
The post-polymerization modification of poly(pentafluorophenyl meth-
acrylate) with allylamine to couple a thiol-terminated peptide domain was
View Online

Figure 1.6 Disulfide reduction and subsequent bridging via addition-elimination

with a dibromomaleimide to obtain a bioconjugate composed of salmon
calcitonin (PDB: 2GLH)74 and PEO.72,73
presented by Klok and coworkers.70 The polymeric side chain modification

was used later on for the synthesis of polyvalent peptide–polymer conjugates
exhibiting HIV-1 inhibitory properties with antiviral activity depending on
the bioconjugate length.71
In proteins, cysteine residues are not always readily accessible, since they
are often involved in disulfide bridges within the complex three-dimensional
biomacromolecular structures. Therefore, only a small number of cysteine
residues can be used for bioconjugation reactions.59 The ligation of polymer
bound dibromomaleimides takes advantage of this circumstance, as it
allows for the functionalization of disulfide moieties. Haddleton and
coworkers demonstrated the applicability of this reaction for bioconjugation
of salmon calcitonin (sCT).72,73
Therein, the Mitsunobu reaction was adapted in order to end-group func-
tionalize a linear PEO with a dibromomaleimide moiety. This modified poly-
mer was conjugated to sCT after reduction by tris(2-carboxyethyl)phosphine
(TCEP) under mild reaction conditions, yielding disulfide rebridging conju-
gation (Figure 1.6).72 The efficient ligation reaction of dibromomaleimides
with cysteine side chains or disulfide bridges, respectively, enables a site
specific protein modification in a fast and equimolar manner. Despite open-
ing a disulfide bridge in a protein, the native structure might be less signifi-
cantly affected since a covalent bridge between both cysteine residues is
reinstalled (cf. Figure 1.6). Furthermore, O’Reilly and coworkers used di-
bromomaleimide monomers for the preparation of profluorescent polymers,
which were capable of chemico-fluorescent responsiveness mediated by thiol
conjugation, resulting in a switch of the fluorescence emission.75
1.3.3 Chemical Ligation by Oxime/Hydrazone Formation

For certain applications, the ligation reactions need to be performed in vivo
without interfering with the given biological system. This severely limits the
number of reactions that can be used due to, for example, the chemically very
complex environment in biological systems and the large variety of functional
groups present in a living system. In this context, the term ‘‘bioorthogonal’’
reaction was first coined by Bertozzi in 200376 in order to summarize efficient
non-toxic chemical reactions that can be used in such systems, e.g.
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Bio inspired polymers Nico Bruns

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The Chemistry of Bio-based Polymers Johannes Karl Fink

Innovations in Bio Inspired Computing and Applications

Towards Bio-based Flame Retardant Polymers 1st Edition

Bio-Inspired Algorithms in PID Controller Optimization

Human Modelling for Bio Inspired Robotics Mechanical

Bio-Inspired Fault-Tolerant Algorithms for Network-on-

Bio-inspired Algorithms for Data Streaming and

A New Bio inspired Optimization Algorithm Based on the

RSC Polymer Chemistry Series

Technology, Hong Kong, China

Titles in the Series:

19: Nitroxide Mediated Polymerization: From Fundamentals to Applications

22: Bio-inspired Polymers

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RSC Polymer Chemistry Series No. 22

synthetic and natural polymers. The diﬀerent aspects of bio-inspiration in

inspired polymers would be a worthwhile endeavour. This book aims to

materials exposed to mechanical stress. Inspired by the stiﬀness change of the

reviewed by Naficy, Spinks, and Baughman in the chapter on bio-inspired

Nico Bruns and Andreas Kilbinger

Chapter 1 Synthetic Aspects of Peptide– and Protein–Polymer

RSC Polymer Chemistry Series No. 22

2.2 Synthesis of Glycopolymers 32

Chapter 3 Synthesis of Non-natural Polymers with Controlled

3.4.3 Successive Radical Insertion 91

Chapter 4 Single-chain Nanoparticles 107

4.1 Introduction 107

Chapter 5 Polymeric Tubular Structures 141

5.1 Introduction – Bio-inspiration 141

5.2.3Other Helical Polymers 159

5.3.1 Block Copolymer Self-assembly 171

Chapter 6 Bio-inspired Polymer Membranes 221

6.1 Introduction 221

Chapter 7 Polymeric Ionic Liquids with Micelle-like Topologies and

7.1 Introduction 259

Chapter 8 Biological and Bio-inspired Heterogeneous Composites:

8.1 Introduction 286

Chapter 9 Translating Mussel Adhesion: Four Uncertainties about

9.1 Introduction 305

9.2 Are Interfacial Films Cleared Away? 306

9.5 Is Interfacial Redox the Same as Seawater Redox? 316

Chapter 10 Mussel Adhesive-inspired Polymers 322

10.1 Introduction 322

Chapter 11 Self-reporting Polymeric Materials with Mechanochromic

11.1 Introduction 354

11.3 Mechano-responsiveness 358

11.3.2 Mechano-responsiveness at the Molecular

Chapter 12 Mechanically Adaptive Nanocomposites Inspired by Sea

12.1 Introduction 402

Chapter 13 Bio-inspired Polymer Artificial Muscles 429

13.1 Introduction 429

13.2 Natural Muscle 431

Chapter 14 Materials for Tissue Engineering and 3D Cell Culture 460