Sequence-Controlled Polymers

Edited by a leading authority in the field, the first book on this important and emerging topic provides an overview of the latest trends in sequence-controlled polymers. Following a brief introduction, the book goes on to discuss various synthetic approaches to sequence-controlled polymers, including template polymerization, genetic engineering and solid-phase chemistry. Moreover, monomer sequence regulation in classical polymerization techniques such as step-growth polymerization, living ionic polymerizations and controlled radical polymerizations are explained, before concluding with a look at the future for sequence-controlled polymers. With its unique coverage of this interdisciplinary field, the text will prove invaluable to polymer and environmental chemists, as well as biochemists and bioengineers.

Auteur

Dr. Jean-François Lutz is CNRS research director, deputy director of the Institut Charles Sadron and head of the Precision Macromolecular Chemistry group in Strasbourg, France. He obtained his PhD from the University of Montpellier II, France, in 2000 and his habilitation degree from the University of Potsdam, Germany, in 2009. Before joining the CNRS, he subsequently was a post-doctoral fellow in the group of Krzysztof Matyjaszewski at Carnegie Mellon University, USA (2001-2003) and group leader Nanotechnology for Life Science at the Fraunhofer Institute for Applied Polymer Research in Potsdam (2003-2010).
He received in 2008 the prize of the polymer division of the French Chemical Society and he is listed since 2015 as an ISI Highly-Cited Researcher in Chemistry. He is also an European Research Council (ERC) laureate since 2010 through successive starting (StG 2010) and proofs of concept (PoC 2015) grants. His current research interests include the synthesis of sequence-controlled polymers, single-chain technologies and the preparation of information-containing macromolecules. He is author of more than 200 publications.

Contenu

1 Defining the Field of Sequence-Controlled Polymers 1
Jean-François Lutz

1.1 Introduction 1

1.2 Glossary 4

1.3 Sequence Regulation in Biopolymers 7

1.3.1 Nucleic Acids 7

1.3.2 Proteins 7

1.4 Bio-Inspired Sequence-Regulated Approaches 8

1.5 Sequence Regulation in Synthetic Macromolecules 9

1.5.1 Step-Growth Polymerizations 11

1.5.2 Chain-Growth Polymerizations 11

1.5.3 Multistep Growth Polymerizations 13

1.6 Characterization of SCPs 15

1.7 Impact in Materials Science 17

1.8 SomeWords About the Future 19

References 20

2 Kinetics and Thermodynamics of Sequence Regulation 27
Pierre Gaspard

2.1 Introduction 27

2.2 Generalities 28

2.2.1 Characterization of Sequences and Information 28

2.2.1.1 Single-Molecule Level of Description 28

2.2.1.2 Many-Molecule Level of Description 29

2.2.2 Precise or Loose Sequence Control during Copolymerization 30

2.2.3 Conditions for Growth or Dissolution 31

2.2.4 Kinetic Equations 32

2.3 Thermodynamics 33

2.3.1 Free Copolymerization 34

2.3.2 Template-Directed Copolymerization 35

2.3.3 Depolymerization 35

2.4 Kinetics Yielding Bernoulli Chains 36

2.5 Kinetics Yielding Markov Chains 36

2.6 Kinetics Yielding Non-Markovian Chains 40

2.7 Effect of Sequence Disorder on Ceiling and Floor Temperatures 40

2.8 Mechanical Power of Sequence Disorder 43

2.9 Template-Directed Copolymerization 44

2.10 Conclusion 45

Acknowledgments 45

References 46

3 Nucleic Acid-Templated Synthesis of Sequence-Defined Synthetic Polymers 49
Zhen Chen and David R. Liu

3.1 Introduction 49

3.2 Enzymatic Templated Syntheses of Non-Natural Nucleic Acids 50

3.2.1 Polymerase-Catalyzed Syntheses of Backbone-Modified Nucleic Acids 50

3.2.2 Polymerase-Catalyzed Syntheses of Nucleobase-Modified Nucleic Acids 52

3.2.3 Polymerase-Catalyzed Syntheses of Sugar-Modified Nucleic Acids 54

3.2.4 Ligase-Catalyzed Syntheses of Non-Natural Nucleic Acids 58

3.3 Ribosomal Synthesis of Non-Natural Peptides 59

3.4 Nonenzymatic Polymerization of Nucleic Acids 61

3.5 Nonenzymatic Polymerization of Non-Nucleic Acid Polymers 67

3.6 Conclusion and Outlook 71

Acknowledgments 73

References 73

4 Design of Sequence-Specific Polymers by Genetic Engineering 91
Davoud Mozhdehi, Kelli M. Luginbuhl, Stefan Roberts, and Ashutosh Chilkoti

4.1 Introduction 91

4.2 Design of Repetitive Protein Polymers 93

4.3 Methods for the Genetic Synthesis of Repetitive Protein Polymers 96

4.4 Expression of Repetitive Protein Polymers 100

4.5 Expanding the Chemical Repertoire of Protein Polymers 100

4.5.1 Chemo-Enzymatic Modification 101

4.5.2 Incorporation of Noncanonical Amino Acids 104

4.5.3 Post-TranslationalModifications 105

4.6 Summary and Outlook 107

References 108

5 Peptide Synthesis and Beyond the Use of Sequence-Defined Segments for Materials Science 117
Niels ten Brummelhuis, PatrickWilke, and Hans G. Börner

5.1 Introduction 117

5.2 The History of Solid-Phase-Supported Peptide Synthesis 118

5.3 Supports for the Chemical Synthesis of Peptides 120

5.4 Synthesis of PeptidePolymer Conjugates 122

5.5 Identification of Functional Sequences 125

5.5.1 Phage Display 125

5.5.2 Split-and-Mix Libraries and SPOT Synthesis 130

5.5.3 Applications of Libraries 134

5.5.4 Dynamic Covalent (Pseudo)Peptide Libraries 136

5.6 SequenceProperty Relationships 136

5.7 Translation of Sequence to Synthetic Precision Polymer Platforms 137

5.8 Conclusion 141 <p&gt...