Bio- and Multifunctional Polymer Architectures

Brigitte Voit is head of the Institute of Macromolecular Chemistry at the Leibniz Institute of Polymer Research (IPF)Dresden, as well as professor of Organic Chemistry of Polymers at the University of Technology Dresden (TUD). In addition, she is heads the IPF Dresden as Managing Director and Chief Scientific Officer (Scientific Director).Rainer Haag is full professor in organic and macromolecular chemistry at the Freie Universität, Berlin.Dietmar Appelhans is a post-doctorial member in the working group of Professor Brigitte Voit at the Leibniz Institute of Polymer Research (IPF) Dresden and focuses on dendritic polymers.

• Preface xiAcknowledgments xiii1 Introduction 11.1 What makes Polymers so Interesting? 11.2 Macromolecular Engineering and Nanostructure Formation 41.3 Specific Needs in Bionanotechnology and Biomedicine 5Reference 62 Terminology 72.1 Polymer Architectures 72.2 Multifunctionality 112.3 Bioconjugates 122.4 Biocompatibility 122.5 Biodegradation 142.6 Bioactivity 142.7 Multivalency 152.8 Bionanotechnology 17References 183 Preparation Methods and Tools 193.1 General Aspects of Polymer Synthesis 193.1.1 Chain Growth Polymerizations 203.1.2 Step Growth Polymerizations 233.1.3 Modification of Polymers 253.2 Controlled Polymer Synthesis 253.2.1 Anionic Polymerization 263.2.2 Cationic Polymerization 303.2.3 Controlled Radical Polymerization 343.2.4 Metal‐Catalyzed Polymerization 373.2.5 Chain Growth Condensation Polymerization 413.3 Effective Polymer Analogous Reactions 433.4 Pegylation 473.5 Bioconjugation 513.5.1 Polynucleotide Conjugates 533.5.2 Protein Conjugates 553.5.3 Polysaccharide Conjugates 573.6 Enzymatic Polymer Synthesis 593.7 Solid Phase Synthesis and Biotechnological Approaches 633.7.1 Solid Phase Synthesis 633.7.2 Biotechnology Approaches in the Synthesis of Biopolymers 753.8 Hydrogels and Hydrogel Scaffolds 813.8.1 Hydrogels 813.8.2 Hydrogels as Scaffold Materials 843.9 Surface Modification and Film Preparation 923.9.1 Self‐Assembled Monolayers 933.9.2 Langmuir–Blodgett Films 953.9.3 Layer‐by‐Layer Deposition 963.9.4 Immobilization by Chemical Binding to Substrates 973.9.5 Low‐Pressure Plasma 993.9.6 Electron Beam Treatment 1013.10 Microengineering of Polymers and Polymeric Surfaces 102References 1074 Analytical Methods 1134.1 Molecular Structure and Molar Mass Determination of Polymers and Biohybrids 1134.1.1 Structural Characterization 1144.1.2 Determination of Molar Mass and Molar Mass Distribution 1324.2 Characterization of Aggregates and Assemblies 1374.2.1 Dynamic Light Scattering 1384.2.2 Pulsed Field Gradient and Electrophoretic Nuclear Magnetic Resonance 1394.2.3 Field‐Flow Fractionation 1424.2.4 UV–Vis Spectroscopy and Fluorescence Spectroscopy 1444.2.5 Electron Microscopy 1454.3 Characterization of Hydrogel Networks 1474.3.1 Network Structure of Hydrogels 1484.3.2 Swelling Degree 1484.3.3 Mechanical Properties 1504.3.4 Deriving Microscopic Network Parameters from Macroscopic Hydrogel Properties 1534.4 Surface Characterization 1544.4.1 X‐Ray Photoelectron Spectroscopy 1544.4.2 Contact Angle Measurements by Axisymmetric Drop Shape Analysis 1574.4.3 Electrokinetic Measurements 1584.4.4 Spectroscopic Ellipsometry 1594.4.5 Quartz Crystal Microbalance with Dissipation Monitoring 1604.4.6 Surface Plasmon Resonance 1614.4.7 Scanning Force Techniques 1624.4.8 Environmental Scanning Electron Microscopy 1644.5 Biophysical Characterization and Biocompatibility 1664.5.1 Biophysical Characterization 1674.5.2 Biocompatibility 175References 1835 Multifunctional Polymer Architectures 1875.1 Multifunctional (Block) Copolymers 1875.1.1 Multifunctionality through Copolymerization 1875.1.2 Multifunctionality by Polymer Analogous Reactions 1895.1.3 Spatially Defined Multifunctionality by Phase Separation and Self‐Assembly of Segmented Copolymers 1905.2 Dendritic Polymers 1965.2.1 Synthesis of Dendrimers and Hyperbranched Polymers 1985.2.2 Properties and Applications 2005.3 Glycopolymers 2035.3.1 Linear Glycopolymers 2055.3.2 Globular Glycomacromolecules 2075.4 Peptide‐Based Structures 2125.4.1 Hierarchical Self‐Assembly of Peptide Molecules 2145.4.2 General Design Concepts for Peptide‐Based Structural Materials 2155.4.3 Noncanonical Amino Acids in Peptide/Protein Engineering 2175.4.4 Peptide‐Based Materials Inspired by Naturally Occurring Structural Proteins 2175.4.5 Polypeptide Materials Based on other Naturally Occurring or De Novo Designed Self‐Assembling Domains such as Coiled Coils 2215.4.6 Self‐Assembly of Short Peptide Derivates and Peptide‐Based Amphiphilic Molecules 2225.5 Biohybrid Hydrogels 2245.5.1 Composition Basic Principles and Formation of Biohybrids 2255.5.2 Polynucleotide Biohybrids 2285.5.3 Polypeptide or Protein Biohybrids 2315.5.4 Polysaccharide Biohybrids 232References 2356 Functional Materials and Applied Systems 2416.1 Organic Nanoparticles and Aggregates for Drug and Gene Delivery 2416.1.1 Polymeric Micelles Polymersomes and Nanocapsules 2416.1.2 Polymeric Beads and Micro/Nanogels Based on Dendritic Structures 2546.1.3 Polyplexes for Gene Delivery 2636.2 Polymer Therapeutics and Targeting Approaches 2646.2.1 Current Status of Polymer Therapeutics 2646.2.2 Implications and Rationale for Effective Delivery Systems 2666.2.3 Cellular Uptake and Targeting 2676.3 Multi‐ and Polyvalent Polymeric Architectures 2716.3.1 Polyvalent Interactions on Biological Interfaces 2726.3.2 Prospects for Multivalent Drugs 2776.4 Bioresponsive Networks 2806.4.1 Active Principle 2806.4.2 Homeostatic Regulation of Blood Coagulation 2816.4.3 Insulin Release in Response to Glucose Concentration 2826.4.4 Urate‐Responsive Release of Urate Oxidase 2836.4.5 Cell‐Responsive Degradation of Hydrogel Networks 2846.5 Biofunctional Surfaces 2846.5.1 Concepts and Aims of Biofunctional Material Surfaces 2846.5.2 Biofunctional Surfaces for the Prevention of Biofouling 2876.5.3 Anticoagulant Coatings for Blood‐Contacting Devices 292References 295Abbreviations 303Index 309