Multivalency

Jurriaan Huskens, PhD (1968) is full professor of "Molecular Nanofabrication" at the University of Twente, Netherlands. Present research interests encompass: supramolecular chemistry at interfaces, supramolecular materials, multivalency, nanofabrication, and solar fuels.
 
Leonard J. Prins, PhD is a professor in Organic Chemistry at the University of Padova, Italy. His current research interests include network reactivity in complex chemical systems and the origin of cooperativity in multivalent catalysts.
 
Rainer Haag, PhD joined the Freie Universität Berlin as full Professor of Organic and Macromolecular Chemistry in 2004. Currently he serves on the Editorial Board of the Angewandte Chemistry and is the spokesperson of the collaborative research center 765 on "multivalency."
 
Bart Jan Ravoo, PhD (1970) is full professor at the Westfälische Wilhelms-Universität Münster, Germany, where he is in charge of the "Synthesis of Nanoscale Systems" group. Since 2016 he is co-director of the Center for Soft Nanoscience (SoN). His main research interest are soft materials made by self-assembly, functional nanoparticles, and self-assembled monolayers.

Connects fundamental knowledge of multivalent interactions with current practice and state-of-the-art applications
 
Multivalency is a widespread phenomenon, with applications spanning supramolecular chemistry, materials chemistry, pharmaceutical chemistry and biochemistry. This advanced textbook provides students and junior scientists with an excellent introduction to the fundamentals of multivalent interactions, whilst expanding the knowledge of experienced researchers in the field.
 
Multivalency: Concepts, Research & Applications is divided into three parts. Part one provides background knowledge on various aspects of multivalency and cooperativity and presents practical methods for their study. Fundamental aspects such as thermodynamics, kinetics and the principle of effective molarity are described, and characterisation methods, experimental methodologies and data treatment methods are also discussed. Parts two and three provide an overview of current systems in which multivalency plays an important role in chemistry and biology, with a focus on the design rules, underlying chemistry and the fundamental principles of multivalency. The systems covered range from chemical/materials-based ones such as dendrimers and sensors, to biological systems including cell recognition and protein binding. Examples and case studies from biochemistry/bioorganic chemistry as well as synthetic systems feature throughout the book.
* Introduces students and young scientists to the field of multivalent interactions and assists experienced researchers utilising the methodologies in their work
* Features examples and case studies from biochemistry/bioorganic chemistry, as well as synthetic systems throughout the book
* Edited by leading experts in the field with contributions from established scientists
 
Multivalency: Concepts, Research & Applications is recommended for graduate students and junior scientists in supramolecular chemistry and related fields, looking for an introduction to multivalent interactions. It is also highly useful to experienced academics and scientists in industry working on research relating to multivalent and cooperative systems in supramolecular chemistry, organic chemistry, pharmaceutical chemistry, chemical biology, biochemistry, materials science and nanotechnology.

List of Contributors xi
 
Foreword xv
 
Preface xvii
 
Part I General Introduction to Multivalent Interactions 1
 
1 Additivity of Energy Contributions in Multivalent Complexes 3
Hans?-Jorg Schneider
 
1.1 Introduction 3
 
1.2 Additivity of Single Interactions - Examples 3
 
1.3 Limitations of Additivity 7
 
1.3.1 Free Energy Values DeltaG Instead of Enthalpic and Entropic Values DeltaH, TDeltaS 7
 
1.3.2 Mismatch as Limitation of Additivity 9
 
1.3.3 Medium Effects as Limiting Factor 12
 
1.3.4 Strain and Induced Fit 12
 
1.4 Cooperativity 13
 
1.5 Allostery 14
 
1.6 Conclusions 17
 
References 18
 
2 Models and Methods in Multivalent Systems 23
Jurriaan Huskens
 
2.1 Introduction 23
 
2.1.1 General Introduction 23
 
2.1.2 Multivalent versus Cooperative Interactions 24
 
2.2 Numerical Data Analysis 25
 
2.2.1 Model Simulations Using a Spreadsheet Approach 26
 
2.2.2 Setting Up and Assessing Titrations 30
 
2.2.3 Using Spreadsheet Simulations to Fit Experimental Data to a Model 36
 
2.3 Models for Multivalent Systems 41
 
2.3.1 The Simplest Multivalent System: A 1:1 Complex with Two Interaction Sites 41
 
2.3.2 Multivalent Binding at Surfaces 46
 
2.4 Special Multivalent Systems 53
 
2.4.1 Increasing the Valency of Interfacial Assemblies: Dendrimers, Oligomers, and Polymers 53
 
2.4.2 Heterotropic Interactions 58
 
2.4.3 Kinetics and Dynamics 63
 
2.5 Conclusions 68
 
Acknowledgments 68
 
References 68
 
3 Design Principles for Super Selectivity using Multivalent Interactions 75
Tine Curk, Jure Dobnikar, and Daan Frenkel
 
3.1 Introduction 75
 
3.1.1 Background: Ultra?-sensitive Response 75
 
3.2 Super Selectivity: An Emergent Property of Multivalency 78
 
3.3 Multivalent Polymer Adsorption 84
 
3.4 Which Systems are Super Selective? 86
 
3.4.1 Rigid Geometry Interactions 86
 
3.4.2 Disordered Multivalency 87
 
3.5 Design Principles for Super?-Selective Targeting 90
 
3.6 Summary: It is interesting, but is it useful? 93
 
Appendix 3.A: What Is Effective Molarity? 95
 
Acknowledgements 98
 
References 98
 
4 Multivalency in Biosystems 103
Jens Dernedde
 
4.1 Introduction 103
 
4.2 Cell-Cell Adhesion 104
 
4.2.1 Homotypic Interactions, Cadherins Keep Cells Together 105
 
4.2.2 Selectins, Heterotypic Cell Adhesion to Fight Infections 106
 
4.2.3 Bacterial Adhesion by FimH 108
 
4.3 Phase Transition, Multivalent Intracellular Assemblies 109
 
4.4 Multivalency in the Fluid Phase, Pathogen Opsonization 111
 
4.5 Conclusion 113
 
Acknowledgment 113
 
References 114
 
Part II Multivalent Systems in Chemistry 121
 
5 Multivalency in Cyclodextrin/Polymer Systems 123
Akihito Hashidzume and Akira Harada
 
5.1 Introduction 123
 
5.2 General Perspectives of Multivalency in Cyclodextrin/Polymer Systems 125
 
5.3 Typical Examples of Multivalency in Cyclodextrin/Polymer Systems 126
 
5.3.1 Formation of Polymer Aggregates from Cyclodextrin?-Polymers and Guest?-Polymers 126
 
5.3.2 Selectivity of Interaction Enhanced by Multivalency 127
 
5.3.3 Self?-Healable Hydrogels Based on Multivalency 134
 
5.4 Summary and Outlook 136
 
Acknowledgments 136
 
References 138
 
6 Cucurbit[n-uril?-Mediated Multiple Interactions 143
Zehuan Huang and Xi Zhang
 
6.1 Introduction to Cucurbit

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