16 10 Supramolecular Polymers, Based on the Host–Guest Chemistry of Pillarenes 10.1 General Aspects 10.2 Host–Guest Complexation Between Pillarenes and Linear Polymers 10.3 Supramolecular Polymers, Derived from Pillarene‐based Host–Guest Interactions 10.4 Hyperbranched and Cross‐linked Assemblies 10.5 Supramolecular Assemblies, Based on Amphiphilic Pillar[5]arenes 10.6 Concluding Remarks References
17 11 Supramolecular Polymers, Formed by Orthogonal Non‐covalent Interactions* 11.1 Introduction 11.2 Orthogonal Combinations of Supramolecular Interactions Involving Metal‐to‐Ligand Coordination 11.3 Orthogonal Combinations of Supramolecular Interactions Involving H-Bonding 11.4 Miscellaneous Orthogonal Combinations of Supramolecular Interactions 11.5 Biomimetic Orthogonal Self‐Assembly: Protein Recognition 11.6 Concluding Remarks References
18 12 Characterization of Supramolecular Polymers 12.1 Introduction 12.2 Estimation of the Molar Mass from the Theories of Supramolecular Polymer Science 12.3 Size‐Exclusion Chromatography 12.4 Viscometry 12.5 Light Scattering 12.6 Vapor Pressure Osmometry 12.7 Analytical Ultracentrifugation 12.8 NMR Spectroscopy 12.9 Mass Spectrometry 12.10 Microscopy Imaging 12.11 Small/Wide‐Angle X‐Ray Scattering 12.12 X‐Ray Crystallography 12.13 Small‐Angle Neutron Scattering 12.14 Asymmetric Flow Field‐Flow Fractionation 12.15 Taylor Dispersion Analysis 12.16 They Are Very Complex Structures but Totally Timely … References
19 Index
List of Tables
2 Chapter 4Table 4.1 Overview over the metallo‐supramolecular block copolymers, based on terpyridine bis‐complexes.
3 Chapter 12Table 12.1 Stability constants and binding enthalpies of various [M(tpy)2]2+ complexes. Source: Holyer et al. [37], Dobrawa et al. [38].
List of Illustrations
1 Chapter 1Figure 1.1 Schematic representation of a polymer based on non‐covalent interactions.Figure 1.2 Schematic representation of the different types of supramolecular polymerization. Source: Winter et al. [39]. © 2012 Elsevier B.V.Figure 1.3 Representation of the theoretical DP as a function of the association constant (Ka in M−1) for a typical supramolecular polymerization according to an isodesmic model at two different concentrations. Source: Brunsveld et al. [27]. © 2001 American Chemical Society.Figure 1.4 Schematic representation of the three main mechanisms known for the supramolecular polymerization processes: (a) isodesmic, (b) ring‐chain mediated, and (c) cooperative supramolecular polymerization. Source: Winter et al. [39]. © 2012 Elsevier B.V. Figure 1.5 Schematic representation of the IDP in which the intermolecular equilibrium constant (K) is independent of the length of the assembly (the mechanism is shown for a bifunctional monomer of the Ia‐type, see also Figure 1.2). Source: Winter et al. [39]. © 2012 Elsevier B.V. Figure 1.6 (a) Schematic drawing of an energy diagram for an IDP (i: size of the oligomer, ΔG0: free energy in arbitrary units). (b) Evolution of the number‐ and weight‐averaged DP (<DP>N and <DP>W) and the dispersity (Đ) as a function of equilibrium constant and total concentration of monomer (K·ct). Source: de Greef et al. [26]. © 2009 American Chemical Society. Figure 1.7 Illustration of the characteristic properties of a temperature‐dependent IDP according to van der Schoot's model: (a) fraction of polymerized material (φ) vs. the dimensionless temperature T/Tm; (b) <DP>N vs. T/Tm. In both plots, the curves obtained for different enthalpies are shown (ΔHp = −30, −40, and −50 kJ mol−1, respectively). Source: van der Schoot et al. [57]. © 2005 Taylor & Francis. Figure 1.8 Illustration of the characteristic properties of a temperature‐dependent IDP according to the “free association” model: (a) fraction of polymerized monomers (φ) vs. T/Tm (assuming fully flexible polymer chains and a cubic lattice); (b) heat capacity at constant volume (CV) vs. T/Tm. In both plots, the curves