Describes the supramolecular properties of molecular assemblies that contain a solid phase, offering an integrated approach to measurement and addressibility. * Offers an integrated approach to measurement and addressibility. * Features case studies describing the major devices developed using this technology. * The prospects for the future of interfacial supramolecular assemblies are considered.

This dissertation describes the design, synthesis, assembly, and characterization of derivatives of 7-substituted-2,4,9-trithiaadamantane (Tripod) in regards to their supramolecular chemistries. Using the synthesized Tripod ligands, 2,4,9-trithiatricyclo[3.3.1.13 ̕ 7]decane-7-dodecylamide and 2,4,9-trithia-tricyclo[3.3.1.13 ̕ 7]decane-7-carboxylic acid 6-ferrocenoyl-hexanoate, the composition and interfacial properties of mixed monolayers were investigated via Polarization Modulation Infrared Reflectance Absorption Spectroscopy (PM-IRRAS), Water Contact Angle (WCA) measurements, and Cyclic Voltammetry (Cv). It was found that perturbations in the monolayers occurred, increasing the degrees of freedom for the attached functionalities with the possibility of forming defects such as tilt domain boundaries. This was verified when the increasing amount of the attached ferrocene end groups at the interface of monolayer and electrolyte solution resulted in a surface charge increase, which is in agreement with the notion that the electrolyte penetration into the monolayer increases. 2,4,9-Trithia-tricyclo[3.3.1.13 ̕ 7]decane-7-carboxylic acid 6-(2-bromo-2-methylpropionyloxy)-hexyl ester was designed and synthesized as a unique tridentate surface anchor for Atom Transfer Radical Polymerization (ATRP) surface-initiated polymerization. The prepared initiator proved effective in the polymerization of tertbutyl acrylate (t-BA) and dimethylaminoethylmethacrylate (DMAEMA) producing domains (40 [plus or minus] 5 nm diameter) extending ~90 nm from the surfaces of gold slides. 2,4,9-Trithia-tricyclo[3.3.1.13 ̕ 7]decane-7-octadecylamide was designed and synthesized as a ligand to cap gold nanoparticles. The ability of the ligand to intercalate the alkyl chains of lipids across the nanoparticle surface was investigated. Solid state thermometric analyses showed that a disruption and intercalation across the nanoparticle surface is marked by a lowering of the glass transition state (Tg) of the Tripod capping agent's alkyl chains. This notion was further confirmed via dispersion tests and 1H NMR showing a decrease in intensity of the peaks corresponding to the CH2 and CH3 of the alkyl chains. Based on the principles of supramolecular chemistry, polymer nanocapsules were also synthesized and surface modified for the study of guest molecule release. Testing nanocapsules with poly(carboxylate) and poly(ethylene)glycol functionalized surfaces, it was found that the polymer nanocapsules are more effective carriers for negatively charged small molecules in aqueous solutions at pH 7.4. The fast releasing rates of the guest molecules were mostly attributed to the small size of the polymer nanocapsules (~60-100 nm) and the low percent of cross-linker used in this study.

The objectives of the ARW were: - identifying areas and highlighting approaches by which large Supramolecular (SM) Assemblies can be synthesised - reviewing and combining methods to characterise and analyse such assemblies. The first part of the ARW is devoted to reviewing synthetic achievements in recent years for several families of SM compounds, and to bringing out principles for crystal structure design, including novel quantum mechanical methods. Synthesis pertains both to the chemical synthesis of components for SM assembly, and to the subsequent assembly process based on complementarity and non-covalent interactions. The elaboration of multiple recognition "algorithms" concurrently employed (for instance, 1t-1t and hydrogen bonds) has recently reached a high degree of sophistication in the sequence: Molecules -7 Supermolecule -7 SM array -7 Crystal or Conglomerate Novel Large Assemblies comprise synthetic entities with molecular weight as high as 15000, and hybrid SM assemblies between synthetic molecules and DNA. Further developments are foreseen at a higher level of organisation, such as between supermolecules or with electromagnetic fields in photochemical processes. Creation of 2D Assemblies is now a powerful tool for creation and study of SM interactions. Moreover, much is to be learned in going from 2D to 3D assemblies in crystal growth and other forms of organisation such as micelles or liquid crystals. On the other hand, crystal engineering based on Molecular Recognition in the Crystal State leads to novel 2D assemblies occurring within predesigned crystal structures (hydrophobic organic clays or nanoporous networks).

Supramolecular chemistry deals with the organisation of molecules into defined assemblies using non-covalent interactions, including weaker and reversible interactions such as hydrogen bonds, and metal-ligand interactions. The aspect of stereochemistry within such chemical architectures, and in particular chirality, is of special interest as it impacts on considerations of molecular recognition, the development of functional materials, the vexed question of homochirality, nanoscale effects of interactions at interfaces, biocatalysis and enzymatic catalysis, and applications in organic synthesis. Chirality in Supramolecular Assemblies addresses many of these aspects, presenting a broad overview of this important and rapidly developing interdisciplinary field. Topics covered include: Origins of molecular and topological chirality Homochirogenesis Chirality in crystallinity Host-guest behavior Chiral influences in functional materials Chirality in network solids and coordination solids Aspects of chirality at interfaces Chirality in organic assemblies Chirality related to biocatalysis and enzymes in organic synthesis. This book is a valuable reference for researchers in the molecular sciences, materials science and biological science working with chiral supramolecular systems. It provides summaries and special insights by acknowledged international experts in the various fields.

This book investigates the latest developments in supramolecular assembly systems for mimicking biological structures and functions. Consisting of 14 chapters, it covers various assembly systems, such as polysaccharides, peptides, proteins, biopolymers, natural materials and various hybrid systems. Further, it focuses on different types of supramolecular systems with particular functions or structures that are relevant to living systems. A number of modern techniques used to study the supramolecular systems, such as total internal reflection fluorescence microscopy (TIRFM) and two-photon confocal microscopy, are also introduced in detail. Unlike conventional books on supramolecular assemblies, this book highlights the functions of the assembly systems, particularly their biological applications. As such, it offers a valuable resource for experienced researchers, as well as graduate students working in the field of supramolecular chemistry and biomimetic systems.

Building on decades of “host-guest” research, recent years have seen a surge of activity in water-soluble supramolecular receptors for protein recognition and assembly. Progress has been particularly rich in the area of calixarenes, cucurbiturils and molecular tweezers. Emerging applications include controlled protein assembly in solution, crystal engineering, supramolecular control of catalysis (both in vitro and in vivo), as well as novel mechanisms of protein-interaction inhibition with relevance to amyloids and disease. One challenge at the interface of supramolecular chemistry and protein science is to increase interaction and collaboration between chemists and biochemists/structural biologists.This book addresses the exciting interface of supramolecular chemistry and protein science. Chapters cover supramolecular approaches to protein recognition, assembly and regulation. Principles outlined will highlight the opportunities that are readily accessible to collaborating chemists and biochemists, enriching the breadth and scope of this multidisciplinary field. Supramolecular Protein Chemistry will be of particular interest to graduate students and researchers working in supramolecular chemistry, protein science, self-assembly, biomaterials, biomedicine and biotechnology.