A comprehensive investigation on the formation dynamics and energetics of adlayer formation at the at the solution/solid interface has been performed using scanning tunneling microscopy (STM) with a custom solution flow cell design that offers new insight into the self-assembly process. Understanding the formation kinetics and thermodynamics of self-assembled monolayers (SAM) provides insight into the delicate balance of intermolecular forces on the molecular scale. We herein investigate the growth, dynamics, and stability of a model non-covalent self-assembler -- Co(II) octaethylporphyrin at the solution/solution interface on the HOPG and Au(111) surfaces. Real-time imaging of the nucleation and growth of the self-assembled layer was captured and studied by in-situ STM, and further explored using computational methods. A custom STM solution flow cell was designed and implemented to allow for in-situ monitoring of self-assembly at very low concentrations and with volatile solvents. Flow studies at low concentration provide insight into early-stage kinetics and structural formation of a SAM. It was found that the choice of organic solvent plays a dramatic role in the kinetics and structure of the SAM. These results, in turn, provide insight into the balance of the intermolecular forces driving the self-assembly. The role of the solvent was particularly strong in the case of 1,2,4-trichlorobenzene (TCB) on both HOPG and Au(111). Under TCB, a very stable rectangular structure is formed and stabilized by solvent-incorporation. A transition to a solvent free pseudo-hexagonal structure was only observed when extremely high concentrations of porphyrin were present in solution. Similarly, in the case of CoOEP adsorbed on Au(111) under toluene, a solvent-incorporated rectangular structure was observed that, like the TCB case, transitioned into a pseudo-hexagonal structure, but this transition occurred at much lower concentrations of porphyrin. Toluene co-adsorption was not observed on HOPG. When deposited from decane, a short-lived pseudo-rectangular structure was observed on Au(111) but not on HOPG. Only the pseudo-hexagonal structure was observed in the porphyrin adlayer when 1-phenyloctane were used as a solvent. On HOPG, mixed solvent competition was tested and gave further insight into the thermodynamic and kinetic roles that solvents play in self-assembly.

Molecular self-assembly at surfaces offers an efficient route to highly-ordered organic films that can be programmed for a variety of applications. However, the success of these materials depends on the ability to program intermolecular interactions that determine ordering at the surface. We study three systems: alkoxybenzonitriles (ABNs), tricarbazolo triazolophane macrocycles (tricarb), and triazolobenzene oligomers in flexible or macrocycle forms. For each model system, experiments employ a range of molecules in which aspects of molecular structure, especially symmetry and peripheral functionalization, are systematically varied to study the impact of intermolecular interactions on 2D supramolecular structure and to gain a deeper understanding of fundamental assembly mechanisms. The supramolecular assemblies are studied by scanning tunneling microscopy (STM) and molecular dynamic (MD) simulations at the solution/graphite interface. Variations in assembly conditions, including solvent, concentration, and temperature, also provide insight into assembly. ABNs exhibit competitive assembly with solvent that can be controlled with alkyl length. MD simulations on nanosecond timescales provide insight into ABN desorption, re-adsorption, and on-surface processes, and simulations reveal an asymmetry in desorption pathways. Triazolobenzene oligomers can be tuned between tight and loose packing of aromatic cores, the latter being separated by lamellar rows of alkanes. Flexible frameworks assemble more slowly compared to macrocycles due to a large conformational space, but self-assembly can be accelerated by co-solutes and STM perturbation. Tricarb exhibits polymorphism, and tricarb-tricarb hydrogen bonding can be controlled by varying the length and symmetry of peripheral alkanes into various structures including a high-density disordered packing. Variable solvent and peripheral group studies indicate that transitions from disordered to ordered structures involve a solution-mediated annealing pathway. MD simulations reveal solvent insertion between tricarb leading to disordered structures, but these can be sterically blocked by longer alkanes. The discoveries presented in this thesis provide insights into the dynamics and design rules of self-assembly.

Materials Nanoarchitectonics: From Integrated Molecular Systems to Advanced Devices provides the latest information on the design and molecular manipulation of self-organized hierarchically structured systems using tailor-made nanoscale materials as structural and functional units. The book is organized into three main sections that focus on molecular design of building blocks and hybrid materials, formation of nanostructures, and applications and devices. Bringing together emerging materials, synthetic aspects, nanostructure strategies, and applications, the book aims to support further progress, by offering different perspectives and a strong interdisciplinary approach to this rapidly growing area of innovation. This is an extremely valuable resource for researchers, advanced students, and scientists in industry, with an interest in nanoarchitectonics, nanostructures, and nanomaterials, or across the areas of nanotechnology, chemistry, surface science, polymer science, electrical engineering, physics, chemical engineering, and materials science. Offers a nanoarchitectonic perspective on emerging fields, such as metal-organic frameworks, porous polymer materials, or biomimetic nanostructures Discusses different approaches to utilizing "soft chemistry" as a source for hierarchically organized materials Offers an interdisciplinary approach to the design and construction of integrated chemical nano systems Discusses novel approaches towards the creation of complex multiscale architectures

This volume explores experimental and computational approaches to measuring the most widely studied protein assemblies, including condensed liquid phases, aggregates, and crystals. The chapters in this book are organized into three parts: Part One looks at the techniques used to measure protein-protein interactions and equilibrium protein phases in dilute and concentrated protein solutions; Part Two describes methods to measure kinetics of aggregation and to characterize the assembled state; and Part Three details several different computational approaches that are currently used to help researchers understand protein self-assembly. Written in the highly successful Methods in Molecular Biology series format, chapters include introductions to their respective topics, lists of the necessary materials and reagents, step-by-step, readily reproducible laboratory protocols, and tips on troubleshooting and avoiding known pitfalls. Thorough and cutting-edge, Protein Self-Assembly: Methods and Protocols is a valuable resource for researchers who are interested in learning more about this developing field.

The book contains six sections. The first section covers general articles; then there is a section concentrating on novel systems and applications. This is followed by one that deals with a range of applications of polymers, surfactants and liquid crystals. This is followed by a section on advances in fundamental understanding. Then there is one on biological systems, and finally there is a section on micelle and vesicle systems, with particular emphasis on dynamic aspects. The contributors, including Physicists, Chemists, Biologists and Chemical Engineers, variously chose to write review-type articles, summaries of their own recent work in the field and its relevance in the general concept of self-assembly, specific short papers related to their particular presentation, or their own thoughts concerning the future development of their particular interest area. All these aspects are addressed in the book. The book covers research at the forefront of the subject, and it is expected to be a very useful addition to the literature in this important field.

Self-assembly is a process in which a disordered system forms an organized structure without external direction. Examples include the formation of molecular crystals, lipid bilayers, and polymer brushes. This book reviews the fabrication and use of various self-assembled materials. In particular, the author pays special attention to self-assembled

Self-Assembly Processes at Interfaces: Multiscale Phenomena provides the conceptual and unifying view of adsorption, self-assembly, and grafting processes at solid–liquid and liquid–gas interfaces, also describing experimental methods where applicable. An invaluable resource for (post)-graduate students looking to bridge the gap between acquiring the field’s existing knowledge and the creation of new insights, the book recalls fundamental concepts, giving rigorous, but first-principle-based, calculations and exercises, and showing how these concepts have been used in recent research articles. Readers will find guidelines on how best to start research in the field of surface chemistry with biological macromolecules and molecules able to undergo self-assembly process at interfaces in the presence of a liquid, along with discussions on the very fundamental aspects and applications using concepts of biomimetic chemistry. By highlighting the interdisciplinary aspects of the field of self-assembly at interfaces, the book is an ideal resource for chemical engineers, chemists, physicists, and biologists. In addition, important equations are demonstrated on the basis of fundamental concepts, and overly complex mathematical developments are avoided. Presents an interdisciplinary work that is ideal for chemical engineers, chemists, physicists, and biologists Provides a unifying view of the field, from fundamentals, to methods and applications Includes concepts applicable at both solid–liquid and liquid–gas interfaces