Thesis (Ph. D.)--University of Delaware, 2008. / Principal faculty advisor: Darrin J. Pochan, Dept. of Materials Science & Engineering. Includes bibliographical references.

Thesis (Ph. D.)--University of Massachusetts Amherst, 2009. / Includes bibliographical references (p. 98-113). Print copy also available.

Thesis (Ph. D.)--University of Massachusetts Amherst, 2009. / Includes bibliographical references (p. 101-110). Print copy also available.

Thesis (Ph.D.)--University of Delaware, 2007. / Principal faculty advisor: Dionisios G. Vlachos, Dept. of Chemical Engineering. Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 157-169).

Defect control in colloidal crystals is essential for these nanostructures to be effective as photonic bandgap (PBG) materials. We have used in-situ monitoring of the PBG of a colloidal crystal to study the structural changes during colloidal self assembly, with a focus on the formation of macroscopic defects such as cracks. These findings allow us to model the final stages of colloidal self assembly and explain the formation of growth defects in colloidal crystal. Our model suggests that cracks are intrinsic to self assembly growth methods. . However, by tuning the interaction potential between the colloids, it is possible to minimize the cracks in colloidal crystals. / Singapore-MIT Alliance (SMA)

Thesis (Ph. D.)--University of Chicago, Dept. of Physics, March 2001. / Includes bibliographical references. Also available on the Internet.

Supramolecular chemistry (chemistry beyond the molecule) is the study and synthesis of complex molecular architectures from simple subunits using non-covalent interactions. The types of non-covalent interactions that are used for the self-assembly of these complex molecular architectures include electrostatic interactions (e.g. ionic, halogen, and hydrogen bonding), π-effects, van der Waals interactions, metal coordination, and hydrophobic effects. While these interactions are often used in concert, some of the most successful and ubiquitous approaches for the design and construction of new host–guest architectures are the incorporation of hydrogen bonding motifs. A popular class of molecules capable of making strong, highly directional hydrogen bonds is barbiturates. Barbiturates have a well-known reputation as potent hypnotics, anticonvulsants, and anxiolytics but recent years have seen a renewed interest in these molecules due to their unique, symmetric acceptor-donor-acceptor hydrogen bonding motif. In addition, receptors with complementary hydrogen bonding motifs capable of binding barbiturates have also been reported, namely those based on the work of Hamilton et al. Collectively, barbiturates and their receptors have seen widespread use in a variety of applications including sensing, optoelectronics, catalysis, and the design of soft materials. The work presented in this dissertation describes the development of novel Hamilton receptors for supramolecular catalysis and barbiturate sensing, as well as the design of new synthetic barbiturates. Together this body of research aims to extend the utility of these types of host–guest systems as well as continue to develop and refine the supramolecular design principles that govern the binding interactions between barbiturates and a variety of Hamilton-type receptors. This dissertation includes both previously published/unpublished and co-authored material.

Nanostructuring has led to materials with novel and improved materials properties driving innovation across fields as varied as transportation, computing, energy and biotechnology. However, the benefits of nanostructured material have not widely been extended into large-scale, three-dimensional applications as deterministic pattern techniques have proven too expensive for devices outside of high value products. This thesis explores how colloidal self-assembly can be used to form macroscopic functional materials with short-range order for electronic, photonic and electrochemical applications at scale. DNA-functionalized nanoparticles are versatile models for exploring colloidal self-assembly due to the highly specific, tunable and thermally reversible binding between DNA strands. Gold nanoparticles coated with DNA were used to investigate the temperature-dependent interaction potentials and the gel formation in DNA-colloidal systems. The electronic conductivity and the plasmonic response of the DNA-gold gels were studied to explore their applicability as porous electrodes and SERS substrates, respectively. Subsequently, silica nanoparticles were assembled into nanostructures that preferentially scatter blue light using both DNA and polymer-colloid interactions. Finally, rod-sphere structures made from DNA-coated gold nanoparticles and viruses were explored, demonstrating how high-aspect ratio building blocks can create composite structures with increased porosity. The gold-virus gel structures inspired the design and assembly of a silicon-carbon nanotube composite material using covalent bonds that shows promise for high energy density anodes.

Two-dimensional (2D) colloidal materials and their assembly are of scientific significance and industrial importance. The development of 2D colloidal structures is a key stepping stone towards three-dimensional (3D) structures in relation to controlled chemical composition, morphology, assembly and so on. Nowadays, uniform colloidal structures with complexity in both shape and interactions have become a popular topic in fundamental colloid science and applications. Being motivated by this, in this thesis, micro-scale colloidal rods and self-assembled dipeptides have been studied experimentally at the air-water interface. Monolayers containing these colloidal materials were created in a Langmuir trough. Surface pressure measurements, microscopic observations and many other techniques were combined for the investigation. The aim of this work is to understand the phase behaviours in complex monolayers, including the phase transitions during compression, the flipping dynamics of micro-rods, the contribution of dipole-dipole interactions between magnetic rods, and the interfacial self-assembly process of dipeptide molecules. Iron oxide micro-rods (β-FeOOH @silica) with different aspect ratios have been synthesized to create the monolayers at an air-water interface. Microscopic observations reveal a sequence of phase transitions by compressing the monolayers. It has been proved that the aspect ratio of the rods plays an important role in the phase transitions, —short rods flip into a perpendicular position relative to the interface to relieve the compressional stress, while longer rods form multilayers under compression. Magnetic rods (Fe3O4) were converted from the synthesized FeOOH rods. They can be aligned in an external field, which further induces the reorganization at the interface. To study these magnetic rods, differential dynamic microscopy (DDM) was carried out to measure the magnetic moment. Their interfacial properties were investigated in an external field applied perpendicular and parallel to the interface, respectively. A magnetic field-induced flipping process has been observed, which proves the theoretical prediction. Besides rod-like particles, naphthalene dipeptides have been successfully trapped at the interface of a low pH subphase, self-assembling into a hydrogel film. The mechanism of interfacial self-assembly has been studied. Both FTIR spectra and AFM images are used to investigate the fibrous structures of the film. The film has elastic properties and buckles under compression. Moreover, dipeptide hydrogel induced by metal ions has been used to create a wet foam system, which owns the advantages of long-term stability (more than two weeks), low cost, and easy preparation.