Structures with well-defined architectures and tailored physical properties can be produced by supramolecular self-assembly of stimuli-sensitive polymeric inclusion complexes consisting of cyclodextrins. Recently, there has been significant interest in the use of double hydrophilic block copolymers to design novel supramolecular nanostructures as these polymers micellize under external stimuli, such as temperature, pH, and complexation. Cyclodextrins (CDs) have the ability to spontaneously complex with water-soluble guest molecules. The complexation of the polymer with CD induces self-assembly of the polymers. In this research, two systems were studied, a PEO-b-PNIPAM/α-CD system and a PPO-b-PMAA/β-CD system. First, the block copolymers were synthesized by ATRP to achieve well-defined monodisperse polymers. The chemical composition of the polymer was determined by NMR and gel permeation chromatography. Then, the microstructure and aggregation behaviour in aqueous solutions were studied using a combination of static and dynamic light scattering, and isothermal titration and differential scanning calorimetric techniques.

In recent years there has been much interest in the self-assembly of materials. Much of this research has been focused on the self-assembly of particles in solution (colloids), typically on the order of nanometres or micrometres in size. While it is easy to imagine the self-assembly of either irregularly shaped particles, or particles under an anisotropic potential, a novel class of colloids with engineerable isotropic interactions have achieved this aim. With the use of Self-Consistent Field Theory (SCFT), a mean-field model first developed for polymer melt systems, we develop a model for a system of particles of two species. One species experiences a long-range repulsive and short-range attractive interaction. The other is inert, acting as a solvent in which the former is suspended. Using this method, we calculated the equilibrium morphologies of the system for various parameters including the total volume fraction of one species relative to the other, the strengths and ranges of both the attractive and repulsive components of the interaction, and the relative particle sizes. In this way, we are able to loosely mimic the polymer-coated colloidal systems that are one of the current subjects of self-assembly research. By reducing our model to a simplified, isotropic interaction, we are able to show that the self-assembly of such systems is the result of the nature of the interaction and not any anisotropy within the model. We have also shown that the phase progressions of this system exhibit remarkable agreement with those of diblock copolymer melt systems despite significant differences in the molecules of these two systems.

Copper oxide with various morphologies, such as nanocubes, nanorods, and nanoribbons was synthesized from the H2O/C2H5OH solution of Cu(OAc)2/NEt3 with or without tetraoctylammonium bromide (TOAB) under mild conditions. In the system of Cu(OAc)2/NEt3 (0.05 mmole : 7.9 mmole) with 0.75 mmole of TOAB in H2O/C2H5OH (10 mL : 40 mL) solution, We found that nanocubes of CuO spontaneously self-assembled into nanorods and then nanosheets with the increasing of reaction time. Structural characterization of the CuO nanorods shows that the rod grows primarily along the [010] direction. Nanorods of CuO were also characterized by TEM, HR-TEM, SAED, and XRD.

Thesis (Ph.D)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Lyon, Louis; Committee Member: Breedveld, Victor; Committee Member: Bunz, Uwe; Committee Member: Collard, David; Committee Member: Srinivasarao, Mohan. Part of the SMARTech Electronic Thesis and Dissertation Collection.

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Structures with well-defined architectures and tailored physical properties can be produced by supramolecular self-assembly of stimuli-sensitive polymeric inclusion complexes consisting of cyclodextrins. Recently, there has been significant interest in the use of double hydrophilic block copolymers to design novel supramolecular nanostructures as these polymers micellize under external stimuli, such as temperature, pH, and complexation. Cyclodextrins (CDs) have the ability to spontaneously complex with water-soluble guest molecules. The complexation of the polymer with CD induces self-assembly of the polymers. In this research, two systems were studied, a PEO-b-PNIPAM/α-CD system and a PPO-b-PMAA/β-CD system. First, the block copolymers were synthesized by ATRP to achieve well-defined monodisperse polymers. The chemical composition of the polymer was determined by NMR and gel permeation chromatography. Then, the microstructure and aggregation behaviour in aqueous solutions were studied using a combination of static and dynamic light scattering, and isothermal titration and differential scanning calorimetric techniques.

In recent years there has been much interest in the self-assembly of materials. Much of this research has been focused on the self-assembly of particles in solution (colloids), typically on the order of nanometres or micrometres in size. While it is easy to imagine the self-assembly of either irregularly shaped particles, or particles under an anisotropic potential, a novel class of colloids with engineerable isotropic interactions have achieved this aim. With the use of Self-Consistent Field Theory (SCFT), a mean-field model first developed for polymer melt systems, we develop a model for a system of particles of two species. One species experiences a long-range repulsive and short-range attractive interaction. The other is inert, acting as a solvent in which the former is suspended. Using this method, we calculated the equilibrium morphologies of the system for various parameters including the total volume fraction of one species relative to the other, the strengths and ranges of both the attractive and repulsive components of the interaction, and the relative particle sizes. In this way, we are able to loosely mimic the polymer-coated colloidal systems that are one of the current subjects of self-assembly research. By reducing our model to a simplified, isotropic interaction, we are able to show that the self-assembly of such systems is the result of the nature of the interaction and not any anisotropy within the model. We have also shown that the phase progressions of this system exhibit remarkable agreement with those of diblock copolymer melt systems despite significant differences in the molecules of these two systems.

Controlling the assembly of amphiphilic molecules and micron-sized, disk-shaped particles at different length scales into ordered structures enables bottom-up organization which is of great interest to emerging technologies based on structured materials. The primary object of this work is the investigation of structure forming components - Zirconium phosphate (ZrP) discotic particles and polymersomes/ amphiphiles on their self-assembly and interactions. The effect of bilayer architecture of polymersomes on surface reactivity was investigated via fluorescent probing method. Established through complementary experiments, correlation between reactivity and molecule diffusivity in polymer-rich environment revealed the mechanism of reduced reactivity when tethered reactive groups are located deeper within the hydrophilic polymer layer. The phase diagram of charged nanoplatelets was constructed as a function of particle concentration, surface cation moiety, and ionic strength. Influence of surface cation on the isotropic-nematic transition was done by measuring the transition boundaries of discotic suspensions prepared by acid-base exfoliation reaction with a series of exfoliating agents. Furthermore, a novel phase transition was found, where platelet-platelet interaction was influenced synergistically by ionic strength and ion exchange. At low pH, directional inter-platelet attractions lead to the formation of low volume fraction colloidal gels. Alternative surface modification approaches, including biomolecule deposition and alkyl chain grafting were explored. Finally, self-assembly of platelets in emulsions and oil-water interface was examined. Surface modification was applied to link surface properties to stable emulsion-forming ability in mixed surfactant-particle system. Emulsion uniformity was achieved by microfluidic flow focusing method. Surface engineering and interaction control was demonstrated throughout this work to be viable approaches to the fundamental understanding of collective behaviors of individual building blocks.

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2008. / Title from title screen (site viewed Feb. 17, 2009). PDF text: xii, 219 p. : ill. (some col.) ; 5 Mb. UMI publication number: AAT 3328256. Includes bibliographical references. Also available in microfilm and microfiche formats.

Self-assembly is an astonishing phenomenon at the base of organized structures’ formation from disordered systems. It occurs in nature from atomic and molecular lengths to galactic distances. Nowadays self-assembly of colloidal solutions can be used to fabricate photonic crystals and metamaterials. This paper analyses the self-assembly and its effect on the electric conductivity of a colloid made up of carbon nanotubes and magnetite microparticles controlled by electrostatic potentials and magnetic fields. Alignment of the carbon nanotubes and creation of sparks and short-circuits are observed when the electrostatic field is applied. The magnetic field induces time-dependent and memory effects in the sample’s structure and conductivity. At constant potential, the electric current through the sample is reported to increase four times during and after the application of the magnetic fields.