Intramolecular conflict : conformation and self-assembly of architecturally complex macromolecules in solution

The solution behavior of linear polymer chains is well understood, having been the subject of intense study throughout the previous century. As plastics have become ubiquitous in everyday life, polymer science has grown into a major field of study. The conformation of a polymer in solution depends on the molecular architecture and its interactions with the surroundings. Developments in synthetic techniques have led to the creation of precision-tailored polymeric materials with varied topologies and functionalities. In order to design materials with the desired properties, it is imperative to understand the relationships between polymer architecture and their conformation and behavior. To meet that need, this thesis investigates the conformation and self-assembly of three architecturally complex macromolecular systems with rich and varied behaviors driven by the resolution of intramolecular conflicts. First we describe the development of a robust and facile synthetic approach to reproducible bottlebrush polymers (Chapter 2). The method was used to produce homologous series of bottlebrush polymers with polynorbornene backbones, which revealed the effect of side-chain and backbone length on the overall conformation in both good and theta solvent conditions (Chapter 3). The side-chain conformation was obtained from a series of SANS experiments and determined to be indistinguishable from the behavior of free linear polymer chains. Using deuterium-labeled bottlebrushes, we were able for the first time to directly observe the backbone conformation of a bottlebrush polymer which showed self-avoiding walk behavior. Secondly, a series of SANS experiments was conducted on a homologous series of Side Group Liquid Crystalline Polymers (SGLCPs) in a perdeuterated small molecule liquid crystal (5CB). Monodomain, aligned, dilute samples of SGLCP-b-PS block copolymers were seen to self-assemble into complex micellar structures with mutually orthogonally oriented anisotropies at different length scales (Chapter 4). Finally, we present the results from the first scattering experiments on a set of fuel-soluble, associating telechelic polymers. We observed the formation of supramolecular aggregates in dilute (≤0.5wt%) solutions of telechelic polymers and determined that the choice of solvent has a significant effect on the strength of association and the size of the supramolecules (Chapter 5). A method was developed for the direct estimation of supramolecular aggregation number from SANS data. The insight into structure-property relationships obtained from this work will enable the more targeted development of these molecular architectures for their respective applications.

Synthetic, kinetic and mechanistic studies in early transition metal systems. I. α- and β-hydrogen elimination reactions in derivatives of permethyltitanocene, -zirconocene, and -hafnocene. II. The reactions of aluminum alkyls with derivatives of permethylniobocene

The thermal decomposition of Cp*Ti(CH_3)_2 (Cp*≡ ƞ^5-C_5Me_5) toluene solution follows cleanly first-order kinetics and produces a single titanium product Cp*(C_5Me_4CH_2)Ti(CH_3) concurrent with the evolution of one equivalent of methane. Labeling studies using Cp*_2Ti- (CD_3)_2 and (Cp*-d_(15))_2Ti(CH_3)_2 show the decomposition to be intramolecular and the methane to be produced by the coupling of a methyl group with a hydrogen from the other TiCH_3 group. Activation parameters, ΔH^‡ and ΔS^‡, and kinetic deuterium isotope effects have been measured. The alternative decomposition pathways of α-hydrogen abstraction and a-hydrogen elimination, both leading to a titanium-methylidene intermediate, are discussed.

The insertion of unactivated acetylenes into the metal-hydride bonds of Cp*_2MH_2 (M = Zr, Hf) proceeds rapidly at low temperature to form monoand/ or bisinsertion products, dependent upon the steric bulk of the acetylene substituents. Cp*_2M(H)(C(Me)=CHMe), Cp*_2M(H)(CH=CHCMe_3), Cp*_2M(H)-(CH=CHPh), Cp*_2M(CH=CHPh)_2, Cp*_2M(CH=CHCH_3)_2 and Cp*_2Zr- (CH=CHCH_2CH_3)_2 have been isolated and characterized. To extend the study of unsaturated-carbon ligands, Cp*_2M(C≡CCH_3)_2 have been prepared by treating Cp*_2MCl_2 with LiC≡CCH_3. The reactivity of many of these complexes with carbon monoxide and dihydrogen is surveyed. The mono(2- butenyl) complexes Cp*_2M(H)(C(Me)=CHMe) rearrange at room temperature, forming the crotyl-hydride species Cp*_2M(H)(ƞ^3-C_4H_7). The bis(propenyl) and bis(l-butenyl) zirconium complexes Cp*_2Zr(CH=CHR)_2 (R = CH_3, CH_2CH_3) also rearrange, forming zirconacyclopentenes. Labeling studies, reaction chemistry, and kinetic measurements, including deuterium isotope effects, demonstrate that the unusual 6-hydrogen elimination from an sp^2-hybridized carbon is the first step in these latter rearrangements but is not observed in the former. Details of these mechanisms and the differences in reactivity of the zirconium and hafnium complexes are discussed.

The reactions of hydride- and alkyl-carbonyl derivatives of permethylniobocene with equimolar amounts of trialkylaluminum reagents occur rapidly producing the carbonyl adducts Cp*_2Nb(R)(COAlR'_3) (R = H, CH_3, CH_2CH_3, CH_2CH_2Ph, C(Me)=CHMe; R' = Me, Et). The hydride adduct Cp*_2NbH_3•AlEt_3 has also been formed. In solution, each of these compounds exists in equilibrium with the uncomplexed species. The formation constants for Cp*_2Nb(H)(COA1R'_R) have been measured. They indicate the steric bulk of the Cp* ligands plays a deciding factor in the isolation of the first example of an aluminum Lewis acid bound to a carbonyl-oxygen in preference to a metalhydride. Reactions of Cp*_2Nb(H)CO with other Lewis acids and of the one:one adducts with H_2, CO and C_2H_4 are also discussed.

Cp*_2Nb(H)(C_2H_4) also reacts with equimolar amounts of trialkylaluminum reagents, forming a one:one complex that ^1H NMR spectroscopy indicates contains a Nb-CH_2CH_2-Al bridge. This adduct also exists in equilibrium with the uncomplexed species in solution. The formation constant for Cp*_2N+/b(H)(CH_2CH_2ĀlEt_3) has been measured. Reactions of Cp*_2Nb(H)(C_2H_4) with other Lewis acids and the reactions of Cp*_2N+b(H)- (CH_2CH_2ĀlEt_3) with CO and C_2H_4 are described, as are the reactions of Cp_*2Nb(H)(CH_2=CHR) (R = Me, Ph), Cp*_2Nb(H)(CH_3C≡CCH_3) and Cp*_2Ti-(C_2H_4) with AlEt_3.

On the solution of first excursion problems by simulation with applications to probabilistic seismic performance assessment

In a probabilistic assessment of the performance of structures subjected to uncertain environmental loads such as earthquakes, an important problem is to determine the probability that the structural response exceeds some specified limits within a given duration of interest. This problem is known as the first excursion problem, and it has been a challenging problem in the theory of stochastic dynamics and reliability analysis. In spite of the enormous amount of attention the problem has received, there is no procedure available for its general solution, especially for engineering problems of interest where the complexity of the system is large and the failure probability is small.

The application of simulation methods to solving the first excursion problem is investigated in this dissertation, with the objective of assessing the probabilistic performance of structures subjected to uncertain earthquake excitations modeled by stochastic processes. From a simulation perspective, the major difficulty in the first excursion problem comes from the large number of uncertain parameters often encountered in the stochastic description of the excitation. Existing simulation tools are examined, with special regard to their applicability in problems with a large number of uncertain parameters. Two efficient simulation methods are developed to solve the first excursion problem. The first method is developed specifically for linear dynamical systems, and it is found to be extremely efficient compared to existing techniques. The second method is more robust to the type of problem, and it is applicable to general dynamical systems. It is efficient for estimating small failure probabilities because the computational effort grows at a much slower rate with decreasing failure probability than standard Monte Carlo simulation. The simulation methods are applied to assess the probabilistic performance of structures subjected to uncertain earthquake excitation. Failure analysis is also carried out using the samples generated during simulation, which provide insight into the probable scenarios that will occur given that a structure fails.

Imaging and tracking single fluorescent nanobeads in solution

In single-particle tracking (SPT), fluorescence video microscopy is used to record the motion images of single particle or single molecule. Here, by using a total-internal-reflection microscope equipped with an argon ion laser and a charge-coupled device (CCD) camera with high-speed and high-sensitivity, video images of single nanobeads in solutions were obtained. From the trajectories, the diffusion coefficient of individual nanobead was determined by the mean square displacements as a function of time. The sizes of nanobeads were calculated by Stokes-Einstein equation, and the results were compared with the actual values.

Evaluation of two alternative carbon capture and storage technologies

4 p.

Alternative trajectories for decarbonizing urban transportation

4 p.

IPCC WGII Fifth Assessment Report (AR5): Expanding the solution space for adaptation

6 p.

Precipitation of nanocrystals in glasses by electron irradiation: An alternative path to form glass ceramics?

This letter demonstrates an alternative method to form gallium silicate glass ceramics using high-energy electron irradiation. Compared with glass ceramics obtained from the conventional thermal treatment method, the distribution and crystal sizes of the precipitated Ga2O3 nanoparticles are the same. An advantage of this method is that the spatial distribution of the precipitated nanoparticles can be easily controlled. However, optically active dopants Ni2+ ions do not participate in the precipitation during electron irradiation. (c) 2007 American Institute of Physics.

Evaluation of Two Alternative Carbon Capture and Storage Technologies: A Stochastic Model

30 p.

Optimización técnico-económica del sistema de refrigeración de una planta termosolar de colectores cilindroparabólicos.

[ES]Este proyecto comprende la realización de un estudio de optimización mediante análisis técnico-económico del sistema de refrigeración de una planta termosolar de colectores cilindroparabólicos. Se incluye una exposición descriptiva de la planta y el sistema de agua de circulación y condensado. El estudio técnico-económico se apoya en la realización de los balances térmicos variando los parámetros dimensionantes relativos a dicho sistema mediante el software Thermoflex, partiendo del valor de estos que proporciona la potencia nominal de la planta. Se calcula la producción eléctrica diferencial e inversión diferencial de cada alternativa de dimensionamiento del sistema, calculándose la rentabilidad económica para cada caso. Se refleja también el cambio legislativo sucedido en cuanto al precio de venta de la electricidad y como afecta éste en la rentabilidad de cada caso. De esta forma se seleccionará la solución óptima y se extraerán las conclusiones.

The lakes of Michoacan (Mexico): A brief history and alternative point of view

This article is intended to open a discussion about the historical development of lakes Zirahuen, Patzcuaro and Cuitzeo in the state of Michoacan, and the postulated relationships between lake ecology and evolution. Dr Fernando De Buen was the first man dedicated to limnology in Mexico who came to the country in the 1930s. He was adviser at the Estacion Limnologica de Patzcuaro and wrote outstanding papers dealing with Mexican lakes. The lakes of Michoacan probably formed in the late Pliocene or Holocene, and were part of a tributary to the Lerma River, which became isolated by successive volanic barriers to form lake basins. Lake Zirahuen is a warm monomictic waterbody with unique water dynamics amongst the Michoacan lakes. Because it is relatively deep (max depth 40m), seasonal patterns of alternating circulation and thermal stratification develop in the lake, a feature not shared by the other two polymictic shallow lakes, Patzcuaro and Cuitzeo.

Instability of solution of phase retrieval in direct diffraction phase-contrast imaging with partially coherent X-ray source

The theoretical model of direct diffraction phase-contrast imaging with partially coherent x-ray source is expressed by an operator of multiple integral. It is presented that the integral operator is linear. The problem of its phase retrieval is described by solving an operator equation of multiple integral. It is demonstrated that the solution of the phase retrieval is unstable. The numerical simulation is performed and the result validates that the solution of the phase retrieval is unstable.