THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Optical properties of chiral thin films and microparticles

In this work I study the optical properties of helical particles and chiral sculptured thin films, using computational modeling (discrete dipole approximation, Berreman calculus), and experimental techniques (glancing angle deposition, ellipsometry, scatterometry, and non-linear optical measurements). The first part of this work focuses on linear optics, namely light scattering from helical microparticles. I study the influence of structural parameters and orientation on the optical properties of particles: circular dichroism (CD) and optical rotation (OR), and show that as a consequence of random orientation, CD and OR can have the opposite sign, compared to that of the oriented particle, potentially resulting in ambiguity of measurement interpretation. Additionally, particles in random orientation scatter light with circular and elliptical polarization states, which implies that in order to study multiple scattering from randomly oriented chiral particles, the polarization state of light cannot be disregarded. To perform experiments and attempt to produce particles, a newly constructed multi stage thin film coating chamber is calibrated. It enables the simultaneous fabrication of multiple sculptured thin film coatings, each with different structure. With it I successfully produce helical thin film coatings with Ti and TiO_{2}. The second part of this work focuses on non-linear optics, with special emphasis on second-harmonic generation. The scientific literature shows extensive experimental and theoretical work on second harmonic generation from chiral thin films. Such films are expected to always show this non-linear effect, due to their lack of inversion symmetry. However no experimental studies report non-linear response of chiral sculptured thin films. In this work I grow films suitable for a second harmonic generation experiment, and report the first measurements of non-linear response.

Special employment centers in Castile and León 2007-2013: effects of the crisis in relation to these centers’ registered legal personalities

The aim of this paper is to carry out an economic and financial study of the Special Employment Centres in Castile and León based on a classification of these entities’ registered legal personalities in order to view how the economic crisis that began at the end of 2007 may have affected them. Various items from the Centres’ financial statements are analysed and the results are compared to those from the period 2007-2013 as to provide a broader perspective of their size, development, growth and behaviour. The following economic figures were used: total assets, turnover and revenue. The variable “employment” is compared with the subsidies received by the Centres, showing that the crisis does affect the Centres depending on their registered legal personalities. Associations and physical persons are the most affected personalities, to the point of possible extinction. An account reversal for the Centres is also included in this article, which measures the percentage of public aid received by the Centres that is returned to society.

Total Synthesis of the Antitumor Macrolides, (+)-Brefeldin A and 4‑Epi-Brefeldin A from D‑Glucose: Use of the Padwa Anionic Allenylsulfone [3+2]-Cycloadditive Elimination To Construct Trans-Configured Chiral Cyclopentane Systems

A new synthesis of (+)-brefeldin A is reported via Padwa allenylsulfone [3+2]-cycloadditive elimination. Cycloadduct 13 was initially elaborated into iodide
27, which, following treatment with Zn, gave aldehyde 28 whose C(9) stereocenter was epimerized. Further elaboration into enoate 38 and Julia−Kocienski olefination with 5 subsequently afforded 39, which was deprotected at C(1) and O(15). Yamaguchi macrolactonization of the seco-acid thereafter afforded a macrocycle that underwent O-desilylation and inversion at C(4) to give (+)-brefeldin A following deprotection

Comportamento de compra por impulso em shopping centers: pesquisa com consumidores de Brasília-DF e Natal-RN

ARAUJO, G. P. ; RAMOS, A. S. M. . Comportamento de Compra por Impulso em Shopping Centers: pesquisa com Consumidores de Brasília-DF e Natal-RN. REAd. Revista Eletrônica de Administração (Porto Alegre. Online) , v. 16, p. 343-364, 2010.

Estratégias competitivas genéricas nas empresas comerciais varejistas de shopping centers: um estudo a partir do modelo de Porter

Os shoppingcenters são grandes instituições repletas de empresas quecompetem entre si formas de como melhor satisfazer as necessidade dosclientes. Sendo assim, cada empresa utiliza-se de estratégias com o intuito deatingir a maior parcela de compradores possíveis sem comprometer suaexistência e sua vantagem competitiva. Este estudo está baseado na teoria dasestratégias competitivas genéricas de Porter (1980; 1985) o qual estabeleceem seu modelo que todas as empresas existentes no mercado possuam pelomenos uma das três abordagens estratégicas (diferenciação, liderança emcusto e enfoque). Desta forma, este trabalho identifica de que maneira estádistribuída as estratégia competitiva nas empresas de shoppingcenters deNatal/RN. Primeiramente buscou-se levantar a relação das estratégias destasempresas com a teoria proposta por Porter (1985) e sua alocação de acordocom os agrupamentos resultantes da combinação das estratégias. Nestemomento, foram aplicados questionários com 89 gerentes de lojas de shoppingcenters que resultou após análises estatísticas em cinco agrupamentos comabordagens válidas. Em seguida foram selecionadas as empresas quepossuíam maior afinidade com cada agrupamento e que melhor representavamos resultados dispostos em cinco clustersacerca da teoria proposta e nestaamostragem foi aplicada entrevista com os gerentes. Os resultados obtidos com as entrevistas validaram a análise dos dados encontrados nosquestionários anteriormente aplicados estando em conformidade com aproposta teoria. Identificou-se também duas modalidades de empresas queutilizavam simultaneamente mais de uma estratégia competitiva (meio-termo),sendo uma dentro e outra fora do modelo proposto pelo autor. Embora omodelo das estratégias competitivas genéricas tenha sido instituído comaspectos voltados as organizações industriais, os resultados obtidos nestetrabalho validaram a aplicação desta teoria em empresas comercias deshopping centers que vem se adequando para obter resultados financeirosmais satisfatórios e melhor posicionamento em relação à concorrência

Comunicação e imagem organizacional: um estudo de suas relações no comércio varejista de shopping centers

This study shows the results of an exploratory-descriptive research that aimed to identify the latent dimensions of communication, as well as finding relations between such dimensions and organizational image. The sample came to a total of 267 respondents, being 89 managers or owners and 178 salespeople of clothing and footwear stores that are situated in the main five shopping centers located in Natal, capital of Rio Grande do Norte. The collection of the data was made by the use of two structuralized and validated instruments, being the answers measured in the likert scale of 6 points. For the measurement of communication it was used the instrument developed by Downs and Hazen (2002), made up of 8 latent dimensions and 32 indicators. For the image it was used the model of Mael and Ashforth (1992) that contains 5 indicators. The analysis of the data was made through of the use of statistical techniques of factorial analysis and structural equations modeling. The results of the factorial analysis demonstrated communication as being formed by five latent dimensions. The modeling, on the other hand, demonstrated to exist positive relations between communication and organizational image, whose results revealed that the image is influenced by the communication with the supervisor, by the organizational integration and as being stronger explained by the vertical communication

Aspects of Chiral Symmetry Breaking in Lattice QCD

Thesis (Ph.D.)--University of Washington, 2016-08

Agreed-upon procedures reports on twelve agreements between the Bureau of Nutrition and Health Services of the Iowa Department of Education and child care centers for the period October 1, 2014 through September 30, 2015

Agreed-upon procedures reports on twelve agreements between the Bureau of Nutrition and Health Services of the Iowa Department of Education and child care centers for the period October 1, 2014 through September 30, 2015

The Addition of Allyltrimethylsilane to Cyclic N-Acyliminium Ions Derived from (S)-(+)-Mandelic Acid and Cyclohexyl-Based Chiral Auxiliaries

A adição de aliltrimetilsilano, promovida por TiCl4, a íons N-aciliminios cíclicos de 5- e 6-membros derivados do ácido (S)-(+)-mandélico, (1R,2S)-trans-2-fenil-1-cicloexanol e (1R,2S,5R)-8-fenilmentol ocorreu com baixas a moderadas razões diastereoisoméricas (1:1-6:1) e forneceu as respectivas amidas e carbamatos em bons rendimentos. A melhor diastereosseleção facial foi observada com o uso de (1R,2S,5R)-8-fenilmentol como auxiliar quiral. As amidas e carbamatos 2-substituídos foram convertidos nos alcalóides (S)- e (R)-propil pirrolidina e coniina com eficiente recuperação dos auxiliares quirais.