Inspirados em reações catalisadas por enzimas a partir de micro-organismos encontrados em ambientes marinhos severos (psicrofílicos), em que a quantidade de oxigênio é restrita, observou-se que a Arthrobacter sp. CCT 7749 realizou diferentes transformações químicas mudando de condições reacionais anaeróbias para aeróbias. Dependendo da presença ou ausência de oxigênio, ambas desracemização de alcoóis ou redução de cetonas com seletividades enantiocomplementares foram realizadas pelo mesmo microorganismo. Estes conceitos foram aplicados tanto para desracemização quanto para redução enantiosseletiva de compostos contendo heteroátomos (silício, fósforo, estanho e boro). Visando a identificação molecular das enzimas responsáveis pelas reações de oxido-redução, buscou-se desenvolver uma metodologia de purificação enzimática usando diferentes técnicas. Inicialmente a lise celular da Arthrobacter sp. CCT 7749 empregando a liticase na presença de β-mercaptoetanol e usando ondas ultrassônicas produziu 28 mg/mL de proteínas. A purificação da oxidorredutase ocorreu através de colunas cromatográficas de troca iônica DEAE FF, seguida por ANX FF. O extrato protéico contendo a enzima parcialmente pura apresentou atividade específica de 4,23 U/mg na oxidação do (R,S)-1-(4-metilfenil)etanol à cetona correspondente. Através do uso das técnicas native-PAGE e zimografia detectou-se uma massa molecular da enzima de ≈240 kDa e que provavelmente se encontrava na forma hetero-hexamérica apresentando três subunidades em ~35 kDa e três em ~45 kDa. Observou-se que, surpreendentemente, a fração protéica parcialmente pura também foi capaz de reduzir a 4-metilacetofenona obtendo-se 17% do (S)-1-(4-metilfenil)etanol com excelente excesso enantiomérico >99%. / Inspired by enzyme-catalyzed reactions with microorganisms found in harsh marine environments (psychrophilic), in which the amount of oxygen is restrict, we have shown that Arthrobacter sp. CCT 7749 can perform different chemical transformations by switching from anaerobic to aerobic reaction conditions. Depending on the presence or absence of oxygen, either alcohol deracemization or ketone reduction with enantiocomplementary selectivities can be performed by the same microorganism. These concepts were applied for both deracemization and enantioselective reduction of heteroatom-containing molecules (silicon, phosphorus, tin and boron). Aiming Enzyme purification, different techniques were employed. Cell lysate of Arthrobacter sp. CCT 7749. Was prepared using lyticase and β-mercaptoethanol bu ultrasonication. Purification of this enzyme occurred through chromatographic columns of DEAE FF ion exchange, followed by ANX FF. The partially pure oxidoreductase presented specific activity of 4.23/mg in the oxidation (RS)-1-(4- methylphenyl)ethanol to the corresponding ketone. Native-PAGE and zymography have shown that the enzyme had ≈240 kDa molecular mass, probably in the form hetero-hexameric with 3 subunits ~35 kDa and three ~45 kDa. Surprisingly, the partially pure protein fraction was able to reduce the 4- methylacetophenone giving 17% of (S)-1-(4-methylphenyl)ethanol with excellent enantiomeric excess >99%.

<p>Syftet med den här uppsatsen är att visa hur vi kan förstå oss själva som kvinnor och män utan att betrakta kön som något naturligt och inneboende.</p><p>Kön är sociala och kulturella konstruktioner och vi lever i ett heteronormativt samhälle där könsskillnaden är genomgripande – vi utgår från heterosexualitet som den normala sexualiteten och vi skiljer på människor i kvinnor och män.</p><p>Genom att analysera mina egna minnen i ett minnesarbete undersöker jag mina erfarenheter av könsnormer. Hur har normer kring manlighet kommit till uttryck under min grundskoletid och hur har de påverkat mitt beteende och min självuppfattning?</p><p>Minnesarbetets fokus ligger på egna erfarenheter och reflektioner, men i förlängningen är syftet att bygga kollektiva identiteter där traditionella förhållanden betraktas på nya sätt.</p> / <p>The purpose of this thesis is to show how we can understand ourselves as women and men without regarding gender as being something self-evident and inherent.</p><p>Gender is a social and cultural construction and we live in a hetero normative society where differences in gender are allinclusive – we act on the assumption that heterosexuality is the normal state of sexuality and that humans are separated into men and women.</p><p>By analysing my own memories in a memory work, I explore my own experiences of gender standards. How was the standard of what is masculine manifested during my time in compulsory school? In addition, in what way has it influenced my own behaviour and self-perception?</p><p>The focus of the memory work lies in my own experiences and reflections; however, in the prolongation the purpose is to build collective identities where traditional contexts are perceived in new ways.</p>

Syftet med den här uppsatsen är att visa hur vi kan förstå oss själva som kvinnor och män utan att betrakta kön som något naturligt och inneboende. Kön är sociala och kulturella konstruktioner och vi lever i ett heteronormativt samhälle där könsskillnaden är genomgripande – vi utgår från heterosexualitet som den normala sexualiteten och vi skiljer på människor i kvinnor och män. Genom att analysera mina egna minnen i ett minnesarbete undersöker jag mina erfarenheter av könsnormer. Hur har normer kring manlighet kommit till uttryck under min grundskoletid och hur har de påverkat mitt beteende och min självuppfattning? Minnesarbetets fokus ligger på egna erfarenheter och reflektioner, men i förlängningen är syftet att bygga kollektiva identiteter där traditionella förhållanden betraktas på nya sätt. / The purpose of this thesis is to show how we can understand ourselves as women and men without regarding gender as being something self-evident and inherent. Gender is a social and cultural construction and we live in a hetero normative society where differences in gender are allinclusive – we act on the assumption that heterosexuality is the normal state of sexuality and that humans are separated into men and women. By analysing my own memories in a memory work, I explore my own experiences of gender standards. How was the standard of what is masculine manifested during my time in compulsory school? In addition, in what way has it influenced my own behaviour and self-perception? The focus of the memory work lies in my own experiences and reflections; however, in the prolongation the purpose is to build collective identities where traditional contexts are perceived in new ways.

Asymmetric catalysis is one of the most effective ways to control a target molecule’s stereochemistry. Through the development of a wide variety of chiral transition metal complexes, synthetic chemists are given the tools they need to synthesize the desired enantiomer of numerous compounds. This work focuses on exploiting the non-innocent ligand reactivity of metal bis-dithiolenes with multiple conjugated π systems in order to synthesize chiral ligands. Recent work has shown that platinum bis-dithiolene reacts with dienes stereoselectively to form a racemic mix of C2 -chiral thioether ligands. The present contribution will show approaches to synthesizing chiral dienes and organometallic complexes with potential applications for asymmetric allylic substitution reactions. Dienes with various chiral auxiliaries were reacted with platinum dithiolene and monitored through NMR spectroscopy. Attempts to synthesis palladium bis-dithiolene complexes, not previously seen in the literature were made, and the reaction of α-β unsaturated ketones with metal bis-dithiolenes was explored.

Asymmetric catalysis is one of the most effective ways to control a target molecule’s stereochemistry. Through the development of a wide variety of chiral transition metal complexes, synthetic chemists are given the tools they need to synthesize the desired enantiomer of numerous compounds. This work focuses on exploiting the non-innocent ligand reactivity of metal bis-dithiolenes with multiple conjugated π systems in order to synthesize chiral ligands. Recent work has shown that platinum bis-dithiolene reacts with dienes stereoselectively to form a racemic mix of C2 -chiral thioether ligands. The present contribution will show approaches to synthesizing chiral dienes and organometallic complexes with potential applications for asymmetric allylic substitution reactions. Dienes with various chiral auxiliaries were reacted with platinum dithiolene and monitored through NMR spectroscopy. Attempts to synthesis palladium bis-dithiolene complexes, not previously seen in the literature were made, and the reaction of α-β unsaturated ketones with metal bis-dithiolenes was explored.

This research reports a simple and novel method to fabricate microlens arrays by soft stamping the unexposed SU-8 photoresist. A SU-8 based stamp composed of micro-nozzle arrays with a reservoir structure on a glass substrate is first fabricated using a process of dosage control exposure. The unexposed SU-8 is then encapsulated in the cross-linked SU-8 shell and was used as the ¡§ink¡¨ for the stamping process. The proposed SU-8 microlens array is then formed by stamping the formed SU-8 structure on a bare glass substrate at a temperature higher than the glass transition temperature (Tg) of the unexposed SU-8 microlens array. Lenses with various radii of curvature can be formed by controlling the working temperature during the stamping process. In addition, this work also employed a simple electric static pulling scheme to manipulate the fabricated lenses profiles. Aspherical SU-8 microlens arrays with a wide range of tunable focal lengths were fabricated with this approach. Furthermore, we develop an advanced localize E-field control technique to fabricate microlenses with various focus length and microlenses with different tilt angle in a single lens array sheet. A novel grayscale mask fabrication technique is also proposed first. This low cost and rapid method is applied on stepwise and continuous tilt plane fabrication for produces a gradually changed E-field. Hetero axes and focus lengths microlenses are fabricated with this approach. In order to farther understand the real E-field distribution, a novel PCF based E-field sensor fabrication technique is also proposed. This technique also shows the potential on various PCF based devices fabrications.

Conjugated polymers are currently being used for a wide range of electronic applications. In this thesis, we studied two different synthetic approaches that lead to novel monomers and polymers that can be potentially used in electrochromic, or photovoltaic devices. The first approach described in this thesis is the utilization of olefin cross metathesis to create a family of dithienogermole (DTG) monomer derivatives in which synthetic control of the solubilizing side chains is achieved through an alkenyl building block. This alkenyl intermediate allows one to functionalize the DTG moiety though olefin cross metathesis to obtain a wide range of alkyl chain lengths and pendant functionalities on the polymer backbone. This work lead to the first example in the literature in which the synthesis of DTG moieties was not limited by the chain length of the solubilizing alkyl units. It provides a route that avoids the use of distillation for the purification the DTG monomer, allowing for the synthesis of a wide range of DTG derivatives that were previously unobtainable though the conventional synthetic methods. Finally, in this thesis we also describe the work of the use of direct (hetero)arylation polymerizations (DHAP) as a means of obtaining 3,4-propylenedioxythiophene-based conjugated polymers for use in electrochromic applications. This synthetic method offers a rapid route to achieving polymers in high yields with simplified purification procedures and low residual metal content, as determined by inductive coupled plasma-mass spectrometry (ICP-MS). The studied polymers possess comparable electrochromic properties to those previously reported by the Reynolds group, implying that their switching ability from a colored to a transmissive state is independent of the residual metallic impurities.

xvii, 159 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Experimental studies on mix-conducting hetero-ionic junctions of anionically (PA A ) and cationically (PA C ) functionalized polyacetylene ionomers, as well as each individual ionomer, in thin-film sandwich configurations are reported for the purpose of better understanding the interaction between ionic and electronic charge transports in mixed ionic-electronic conductor (MIEC) systems. The transport of ions in both individual ionomers as well as their hetero-ionic junction was investigated via small-amplitude AC impedance spectroscopy in the absence of significant interference from the electronic charge transport. Modeling of the impedance results reveal important information about the materials such as: ion conductivity, activation energy of ion conduction, ion hopping frequency, dielectric constant, interfacial capacitance, and estimates of effective ion density. Electrochemical injection of electronic charge carriers into PA A and PA C from gold electrodes was monitored to determine the applied potentials needed to drive hole and electron injection into each ionomer. It is found that for both ionomers, the onset voltages for unipolar and bipolar charge injection are similar, and holes can be injected at close to zero bias. The responses of the complete Au|PA A |PA C |Au hetero-ionic junction, as well as each constituent ionomer layer in Au|Ionomer|Au configuration, to various stepping biases were investigated through current-voltage and impedance measurements to study the origin of the asymmetric current-voltage response observed in the hetero-ionic junction. Analysis of the results reveal a working mechanism of a mix-conducting junction that is fundamentally different from that of a purely electronic pn junction. When illuminated with light, the Au|PA A |PA C |Au junction exhibits unidirectional photovoltage and photocurrent with the PA A side at higher potential, while the Au|PA A |Au and Au|PA C |Au samples exhibit symmetric photoresponses. The efficiency of photocurrent generation in the Au|PA A |PA C |Au junction was found to be strongly dependent on the direction of illumination and on the sample thickness. These observations can be explained by the difference in the mobility of holes and electrons and the existence of a built-in ionic space charge region at the PA A |PA C interface. A mechanism of photoresponse unique to MIEC junctions was proposed, and the magnitude of built-in potential was estimated. / Committee in charge: J David Cohen, Chairperson, Physics; Mark Lonergan, Advisor, Chemistry; Roger Haydock, Member, Physics; David Strom, Member, Physics; David Tyler, Outside Member, Chemistry

Orientador: Prof. Dr. Raphael Yokoingawa de Camargo / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Neurociência e Cognição, 2014.

Legal and bioethical principles. Separation, connection, integrationThis work is intended to establish relationships between legal and bioethical principles especially when bioethical principles complement and enrich legal ones in order to solve a specific case. Prior author’s contributions on bioethical principles as legal topics and legal bioethics creation in terms of a branch of bioethics which studies legal regulations as well as legal implementation and scope of bioethical problems are referred, making a critical reflection on growing and fruitful relationships between bioethics and law. An Interdisciplinary integration proposed in order to realize cooperation between both fields rejecting a separation or mere connection is suggested: «hetero integration», an integrating system produced by development of common and related principles. The article concludes stating that law structure is a «textual» subject not just involve on the writing of the law but capable to be analyzed from a social sense point of view, conferred to different manifestation of this discipline together with several social practices; a path warning by the need to broad theoretical-practical frameworks in order to move towards the interdisciplinarity taking into account bioethics from its foundations. / El objetivo de este trabajo es examinar la relación que existe entre los principios jurídicos y los principios bioéticos, en particular cuando los principios bioéticos enriquecen y complementan los principios jurídicos en la solución del caso concreto. Se acude a aportes anteriores del autor sobre los principios bioéticos como tópicos jurídicos y la creación de la bioética jurídica como rama de la bioética que estudia la regulación jurídica y las proyecciones y aplicaciones jurídicas de la problemática bioética y permite, como se procura aquí, una reflexión crítica sobre las crecientes y fecundas relaciones entre bioética y derecho. Desechada la separación y aun la mera vinculación, se propone una integración interdisciplinaria tendiente a instrumentar la cooperación entre ambos campos: heterointegración, producida por desarrollo de principios comunes y afines. Se concluye que el derecho constituye una materia textual, susceptible de ser analizada desde una perspectiva que no se agota en la mera escritura de la ley, sino que intenta captar la producción de sentido social que se inviste en las diversas manifestaciones de esta disciplina y que abarca distintas prácticas sociales, senda por la que se advierte la necesidad de ampliar los marcos teórico-prácticos para poder transitar la interdisciplinariedad y en la que no debe faltar la bioética desde sus principios