Proton transfers at the air-water interface

Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes.

Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H₃O⁺(g), can protonate most (non-alkane) organic species, whereas H₃O⁺(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the ‘function’ of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided valuable information regarding the structure of aqueous interfaces, but structure alone is inadequate to decipher the function. By similar analogy, theoretical predictions based on classical molecular dynamics have remained limited in their scope.

Recently, we have adapted an analytical electrospray ionization mass spectrometer (ESIMS) for probing reactions at the gas-liquid interface in real time. This technique is direct, surface-specific,and provides unambiguous mass-to-charge ratios of interfacial species. With this innovation, we have been able to investigate the following:

1. How do anions mediate proton transfers at the air-water interface?

2. What is the basis for the negative surface potential at the air-water interface?

3. What is the mechanism for catalysis ‘on-water’?

In addition to our experiments with the ESIMS, we applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the molecular scale. Our results unambiguously demonstrated the role of electrostatic-reorganization of interfacial water during proton transfer events. With our experimental and theoretical results on the ‘superacidity’ of the surface of mildly acidic water, we also explored implications on atmospheric chemistry and green chemistry. Our most recent results explained the basis for the negative charge of the air-water interface and showed that the water-hydrophobe interface could serve as a site for enhanced autodissociation of water compared to the condensed phase.

Reflection and refraction of light at the interface of a uniaxial bicrystal

This paper deals with a theoretical analysis of the reflection and refraction of light at the interface of a bicrystal by use of Maxwell's equations. For a general case, the formulas of Snell's Law and the four Fresnel coefficients for the reflection and refraction of extraordinary light at the interface of a uniaxial bicrystal are derived for the first time, as well as the Brewster angle value. The condition for total reflection is presented and the electromagnetic fields distributions at both sides of a bicrystal are presented when total reflection occurs.

Investigation of the influence of the aberration induced by a plane interface on STED microscopy

The structure of the inhibition patterns is important to the stimulated emission depletion (STED) microscopy. Usually, Laguerre-Gaussian (LG) beam and the central zero-intensity patterns created by inserting phase masks in Gaussian beams are used as the erase beam in STED microscopy. Aberration is generated when focusing beams through an interface between the media of the mismatched refractive indices. By use of the vectorial integral, the effects of such aberration on the shape of depletion patterns and the size of fluorescence emission spot in the STED microscopy are studied. Results are presented as a comparison between the aberration-free case and the aberrated cases. (C) 2009 Optical Society of America

A quase conversação na comentosfera dos j-blogs: um estudo das interações na interface de comentários de quatro blogs jornalísticos institucionais

Este trabalho se situa na fronteira entre as áreas de Comunicação Social e Linguística e é voltado à investigação das interações ocorridas nos espaços dedicados à publicação de comentários de leitores em quatro blogs jornalísticos institucionais: Blog do Noblat, Blog MiriamLeitão.com, Blog do Reinaldo Azevedo e Blog do Josias de Souza. Com ele, pretende-se definir como cada leitor utiliza seus comentários para se relacionar com o jornalista autor do blog (o blogueiro), com outros leitores que também publicam suas opiniões (os leitores-comentaristas) e com o tópico tratado no texto (postagem) escrito pelo blogueiro. Além disso, considerando que autores da área de Comunicação Social discutem os blogs como um dispositivo amplamente conversacional, o propósito desta pesquisa é também esclarecer, à luz dos princípios da Análise da Conversação, se efetivamente ocorre uma conversação entre os participantes no ambiente de troca de mensagens dos blogs. Para a realização do estudo, foi compilado um corpus de 400 comentários cujo conteúdo demonstra a visão crítica de leitores dos blogs acima citados acerca de um mesmo tema: o apagão ocorrido em 10 de novembro de 2009 em 18 estados brasileiros. Tais mensagens foram trabalhadas a partir de um método predominantemente qualitativo e interpretativo, sendo que uma abordagem quantitativa também foi considerada para permitir uma visão mais abrangente e comparativa dos dados. Na ausência de um referencial teórico da Linguística que abrangesse os fenômenos interacionais percebidos nos comentários dos blogs, optou-se por desenvolver uma proposta de análise de base empírica, que norteou todo o desenvolvimento do trabalho. Entre as conclusões preliminares da pesquisa, pode-se dizer que, ao mesmo tempo em que os blogs inauguraram uma nova forma de relacionamento entre o jornalista e sua audiência, há indícios de grande parte dos leitores utilizem os blogs como um espaço restrito à publicação de opiniões isoladas, em vez de enxergá-lo como um ambiente com amplas possibilidades interativas, e, consequentemente, propício à discussão

Eros adormecido : violência e laço social na interface entre literatura e psicanálise?

Esta pesquisa objetivou discutir a violência e o laço social, tomando como fonte de inspiração a relação com o semelhante, desvelada na obra de Rubem Fonseca. A literatura é apreendida como espaço ético no qual os processos de subjetivação são expressos e forjados, dando forma ao mal-estar que a psicanálise institui como próprio do existir humano. Considerando a violência constituinte do dualismo pulsional Eros-Tanatos, hipotetiza-se que as trocas sociais, na atualidade, efetuam-se pelo ódio indiferenciado ao outro, reificando-o e destituindo-o de sua singularidade. As personagens de Rubem Fonseca protagonizam, juntamente com o cenário urbano, a tragédia contemporânea na qual a melancolia parece ser a tônica da trama coletiva e os atos violentos despropositados contra o outro, uma forma de resposta contra a desvitalização e a impotência subjetivas. Em um universo social caracterizado pela retração dos poderes regeneradores e unificadores de Eros, a erótica predominante se afirma pela violência em relação ao próximo, não posto no lugar de parceiro na construção da coletividade.

Investigations of the conductor-semiconductor interface

I. Schottky barriers produced by polymeric sulfur nitride, (SN)_x, on nine common III-V and II-VI compound semiconductors are compared to barriers formed by Au. The conductor (SN)_x produces significantly higher barriers to n-type semiconductors and lower barriers to p-type semiconductors than Au, the most electronegative elemental metal. The barrier height improvement, defined as ɸ(SN)_x - ɸ(Au), is smaller on covalent semiconductors than on ionic semiconductors; (SN)x barriers follow the ionic-covalent transition. Details of (SN)_x film deposition, samples preparation, and barrier height measurements are described.

II. The rate of dissolution of amorphous Si into solid Al is measured. The rate of movement of the amorphous Si/Al interface is found to be much faster than predicted by a simple model of the transport of Si through Al. This result is related to defects in the growth of epitaxial Si using the solid phase epitaxy process.

The distribution of native and introduced species of crayfish in Austria

This account concentrates on the six species of crayfish found in Austria, and the current state of knowledge on their distribution and laws affecting conservation. In general the occurrence and distribution of crayfish in Austria is poorly known, although information obtained by researchers and the general public, after careful checking, is increasing. Three native crayfish species occur in Austria: Austropotamobius torrentium which is relatively widespread, A. pallipes with a restricted distribution, and Astacus astacus which is widespread. Three species of non-native (alien) crayfish have been recorded from a total of 158 localities in Austria. They are Astacus leptodactylus from eastern Europe, and two Nearctic species: Pacifastacus leniusculus and Orconectes limosus. The introduction of alien species causes considerable problems as they act as vectors of crayfish plague and are able to outcompete native species by higher reproductive capacities.