Amplifying vibrational circular dichroism by manipulation of the electronic manifold

Vibrational circular dichroism is a powerful technique to study the stereochemistry of chiral molecules, but often suffers from small signal intensities. Electrochemical modulation of the energies of the electronically excited state manifold is now demonstrated to lead to an order of magnitude enhancement of the differential absorption. Quantum-chemical calculations show that increased mixing between ground and excited states is at the origin of this amplification.

An optically transparent thin-layer electrochemical cell for the study of vibrational circular dichroism of chiral redox-active molecules

An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.

Switchable amplification of vibrational circular dichroism as a probe of local chiral structure

A new method to detect the vibrational circular dichroism (VCD) of a localized part of a chiral molecular system is reported. A local VCD amplifier was implemented, and the distance dependence of the amplification was investigated in a series of peptides. The results indicate a characteristic distance of 2.0±0.3 bonds, which suggests that the amplification is a localized phenomenon. The amplifier can be covalently coupled to a specific part of a molecule, and can be switched ON and OFF electrochemically. By subtracting the VCD spectra obtained when the amplifier is in the ON and OFF states, the VCD of the local environment of the amplifier can be separated from the total VCD spectrum. Switchable local VCD amplification thus makes it possible to “zoom in” on a specific part of a chiral molecule.

Elucidating the structure of chiral molecules by using amplified vibrational circular dichroism: from theory to experimental realization

Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low-lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure.

FORCED CONVECTION TO LAMINAR FLOW OF LIQUID EGG YOLK IN CIRCULAR AND ANNULAR DUCTS

The steady-state heat transfer in laminar flow of liquid egg yolk - an important pseudoplastic fluid food - in circular and concentric annular ducts was experimentally investigated. The average convection heat transfer coefficients, determined by measuring temperatures before and after heating sections with constant temperatures at the tube wall, were used to obtain simple new empirical expressions to estimate the Nusselt numbers for fully established flows at the thermal entrance of the considered geometries. The comparisons with existing correlations for Newtonian and non-Newtonian fluids resulted in excellent agreement. The main contribution of this work is to supply practical and easily applicable correlations, which are, especially for the case of annulus, rather scarce and extensively required in the design of heat transfer operations dealing with similar shear-thinning products. In addition, the experimental results may support existing theoretical analyses.

gamma-zein secondary structure in solution by circular dichroism

The proline-rich N-terminal domain of gamma-zein has been reported in relevant process, which include its ability to cross the cell membranes. Evidences indicate that synthetic hexapeptide (PPPVHL), naturally found in N-terminal portion of gamma-zein, can adopt the polyproline II (PPII) conformation in aqueous solution. The secondary structure of gamma-zein in maize protein bodies had been analyzed by solid state Fourier transform infrared and nuclear magnetic resonance spectroscopies. However, it was not possible to measure PPII content in physiological environment since the beta-sheet and PPII signals overlap in both solid state techniques. Here, the secondary structure of gamma-zein has been analyzed by circular dichroism in SDS aqueous solution with and without ditiothreitol (DTT), and in 60% of 2-propanol and water with DTT The results show that gamma-zein has high helical content in all solutions. The PPII conformation was present at about 7% only in water/DTT solution. (c) 2007 Wiley Periodicals, Inc.

Conformational Properties of Angiotensin II and Its Active and Inactive TOAC-Labeled Analogs in the Presence of Micelles. Electron Paramagnetic Resonance, Fluorescence, and Circular Dichroism Studies

The interaction between angiotensin II (AII, DRVYIHPF) and its analogs carrying 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (TOAC) and detergents-negatively charged sodium dodecyl sulfate (SDS) and zwitterionic N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS)-was examined by means of EPR, CD, and fluorescence. EPR spectra of partially active TOAC(1)-AII and inactive TOAC(3)-AII in aqueous solution indicated fast tumbling, the freedom of motion being greater at the N-terminus. Line broadening occurred upon interaction with micelles. Below SDS critical micelle concentration, broader lines indicated complex formation with tighter molecular packing than in micelles. Small changes in hyperfine splittings evinced TOAC location at the micelle-water interface. The interaction with anionic micelles was more effective than with zwitterionic micelles. Peptide-micelle interaction caused fluorescence increase. The TOAC-promoted intramolecular fluorescence quenching was more, pronounced for TOAC(3)-AII because of the proximity between the nitroxide and Tyr(4). CD spectra showed that although both AII and TOAC(1)-AII presented flexible conformations in water, TOAC(3)-AII displayed conformational restriction because of the TOAC-imposed bend (Schreier et al., Biopolymers 2004, 74, 389). In HPS, conformational changes were observed for the labeled peptides at neutral and basic pH. In SDS, all peptides underwent pH-dependent conformational changes. Although the spectra suggested similar folds for All and TOAC(1)-AII, different conformations were acquired by TOAC(3)-AII. The membrane environment has been hypothesized to shift conformational equilibria so as to stabilize the receptor-bound conformation of ligands. The fact that TOAC(3)-AII is unable to acquire conformations similar to those of native AII and partially active TOAC(1)-AII is probably the explanation for its lack of biological activity. (C) 2009 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 92: 525-537, 2009.

Single-mode acceleration of matter waves in circular waveguides

Ultracold gases in ring geometries hold promise for significant improvements of gyroscopic sensitivity. Recent experiments have realized atomic and molecular storage rings with radii in the centimeter range, sizes whose practical use in inertial sensors requires velocities significantly in excess of typical recoil velocities. We use a combination of analytical and numerical techniques to study the coherent acceleration of matter waves in circular waveguides, with particular emphasis on its impact on single-mode propagation. In the simplest case we find that single-mode propagation is best maintained by the application of time-dependent acceleration force with the temporal profile of a Blackmann pulse. We also assess the impact of classical noise on the acceleration process.

Thomas-Fermi ground state of dipolar fermions in a circular storage ring

Recent developments in the field of ultracold gases has led to the production of degenerate samples of polar molecules. These have large static electric-dipole moments, which in turn causes the molecules to interact strongly. We investigate the interaction of polar particles in waveguide geometries subject to an applied polarizing field. For circular waveguides, tilting the direction of the polarizing field creates a periodic inhomogeneity of the interparticle interaction. We explore the consequences of geometry and interaction for stability of the ground state within the Thomas-Fermi model. Certain combinations of tilt angles and interaction strengths are found to preclude the existence of a stable Thomas-Fermi ground state. The system is shown to exhibit different behavior for quasi-one-dimensional and three-dimensional trapping geometries.

Luis Millones, Charles A. Dana Associate Professor of Spanish

Luis Millones, Charles A. Dana Associate Professor of Spanish reading Pliny's A Historie of the World

Dança: forma, técnica e poesia do movimento : na perspectiva de construção de sentidos coreográficos

A presente dissertação se construiu sobre o pressuposto de que forma, técnica e poesia são premissas que embasam uma determinada visão de dança enquanto manifestação artística do corpo humano em movimento. Norteia também este estudo a perspectiva de que as relações que se estabelecem no momento de execução de uma dança instauram processos de significação. Desse modo, este trabalho teve como principais objetivos: - entender a dança enquanto uma atividade artística que se constrói no(s) corpo(s) em movimento; - refletir sobre a elaboração de possíveis significados quando da criação e execução de uma dança; - descrever a dança como uma ação criadora que se faz no corpo humano em movimento. Para atingir os objetivos propostos utilizou-se a fenomenologia como método de investigação, optando-se, assim, por realizar uma descrição da dança que já é, ao mesmo tempo, uma maneira de compreendê-la. Como conseqüência deste procedimento buscou-se demontrar que: - a dança dever ser entendida enquanto arte porque ela resulta de um processo de transformação de uma matéria-prima - o movimento humano - através do uso de procedimentos técnicos e formativos, que resultam em obras coreográficas que se dão a reconhecer através de seu intrínseco caráter de forma; - o movimento é o que toma visível os possíveis sentidos/significados de uma dança: a realização de sentidos coreográficos se dá no contexto de uma coreografia e só se efetua plenamente quando os sentidos são retomados e revividos pelos espectadores; - os processos de criação coreográfica baseados em ações formativas proporcionam o desenvolvimento de uma disponibilidade corporal para a dança. Tal disponibilidade corporal está alicerçada, principalmente, numa inteligência e numa memória corporais, que dispõem o dançarino a exercer suas potencialidades criadoras através da dança. A concepção da dança como forma, técnica e poesia do movimento aponta para uma possibilidade de recuperação, através da dança, de saberes relativos ao corpo, ao movimento e à sensibilidade.

Relações de fornecimento na indústria automobilística paranaense : o caso Chrysler-Dana

Em um mundo de intensa competição global, a busca por menores prazos, custos competitivos, qualidade e flexibilidade é uma constante. Percebe-se que, para alcançá-los, é necessário, além de estratégias, alianças estratégicas. Assim a lógica da colaboração se torna uma parte essencial da estratégia de negócios. As relações de fornecimento, firmadas a longo prazo entre as empresas, passam a ser consideradas como chave para o sucesso das metas empresariais das organizações. Aquelas empresas que estabelecerem e cultivarem os benefícios mútuos advindos dessas formas de parcerias poderão esperar um desempenho competitivo superior. Nesse contexto, o objetivo central deste estudo é identificar os elementos constituintes de uma relação de fornecimento, buscando um modelo conceitual para este tipo de relacionamento. A fim de se verificar a presença de tais elementos nas relações de fornecimento da indústria automobilística, a partir de uma abordagem exploratória, empregou-se o método de estudo de caso. Foram investigadas duas empresas. A Chrysler e a Dana e sua respectiva relação de fornecimento. A presente investigação ocorreu entre os meses de setembro de 2000 a setembro de 2001. O Esse estudo apresenta o resultado do caso investigado e uma análise comparada à literatura existente no que diz respeito aos elementos identificados na relação de fornecimento. Por fim, são apresentadas implicações do estudo que poderiam ser aprofundadas em novas pesquisas na área de relações de fornecimento, bem como as limitações do referido trabalho.