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.

Room Temperature Ionic Liquid-Lithium Salt Mixtures: Optical Kerr Effect Dynamical Measurements

The addition of lithium salts to ionic liquids causes an increase in viscosity and a decrease in ionic mobility that hinders their possible application as an alternative solvent in lithium ion batteries. Optically heterodyne-detected optical Kerr effect spectroscopy was used to study the change in dynamics, principally orientational relaxation, caused by the addition of lithium bis(trifluoromethylsulfonyl)imide to the ionic liquid 1-buty1-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Over the time scales studied (1 ps-16 ns) for the pure ionic liquid, two temperature-independent power laws were observed: the intermediate power law (1 ps to similar to 1 ns), followed by the von Schweidler power law. The von Schweidler power law is followed by the final complete exponential relaxation, which is highly sensitive to temperature. The lithium salt concentration, however, was found to affect both power laws, and a discontinuity could be found in the trend observed for the intermediate power law when the concentration (mole fraction) of lithium salt is close to chi(LiTf(2)N) = 0.2. A mode coupling theory (MCT) schematic model was also used to fit the data for both the pure ionic liquid and the different salt concentration mixtures. It was found that dynamics in both types of liquids are described very well by MCT.

Theoretical Characterization of Hydrogen Polyoxides: HOOH, HOOOH, HOOOOH, and HOOO

We have investigated the polyoxides HOOH, HOOOH, HOOOOH, and HOOO employing the CCSD(T) methodology, and the correlation consistent basis sets. For all molecules, we have computed fundamental vibrational frequencies, structural parameters, rotational constants, and rotation-vibration corrections. For HOOOH, we have obtained a good agreement between our results and microwave and infrared spectra measurements, although for the symmetric OO stretch some important differences were found. Heats of formation were computed using atomization energies, and our recommendation is as follows: Delta H degrees(f,298)(HOOOH) = -21.50 kcal/mol and Delta H degrees(f,298)(HOOOOH) = -10.61 kcal/mol. In the case of HOOO, to estimate the heat of formation, we have constructed three isodesmic reactions to cancel high order correlation effects. The results obtained confirmed that the latter effects are very important for HOOO. The new Delta H degrees(f,298)(HOOO) obtained is 5.5 kcal/mol. We have also calculated the zero-point energies of DO and DOOO to correct the experimental lower limit determined for the Delta H degrees(f,298)(HOOO). The Delta(Delta ZPE) decreases the binding energy of HOOO by 0.56 kcal/mol. Employing the latter value, the new experimental lower limit for Delta H degrees(f,298)(HOOO) is 3.07 kcal/mol, just 2.4 kcal/mol lower than our determination. We expect that the fundamental vibrational frequencies and rotational constants determined for HOOOOH and DOOOOD contribute to its identification in the gas phase. The vibrational spectrum of HOOOOH shows some overlapping with that of HOOOH thus indicating that one may encounter some difficulties in its characterization. We discuss the consequences of the thermochemical properties determined in this work, and suggest that the amount of HOOO present in the atmosphere is smaller than that proposed recently in this journal (J. Phys. Chem A 2007, 111, 4727).

Intrachain Energy Migration to Weak Charge-Transfer State in Polyfluorene End-Capped with Naphthalimide Derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1 8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CI) of the end group BNI The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state polyfluorene backbone decay and ICCT deactivation Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0 8-1 4 ns depending on the solvent showing that depolarization occurs from two different processes energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF BNI ascribed to the conversion of S(1) to the ICCT excited state From the ratio of asymptotic and initial amplitudes of the transient absorption measurement the efficiency of intrachain ICCT formation is estimated in 0 5 which means that on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state

Interaction of bovine serum albumin (BSA) with ionic surfactants evaluated by electron paramagnetic resonance (EPR) spectroscopy

EPR spectra of 5- and 16-doxyl stearic acid nitroxide probes (5-DSA and 16-DSA, respectively) bound to bovine serum albumin (BSA) revealed that in the presence of ionic surfactants, at least, two label populations coexist in equilibrium. The rotational correlation times (tau) indicated that component I displays a more restricted mobility state, associated to the spin labels bound to the protein; the less immobilized component 2 is due to label localization in the surfactant aggregates. For both probes, the increase of surfactant concentration leads to higher motional levels of component 1 followed by a simultaneous decrease of this fraction of nitroxides and its conversion into component 2. For 10 mM cethyltrimethylammonium chloride (CTAC), the nitroxides are 100% bound to the protein, whereas at 10mM N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and sodium dodecyl sulfate (SDS) the fractions of bound nitroxides are reduced to 18% and 86%, respectively. No significant polarity changes were observed in the whole surfactant concentration range for component 1. Moreover, at higher surfactant concentration, component 2 exhibited a similar polarity as in the pure surfactant micelles. For 16-DSA the surfactant effect is different: at 10mM of HPS and CTAC the fractions of bound nitroxides are 76% and 49%, respectively, while at 10 mM SDS they are present exclusively in a micellar environment, consistent with 100% of component 2. Overall, both SDS and HPS are able to effectively displace the nitroxide probes from the protein binding sites. while CTAC seems to affect the nitroxide binding to a significantly smaller extent. (C) 2008 Elsevier B.V. All rights reserved.

Ways of knowing in ways of moving : A study of the meaning of capability to move

The overall aim of this thesis has been to investigate the meaning of the capability to move in order to identify and describe this capability from the perspective of the one who moves in relation to specific movements. It has been my ambition to develop ways to explicate, and thereby open up for discussion, what might form an educational goal in the context of movements and movement activities in the school subject of physical education and health (PEH). In this study I have used a practical epistemological perspective on capability to move, a perspective that challenges the traditional distinction between mental and physical skills as well as between theoretical and practical knowledge. Movement actions, or ways of moving, are seen as expressions of knowing. In order to explore an understanding of the knowing involved in specific ways of moving, observations of  actors’ ways of moving and their own experiences of moving were brought together. Informants from three different arenas took part: from PEH in upper secondary school, from athletics and from free-skiing. The results of the analyses suggest it is possible to describe practitioners’ developed knowing as a number of specific ways of knowing that are in turn related to specific ways of moving. Examples of such specific ways of moving may be discerning and modifying one’s own rotational velocity and navigating one’s (bodily) awareness. Additionally, exploring learners’ pre-knowing of a movement ‘as something’ may be fruitful when planning the teaching and learning of capability to move. I have suggested that these specific ways of knowing might be regarded as educational goals in PEH. In conducting this study, I have also had the ambition to contribute to the ongoing discussion of what ‘ability’ in the PEH context might mean. In considering specific ways of knowing in moving, the implicit and taken-for-granted meaning of ‘standards of excellence’ and ‘sports ability’can be discussed, and challenged.

Polarizing beam splitter for dipolar molecules

We propose a coherent beam splitter for polarized heteronuclear molecules based on a stimulated Raman adiabatic passage scheme that uses a tripod linkage of electrotranslational molecular states. We show that for strongly polarized molecules the rotational dynamics imposes significantly larger Rabi frequencies than would otherwise be expected, but within this limitation, a full transfer of the molecules to two counterpropagating ground-state wave packets is possible.

Influência de parâmetros moleculares em funções de correlação temporal na dinâmica de solvatação mecânica

No presente trabalho descrevemos nossos resultados relativos à investigação da dinâmica de solvatação mecânica por meio de simulações por dinâmica molecular, respeitando o regime da resposta linear, em sistemas-modelo de argônio líquido com um soluto monoatômico ou diatômico dissolvido. Estudamos sistematicamente a influência dos parâmetros moleculares dos solutos (tamanho, polarizabilidade) e da densidade frente a vários modelos de solvatação. Funções de Correlação Temporal da Energia de Solvatação foram calculadas com relação à correlações de n-corpos (n = 2; 3) distinguindo interações repulsivas e atrativas para ambos os sistemas líquidos. Também obtivemos segundas derivadas temporais dessas funções referindo-se à parcelas translacionais, rotacionais e roto-translacionais na solução do diatômico. Encontramos que funções de correlação temporal coletivas podem ser razoavelmente bem aproximadas por correlações binárias a densidades baixas e, a densidades altas, correlações ternárias tornam-se mais importantes produzindo um descorrelacionamento mais rápido das funções coletivas devido a efeitos de cancelamento parciais. As funções de correlação para interações repulsivas e atrativas exibem comportamentos dinâmicos independentes do modelo de solvatação devido a fatores de escalonamento linear que afetam apenas as amplitudes das dessas funções de correlação temporal. Em geral, os sistemas com grau de liberdade rotacional apresentam tempos de correlação mais curtos para a dinâmica coletiva e tempos de correlação mais longos para as funções binárias e ternárias. Finalmente, esse estudo mostra que os sistemas contendo o diatômico relaxam-se predominantemente por mecanismos translacionais binários em modelos de solvatação envolvendo alterações apenas na polarizabilidade do soluto, e por mecanismos rotacionais atrativos binários em modelos envolvendo alterações no comprimento de ligação.

Development of an active orthosis prototype for lower limbs

ARAUJO, Márcio V. ; ALSINA, Pablo J. ; MEDEIROS, Adelardo A. D. ; PEREIRA, Jonathan P.P. ; DOMINGOS, Elber C. ; ARAÚJO, Fábio M.U. ; SILVA, Jáder S. . Development of an Active Orthosis Prototype for Lower Limbs. In: INTERNATIONAL CONGRESS OF MECHANICAL ENGINEERING, 20., 2009, Gramado, RS. Proceedings… Gramado, RS: [s. n.], 2009

Modelagem dinâmica e simulação computacional de poços de petróleo verticais e direcionais com elevação por bombeio mecânico

LINS, Filipe C. A. et al. Modelagem dinâmica e simulação computacional de poços de petróleo verticais e direcionais com elevação por bombeio mecânico. In: CONGRESSO BRASILEIRO DE PESQUISA E DESENVOLVIMENTO EM PETRÓLEO E GÁS, 5. 2009, Fortaleza, CE. Anais... Fortaleza: CBPDPetro, 2009.

Produção de snacks funcionais à base de farinha de soja e polvilho azedo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Reproductive and behavioral aspects of red-winged tinamous (Rhynchotus rufescens) in groups with different sex ratios

The aim of this research study was to evaluate the reproductive performance of tinamous submitted to five different male:female ratios. The study was carried out with 72 birds in a randomized experimental design with 4 replications. Tinamous were housed in cages, using the ratios of one (1:1), two (2:1), three (3:1) and four (4:1) females per male, and also one male was housed with three females individually (3R:1), in a rotational system. Reproductive records of the breeding season from September 2004 to March 2005 were used. The reproductive traits studied were: number of eggs laid, fertility, and percentage of eggs damaged and cracked by pecking. Nonparametric analyses of these traits were performed using Kruskal-Wallis test. Two replications of treatments 1:1 and 4:1, and one of treatment 2:1 were video-taped for three days, 12 hours/day. The videotapes were sampled according to the scan method to fit an ethogram. Birds were also watched for one hour per day to study dominance and agonistic behavior. None of the reproductive traits was affected by mating sex ratio (p<0.05). Female dominance could be related to displacement behavior (r=1.00), and male sitting in immobility plus sitting in activity behaviors were related to lower number of damaged eggs (r=-0.90). Social dominance was indirectly determined by displacement behavior in the study situation. A large number of damaged eggs occurred in all treatments, thereby not allowing a clear conclusion on the best male:female ratio.

Predição do Consumo Voluntário do Capim-Tanzânia (Panicum maximum, J. cv. tanzânia), sob Pastejo, por Vacas em Lactação, a partir das Características de Degradação

O consumo de matéria seca (CMS) do capim tanzânia de 24 vacas lactantes mestiças (HPB x Gir) e Gir, sob pastejo, foi estimado no mês de janeiro de 1998, a partir da relação entre a digestibilidade da MS da forragem e a produção fecal obtida com auxílio do cromo mordente por meio de um modelo não-linear. Os resultados do consumo estimado foram comparados aos consumos preditos por diferentes equações baseadas nos dados de degradabilidade do capim, no rúmen. A pastagem foi manejada com taxa de lotação de dois animais/ha, em sistema de pastejo rotativo com três dias de ocupação do piquete e 39 dias de descanso. Foram utilizadas para predizer o CMS diferentes equações: CMS = -1,19 + 0,035 (a+ b) + 28,5c (1), CMS = -0,822 + 0,0748 (a+ b) + 40,7c (2), CMS = -8,286 + 0,266a + 0,102b +17,696c (3) e CMS = [%FDN na MS]* [consumo de FDN ] / [(1-a-b)/K P +b/(c+ k p)]/24] (4). As equações, em geral, subestimaram o consumo obtido no modelo não-linear (9,6 kg/vaca/dia). Os consumos médios de capim de 6,2 e 6,0 kg MS/vaca/dia obtidas, respectivamente, nas equações de (2) e (4) foram semelhantes entre si e inferiores ao das equações de (1) (12,7 kg/vaca/dia) e (3) (8,1 kg/vaca/dia). A predição do consumo de forrageiras tropicais, sob pastejo, utilizando-se as equações baseadas nas variáveis da degradação in situ, constitui um importante potencial para estas avaliações. Entretanto, mais estudos dessa natureza devem ser realizados para validar o uso destas equações na prática.

Estimativa da ingestão voluntária a partir das características de degradação do capim-coastcross (Cynodon dactylon L. Pers.), sob pastejo, por vacas em lactação

O consumo de matéria seca (CMS) do capim-coastcross, sob pastejo, de vacas lactantes mestiças (HPB x Gir) e Gir, foi calculado a partir da relação entre a digestibilidade in vitro da MS (DIVMS) da forragem (extrusa colhida com animais esôfago- fistulados) e a produção fecal obtida com auxílio do cromo mordante por meio de um modelo não-linear. A pastagem foi manejada com uma taxa de lotação de 1,6 e 3,2 animais/ha, respectivamente para as épocas seca e chuvosa do ano, num sistema de pastejo rotativo com três dias de ocupação e 27 dias de descanso. Quatro diferentes equações baseadas em variáveis de degradação ruminal foram utilizadas para predizer o consumo de MS: CMS = -1,19 + 0,035 (a+ b) + 28,5c (1), CMS = -0,822 + 0,0748 (a+ b) + 40,7c (2), CMS = -8,286 + 0,266a + 0,102b +17,696c (3) e CMS = [%FDN na MS]* [consumo de FDN ] / [(1-a-b)/K P +b/(c+ k p)]/24] (4). Os dados observados utilizando as equações 1 e 2 (12,2 e 12,7 kg/vaca/dia respectivamente) foram similares entre si e superiores aos resultados obtidos na equação 4 (7,8 kg/vaca/dia). Já o resultado obtido pela equação 3 (5,5 kg/vaca/dia) foi menor do que aqueles determinados pelas outras equações, subestimando o CMS calculado a partir do cromo mordante (6,3 kg/vaca/dia). A predição do consumo de forrageiras tropicais sob pastejo, utilizando equações baseadas nas variáveis de degradação, constitui um importante potencial para estas avaliações. Entretanto, mais estudos devem ser realizados antes de se usarem estas equações na prática.

Efeito do dia de ocupação sobre a produção leiteira de vacas mestiças em pastejo rotacionado de forrageiras tropicais

O trabalho foi conduzido para se observar as flutuações na produção leiteira de vacas mestiças em sistema de pastejo rotacionado de capim-elefante cv. Guaçu (Pennisetum purpureum Schum.) e capim-tanzânia (Panicum maximum Jacq.), de acordo com períodos de ocupação (dois dias de ocupação e 40 de descanso e três dias de ocupação e 33 de descanso, respectivamente), adubados com 200 kg de N/ha/ano. Foram estudados 19 piquetes de capim-elefante e 15 de capim-tanzânia. A análise estatística foi realizada considerando-se fase de lactação das vacas, piquete e dia de ocupação. Para o capim-elefante houve efeito da fase da lactação com interação com o dia de ocupação, mas não houve diferença para o dia de ocupação. As médias foram 10,3 ± 3,3 e 10,4 ± 3,2 kg de leite/vaca/dia para o 1º e 2º dia de ocupação, respectivamente. Para o capim-tanzânia, houve diferença significativa na produção de leite, conforme o dia de ocupação, e interação significativa para piquete e dia de ocupação. As médias foram 10,6 ± 3,0; 11,0 ± 3,1; 10,6 ± 3,2 kg de leite/vaca/dia, respectivamente, para o primeiro, segundo e terceiro dias de ocupação.