Solvent effects on the electronic absorption spectrum of camphor using continuum, discrete or explicit approaches

We address the effect of solvation on the lowest electronic excitation energy of camphor. The solvents considered represent a large variation in-solvent polarity. We consider three conceptually different ways of accounting for the solvent using either an implicit, a discrete or an explicit solvation model. The solvatochromic shifts in polar solvents are found to be in good agreement with the experimental data for all three solvent models. However, both the implicit and discrete solvation models are less successful in predicting solvatochromic shifts for solvents of low polarity. The results presented suggest the importance of using explicit solvent molecules in the case of nonpolar solvents. (C) 2009 Elsevier B.V. All rights reserved.

Solvent Effects in Chemical Processes. Water-Assisted Proton Transfer Reaction of Pterin in Aqueous Environment

Pterins are members of a family of heterocyclic compounds present in a wide variety of biological systems and may exist in two forms, corresponding to an acid and a basic tautomer. In this work, the proton transfer reaction between these tautomeric forms was investigated in the gas phase and in aqueous solution. In gas phase, the intramolecular mechanism was carried out for die isolated pterin by quantum mechanical second-order Moller-Plesset Perturbation theory (MP2/aug-cc-pVDZ) calculations and it indicates that the acid form is more stable than the basic form by -1.4 kcal/mol with a barrier of 34.2 kcal/mol with respect to the basic form. In aqueous solution, the role of the water molecules in the proton transfer reaction was analyzed in two separated parts, the direct participation of one water molecule in the reaction path, called water-assisted mechanism, and the complementary participation of the aqueous solvation. The water-assisted mechanism was carried out for one pterin-water cluster by quantum mechanical calculations and it indicates that the acid form is still more stable by -3.3 kcal/mol with a drastic reduction of 70% of the barrier, The bulk solution effect on the intramolecular and water-assisted mechanisms was included by free energy perturbation implemented on Monte Carlo simulations. The bulk water effect is found to be substantial and decisive when the reaction path involves the water-assisted mechanism. In this case, the free energy barrier is only 6.7 kcal/mol and the calculated relative Gibbs free energy for the two tautomers is -11.2 kcal/mol. This value is used to calculate the pK(a) value of 8.2 +/- 0.6 that is in excellent agreement with the experimental result of 7.9.

Thermodynamic characterization of the palm tree Roystonea regia peroxidase stability

The structural stability of a peroxidase, a dimeric protein from royal palm tree (Roystonea regia) leaves, has been characterized by high-sensitivity differential scanning calorimetry, circular dichroism, steady-state tryptophan fluorescence and analytical ultracentifugation under different solvent conditions. It is shown that the thermal and chemical (using guanidine hydrochloride (Gdn-HCl)) folding/unfolding of royal palm tree peroxidase (RPTP) at pH 7 is a reversible process involving a highly cooperative transition between the folded dimer and unfolded monomers, with a free stabilization energy of about 23 kcal per mol of monomer at 25 degrees C. The structural stability of RPTP is pH-dependent. At pH 3, where ion pairs have disappeared due to protonation, the thermally induced denaturation of RPTP is irreversible and strongly dependent upon the scan rate, suggesting that this process is under kinetic control. Moreover, thermally induced transitions at this pH value are dependent on the protein concentration, allowing it to be concluded that in solution RPTP behaves as dimer, which undergoes thermal denaturation coupled with dissociation. Analysis of the kinetic parameters of RPTP denaturation at pH 3 was accomplished on the basis of the simple kinetic scheme N ->(k) D, where k is a first-order kinetic constant that changes with temperature, as given by the Arrhenius equation; N is the native state, and D is the denatured state, and thermodynamic information was obtained by extrapolation of the kinetic transition parameters to an infinite heating rate. Obtained in this way, the value of RPTP stability at 25 degrees C is ca. 8 kcal per mole of monomer lower than at pH 7. In all probability, this quantity reflects the contribution of ion pair interactions to the structural stability of RPTP. From a comparison of the stability of RPTP with other plant peroxidases it is proposed that one of the main factors responsible for the unusually high stability of RPTP which enhances its potential use for biotechnological purposes, is its dimerization. (c) 2008 Elsevier Masson SAS. All rights reserved.

Evidence that OGG1 glycosylase protects neurons against oxidative DNA damage and cell death under ischemic conditions

7,8-Dihydro-8-oxoguanine DNA glycosylase (OGG1) is a major DNA glycosylase involved in base-excision repair (BER) of oxidative DNA damage to nuclear and mitochondrial DNA (mtDNA). We used OGG1-deficient (OGG1(-/-)) mice to examine the possible roles of OGG1 in the vulnerability of neurons to ischemic and oxidative stress. After exposure of cultured neurons to oxidative and metabolic stress levels of OGG1 in the nucleus were elevated and mitochondria exhibited fragmentation and increased levels of the mitochondrial fission protein dynamin-related protein 1 (Drp1) and reduced membrane potential. Cortical neurons isolated from OGG1(-/-) mice were more vulnerable to oxidative insults than were OGG1(+/+) neurons, and OGG1(-/-) mice developed larger cortical infarcts and behavioral deficits after permanent middle cerebral artery occlusion compared with OGG1(+/+) mice. Accumulations of oxidative DNA base lesions (8-oxoG, FapyAde, and FapyGua) were elevated in response to ischemia in both the ipsilateral and contralateral hemispheres, and to a greater extent in the contralateral cortex of OGG1(-/-) mice compared with OGG1(+/+) mice. Ischemia-induced elevation of 8-oxoG incision activity involved increased levels of a nuclear isoform OGG1, suggesting an adaptive response to oxidative nuclear DNA damage. Thus, OGG1 has a pivotal role in repairing oxidative damage to nuclear DNA under ischemic conditions, thereby reducing brain damage and improving functional outcome. Journal of Cerebral Blood Flow & Metabolism (2011) 31, 680-692; doi:10.1038/jcbfm.2010.147; published online 25 August 2010

A ditryptophan cross-link is responsible for the covalent dimerization of human superoxide dismutase 1 during its bicarbonate-dependent peroxidase activity

Unlike intermolecular disulfide bonds, other protein cross-links arising from oxidative modifications cannot be reversed and are presumably more toxic to cells because they may accumulate and induce protein aggregation. However, most of these irreversible protein cross-links remain poorly characterized. For instance, the antioxidant enzyme human superoxide dismutase 1 (hSod1) has been reported to undergo non-disulfide covalent dimerization and further oligomerization during its bicarbonate-dependent peroxidase activity. The dimerization was shown to be dependent on the oxidation of the single, solvent-exposed TrP(32) residue of hSod1, but the covalent dimer was not isolated nor was its structure determined. In this work, the hSod1 covalent dimer was isolated, digested with trypsin in H(2)O and H(2)(18)O, and analyzed by UV-Vis spectroscopy and mass spectrometry (MS). The results demonstrate that the covalent dimer consists of two hSod1 subunits cross-linked by a ditryptophan, which contains a bond between C3 and N1 of the respective Trp(32) residues. We further demonstrate that the cross-link cleaves under usual MS/MS conditions leading to apparently unmodified Trp(32), partially hinders proteolysis, and provides a mechanism to explain the formation of hSod1 covalent trimers and tetramers. This characterization of the covalent hSod1 dimer identifies a novel oxidative modification of protein Trp residues and provides clues for studying its occurrence in vivo. (C) 2010 Elsevier Inc. All rights reserved.

Effect of solvent on the adsorption behavior and on the surface properties of Sterculia striata polysaccharide

Characterization of Sterculia striate polysaccharide (SSP) films adsorbed onto Si wafers from solutions prepared in ethyl methyl imidazolium acetate (EmimAc), water or NaOH 0.01 mol/L was systematically studied by means of ellipsometry, atomic force microscopy and contact angle measurements. SSP adsorbed from EmimAc onto Si wafer as homogeneous monolayers (similar to 0.5 nm thick), while from water or NaOH 0.01 mol/L SSP formed layers of similar to 4.0 nm and similar to 1.5 nm thick, respectively. Surface energy values found for SSP adsorbed from EmimAc or water were 68 +/- 2 mJ/m(2) and 65 +/- 2 mJ/m(2), respectively, whereas from NaOH it amounted to 57 +/- 3 mJ/m(2). The immobilization of lysozyme (LYS) onto SSP films was also investigated. The mean thickness of LYS (d(LYS)) immobilized onto SSP films adsorbed from each solvent tended to increase with the decrease of gamma(P)(S) and gamma(total)(S). However, the enzymatic activity of LYS molecules was higher when they were immobilized onto SSP films with higher gamma(P)(S) and gamma(total)(S) values. (C) 2010 Elsevier Ltd. All rights reserved.

Cellulose swelling by protic solvents: which properties of the biopolymer and the solvent matter?

The question posed in the title has been addressed by studying the swelling of celluloses at 20 C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand`s solubility parameters, Gutmann`s acceptor and donor numbers, solvent molar volume, V(S), as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, E(T)(30), solvent ""acidity"", alpha(S), ""basicity"", beta(S), and dipolarity/polarizability, pi(S)*, respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being pi(S)* for MC, cotton, and eucalyptus, and V(S) for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or alpha(S)) beta(S), pi(S)*, and V(S), respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand`s solubility parameters and/or Gutmann`s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed.

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations. HPS presented a smaller effect at concentrations above 1.5 mM. At 10 mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. (C) 2011 Elsevier B.V. All rights reserved.

Performance Evaluation of Different PV-Array Configurations under Weak Light Conditions and Partial Shadings

The paper analyses empirical performance data of five commercial PV-plants in Germany. The purpose was on one side to investigate the weak light performance of the different PV-modules used. On the other hand it was to quantify and compare the shading losses of different PV-array configurations. The importance of this study relies on the fact that even if the behavior under weak light conditions or the shading losses might seem to be a relatively small percentage of the total yearly output; in projects where a performance guarantee is given, these variation can make the difference between meeting or not the conditions.When analyzing the data, a high dispersion was found. To reduce the optical losses and spectral effects, a series of data filters were applied based on the angle of incidence and absolute Air Mass. To compensate for the temperature effects and translate the values to STC (25°C), five different methods were assessed. At the end, the Procedure 2 of IEC 60891 was selected due to its relative simplicity, usage of mostly standard parameters found in datasheets, good accuracy even with missing values, and its potential to improve the results when the complete set of inputs is available.After analyzing the data, the weak light performance of the modules did not show a clear superiority of a certain technology or technology group over the others. Moreover, the uncertainties in the measurements restrictive the conclusiveness of the results.In the partial shading analysis, the landscape mounting of mc-Si PV-modules in free-field showed a significantly better performance than the portrait one. The cross-table string using CIGS modules did not proved the benefits expected and performed actually poorer than a regular one-string-per-table layout. Parallel substrings with CdTe showed a proper functioning and relatively low losses. Among the two product generations of CdTe analyzed, none showed a significantly better performance under partial shadings.

High female mortality resulting in herd collapse in free-ranging domesticated reindeer (Rangifer tarandus tarandus) in Sweden

Reindeer herding in Sweden is a form of pastoralism practised by the indigenous Sami population. The economy is mainly based on meat production. Herd size is generally regulated by harvest in order not to overuse grazing ranges and keep a productive herd. Nonetheless, herd growth and room for harvest is currently small in many areas. Negative herd growth and low harvest rate were observed in one of two herds in a reindeer herding community in Central Sweden. The herds (A and B) used the same ranges from April until the autumn gathering in October-December, but were separated on different ranges over winter. Analyses of capture-recapture for 723 adult female reindeer over five years (2007-2012) revealed high annual losses (7.1% and 18.4%, for herd A and B respectively). A continuing decline in the total reindeer number in herd B demonstrated an inability to maintain the herd size in spite of a very small harvest. An estimated breakpoint for when herd size cannot be kept stable confirmed that the observed female mortality rate in herd B represented a state of herd collapse. Lower calving success in herd B compared to A indicated differences in winter foraging conditions. However, we found only minor differences in animal body condition between the herds in autumn. We found no evidence that a lower autumn body mass generally increased the risk for a female of dying from one autumn to the next. We conclude that the prime driver of the on-going collapse of herd B is not high animal density or poor body condition. Accidents or disease seem unlikely as major causes of mortality. Predation, primarily by lynx and wolverine, appears to be the most plausible reason for the high female mortality and state of collapse in the studied reindeer herding community.

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Free and total GMP (glycomacropeptide) contents of milk during bovine lactation

Amostras quinzenais, desde o parto até o final do período de lactação, obtidas de 34 vacas de três diferentes raças e propriedades, foram analisadas quanto à presença de GMP livre. Um pool das amostras quinzenais de cada rebanho foi analisada tanto para o conteúdo de GMP livre quanto para o GMP total (liberado da k-caseína pela ação da renina), correlacionando-os com as condições sanitárias do animal e do úbere, à fase da lactação e à produção de leite. A maioria dos problemas sanitários concentrou-se próximo ao parto, com poucas e espaçadas ocorrências de mastites clínicas. Os resultados do teste de CMT mostraram reações compatíveis às fases da lactação. Para o GMP livre as maiores variações ocorreram em função do período de lactação e em conseqüência de mastites clínicas e subclínicas. Valores elevados foram observados no início da lactação (5,87mg de ácido siálico/L de leite), normalizando para valores próximos de 3,30mg/L já ao final do segundo mês e voltando a elevar-se no terço final da lactação. em média, as mesmas tendências foram observadas para o teor de GMP total liberado pela ação de coalho comercial, iniciando com valores ligeiramente elevados (35,59mg/L), tornando-se normal e assim se mantendo até o sexto mês com valores próximos a 27,15mg/L, e novamente elevando-se gradualmente até o final da lactação, com 58,35mg de ácido siálico/L de leite. Esses resultados mostram-se úteis para a correta interpretação de métodos aplicados à seleção do leite, seja em relação ao status proteolítico da matéria-prima ou mesmo para coibição de fraudes por adição de soro ao leite.

Preparation and characterization of free films of high amylose/pectin mixtures cross-linked with sodium trimetaphosphate

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Performance, carcass yield, and meat quality of free-range broilers fed wet grain corn silage

This study aimed at evaluating the effect of total replacement of dry corn by wet grain corn silage (WGCS) in the feed of label broilers older than 28 days of age on performance, mortality, carcass, parts, breast meat and thighs meat yields, and meat quality. A mixed-sex flock of 448 ISA S 757-N (naked-neck ISA JA Label) day-old chicks was randomly distributed in to randomized block experimental design with four treatments (T1 - with no WGCS; T2 - WGCS between 28 and 83 days; T3 - WGCS between 42 and 83 days; and T4 - WGCS between 63 and 83 days) and four replicates of 28 birds each. Birds were raised under the same management and feeding conditions until 28 days of age, when they started to have free access to paddock with pasture (at least 3m²/bird) and to be fed the experimental diets. Feed and water were offered ad libitum throughout the rearing period, which was divided in three stages: starter (1 to 28 days), grower (29 to 63 days), and finisher (64 to 83 days) according to the feeding schedule. During the short periods of WGCS use (group T2 during grower stage and T4 during the finisher stage), performance and mortality results were similar as to those of the control group (T1). At the end of the experiment, it was observed that the extended use of WGCS (T2 and T3) determined a negative effect on feed conversion ratio. However, the best results of breast meat yield were observed with birds fed WGCS since 28 days (T2). It was concluded that WGCS can replace dry corn grain for short periods during the grower and finisher stages with no impairment of meat quality and yield in slow growth broilers.

Subgingival microbiota from Cebus apella (capuchin monkey) with different periodontal conditions

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