Biosynthesis and characterization of biodegradable Poly(3-hydroxybutyrate) from renewable sources

Poly(3-hydroxybutyrate) was produced in fed-batch cultures of Ralstonia eutropha DSM 428 and Alcaligenes latus ATCC 29712 on a mineral medium with different carbon sources such as sucrose, sodium lactate, lactic acid, soybean oil and fatty acid. The bacteria converted the different carbon sources supplied into P3HB. The best results were obtained when lactate or soybean oil were supplied as the sole carbon source. The range of number average molar mass (Mn) for the polymers, analyzed by Gel Permeation Chromatography was 1.65 to 0.79 x 10(5) g mol(-1). FTIR spectroscopy revealed a characteristic absorbance associated with polyester structures. The crystallinity degree, determinate from X-ray diffractograms, was about 69% in all synthesized polymers. The thermal properties associated to semicrystalline polymers indicated a glass transition at 0.1 degrees C and a melting point at about 175 degrees C and enthalpy of 63-89 J g(-1). The (1)H-NMR and (13)C-NMR spectra of the polymers were in agreement with the calculated chemical shifts associated with P3HB structures.

Synthesis, mechanism of formation, and molecular orbital calculations of arylamidoximes

A simple and easy synthesis of ten arylamidoximes from arylnitriles and hydroxylamine is described. The formation of the arylamides has been observed to a much lesser extent in the present work. A new mechanism for the formation of arylamidoximes, as well as arylamides, from arylnitriles and hydroxylamine is suggested. Quantum mechanical calculations have been carried out to support this mechanism. The enthalpy of formation in conjunction with atomic charges of the reactants and intermediates helped to understand more about the generation of the products.

ABELIANIZED OBSTRUCTION FOR FIXED POINTS OF FIBER-PRESERVING MAPS OF SURFACE BUNDLES

Let f: M -> M be a fiber-preserving map where S -> M -> B is a bundle and S is a closed surface. We study the abelianized obstruction, which is a cohomology class in dimension 2, to deform f to a fixed point free map by a fiber-preserving homotopy. The vanishing of this obstruction is only a necessary condition in order to have such deformation, but in some cases it is sufficient. We describe this obstruction and we prove that the vanishing of this class is equivalent to the existence of solution of a system of equations over a certain group ring with coefficients given by Fox derivatives.

Fast batch injection analysis of H(2)O(2) using an array of Pt-modified gold microelectrodes obtained from split electronic chips

A fast and robust analytical method for amperometric determination of hydrogen peroxide (H(2)O(2)) based on batch injection analysis (BIA) on an array of gold microelectrodes modified with platinum is proposed. The gold microelectrode array (n = 14) was obtained from electronic chips developed for surface mounted device technology (SMD), whose size offers advantages to adapt them in batch cells. The effect of the dispensing rate, volume injected, distance between the platinum microelectrodes and the pipette tip, as well as the volume of solution in the cell on the analytical response were evaluated. The method allows the H(2)O(2) amperometric determination in the concentration range from 0.8 mu mol L(-1) to 100 mu mol L(-1). The analytical frequency can attain 300 determinations per hour and the detection limit was estimated in 0.34 mu mol L(-1) (3 sigma). The anodic current peaks obtained after a series of 23 successive injections of 50 mu L of 25 mu mol L(-1) H(2)O(2) showed an RSD < 0.9%. To ensure the good selectivity to detect H(2)O(2), its determination was performed in a differential mode, with selective destruction of the H(2)O(2) with catalase in 10 mmol L(-1) phosphate buffer solution. Practical application of the analytical procedure involved H(2)O(2) determination in rainwater of Sao Paulo City. A comparison of the results obtained by the proposed ampermetric method with another one which combines flow injection analysis (FIA) with spectrophotometric detection showed good agreement. (C) 2011 Elsevier B.V. All rights reserved.

Thiothionyl bromide (S=SBr2): The elusive isomer of dibromodisulfane (BrSSBr)

CCSD(T) with a series of correlation consistent basis up to quadruple-zeta is used to investigate the structures, vibrational spectra, relative stability, heats of formation, and barrier to isomerization of S=SBr2 and BrSSBr. It represents the most accurate and detailed characterization of these molecules to date. We show that the frequency mode at 302 cm(-1), detected in various studies and assigned to impurities by some authors, and to the anti-symmetric SBr stretch in BrSSBr by others, thus in fact corresponds to the anti-symmetric SBr stretch in the elusive S=SBr2 species; it thus corroborates and complements an earlier partial IR spectra study attributable to S=SBr2. Including corrections for relativistic and core-valence correlation effects, we also predict 26.33 (12.74) kcal/mol for Delta H-f (298.15 K) of S=SBr2 (BrSSBr). For the S=SBr2 -> BrSSBr reaction, our best estimates for the Gibbs free energy and the enthalpy of the reaction at 298.15 K are -13.71 and -13.44 kcal/mol, respectively. For a value of Delta G(#) equal to 23.52 kcal/mol, we estimate a TST rate constant, at 298.15 K, of 3.57 x 10(-5) s(-1). (c) 2007 Elsevier B.V. All rights reserved.

Computational study of the step size parameter of the subgradient optimization method

The subgradient optimization method is a simple and flexible linear programming iterative algorithm. It is much simpler than Newton's method and can be applied to a wider variety of problems. It also converges when the objective function is non-differentiable. Since an efficient algorithm will not only produce a good solution but also take less computing time, we always prefer a simpler algorithm with high quality. In this study a series of step size parameters in the subgradient equation is studied. The performance is compared for a general piecewise function and a specific p-median problem. We examine how the quality of solution changes by setting five forms of step size parameter.

Equilíbrio líquido-líquido de sistemas aquosos com tensoativos polietoxilados: dados experimentais e modelagem

The nonionic surfactants when in aqueous solution, have the property of separating into two phases, one called diluted phase, with low concentration of surfactant, and the other one rich in surfactants called coacervate. The application of this kind of surfactant in extraction processes from aqueous solutions has been increasing over time, which implies the need for knowledge of the thermodynamic properties of these surfactants. In this study were determined the cloud point of polyethoxylated surfactants from nonilphenolpolietoxylated family (9,5 , 10 , 11, 12 and 13), the family from octilphenolpolietoxylated (10 e 11) and polyethoxylated lauryl alcohol (6 , 7, 8 and 9) varying the degree of ethoxylation. The method used to determine the cloud point was the observation of the turbidity of the solution heating to a ramp of 0.1 ° C / minute and for the pressure studies was used a cell high-pressure maximum ( 300 bar). Through the experimental data of the studied surfactants were used to the Flory - Huggins models, UNIQUAC and NRTL to describe the curves of cloud point, and it was studied the influence of NaCl concentration and pressure of the systems in the cloud point. This last parameter is important for the processes of oil recovery in which surfactant in solution are used in high pressures. While the effect of NaCl allows obtaining cloud points for temperatures closer to the room temperature, it is possible to use in processes without temperature control. The numerical method used to adjust the parameters was the Levenberg - Marquardt. For the model Flory- Huggins parameter settings were determined as enthalpy of the mixing, mixing entropy and the number of aggregations. For the UNIQUAC and NRTL models were adjusted interaction parameters aij using a quadratic dependence with temperature. The parameters obtained had good adjust to the experimental data RSMD < 0.3 %. The results showed that both, ethoxylation degree and pressure increase the cloudy points, whereas the NaCl decrease

Effects of aspirin on mesenteric lymph nodes of rabbits as basis for its use on lymph nodes metastases

OBJETIVO: Avaliar os efeitos do ácido acetilsalicílico a 10% e 20% em linfonodos mesentéricos de coelhos para posterior embasamento e uso em metástases linfonodais. MÉTODOS: Um total de 20 linfonodos de 20 coelhos (divididos aleatoriamente em quatro grupos) foi avaliado. As soluções de aspirina a 10% (grupos A e C) e 20% (grupos B e D) foram injetadas em linfonodos mesentéricos de coelhos sadios e seus efeitos macroscópicos e histológicos foram avaliados em 24 horas (grupos A e B) e em sete dias (grupos C e D). RESULTADOS: Nos grupos avaliados em 24 horas (A e B) foi verificada intensa necrose e hemorragia, aumento importante de apoptose em todo o linfonodo, com alargamento dos seios medulares e aumento dos centros germinativos. Nos grupos avaliados em sete dias (C e D) também houve aumento da apoptose, com maior elevação de histiócitos e diminuição importante da necrose; a hemorragia foi ausente e aumento de células gigantes foi visualizado, conferindo processo inflamatório crônico do tipo corpo estranho. Não houve diferença entre as concentrações utilizadas (10 e 20%) em nenhuma das comparações. CONCLUSÕES: A injeção de aspirina em linfonodos causou necrose e um aumento de apoptose após 24 horas e após sete dias de tratamento, houve regeneração dos gânglios linfáticos, com diminuição intensa de necrose e grande aumento de apoptose. Uma vez que o aumento de apoptose é um dos pilares dos tratamentos antineoplásicos, estes resultados experimentais embasam eventual aplicação clínica da aspirina no tratamento de metástases linfonodais.

Evaluation of a portable clinical analyzer for the determination of blood gas partial pressures, electrolyte concentrations, and hematocrit in venous blood samples collected from cattle, horses, and sheep

Objective To compare results reported for blood gas partial pressures, electrolyte concentrations, and Hct in venous blood samples collected from cattle, horses, and sheep and analyzed by use of a portable clinical analyzer (PCA) and reference analyzer (RA).Animals-Clinically normal animals (24 cattle, 22 horses, and 22 sheep).Procedures-pH; Pco(2); Po(2); total carbon dioxide concentration; oxygen saturation; base excess; concentrations of HCO(3)(-), Na(+), K(+), and ionized calcium; Hct; and hemoglobin concentration were determined with a PCA. Results were compared with those obtained for the same blood sample with an RA. Bias (mean difference) and variability (95% confidence interval) were determined for all data reported. Data were also subjected to analyses by Deming regression and Pearson correlation.Results-Analysis of Bland-Altman plots revealed good agreement between results obtained with the PCA and those obtained with the RA for pH and total carbon dioxide concentration in cattle, K(+) concentration in horses and sheep, and base excess in horses. Except for Na(+) concentration and Hct in horses and sheep, correlation was good or excellent for most variables reported.Conclusions and Clinical Relevance-Data from blood gas and electrolyte analyses obtained by use of the PCA can be used to evaluate the health status of cattle, horses, and sheep. Furthermore, the handheld PCA device may have a great advantage over the RA device as a result of the ability to analyze blood samples on farms that may be located far from urban centers. (Am J Vet Res 2010;71:515-521)

Determination of lead in the absence of supporting electrolyte using carbon fiber ultramicroelectrode without mercury film

The determination of lead ions directly in water, for application in analysis of samples of environmental interest, was studied by electroanalytical techniques. Linear sweep anodic stripping voltammetry with a carbon fiber disk ultramicroelectrode (7.0 mu m in diameter), without mercury film, has been used for lead determination, by standard addition, in purified water in the absence of supporting electrolyte. The response was linear in the range from 10.0 to 50.0 mu g L-1, with a detection limit of 0.8 mu g L-1, for 300 s preconcentration time, at -1.2 V and 1.0 V s(-1) scan rate. The reliability of the analytical procedure was evaluated by precision using relative standard deviations (5.6%, for three repetitive stripping current measurements of solution with 10.0 mu g L-1 lead ions) and by the accuracy with recovery experiments (mean of 110.8%) for the same concentration.

Aspirin increases tolerance to high temperature in seeds of Raphanus sativus L. cvar Early Scarlet Globe

The incubation of seeds of Raphanus sativus L. cvar Early Scarlet Globe with 10 mu M aspirin resulted in increase in the temperature range for germination. The analysis of percentage germination and germination rates indicated the increase in the optimum temperature from 21.4 to 26 degrees C although at 32.6 degrees C 80.8% of seeds germinated with aspirin and no germination in the control. The analysis of the kinetics of seed germination indicated that aspirin treatment resulted in germination by decreasing the enthalpy of activation of the process. The aspirin treatment also resulted in the synchronization of seed germination. on the base of our results we propose aspirin application in practice to increase the tolerance to high temperature and to synchronize seed germination at least in Raphanus sativus L. cvar early scarlet globe.

Effective diffusion coefficients behavior in osmotic dehydration of apple slices considering shrinking and local concentration dependence

The mass transfer during osmotic dehydration of apple slices immersed in 40, 50 and 60% (w/w) aqueous sucrose solutions was investigated to evaluate the influence of solution concentration on diffusivities. In the mathematical model, the diffusion coefficients were functions of the local water and sucrose concentration. The mass transfer equations were, simultaneously, solved for water and sucrose using an implicit numerical method. Material coordinates following the shrinkage of the solid were used. The predicted concentration profiles were integrated and compared to experimental data, showing a reasonable agreement with the measured data. on average, the effective diffusion coefficients for water and sucrose decreased as the osmotic solution concentration increased; that is the behavior of the binary coefficients in water-sucrose solutions. However, the diffusivities expressed as a function of the local concentration in the slices varied between the treatments. Water diffusion coefficients showed a remarkable variation throughout the slice and unusual behavior, which was associated to the cellular structure changes observed in tissue immersed in osmotic solutions. Cell structure changes occurred in different ways: moderate plasmolysis at 40%, accentuated plasmolysis at 50% and generalized damage of the cells at 60%. Intact vacuoles were observed after a long time of exposure (30 h) to 40 and 50% solutions. Effects of the concentration on tissue changes make it difficult to generalize the behavior of diffusion coefficients.

Vesicle-to-micelle transition in dioctadecyldimethylammonium bromide and dioctadecyldimethylammonium chloride dispersions induced by octaethylene glycol n-dodecyl monoether. An isothermal titration calorimetry study

We have used isothermal titration calorimetry to investigate the vesicle-to-micelle transition in dioctadecyldimethylammonium bromide (DODAB) and chloride (DODAC) vesicle dispersions induced by the nonionic surfactant octaethylene glycol n-dodecyl monoether (C12E8) at room temperature. Small and giant unilamellar vesicles were prepared by sonication and without sonication, respectively, of the pure cationic surfactants at low concentrations in water. The titration of 1.0 mM DODAX (X = Cl- and Br-) by a concentrated micellar solution of C12E8 shows that the enthalpy of interaction (DeltaH(obs)) of C12E8 in micellar form with DODAX is always endothermic. The titration curves are understood on the basis of superposition of the enthalpies of partitioning of C12E8 into the bilayer, of micelle formation and of vesicle-to-micelle transformation. The enthalpy, DeltaH(obs), initially increases owing to the incorporation of C12E8 into the vesicle bilayer until the C12E8/DODAX saturation ratio (R-sat) is reached, then DeltaH(obs) decreases, in different ways for DODAB and DODAC, owing to degradation of vesicles and formation of mixed micelles and intermediary structures up to the C12E8/DODAX solubilization ratio, R-sol. Above R-sol only mixed micelles exist. The surfactant solubilization takes place in three stages. All the critical ratios are lower for DODAB than for DODAC, meaning that C12E8 solubilizes more strongly in DODAB for example, R-sat is 0.8 for DODAB and 1.2 for DODAC. Sonication has no significant effect on the transition.

Influence of chemical activation of a 35% hydrogen peroxide bleaching gel on its penetration and efficacy-In vitro study

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thermodynamics of quasi-particles at finite chemical potential

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