Phase separation in aqueous solutions of lens gamma-crystallins: special role of gamma s.

We have studied liquid-liquid phase separation in aqueous ternary solutions of calf lens gamma-crystallin proteins. Specifically, we have examined two ternary systems containing gamma s--namely, gamma IVa with gamma s in water and gamma II with gamma s in water. For each system, the phase-separation temperatures (Tph (phi)) alpha as a function of the overall protein volume fraction phi at various fixed compositions alpha (the "cloud-point curves") were measured. For the gamma IVa, gamma s, and water ternary solution, a binodal curve composed of pairs of coexisting points, (phi I, alpha 1) and (phi II, alpha II), at a fixed temperature (20 degrees C) was also determined. We observe that on the cloud-point curve the critical point is at a higher volume fraction than the maximum phase-separation temperature point. We also find that typically the difference in composition between the coexisting phases is at least as significant as the difference in volume fraction. We show that the asymmetric shape of the cloud-point curve is a consequence of this significant composition difference. Our observation that the phase-separation temperature of the mixtures in the high volume fraction region is strongly suppressed suggests that gamma s-crystallin may play an important role in maintaining the transparency of the lens.

Liquid-phase combinatorial synthesis.

A concept termed liquid-phase combinatorial synthesis (LPCS) is described. The central feature of this methodology is that it combines the advantages that classic organic synthesis in solution offers with those that solid-phase synthesis can provide, through the application of a linear homogeneous polymer. To validate this concept two libraries were prepared, one of peptide and the second of nonpeptide origin. The peptide-based library was synthesized by a recursive deconvolution strategy [Erb, E., Janda, K. D. & Brenner, S. (1994) Proc. Natl. Acad. Sci. USA 91, 11422-11426] and several ligands were found within this library to bind a monoclonal antibody elicited against beta-endorphin. The non-peptide molecules synthesized were arylsulfonamides, a class of compounds of known clinical bactericidal efficacy. The results indicate that the reaction scope of LPCS should be general, and its value to multiple, high-throughput screening assays could be of particular merit, since multimilligram quantities of each library member can readily be attained.

Diagnóstico da exposição fetal ao álcool através de biomarcadores em mecônio

A grande prevalência do consumo de álcool por mulheres em idade reprodutiva aliada à gravidez não planejada expõe a gestante a um elevado risco de se alcoolizar em algum momento da gestação, principalmente no início do período gestacional em que a maioria delas ainda não tomou ciência do fato. Assim, torna-se extremamente relevante o desenvolvimento de métodos de detecção precoce de recém-nascidos em risco de desenvolvimento de problemas do espectro dos transtornos relacionados à exposição fetal ao álcool. O objetivo desse estudo foi desenvolver, validar e avaliar a eficácia de um método de quantificação de ésteres etílicos de ácidos graxos (FAEEs) no mecônio de recém-nascidos para avaliação da exposição fetal ao álcool. Os FAEEs avaliados foram: palmitato de etila, estearato de etila, oleato de etila e linoleato de etila.O método consistiu no preparo das amostras pela extração líquido-líquido utilizando água, acetona e hexano, seguida de extração em fase sólida empregando cartuchos de aminopropilsilica. A separação e quantificação dos analitos foi realizada por cromatografia em fase gasosa acoplada à espectrometria de massas. Os limites de quantificação (LQ) variaram entre 50-100ng/g. A curva de calibração foi linear de LQ até 2000ng/g para todos os analitos. A recuperação variou de 69,79% a 106,57%. Os analitos demonstraram estabilidade no ensaio de pós-processamento e em solução. O método foi aplicado em amostras de mecônio de 160 recém-nascidos recrutados em uma maternidade pública de Ribeirão Preto-SP. O consumo de álcool materno foi reportado utilizando questionários de rastreamento validados T-ACE e AUDIT e relatos retrospectivos da quantidade e frequência de álcool consumida ao longo da gestação. A eficácia do método analítico em identificar os casos positivos foi determinada pela curva Receiver Operating Characteristic (ROC). O consumo alcoólico de risco foi identificado pelo T-ACE em 31,3% das participantes e 50% reportaram o uso de álcool durante a gestação. 51,3% dos recém-nascidos apresentaram FAEEs em seu mecônio, sendo que 33,1% apresentaram altas concentrações para a somatória dos FAEEs (maior que 500ng/g), compatível com um consumo abusivo de álcool. O oleato de etila foi o biomarcador mais prevalente e o linoleato de etila foi o biomarcador que apresentou as maiores concentrações. Houve uma variabilidade no perfil de distribuição dos FAEEs entre os indivíduos, e discordâncias entre a presença de FAEEs e o consumo reportado pela mãe. A concentração total dos FAEEs nos mecônio mostrou-se como melhor indicador da exposição fetal ao álcool quando comparado com o uso de um único biomarcador. O ponto de corte para esta população foi de aproximadamente 600ng/g para uso tipo binge (três ou mais doses por ocasião) com sensibilidade de 71,43% e especificidade de 84,37%. Este estudo reforça a importância da utilização de métodos laboratoriais na identificação da exposição fetal ao álcool.

Separation and fractionation of order and disorder in highly polydisperse systems

We study a polydisperse soft-spheres model for colloids by means of microcanonical Monte Carlo simulations. We consider a polydispersity as high as 24%. Although solidification occurs, neither a crystal nor an amorphous state are thermodynamically stable. A finite size scaling analysis reveals that in the thermodynamic limit: a the fluid-solid transition is rather a crystal-amorphous phase-separation, b such phase-separation is preceded by the dynamic glass transition, and c small and big particles arrange themselves in the two phases according to a complex pattern not predicted by any fractionation scenario.

Estudo da intensificação da coalescência de emulsões de água em óleo com a aplicação de onda estacionária de ultrassom.

Considerando que o petróleo quando extraído dos poços em águas profundas chega a ter teor de água superior a 50% e que antes de ser enviado à refinaria deve ter uma quantidade de água inferior a 1%, torna-se necessário o uso de técnicas de redução da quantidade de água. Durante a extração do petróleo formam-se emulsões de água em óleo que são muito estáveis devido a um filme interfacial contendo asfaltenos e/ou resinas ao redor das gotas de água. Nesse trabalho é apresentada a utilização de ondas estacionárias de ultrassom para realizar a quebra dessas emulsões. Quando gotículas de água com dimensões da ordem de 10m, muito menores que o comprimento de onda, são submetidas a um campo acústico estacionário em óleo, a força de radiação acústica empurra as gotículas para os nós de pressão da onda. Uma célula de coalescência com frequência central ao redor de 1 MHz, constituída por quatro camadas sendo uma piezelétrica, uma de acoplamento sólido, uma com o líquido e outra refletora, foi modelada empregando o método da matriz de transferência, que permite calcular a impedância elétrica em função da frequência. Para minimizar o efeito do gradiente de temperatura entre a entrada e a saída da cavidade da célula, quando está em operação, foram utilizados dois transdutores piezelétricos posicionados transversalmente ao fluxo que são excitados e controlados independentemente. Foi implementado um controlador digital para ajustar a frequência e a potência de cada transdutor. O controlador tem como entrada o módulo e a fase da corrente elétrica no transdutor e como saída a amplitude da tensão elétrica e a frequência. Para as células desenvolvidas, o algoritmo de controle segue um determinado pico de ressonância no interior da cavidade da célula no intervalo de frequência de 1,09 a 1,15 MHz. A separação acústica de emulsões de água em óleo foi realizada em uma planta de laboratório de processamento de petróleo no CENPES/PETROBRAS. Foram testados a variação da quantidade de desemulsificante, o teor inicial de água na emulsão e a influência da vazão do sistema, com uma potência de 80 W. O teor final de água na emulsão mostrou que a aplicação de ultrassom aumentou a coalescência de água da emulsão, em todas as condições testadas, quando comparada a um teste sem aplicação de ultrassom. Identificou-se o tempo de residência no interior da célula de separação como um fator importante no processo de coalescência de emulsões de água e óleo. O uso de desemulsificante químico é necessário para realizar a separação, porém, em quantidades elevadas implicaria no uso de processos adicionais antes do repasse final do petróleo à refinaria. Os teores iniciais de água na emulsão de 30 e 50% indicam que o uso da onda estacionária na coalescência de emulsões não tem limitação quanto a esse parâmetro. De acordo com os resultados obtidos em laboratório, essa técnica seria indicada como uma alternativa para integrar um sistema de processamento primário em conjunto com um separador eletrostático.

Optimal synthesis of liquid-liquid multistage extractors

Presentation in the 11th European Symposium of the Working Party on Computer Aided Process Engineering, Kolding, Denmark, May 27-30, 2001.

Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions

Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101–107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14–46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π–π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples.

Mapping Binary Liquid-Vapor or Liquid-Liquid-Vapor Equilibria Regions, including the Different Azeotropic Behaviours, as a Function of the NRTL Binary Parameters

13th Mediterranean Congress of Chemical Engineering (Sociedad Española de Química Industrial e Ingeniería Química, Fira Barcelona, Expoquimia), Barcelona, September 30-October 3, 2014

Beyond the H2/CO2 upper bound: one-step crystallization and separation of nano-sized ZIF-11 by centrifugation and its application in mixed matrix membranes

The synthesis of nano-sized ZIF-11 with an average size of 36 ± 6 nm is reported. This material has been named nano-zeolitic imidazolate framework-11 (nZIF-11). It has the same chemical composition and thermal stability and analogous H2 and CO2 adsorption properties to the conventional microcrystalline ZIF-11 (i.e. 1.9 ± 0.9 μm). nZIF-11 has been obtained following the centrifugation route, typically used for solid separation, as a fast new technique (pioneering for MOFs) for obtaining nanomaterials where the temperature, time and rotation speed can easily be controlled. Compared to the traditional synthesis consisting of stirring + separation, the reaction time was lowered from several hours to a few minutes when using this centrifugation synthesis technique. Employing the same reaction time (2, 5 or 10 min), micro-sized ZIF-11 was obtained using the traditional synthesis while nano-scale ZIF-11 was achieved only by using centrifugation synthesis. The small particle size obtained for nZIF-11 allowed the use of the wet MOF sample as a colloidal suspension stable in chloroform. This helped to prepare mixed matrix membranes (MMMs) by direct addition of the membrane polymer (polyimide Matrimid®) to the colloidal suspension, avoiding particle agglomeration resulting from drying. The MMMs were tested for H2/CO2 separation, improving the pure polymer membrane performance, with permeation values of 95.9 Barrer of H2 and a H2/CO2 separation selectivity of 4.4 at 35 °C. When measured at 200 °C, these values increased to 535 Barrer and 9.1.

Determination of fat-soluble vitamins in vegetable oils through microwave-assisted high-performance liquid chromatography

In this manuscript, a study of the effect of microwave radiation on the high-performance liquid chromatography separation of tocopherols and vitamin K1 was conducted. The novelty of the application was the use of a relatively low polarity mobile phase in which the dielectric heating effect was minimized to evaluate the nonthermal effect of the microwave radiation over the separation process. Results obtained show that microwave-assisted high-performance liquid chromatography had a shorter analysis time from 31.5 to 13.3 min when the lowest microwave power was used. Moreover, narrower peaks were obtained; hence the separation was more efficient maintaining or even increasing the resolution between the peaks. This result confirms that the increase in mobile phase temperature is not the only variable for improving the separation process but also other nonthermal processes must intervene. Fluorescence detection demonstrated better signal-to-noise compared to photodiode arrayed detection mainly due to the independent effect of microwave pulses on the baseline noise, but photodiode array detection was finally chosen as it allowed a simultaneous detection of nonfluorescent compounds. Finally, a determination of the content of the vitamin E homologs was carried out in different vegetable oils. Results were coherent with those found in the literature.

Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

In early spring the Baltic region is frequently affected by high-pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ngm-3 and black carbon (BC) up to 17 μgm-3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf/ was the dominant fraction of PM1, with the primary (POCnf/ and secondary (SOCnf/ fractions contributing 26–44% and 13–23% to the total carbon (TC), respectively. 5–8% of the TC had a primary fossil origin (POCf/, whereas the contribution of fossil secondary organic carbon (SOCf/ was 4–13 %. Nonfossil EC (ECnf/ and fossil EC (ECf/ ranged from 13–24 and 7–13 %, respectively. Isotope ratios of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

Source separation collection and processing equipment : final report.

"January 1981"--Cover.

Source separation : the community awareness program in Somerville and Marblehead, Massachusetts /

Mode of access: Internet.

Multimaterial source separation in Marblehead and Somerville, Massachusetts /

December 1979.

Liquid thermal diffusion /

"Other copies of this report may bear the number NRL-O-2982"--Page 2 of cover.