Analytical method development for the uptake study of different organic pollutants by crops cultivated in compost-amended soils

256 p.

M(C6H16N3)2(VO3)4 as heterogeneous catalysts. Study of three new hybrid vanadates of cobalt(II), nickel(II) and copper(II) with 1-(2-aminoethyl)piperazonium.

postprint

Síntese de ésteres derivados do ácido oléico empregando lipases produzidas por Yarrowia lipolytica

Biodiesel é um biocombustível que consiste na mistura de ésteres monoalquílicos de ácidos graxos de cadeia longa. O processo usual de produção deste combustível é a transesterificação de óleos vegetais com álcoois de cadeia curta. Nesse processo, a matéria prima deve conter baixo conteúdo de ácido graxos livres ( ≤ 1%) e água (≤ 0,5%). Como alternativa ao processo de transesterificação, destaca-se o emprego de matérias-primas de baixo custo, com elevado teor de ácidos graxos livres, para a síntese de ésteres alquílicos através de reações de esterificação. As reações de produção do biodiesel podem ser catalisadas por via química (ácida e básica) ou enzimática. Na catálise enzimática, os biocatalisadores empregados são as lipases, que catalisam a hidrólise e síntese de ésteres e podem ser obtidas a partir de microrganismos, plantas ou tecido animal, sendo as de origem microbiana as mais utilizadas. O objetivo principal deste trabalho foi avaliar o potencial da lipase de Yarrowia lipolytica, uma levedura não convencional, na síntese de ésteres do ácido oleico visando à obtenção de ésteres alquílicos (biodiesel). Foram estudados os efeitos da temperatura (25, 30, 35, 40, 50 e 60oC), do teor enzimático (5, 10, 20, 30 e 40% v/v) e do tipo de álcool (metanol, etanol, n-propanol e n-butanol ) nas reações de esterificação do ácido oleico empregando o extrato enzimático líquido produzido por Yarrowia lipolytica. Os resultados obtidos mostraram que as reações conduzidas a 30oC e com 10% v/v do extrato enzimático apresentaram maior taxa inicial de reação. Também foi avaliada a utilização do extrato enzimático liofilizado (5% m/v) e do PES (produto enzimático sólido) (5% m/v) de Yarrowia lipolytica na reação de esterificação do ácido oleico com n-butanol a 30oC. O maior consumo de ácido oleico ocorreu na reação conduzida com o PES. O efeito da temperatura (25, 30, 35, 40 e 50oC) na síntese de oleato de butila foi, então, investigado nas reações empregando PES como biocatalisador e a maior conversão de ácido oleico foi verificada na temperatura de 40oC

Preparação, caracterização e avaliação de nanocompósitos de PBAT/amido de milho e vermiculita organofilizada

Nos últimos 20-30 anos polímeros biodegradáveis vêm sendo estudados e desenvolvidos e atualmente já são comercializados. Contudo, o custo, a processabilidade e algumas propriedades ainda dificultam a penetração desses polímeros no mercado e a competição com as chamadas commodities. Não são poucos os autores que se dedicam a desenvolver aditivos e formulações para superar essas limitações. Desta forma, esta Tese se dedicou ao desenvolvimento de compósitos de Ecobras, fabricado pela Basf e comercializado pela Corn Products, utilizando como carga mineral resíduo da extração da bauxita, no município de Santa Luzia/PB, o qual consiste em sua totalidade de vermiculita. Esta vermiculita foi quimicamente modificada com sais de alquil fosfônio para melhorar a compatibilidade com a matriz polimérica e também espaçar as camadas de aluminossilicato. De fato, a modificação com o brometo de hexadecil tributil fosfônio resultou na esfoliação da vermiculita tornando-a potencialmente apropriada para a obtenção de nanocompósitos. A preparação dos compósitos foi realizada pelo método de intercalação no estado fundido e foram comparadas a utilização da câmara interna de mistura e da mini extrusora de dupla rosca, sendo esta última mais eficaz na dispersão da vermiculita, conforme revelado pela microscopia eletrônica de varredura, difração de raios-X e reometria de placas. O grau de dispersão também foi influenciado pela estrutura química do modificador da vermiculita e pelo teor dessa carga incorporada à matriz. Teores mais elevados levaram a formação de aglomerados, enquanto a modificação da carga implicou na formação de micro e nanocompósitos. Ainda houve alterações das propriedades térmicas com aumento dos valores da temperatura de transição vítrea, de cristalização e fusão, embora o grau de cristalinidade tenha sido mantido. Nitidamente, foram obtidos materiais mais rígidos, com maior módulo e menor capacidade de deformação. Cerca de 58% de perda de massa foi observada para os micro e nanocompósitos obtidos após 17 semanas de enterro em solo simulado para avaliação da biodegradabilidade, valor bem próximo ao Ecobras puro. De modo geral, a incorporação das diferentes vermiculitas retardou nas primeiras semanas a biodegradação, provavelmente em função de modificações na estrutura cristalina, conforme sugerido pelos maiores valores de temperatura de fusão observados durante o acompanhamento do processo de biodegradação. No entanto, após 7 semanas os perfis de biodegradação dos micro e nanocompósitos se aproximaram bastante do Ecobras puro. Desta forma, foi possível nesta Tese obter um nanocompósito de Ecobras com vermiculita modificada com brometo de hexadecil fosfônio utilizando ferramentas comuns de processamento no estado fundido com biodegradabilidade próxima ao polímero de partida, porém mais rígido e menos deformável

Effects of natural gas pipeline condensate and crude oil spills, and comments on remediation, with emphasis on south Louisiana salt marshes: a review

This report reviews some of the natural ecological processes at work within a salt marsh as they relate to a spill of natural gas condensate - a mixture of aliphatic hydrocarbons, n-hexane, benzene, toluene, and xylene. It also reviews the environmental impacts of some of the components of natural gas condensate as well as related compounds (crude oil, higher molecular weight hydrocarbons, polycyclic aromatic hydrocarons - PAHs, linear alkyl-benzenes - LABs, etc.) on salt marsh ecosystems in southern Louisiana and elsewhere in the world. The behavior and persistence of these compounds once they have entered the environment is also considered.

The effect of dopants on the twist elastic constant and the rotational viscosity coefficient for nematics

The twist elastic constant, K2, and the rotational viscosity coefficient, γ1, are of importance when the response lime for the in-plane switching mode is studied. Since adding dopants is one technique to improve the response characteristics, the effect of dopants on these physical properties is significant. The effect on K2 and γ1 of adding alkyl(alkoxy) phenylcyclopentenones and alkyl(alkoxy) cyanobiphenyls to the base mixture ZLI-4792 together with their temperature dependence have been investigated using different temperature scales. The reduced temperature scale showed the effect of these dopants on K2 is small. On the other hand, the temperature dependence of γ1 depends on both the absolute temperature scale and the reduced temperature scale. Therefore, it is clear that the choice of temperature scale with which to compare γ1 for different systems raises fundamental questions which way not have a unique answer. 2000 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint.

New chiral ether derivatives of 2-arylidene-p-menthane-3-ones as components of induced ferroelectric systems

New 2-arylidene-p-menthane-3-ones containing the ether bridging group in the arylidene fragment have been synthesized and studied as chiral dopants in ferroelectric liquid crystal mixtures. The ferroelectric properties of these compositions were compared with those for compositions including chiral dopants that do not contain any bridging group. The influence of bridging group and terminal alkyl substituent length in the dopant molecule on the ferroelectric parameters of systems studied is discussed. © 2001 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group,.

Perylene-based fluorescent liquid crystal dye guest-host mixtures

We present a study on a series of dye guest-host mixtures using fluorescent perylene-based molecules as the guest dye in an organosiloxane host. These hosts have temperature-independent switching, at room temperature, through 90° for fields of the order of 10 Vrms/μm. Perylene molecules have been grafted onto the organosiloxane moiety via an alkyl spacer producing novel and rugged fluorescent dyes that are readily miscible in the host. Micro-separation of the low molar mass siloxane groups in the mesophases tend to form smectic phases. These planes produce an effective two-dimensional polymer backbonethat engenders the rugged mechanical properties of polymeric liquid crystals onto these low molar mass ferroelectric liquid crystals. In this study we show how the introduction of the dye molecules affects the electro-optic properties of the organosiloxane host. © 2001 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group,.

Photo-assisted hydrosilylation of silicon nanoparticles: Dependence of particle size on grafting chemistry

Silicon nanoparticles between 2.5 nm and 30 nm in diameter were functionalized by means of photoassisted hydrosilylation reactions in the aerosol phase with terminal alkenes of varying chain length. Using infrared spectroscopy and nuclear magnetic resonance, the chemical composition of the alkyl layer was determined for each combination of particle size and alkyl chain length. The spectroscopic techniques were used to determine that smaller particles functionalized with short chains in the aerosol phase tend to attach to the interior (β) alkenyl carbon atom, whereas particles >10 nm in diameter exhibit attachment primarily with the exterior (α) alkenyl carbon atom, regardless of chain length. © 2011 American Chemical Society.

Flexoelectric and elastic coefficients of odd and even homologous bimesogens.

It is known that bimesogenic liquid crystals exhibit a marked "odd-even" effect in the flexoelastic ratio (the effective flexoelectric coefficient to the average elastic coefficient), with the ratio being higher for the "odd-spaced" bimesogens (those with an odd number of alkyl groups in the spacer chain) than their neighboring even-spaced counterparts. To determine the contribution of each property to the flexoelastic ratio, we present experimental results on the flexoelectric and elastic coefficients of two homologous nonsymmetric bimesogens which possess odd and even alkyl spacers. Our results show that, although there are differences in the flexoelectric coefficients, there are substantially larger differences in the effective elastic coefficient. Specifically, the odd bimesogen is found to have both a low splay elastic coefficient and a very low bend elastic coefficient which, when combined, results in a significantly lower effective elastic coefficient and consequently a higher flexoelastic ratio.

Flexoelectric and elastic coefficients of odd and even homologous bimesogens.

It is known that bimesogenic liquid crystals exhibit a marked "odd-even" effect in the flexoelastic ratio (the effective flexoelectric coefficient to the average elastic coefficient), with the ratio being higher for the "odd-spaced" bimesogens (those with an odd number of alkyl groups in the spacer chain) than their neighboring even-spaced counterparts. To determine the contribution of each property to the flexoelastic ratio, we present experimental results on the flexoelectric and elastic coefficients of two homologous nonsymmetric bimesogens which possess odd and even alkyl spacers. Our results show that, although there are differences in the flexoelectric coefficients, there are substantially larger differences in the effective elastic coefficient. Specifically, the odd bimesogen is found to have both a low splay elastic coefficient and a very low bend elastic coefficient which, when combined, results in a significantly lower effective elastic coefficient and consequently a higher flexoelastic ratio.

Calibration of alkenone unsaturation index with growth temperature for a lacustrine species, Chrysotila lamellosa (Haptophyceae)

Although long chain alkenones (LCKs) occur widely in lacustrine sediments, their origin is not clear. Here, we report a lacustrine source, the non-calcifying species Chrysotila lamellosa Anand (Haptophyceae), collected and isolated from an inland saline water body, Lake Xiarinur (Inner Mongolia, China). Its alketione pattern is similar to those of coastal marine strains of C lamellosa,but the relationship between U-37(K') index and culture temperature for the lacustrine species is quite different from that of the coastal species. A significant feature of the alkenones in this strain of C lamellosa is a lack of C-38 methyl alkenones, which might be used to distinguish the species from the marine haptophyte species Emiliania huxleyi and Gephyrocapsa oceanica. The higher C-38 tetraunsaturated compound abundance might be another important feature for distinguishing the C lamellosa alkenone producer from the coastal species Isochrysis galbana. This alkenone distribution pattern has been detected in many lakes, which suggests that C lamellosa or a closely related species might be a very common alkenone precursor in lacustrine systems. We examined U-37(K') and U-37(K) values for C lamellosa as a function of culture temperature in a batch culture experiment. The calibration for U-37(K') vs. culture temperature (T) was U-37(K') = 0.0011 x T-2 - 0.0157 x T + 0.1057(n = 14, r(2) = 0.99) from 10 degrees C to 22 degrees C or U-37(K') = 0.0257 x T - 0.2608(n = 9, r(2) = 0.97) from 14 degrees C to 22 degrees C. U-37(K) vs. culture temperature was U-37(K) = 0 0377 x T - 0.5992(n = 14, r(2) = 0.98) from 10 degrees C to 22 degrees C. Our experiments show that the alkenone unsaturation index (U-37(K')) is strongly controlled by culture temperature and can be used for palaeoclimate reconstruction. (C) 2007 Elsevier Ltd. All rights reserved.

Estrogenic effects from household stoves

With the application of a genetically modified yeast, estrogen receptor-activating compounds were detected in the soot and emission gas of a wood-burning household stove. The EC50 value of 17beta-estradiol was divided by the EC50 value of soot, and the obtained relative estrogenic value for raw soot was 2.37E-5, indicating that soot was about 100,000 times less estrogenic than 17beta-estradiol. Chemical analysis revealed that alkyl phenol, benzonic acid, and PAHs represented the major constituents in the most potent fractions of the soot. Along with PAHs, other constituents might also contribute to the estrogenicity of soot. (C) 2002 Elsevier Science (USA).

含氮氧磷多齿配体稀土烷基配合物的合成、表征及催化丙交酯聚合

1. 合成了三齿水杨醛稀土配合物，发现配体中含有柔性取代基易生成均配物，而刚性较强的配体生成单烷基配合物。考察了单体浓度、聚合时间等因素对配合物催化丙交酯聚合活性的影响。 2. 以含二苯基膦苯胺的β-二酮单亚胺三齿配体合成了双配体单烷基稀土配合物，空间位阻比较大，因而引发丙交酯聚合的速度比较快。 3. 合成了含甲氧基侧基的芳氧胺四齿双烷基配合物，并合成了芳氧胺与茂（茚）混配的稀土单烷基配合物。首次将它们用于丙交酯的聚合，实验结果发现，双烷基配合物中的双烷基是作为双活性中心起作用的。 4. 合成了含双吡咯烷的稀土烷基配合物，将之应用于丙交酯的聚合，发现位阻大的配合物催化聚合可控性好。并应用双吡咯烷配合物进行了丙交酯和己内酯的共聚合研究。