Determinação de bussulfano em plasma através de cromatografia líquida de alta eficiência com detector de arranjo de diodos e derivatização com dietilditiocarbamato de sódio

A high performance liquid chromatographic-diode array detection method for the determination of busulfan in plasma was developed and validated. Sample preparation consisted of protein precipitation followed by derivatization with sodium diethyldithiocarbamate and liquid-liquid extraction with methyl-tert-butyl ether. Chromatograms were monitored at 277 nm. Separation was carried out on a Lichrospher RP 18 column (5 µm, 250 x 4 mm). The mobile phase consisted of water and acetonitrile (20:80, v/v). The method presented adequate specificity, linearity, precision and accuracy and allowed reliable determination of busulfan in clinical plasma samples, being applied to three patients submitted to bone marrow transplantation.

Síntese e caracterização de copolímeros de cadeia lateral derivados de acrilatos de 4,5-di-hidroisoxazol e do (-)-mentol

Five monomers 5-[4-(5-cyano-4,5-dihydroisoxazol-3-yl)phenoxy]undecyl acrylate (7a); n-alkyl 3-{4-[5-(acryloyloxyundecyl)oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylate (7b,c for n-butyl and n-hexyl, respectively); 3-{4-[5-(acryloyloxyundecyl) oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylic acid (7d) and (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl acrylate (9) and the corresponding copolymers 10a-d,11 and homopolymers 12 from 7a and 13 from 9 were designed and synthesized. Except for acrylate 9 which is derived from (-)-menthol, all of the monomers belong to the series containing the isoxazoline ring linked to the acrylate unit by a flexible spacer chain of eleven methylene units. They presented low glass temperature and despite birefringence behavior, these copolymers showed no mesomorphic properties.

Epoxidação do óleo de soja com o sistema catalítico [MoO2(acac)2]/TBHP EM [bmim][PF6]

Epoxidation of soybean oil was investigated using 1-n-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] ionic liquid as biphasic medium with molybdenum(VI) acetylacetonate complex and tert-butyl hydroperoxide TBHP as oxidizing agent. Reaction conditions were molar ratio TBHP:number of double bonds of oil:catalyst of 100:100:1, reaction temperature of 60 ºC and reaction time between 2 and 24 h. The proposed system showed catalytic activity for epoxidation reactions under tested conditions. Reuse of ionic liquid/catalyst system for epoxidation reactions was also investigated. Evaluation of epoxidation observed in this catalytic system was done by quantitative ¹H NMR data.

Triagem de suportes orgânicos e protocolos de ativação na imobilização e estabilização de lipase de Thermomyces lanuginosus

Lipase from Thermomyces lanuginosus was covalently immobilized on activated poly-hydroxybutyrate, sugarcane bagasse and the chemically modified hybrid hydrogel chitosan-alginate prepared by different strategies. Among the tested supports, chitosan-alginate chemically modified with 2,4,6-trinitrobenzenesulfonic acid rendered derivatives with the highest hydrolytic activity and thermal-stability, 45-fold more stable than soluble lipase and was then selected for further studies. The pH of maximum activity was similar for both immobilized and free lipase (pH 8.0) while optimum temperature was 5 - 10 ºC higher for the immobilized lipase. Higher yields in the butyl butyrate synthesis were found for the derivatives prepared by activation with glycidol and epichlorohydrin.

Determinação da constante de velocidade absoluta para a reação de abstração de hidrogênio fenólico pelo estado excitado triplete de xantona em acetonitrila e no líquido iônico hexafluorfosfato de 1-butil-3-metil-imidazólio [bmim.PF6]

The triplet excited state of xanthone was generated and characterized by laser flash photolysis in acetonitrile (λmax=620 nm; t=1.8 ms) and in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim.PF6] (λmax=620 nm; t=3.0 ms). It reacts with phenols yielding the corresponding xanthone ketyl radical. Stern-Volmer plots for the reaction of triplet xanthone with phenols led to the determination of absolute rate constants for phenolic hydrogen abstraction in the order of ~10(9) Lmol-1s-1 in acetonitrile and ~10(8) Lmol-1s-1 in [bmim.PF6]. The lower diffusioncontrolled rate constant for [bmim.PF6] is responsible for the difference in the phenolic hydrogen abstraction rate constants in this solvent.

Equipamento de baixo custo para extração em fase sólida em amostras aquosas de grande volume utilizando pressão positiva de N

Extraction/concentration is a crucial step for the analysis of organic compounds at trace level concentrations and dispersed in complex matrices. Solid-phase extraction (SPE) is one of the techniques used for this purpose. In this work, a low cost apparatus for SPE was developed that uses nitrogen under positive pressure and ensures the maintenance of the sample flow, while also allows the simultaneous extraction of different samples without cross-contamination and sample contact with plastic materials. For the system set up, easily accessible materials were used such as hypodermic needles, stainless steel tubes, rubber stoppers, and 3-way valves from serum delivery apparatus.

Constituintes químicos das cascas do caule de Vochysia thyrsoidea Pohl. (Vochysiaceae) e avaliação das atividades citotóxica e inibitória frente as catepsinas B e K

A new flavonoid, catechin-3-O-(3"-O-trans-cinnamoyl)-α-rhamnopyranoside, along with known compounds, catechin-3-O-α-rhamnopyranoside, 3-oxo-urs-12-en-28-oic acid, 2,4,6-trimethoxybenzoic acid, 2-butyl-D-fructofuranoside and 1-butyl-D-fructofuranoside, has been isolated from the stem bark of V. thyrsoidea. These compounds were assayed for inhibition of protease activity (cathepsins B and K) and against cancer cell lines. Catechin-3-O-(3"-O-trans-cinnamoyl)-α-rhamnopyranoside showed moderate inhibitory activity (IC50 = 62.02 µM) against cathepsin B while 2-butyl-D-fructofuranoside was the most potent against a strain of CNS (SF-295) and human leukemia (HL-60) with IC50 = 36.80 µM and IC50 = 25.37 µM, respectively.

Interacciones de la glicina en soluciones acuosas de tetrafluoroborato de 1-butil, 3-metilimidazolio a diferentes temperaturas

Densities of glycine in aqueous solutions of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate were determined at temperatures ranging from 283.15 to 313.15 K. The apparent molar volume, infinite dilution apparent molar volume, second derivative of the infinite dilution partial molar volume with respect to temperature, partial molar volume of transfer at infinite dilution, and the number of hydration were determined. It was found that the apparent molar volume at infinite dilution was positive, but decreased with increasing ionic liquid concentration and increased with increasing temperature. On the other hand, the partial molar volume of transfer at infinite dilution behaved in a similar manner, but was negative.

Estudio de copolimerización injerto del acrilato de butilo sobre almidón empleando sistema iniciador redox

The mixture of synthetic and natural materials yields a material with improved physical-chemical properties. One way of obtaining this kind of material is through graft copolymerization. Some natural materials have been used in graft copolymerization with synthetic monomers. In this work, graft copolymerization of butyl acrylate (BA) onto starch using a redox initiator system was carried out. The graft yield was evaluated for different reaction conditions. The graft copolymer was characterized by infrared spectroscopy, thermal analysis and scanning electron microscopy (SEM).

Synthesis, characterization and computational studies of (E)-2-{[(2-aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butylphenol

(E)-2-{[(2-Aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butyl-phenol ( 3: ), a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, ¹H-NMR, 13C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL) charge transfer.

Líquidos iônicos como plastificantes em blendas de borracha nitrílica/polianilina

Two imidazolium-based ionic liquids (C4MIMTf2N and C4MIMBF4) were used to verify their influence on polyaniline (PANI) and nitrile rubber (NBR)/PANI blend properties and the vulcanization process. High conductivity values were observed for PANI-C4MIMTf2N samples and no interference was found for the C4MIMBF4 samples. These materials were added to NBR by mechanical mixing. Based on the torque results, the presence of C4MIMBF4 does not protect the vulcanization reaction of NBR with PANI as performed by C4MIMTf2N. The highest conductivity value was obtained with 7 wt. % of PANI-DSBA-C4MIMTf2N (10-6 S/cm). This result is attributed to the more effective interaction of PANI and NBR phases promoted by the ionic liquid.

APROVEITAMENTO DE RESÍDUO DE BIODIESEL PARA PREPARAÇÃO DE CARVÕES ÁCIDOS COM ELEVADA ATIVIDADE CATALÍTICA NA REAÇÃO DE ETERIFICAÇÃO DO GLICEROL

Environmentally friendly acid carbon (CG) catalysts, containing a high amount of sulfonated and oxygenated groups, were prepared from glycerin, a biodiesel waste. CGs were produced by glycerin carbonization in the presence of H2SO4 at 1:3 m:m ratio in a closed autoclave at 180ºC for different times: 0.25; 1; 3 and 6 hours (CG-0.25h; CG-1h; CG-3h and CG-6h, respectively). The catalyst properties for all carbons were evaluated in the glycerol etherification reaction with tert-butyl alcohol (TBA). The yield for mono-tert-butyl glycerol (MTBG), di-tert-butyl glycerol (DTBG) and tri-tert-butyl-glycerol (TTBG) was high and very similar for all CGs, of about 43% and 20% for the MTBG and DTBG + TTBG, respectively. Furthermore, the activity of these catalysts were close to those obtained using a commercial resin, Amberlyst-15, of about 50% and 27% for MTBG and DTBG + TTBG, respectively.

Molecular characterization of Brazilian Dicyma pulvinata isolates

Forty-nine Brazilian Dicyma pulvinata isolates were examined by morphological traits and RFLP, RAPD and AFLP analyses. This fungus is a mycoparasite of Microcyclus ulei, the causal agent of the most devastating rubber (Hevea brasiliensis) disease, known as "South American Leaf Blight" (SALB). These isolates were compared with an Indian isolate from Cercosporidium sp., and a French isolate from Cladosporium fulvum. They were also compared with Dicyma ampullifera from Papua New Guinea. The morphological parameters analyzed confirmed the identification of the Brazilian isolates. The graphic representations of the distance matrices of each molecular marker showed similar results. Dicyma pulvinata isolates from M. ulei were closely related, whereas the reference isolates examined were dispersed. Among the D. pulvinata isolates obtained from M. ulei, a significant pairwise distance was obtained, for all the molecular markers, between the isolates from the areas favorable to the occurrence of SALB (North and Northeast of Brazil) and the region of escape for the disease (Mato Grosso State).

Lipase-catalyzed Approaches towards Secondary Alcohols: Intermediates for Enantiopure Drugs

The use of enantiopure intermediates for drug synthesis is a trend in pharmaceutical industry. Different physiological effects are associated with the enantiomers of chiral molecules. Thus, the safety profile of a drug based on an enantiopure active pharmaceutical ingredient is more reliable. Biocatalysis is an important tool to access enantiopure molecules. In biocatalysis, the advantage of selectivity (chemo-, regio- and stereoselectivity) is combined with the benefits of a green synthesis strategy. Chemoenzymatic syntheses of drug molecules, obtained by combining biocatalysis with modern chemical synthesis steps usually consists of fewer reaction steps, reduced waste production and improved overall synthetic efficiency both in yields and enantio- and/or diastereoselectivities compared with classical chemical synthesis. The experimental work together with the literature review clearly indicates that lipase catalysis is highly applicable in the synthesis of enantiopure intermediates of drug molecules as the basis to infer the correct stereochemistry. By lipase catalysis, enantiopure secondary alcohols used as intermediates in the synthesis of Dorzolamide, an antiglaucoma drug, were obtained. Enantiopure _-hydroxy nitriles as potential intermediates for the synthesis of antidepressant drugs with 1-aryl-3- methylaminopropan-1-ol structure were also obtained with lipases. Kinetic resolution of racemates was the main biocatalytic approach applied. Candida Antarctica lipase B, Burkholderia cepacia lipase and Thermomyces lanuginosus lipase were applied for the acylation of alcohols and the alcoholysis of their esters in organic solvents, such as in diisopropyl ether and tert-butyl methyl ether. Candida Antarctica lipase B was used under solvent free conditions for the acylation of ethyl 3-hydroxybutanoate.

Optimization of NMP extraction in 1, 3-butadiene production line

N-methylpyrrolidone is a powerful solvent for variety of chemical processes due to its vast chemical properties. It has been used in manufacturing processes of polymers, detergents, pharmaceuticals rubber and many more chemical substances. However, it creates large amount of residue in some of these processes which has to be dealt with. Many well known methods such as BASF in rubber producing units have tried to regenerate the solvent at the end of each run, however, there is still discarding of large amount of residue containing NMP, which over time, could cause environmental concerns. In this study, we have tried to optimize regeneration of the NMP extraction from butadiene production. It is shown that at higher temperatures NMP is separated from the residue with close to 90% efficiency, and the solvent residue proved to be the most effective with a 6: 1 ratio.