Determinação das propriedades catalíticas em meio aquoso e orgânico da lipase de Candida rugosa imobilizada em celulignina quimicamente modificada por carbonildiimidazol

Microbial lipase from Candida rugosa was immobilized by covalent binding on wood cellulignin (Eucaliptus grandis) chemically modified with carbonyldiimidazole. The immobilized system was fully evaluated in aqueous (olive oil hydrolysis) and organic (ester synthesis) media. A comparative study between free and immobilized lipase was carried out in terms of pH, temperature and thermal stability. A higher pH value (8.0) was found optimal for the immobilized lipase. The optimal reaction temperature shifted from 37 °C for the free lipase to 45 °C for the immobilized lipase. The pattern of heat stability indicated that the immobilization process tends to stabilize the enzyme. Kinetics tests at 37 °C following the hydrolysis of olive oil obeyed the Michaelis-Menten rate equation. Values for Km = 924.9 mM and Vmax = 198.3 U/mg were lower than for free lipase, suggesting that the affinity towards the substrate changed and the activity of the immobilized lipase decreased during the course of immobilization. The immobilized derivative was also tested in the ester synthesis from several alcohols and carboxylic acids.

Efeitos de substituintes na ligação de hidrogênio do 3-hidroxipropenal

The effect of substituents on the energies and geometries of 3-hydroxypropenal was studied using the B3LYP/6-311++G(d,p) model. The hydrogen bond energies indicate that the strongest donors and the weakest acceptors present the highest and the weakest hydrogen bonds, respectively, indicating the validity of the Madsen RAHB model. Geometric parameters indicate that the intensity of the hydrogen bond is proportional to the resonance, as suggested by the RHAB model. The effect of substituents diverges from the model proposed by Gilli et al. Sometimes the results indicate that the donor or acceptor effect is more important than the point of substitution.

Controle da biossíntese de poli-hidroxialcanoatos bacterianos através do fluxo de substratos

Manipulation of the flux of substrates was utilized to control the amount of 3-hydroxyvalerate and 3-hydroxy-4-pentenoate produced by Burkohlderia sp. The 3HV production rate was directly proportional to the propionic acid uptake rate with the last one completely directed to 3HV biosynthesis. The 3HPE production rate was inversely proportional to the sucrose uptake rate probably due to operation of the glyoxylate cycle.

Estatinas hipolipêmicas e novas tendências terapêuticas

Statins are the most used drugs for the treatment of hyperlipidemia in primary and secondary prevention, with the aim of decreasing the levels of plasmatic cholesterol- lipoproteins. Owing to their structural similarity to the substrate HMG-CoA (3-hydroxy-3-methylglutaryl-CoA), they inhibit the HMG-CoA reductase enzyme, disrupting the cholesterol biosynthesis. Currently, six therapeutic statins are available: lovastatin (Mevacor) and pravastatin (Pravachol), which are natural, sinvastatin (Zocor), a semi-synthetic derivative, and the totally synthetic statins, fluvastatin (Lescol), atorvastatin (Lipitor) and rosuvastatin (Crestor). Recent investigations have showed other important effects of statins, such as antineoplastic action and improvement in endothelial function.

Síntese de complexo ferro(II)-nitrogênio: abordagem dos conceitos de reatividade e retro-doação para alunos de graduação em química

There has been a considerable interest in coordination complexes of molecular nitrogen (N2), partly due to a possible relationship between such complexes and the nitrogen activation process in nature. The present paper describes the synthesis and infrared spectroscopic characterization of an iron-nitrogen derivative with ethylenediamine-N,N,N',N'-tetraacetate (edta) as an experiment for an undergraduate course. The topics covered here include synthesis, reactivity and spectroscopy.

Síntese e avaliação da propriedade reguladora de crescimento vegetal de compostos indólicos derivados do safrol

The present work describes the use of piperonal, a derivative of the secondary metabolite safrole, for the synthesis of new 5,6-methylenedioxysubstituted indole carboxylic acids structurally related to the indol-3-yl-acetic acid (AIA, I). The route comprises six steps beginning with piperonal with an overall yield of 19%. Compound IX was tested towards its plant growth regulator properties in bioassays specific for auxine activity. The in vitro assays were performed in a germination chamber and were of two types: root growth in germinated seeds of Lactuca sativa, Cucumbis sativus and Raphanus sativus and peciole biotest using Phaseolus vulgaris.

Identification of acetates in elasmopalpulus lignosellus pheromone glands using a newly created mass spectral database and kóvats retention indices

Based on a specially created mass spectral database utilizing 23 tetradecenyl and 22 hexadecenyl acetate standards along with Kóvats retention indices obtained on a very polar stationary phase [poly (biscyanopropyl siloxane)] (SP 2340), (Z)-9-hexadecenyl acetate, (Z)-11-hexadecenyl acetate and (E)-8-hexadecenyl acetate were identified in active pheromone extracts of Elasmopalpus lignosellus. This identification was more efficient than our previous study using gas chromatography/mass spectrometry with a dimethyl disulfide derivative where we could only identify the first two acetates. The acetate composition of the pheromone gland differed from region to region in Brazil and from that from the Tifton (GA, USA) population, suggesting polymorphism or a different sub-species.

Dissolution test for glibenclamide tablets

The aim of this work is to develop and validate a dissolution test for glibenclamide tablets. Optimal conditions to carry out the dissolution test are 500 mL of phosphate buffer at pH 8.0, paddles at 75 rpm stirring speed, time test set to 60 min and using equipment with six vessels. The derivative UV spectrophotometric method for determination of glibenclamide released was developed, validated and compared with the HPLC method. The UVDS method presents linearity (r² = 0.9999) in the concentration range of 5-14 µg/mL. Precision and recoveries were 0.42% and 100.25%, respectively. The method was applied to three products commercially available on the Brazilian market.

Comparison of GC and HPLC for quantification of organic acids in two jaboticaba (Myrciaria) fruit varieties

Gas chromatography (GC) with trimethylsilyl derivative formation was compared to high-performance liquid chromatography (HPLC) for quantification of organic acids (OAs) in two jaboticaba (Myrciaria) fruit (pulp and pericarp) varieties (Sabará and Açu Paulista). Succinic and citric acids were the major OAs found in all the samples analyzed. Besides being much more tedious, the results obtained with GC were significantly lower than HPLC (p<0.05) when the data (acids, variety, two parts and flowering days) were considered together. The presence of both acids was confirmed by gas chromatography-mass spectrometry (GC-MS).

Desenvolvimento de abordagem objetivando a síntese da 3-desidroxi-4-metoxi-tubastrina

We report the synthesis of amino(2-hydroxy-2-(4-methoxyphenyl)ethylamino)methaniminium (14) as a direct precursor of a tubastrine derivative (3-dehydroxy-4-methoxytubastrine). The synthetic steps involved functional group interconversions starting from 1-(4-methoxyphenyl)ethanone to obtain the guanidine-protected derivative 13. Tentative dehydration of 13 with SiOH-adsorbed CuSO4 resulted in guanidine deprotection only. This was an unexpected result, since there are no reports of CuSO4.SiOH as Boc-deprotecting of guanidines. The product 14 was obtained in five steps and 5.4 % overall yield, and constitutes a direct precursor of 3-dehydroxy-4-methoxytubastrine.

Síntese, avaliação biológica e modelagem molecular de arilfuranos como inibidores da enzima tripanotiona redutase

Trypanosoma cruzi is a protozoan parasite that causes a severe disease (Chagas'disease) in Central and South America. The currently available chemotherapeutic agents against this disease are still inadequate. The enzyme trypanothione reductase (TR) is considered a validated molecular target for the development of new drugs against this parasite. In this regard, a series of arylfurans based on 2,5-bis-(4-acetamidophenyl)furan was synthesized and tested for their in vitro inhibitory activity against TR. Molecular modeling studies of putative enzyme-inhibitor complexes revealed a possible mechanism of interaction. From synthesized compounds, a benzylaminofuran derivative was found to be more active than the lead compound.

Avaliação da estabilidade do marcador plasmático do estresse oxidativo: malondialdeído

Malondialdehyde (MDA) is one of the lipid peroxidation products widely used as indicator of cellular injury. However, the short-term and the long-term stability of this biomarker remain unclear. The objective of this work was to evaluate the stability of plasmatic MDA at -20 ºC, utilizing thiobarbituric acid (TBA) as derivative in spectrophotometric and chromatographic analysis. The results showed that MDA was stable for 24 h after blood collection, was not stable when stored after alkaline hydrolysis, remained stable for 30 days after TBA derivatization and was stable for 3 days when stored after n-butanol extraction, all at -20 ºC.

Repensando la relación entre la ley y la violencia hacia las mujeres. Una aproximación a los discursos de los/las agentes del ámbito judicial en relación a la ley integral de violencia de género en España = Rethinking the relationship between law and violence against women. an approach to the juridical agents' discourses in relation to the integral law of gender-based violence

Of the many dimensions of the problem of violence exercised by men toward women in the context of the relations of partner or ex partner, this article deals with the analysis of the discursive productions of the institutional actors that are part of the judicial process. Our intention is to investigate the relationship between criminal law and gender-based violence starting from the implementation of the Law of Integral Gender-based Violence in Spain (LO. 1 / 2004) from a theoretical perspective which includes contributions from social psychology, and socio-legal feminism. We have approached the legal instrument - the Law of Integral Gender-based Violence - through the discourse of legal officers with a perspective that questions the values, so often proclaimed, of universality, objectivity and neutrality of the law

HPLC-ESI-MS/MS analysis of oxidized di-caffeoylquinic acids generated by metalloporphyrin-catalyzed reactions

This paper reports an HPLC-ESI-MS/MS investigation on the oxidation of 3,5- and 4,5- dicaffeoylquinic acid using iron(III) tetraphenylporphyrin chloride as catalyst. Two major mono-oxidised products of the quinic acid moiety have been identified for both compounds. However, only the 4,5-derivative afforded two different tri-oxo products. Thus, it seems that the oxidation pattern depends on the number and positions of the caffeic acid moieties present in caffeoylquinic acid molecules.

Polarimetric 3D integral imaging in photon-starved conditions

We develop a method for obtaining 3D polarimetric integral images from elemental images recorded in low light illumination conditions. Since photon-counting images are very sparse, calculation of the Stokes parameters and the degree of polarization should be handled carefully. In our approach, polarimetric 3D integral images are generated using the Maximum Likelihood Estimation and subsequently reconstructed by means of a Total Variation Denoising filter. In this way, polarimetric results are comparable to those obtained in conventional illumination conditions. We also show that polarimetric information retrieved from photon starved images can be used in 3D object recognition problems. To the best of our knowledge, this is the first report on 3D polarimetric photon counting integral imaging.