O uso do forno de microondas na síntese orgânica em fase sólida

Solid-phase organic synthesis (SPOS) has been considered the main strategy for the construction of combinatorial libraries, because its simplicity leads to faster synthetic procedures. In addition to that, a series of reports in the specialized literature show great advantages in the use of microwave activation, when compared to classical heating, for instance: shorter reaction times, in some cases from several hours to a few minutes, increase of selectivity and product yields, energy economy and reduction and/or elimination of solvent. This review describes the use of microwave ovens/reactors in solid phase organic synthesis, describing the advantages, equipment and reactions using both techniques.

Efeito do teor metálico em catalisadores Co/Al2O3 aplicados à reação de reforma a vapor de etanol

The development of cobalt catalysts to produce hydrogen from ethanol is the goal of this investigation. Co/Al2O3 catalysts were prepared by impregnation and characterized by atomic absorption, nitrogen adsorption, X-ray diffraction, Raman spectroscopy, temperature programmed reduction and carbon analysis. The catalysts contained Co3O4 oxide and Co3+ and Co2+ species interacting with alumina. The cobalt load affects the crystal size and the crystalline structure and higher Co loads influence the reaction mechanism, changing the selectivity of the catalysts, decreasing the amount of CO produced and avoiding the formation of products catalyzed by the support. The ethanol conversion was 50-70% with 10-<1% of CO in the hydrogen.

Potencial de biocatálise enantiosseletiva de lipases microbianas

Microbial lipases have a great potential for commercial applications due to their stability, selectivity and broad substrate specificity because many non-natural acids, alcohols or amines can be used as the substrate. Three microbial lipases isolated from Brazilian soil samples (Aspergillus niger; Geotrichum candidum; Penicillium solitum) were compared in terms of their stability and as biocatalysts in the enantioselective esterification using racemic substrates in organic medium. The lipase from Aspergillus niger showed the highest activity (18.2 U/mL) and was highly thermostable, retaining 90% and 60% activity at 50 ºC and 60 ºC after 1 hour, respectively. In organic medium, this lipase provided the best results in terms of enantiomeric excess of the (S)-active acid (ee = 6.1%) and conversion value (c = 20%) in the esterification of (R,S)-ibuprofen with 1-propanol in isooctane. The esterification reaction of the racemic mixture of (R,S)-2-octanol with decanoic acid proceeded with high enantioselectivity when lipase from Aspergillus niger (E = 13.2) and commercial lipase from Candida antarctica (E = 20) were employed.

Separação de CO2 por meio da tecnologia PSA

This paper describes the separation of CO2 from a gas mixture containing 25% CO2, 4% O2 and 71% N2 using the pressure swing adsorption (PSA) technique. The adsorbent selected was the zeolite 13X due to its great adsorption capacity for CO2 and selectivity towards the other components of the gas mixture. The experimental technique was designed to identify the most important variables for the process and to optimize it. It is shown that the PSA technique can be used to separate CO2 from O2 and N2 to obtain an effluent containing 2% CO2 with 99% separation efficiency.

Polímeros biomiméticos em química analítica. Parte 1: preparo e aplicações de MIP ("Molecularly Imprinted Polymers") em técnicas de extração e separação

MIPs are synthetic polymers that are used as biomimetic materials simulating the mechanism verified in natural entities such as antibodies and enzymes. Although MIPs have been successfully used as an outstanding tool for enhancing the selectivity or different analytical approaches, such as separation science and electrochemical and optical sensors, several parameters must be optimized during their synthesis. Therefore, the state-of-the-art of MIP production as well as the different polymerization methods are discussed. The potential selectivity of MIPs in the extraction and separation techniques focusing mainly on environmental, clinical and pharmaceutical samples as applications for analytical purposes is presented.

Efeito dos ácidos hexenurônicos e da lignina no desempenho da ozonólize, em diferentes pHs da reação

The effect of pH on the performance of the ozonolysis stage in pulp production was evaluated for conventional and acid treated brown and oxygen delignified eucalyptus kraft pulps. The objective was to determine separately the effects of lignin and hexenuronic acid on the performance of the ozonolysis stage. The reaction of ozone with hexenuronic acid is less sensitive to pH than the reaction of ozone with lignin. The efficiency and the selectivity of the reaction of ozone with pulp decreases after removal of hexenuronic acids. Increasing up to 7.0 the pH during the ozonolysis is viable in the sequence Z/D(EOP)D, resulting in savings of H2SO4 (8,5 kg/tsa) and NaOH (5 kg/tsa), but is not recommended in the sequence Z/ED(PO).

Recentes avanços e novas perspectivas dos eletrodos íon-seletivos

This paper describes the recent progress in the development of polymeric membranes for ion-selective electrodes. The importance of knowing the mechanism of potential development in membranes for ion-selective electrodes to reach lower detection limits and improve selectivity are discussed. Recent advances and future trends of research on ion-selective electrodes are also reported.

Pró-fármaco ativado por enzima, uma estratégia promissora na quimioterapia

Strategies that promote selective activation of prodrugs by enzymes can be divided into two major classes: 1) deliver of a monoclonal antibody-enzyme immunoconjugate that can recognize a specific antigen and promote the prodrug to a citotoxic drug, with a high selectivity for the target cells, and 2) selective gene delivery encoding an enzyme that can promote the prodrug to a citotoxic drug for the target cells. In this article are discussed ADEPT (antibody-directed enzyme prodrug therapy), GDEPT (gene-directed enzyme prodrug therapy), VDEPT (virus-directed enzyme prodrug therapy), GPAT (genetic prodrug activation therapy) and PDEPT (polymer-directed enzyme prodrug therapy) approaches, their clinical trials, advantages, disadvantages and perspectives.

Sensores eletroquímicos: considerações sobre mecanismos de funcionamento e aplicações no monitoramento de espécies químicas em ambientes microscópicos

Electrochemical sensors have attracted considerable attention in recent years because they provide data about the chemical state of our surroundings and the dynamics of the chemical transformations in the form a spatially resolved image. Particular interest has been directed to measurements in restricted-volume samples as new technologies enable the fabrication of miniaturized versions of sensors with reproducible characteristics. Taking these aspects into consideration, this review focuses on the use of electrodes of micrometer dimensions to acquire chemical information in microdomains in which concentrations may not be spatially homogeneous. This is possible because microelectrodes allow fast-response measurements with micrometer resolution to be performed. On the other hand, the use of microelectrodes as amperometric sensors presents an inherent drawback owing to the insufficient specificity toward the substrate of interest. Hence, some comments on strategies to enhance the selectivity of amperometric sensors are also made. Finally, recent applications of structurally microscopic electrodes as in vivo sensors are shown, as well as a prospect of the future trend in this field.

Antimycobacterial and cytotoxicity activity of synthetic and natural compounds

Antimycobacterial and cytotoxicity activity of synthetic and natural compounds. Secondary metabolites from Curvularia eragrostidis and Drechslera dematioidea, Clusia sp. floral resin, alkaloids from Pilocarpus alatus, salicylideneanilines, piperidine amides, the amine 1-cinnamylpiperazine and chiral pyridinium salts were assayed on Mycobacterium tuberculosis H37Rv. N-(salicylidene)-2-hydroxyaniline was the most effective compound with a minimal inhibitory concentration (MIC) of 8 µmol/L. Dihydrocurvularin was moderately effective with a MIC of 40 µmol/L. Clusia sp. floral resin and a gallocatechin-epigallocatechin mixture showed MIC of 0.02 g/L and 38 µmol/L, respectively. The cytotoxicity was evaluated for N-(salicylidene)-2-hydroxyaniline, curvularin, dihydrocurvularin and Clusia sp. floral resin, and the selectivity indexes were > 125, 0.47, 0.75 and 5, respectively.

Indução assimétrica 1,5-Anti na adição de enolatos de boro de metilcetonas beta-oxigenadas a aldeídos

High levels of substrate-based 1,5-stereoinduction are obtained in the boron-mediated aldol reactions of beta-oxygenated methyl ketones with achiral and chiral aldehydes. Remote induction from the boron enolates gives the 1,5-anti adducts, with the enolate pi-facial selectivity critically dependent upon the nature of the beta-alkoxy protecting group. This 1,5-anti aldol methodology has been strategically employed in the total synthesis of several natural products. At present, the origin of the high level of 1,5-anti induction obtained with the boron enolates is unclear, although a model based on a hydrogen bonding between the alkoxy oxygen and the formyl hydrogen has been recently proposed.

Sílica quimicamente modificada com os grupos p-anisidina, p-fenitidina e p-fenilenodiamina usada como adsorvente para Pb2+, Cu2+, Cd2+ e Ni2+ em soluções aquosa e etanólica

Silica gel was chemically modified with the aromatic amines p-anisidine, p-phenytidine and p-phenylenediamine, using grafting reactions. The resulting modified silicas were characterized by infrared spectroscopy and N2 adsorption/desorption isotherms. The organic groups were covalently immobilized in a monolayer form. These modified silicas were investigated as adsorbents for Pb2+, Cu2+, Cd2+ and Ni2+ in aqueous and ethanol solutions. In a general way, the adsorption capacity values for all adsorbents presented the following sequence: Pb2+ >> Cu2+ @Cd2+ @ Ni2+. Adsorption studies for all adsorbents, in competitive medium, showed better selectivity for Cu2+ and Pb2+ in aqueous medium and for Pb2+ in ethanol solution. Desorption studies were carried out using HCl and HNO3 as eluents.

Epoxidação do óleo de mamona e derivados empregando o sistema catalítico VO(acac)2/TBHP

The alternative system VO(acac)2/TBHP was investigated for the epoxidation reaction of castor oil and its derivatives. Results of 88% of conversion, 73% of epoxidation and 82% of selectivity were obtained for the system containing 20% excess of TBHP and 1% of VO(acac)2 catalyst, during 3 h under toluene reflux. The product was characterized by GC/MS as methyl-cis-9, 10-epoxi, 12-hydroxystearate and quantitative ¹H NMR was used to calculate the data above. Preliminary results indicate that the heterogeneous system VO(acac)2 grafted on K10 clay can also promote epoxidation of castor oil.

Can affinity interactions influence the partitioning of glucose-6-phosphate dehydrogenase in two-phase aqueous micellar systems?

In this work, we provide an investigation of the role and strength of affinity interactions on the partitioning of the glucose-6-phosphate dehydrogenase in aqueous two-phase micellar systems. These systems are constituted of micellar surfactant solutions and offer both hydrophobic and hydrophilic environments, providing selectivity to biomolecules. We studied G6PD partitioning in systems composed of the nonionic surfactants, separately, in the presence and absence of affinity ligands. We observed that G6PD partitions to the micelle-poor phase, owing to the strength of excluded-volume interactions in these systems that drive the protein to the micelle-poor phase, where there is more free volume available.

Desenvolvimento e validação de método por cromatografia líquida de alta eficiência para determinação simultânea das impurezas timina e timidina na matéria-prima estavudina

A HPLC method was developed to quantify thymine and thymidine impurities in stavudine bulk drug. The separation was carried out in isocratic mode using methanol/water (20:80) as mobile phase, a C18 column and UV detection at 266 nm. The method provided selectivity based on peak purities and resolution among peaks. It was linear over the range of 0.5-5.0 µg/mL. The quantitation limits were 0.021 µg/mL for thymine and 0.134 µg/mL for thymidine. The average accuracies of three concentrations ranged from 97.06 to 102.61% and precision was close to 1%. The method showed robustness, remaining unaffected by deliberate variations in relevant parameters.