Lipase Improvement: Goals and strategies

Lipases have received great attention as industrial biocatalysts in areas like oils and fats processing, detergents, baking, cheese making, surface cleaning, or fine chemistry . They can catalyse reactions of insoluble substrates at the lipid-water interface, preserving their catalytic activity in organic solvents. This makes of lipases powerful tools for catalysing not only hydrolysis, but also various reverse reactions such as esterification, transesterification, aminolysis, or thiotransesterifications in anhydrous organic solvents. Moreover, lipases catalyse reactions with high specificity, regio and enantioselectivity, becoming the most used enzymes in synthetic organic chemistry. Therefore, they display important advantages over classical catalysts, as they can catalyse reactions with reduced side products, lowered waste treatment costs, and under mild temperature and pressure conditions. Accordingly, the use of lipases holds a great promise for green and economical process chemistry.

Preparação de nanocompósitos através do encapsulamento de polímeros condutores em 2H-MoS2 e 1T-TiS2

Nanocomposites obtained by the encapsulation of conducting polymers such as polyaniline and polydiphenylamine in 2H-MoS2 and 1T-TiS2 are synthesized and characterized by X-ray diffraction and infrared spectrophotometry. The synthesis consists in intercalating the layered compound with n-butyllithium and subsequent exfoliation in water and organic solvents. The nanocomposites are obtained by the adsorption of the polymers into the single-layers sulfides and posterior restacking. The X-ray diffraction measurements showed that the organic conducting polymers are encapsulated in mono and bilayers arrangement in a well-ordered fashion to produce single phase compounds.

Organo-gel: um novo sistema para a imobilização de lipases e sua aplicação em síntese orgânica

Lipases have been immobilized in microemulsion-based organogels (MBG's) and successfully utilized for the enantioselective esterification, diesterification and transesterification reactions, in organic solvents at 25ºC. This methodology is described as a new alternative for the use of enzymes in organic solvents. High enzymic stability has been observed. We have also used this methodology for the successful resolution of chiral secondary alcohols. This is a convenient way of using this catalyst in organic solvents which employs small amounts of the enzyme (250mg/mL).

Supramolecular Gold Metallogelators: The Key Role of Metallophilic Interactions

Gold metallogelators is an emerging area of research. The number of results published in the literature is still scarce. The majority of these gels is observed in organic solvents, and the potential applications are still to be explored. In this work, we present an overview about gold metallogelators divided in two different groups depending on the type of solvent used in the gelation process (organogelators and hydrogelators). A careful analysis of the data shows that aurophilic interactions are a common motif directly involved in gelation involving Au(I) complexes. There are also some Au(III) derivatives able to produce gels but in this case the organic ligands determine the aggregation process. A last section is included about the potential applications that have been reported until now with this new and amazing class of supramolecular assemblies.

Nuclear magnetic resonance investigation of structure and dynamics of some electrolyte solutions

Electrolyte solutions are of importance in a wide range of scientific contexts and as such have attracted considerable theoretical and experimental effort over many years. Nuclear Magnetic resonance provides a precise and versatile tool for investigation of electrolyte solutions, both in water and in organic solvents. Many structural and dynamic properties can be obtained through NMR experiments. The solution of aluminum chloride in water was studied. Different concentrations were taken for investigation. Independence of maximum line shift from concentration and acidity was shown. Six-coordinated structure of solvation shell was confirmed by experiments on 'H and 27A1 nuclei. Diffusion coefficients were studied. The solution of nickel chloride in methanol was studied. Lines, corresponding to coordinated and bulk methanol were found. Four-, five- and six-coordinated structures were found in different temperatures. The line for coordinated -OD group of deuterated methanol was observed on 2H spectrum for the first time. Partial deuteration of CH3 group was detected. Inability to observe coordinated -OH group was explained.

Biocatálise em meios aquo-restritos: fundamentos e aplicações em química analítica

The ability of enzymes to function in aquo-restricted media (commonly reported as non-aqueous media) has greatly enlarged the applications in numerous fields. The development of biosensors was also benefited with this area, expanding their applications toward many previously inaccessible analytes, enlarging significantly the scope of applications. In this review, some basic factors that influence biocatalytical reactions in aquo-restricted media is discussed. Attention is focused on the development, advantages and analytical applications of biosensors in non-aqueous media. Recent examples and relevant applications of their use are presented.

O emprego de lipases como agentes de resolução cinética de enantiômeros em síntese orgânica: aspectos gerais sobre a influência do solvente

In organic synthesis, lipases are the most frequently used biocatalysts. They are efficient stereoselective catalysts in the kinetic resolution of a wide variety of chiral compounds. The discovery that enzymes possess catalytic activity in organic solvents has made it possible to address the question of reaction medium influence on enzymatic specificity. Perhaps the most exciting and significant development in this emerging area is the discovery that enzyme specificity, in particular enantioselectivity, can be affected by changing from one organic solvent to another. This article discusses the scope and possible mechanistic models of this phenomenon in hydrolases, specially lipases, as well as directions of future research in the area.

A convenient method for the determination of moisture in aromatic plants

A method is proposed for the determination of the moisture content of aromatic plants. This method is based on the co-distillation of the starting material in a modified Clevenger apparatus with four organic solvents (toluene, cyclohexane, dichloromethane and carbon tetrachloride). The results were compared with those obtained by oven drying at 105 ºC and steam distillation of the essential oil. The efficiencies of the methods were shown to be equivalent. The solvent distillation method was more practical, especially with respect to operating time (2 h).

Sistema aquoso bifásico: uma alternativa eficiente para extração de íons

Solvent extraction has been successfully applied to metal ion preconcentration and often meant the use of toxic organic diluents. However, regulatory pressure is increasingly focusing on the use and disposal of organic solvents, and thus the development of nonhazardous alternatives is important. In this review, we examine the application of aqueous biphasic systems (ABS) to extraction of ions, analyzing their potential and limitations and suggest that ABSs could be an efficient substitute for oil/water biphasic systems. ABSs are formed by mixing certain inorganic salts and water-soluble polymers, or by mixing two water-soluble polymers.

Cafeína: revisão sobre métodos de análise

Gravimetric and Bailey-Andrew methods are tedious and provide inflated results. Spectrofotometry is adequate for caffeine analysis but is lengthy. Gas chromatography also is applied to the caffeine analysis but derivatization is needed. High performance liquid chromatography with ultraviolet detection (HPLC-UV) and reversed phase is simple and rapid for xanthine multianalysis. In HPLC-UV-gel permeation, organic solvents are not used. HPLC-mass spectrometry provides an unequivocal structural identification of xanthines. Capillary electrophoresis is fast and the solvent consumption is smaller than in HPLC. Chemometric methods offer an effective means for chemical data handling in multivariate analysis. Infrared spectroscopy alone or associated with chemometries could predict the caffeine content in a very accurate form. Electroanalytical methods are considered of low cost and easy application in caffeine analysis.

Imobilização de lipases em filme de caseinato de sódio/glicerol: aplicação na síntese de ésteres

Lipases from different sources were immobilized in sodium caseinate/glycerol film and used in the esterification reactions of aliphatic acids with alcohols in the presence of organic solvents. Lipases from Pseudomonas sp and Rhizopus oryzae were selected and the influence of several parameters was analyzed, including: lipase loading, organic solvent polarity, reaction temperature, chain length of alcohol and acid and enzyme/support reuse. For comparison, free enzymes were used under similar experimental conditions.

Microextração em fase líquida (LPME): fundamentos da técnica e aplicações na análise de fármacos em fluidos biológicos

The analysis of drugs and metabolites in biological fluids usually requires extraction procedures to achieve sample clean-up and analyte preconcentration. Commonly, extraction procedures are performed using liquid-liquid extraction or solid-phase extraction. Nevertheless, these extraction techniques are considered to be time-consuming and require a large amount of organic solvents. On this basis, microextraction techniques have been developed. Among them, liquid-phase microextraction has been standing out. This review describes the liquid-phase microextraction technique based on hollow fibers as a novel and promising alternative in sample preparation prior to chromatographic or electrophoretic analysis. The basic concepts related to this technique and its applicability in extraction of drugs are discussed.

Quantificação simultânea de indicadores biológicos de exposição a solventes orgânicos por cromatografia líquida de alta eficiência

Biological monitoring is very important to guarantee health to workers. This method was developed for simultaneous determination of xylene, toluene, styrene and ethylbenzene metabolites. It involves only dilution and centrifugation of urine samples and improved chromatographic conditions. Analyses show recovery > 95%; r² > 0.99; intermediate precision CV% < 6% and % bias < ±10. Exposed subjects presented at least three metabolites in urine. The method proved to be feasible, reliable and important in biological monitoring, especially in exposure to organic solvent mixtures.

Imobilização de enzimas em suportes cromatográficos: uma ferramenta na busca por substâncias bioativas

The development and characterization of bioreactors or IMER (immobilized enzyme reactors) as research tools are important in the scope of medicinal chemistry and constitute an alternative for the rational development of drugs. This approach does not require highly purified enzymes or a great amount of protein, but increase the enzymatic stability against heat, organic solvents and pH, without too much loss of catalyst activity. Immobilized enzyme reactors (IMER) can be used for the accomplishment of high efficiency screening on-line and, thus inhibitors can be quickly identified. Here, we emphasize the development of IMER by use of different methods of immobilization and chromatographic supports. Their applications, in different areas of research, are also fully discussed.

Líquido iônico [bmim.PF6] como solvente: um meio conveniente para estudos por fotólise por pulso de laser

The spectroscopic behavior of thioxanthone and benzil (diphenylethanedione or dibenzoyl) in the ionic liquid [bmim.PF6] has been investigated employing the laser flash photolysis technique. Triplet-triplet absorption spectra for these carbonyl compounds in [bmim.PF6] are similar to those observed in organic solvents. The triplet lifetime for thioxanthone in desogygenated samples is very long (71 μs), whereas in oxygen-saturated solution is 500 ns, which indicates the low oxygen solubility in this solvent. For benzil, lifetimes of 10 μs in [bmim.PF6] and 3.8 μs in acetonitrile were obtained. The decay for triplet thioxanthone and benzil follows a clear first order kinetics in [bmim.PF6], from which one can conclude that triplet-triplet annihilation is not an important decay process in this solvent.