Efeito das interações hiperconjugativas na constante de acoplamento ¹J CH da hexametilenotetramina e do adamantano: estudo teórico e experimental

The objective of this work was to determine the influence of hyperconjugative interactions on the ¹J CH coupling constant for hexamethylenetetramine (1) and adamantane (2). For this end, theoretical and experimental ¹J CH were obtained and hyperconjugative interactions were investigated using NBO. It was observed, theoretically and experimentally, that ¹J CH in 1 is 20 Hz larger than in 2, mainly due to the nN®s*C-H hyperconjugative interaction. This interaction occurs only in 1, with an energy of 9.30 kcal mol-1. It increases the s-character of the carbon atom in the C-H bond and the occupancy of the sigma*C-H orbital in (1).

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.

A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopolímeros na remoção catiônica

This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.

Simultaneous determination of B-Group vitamins in enriched cookies

The objective of this research was to determine the levels of enrichment of vitamins B1, B2, B6 and B3 in different types and brands of enriched cookies. The chromatographic separation was performed in a C18 column with gradient elution and UV detection at 254 and 287 nm. The results show that only 5 of the 24 brands evaluated are in accordance with the Brazilian legislation with respect to the vitamin content declared on the labels. However, consumption of approximately 100-150 g of most of the brands supplies the recommended dietary intake for children and adults of the vitamins evaluated.

Glutationa e enzimas relacionadas: papel biológico e importância em processos patológicos

Glutathione (GSH) and related enzymes are pivotal for the normal functioning of several important biological processes. In this review we discuss the biosynthesis and the catalytic cycles of glutathione as well as the major GSH-related enzymes. We also present how glutathione and enzymes are involved in cancer and the chromatographic and non-chromatographic methods used to analyze glutathione and/or its derivatives.

Supercritical CO2 recovery of caffeine from green coffee oil: new experimental solubility data and modeling

The caffeine solubility in supercritical CO2 was studied by assessing the effects of pressure and temperature on the extraction of green coffee oil (GCO). The Peng-Robinson¹ equation of state was used to correlate the solubility of caffeine with a thermodynamic model and two mixing rules were evaluated: the classical mixing rule of van der Waals with two adjustable parameters (PR-VDW) and a density dependent one, proposed by Mohamed and Holder² with two (PR-MH, two parameters adjusted to the attractive term) and three (PR-MH3 two parameters adjusted to the attractive and one to the repulsive term) adjustable parameters. The best results were obtained with the mixing rule of Mohamed and Holder² with three parameters.

Cutinases fúngicas: propriedades e aplicações industriais

Cutinases (EC 3.1.1.74) are also known as cutin hidrolases. These enzymes share catalytic properties of lipases and esterases, presenting a unique feature of being active regardless the presence of an oil-water interface, making them interesting as biocatalysts in several industrial processes involving hydrolysis, esterification and trans-esterification reactions. They are also active in different reaction media, allowing their applications in different areas such as food industry, cosmetics, fine chemicals, pesticide and insecticide degradation, treatment and laundry of fiber textiles and polymer chemistry. The present review describes the characteristics, potential applications and new perspectives for these enzymes.

Estado da arte de figuras de mérito em calibração multivariada

The validation of an analytical procedure must be certified through the determination of parameters known as figures of merit. For first order data, the acuracy, precision, robustness and bias is similar to the methods of univariate calibration. Linearity, sensitivity, signal to noise ratio, adjustment, selectivity and confidence intervals need different approaches, specific for multivariate data. Selectivity and signal to noise ratio are more critical and they only can be estimated by means of the calculation of the net analyte signal. In second order calibration, some differentes approaches are necessary due to data structure.

Sensores ópticos com detecção no infravermelho próximo e médio

Optical chemical sensors with detection in the near and mid infrared region are reviewed. Fundamental concepts of infrared spectroscopy and optical chemical sensors are briefly described, before presenting some aspects on optical chemical sensors, such as synthesis of NIR and IR reagents, preparation of new materials as well as application in determinations of species of biological, industrial and environmental importance.

Construção de um calorímetro isotérmico diferencial de alta sensibilidade e baixo custo

The high cost of sensitivity commercial calorimeters may represent an obstacle for many calorimetric research groups. This work describes the construction and calibration of a batch differential heat conduction calorimeter with sample cells volumes of about 400 μL. The calorimeter was built using two small high sensibility square Peltier thermoelectric sensors and the total cost was estimated to be about US$ 500. The calorimeter was used to study the excess enthalpy of solution of binary mixtures of liquids, as a function of composition, for the following binary systems of solvents: water + 1,4-dioxane or + dimethylsulfoxide at 298,2 ± 0,5 K.

Synthesis, characterization, DFT and Td-dfT study of the [Fe(mnt)(L)(t-BuNC) 2] octahedral complex (L = phen, bipy)

FeBr2 has reacted with an equivalent of mnt2- (mnt = cis-1,2-dicyanoethylene-1,2-dithiolate) and the α-diimine L (L = 1,10'-phenantroline, 2,2'-bipyridine) in THF solution, and followed by adding of t-butyl-isocyanide to give [Fe(mnt)(L)(t-BuNC)2] neutral compound. The products were characterized by infrared, UV-visible and Mössbauer spectroscopy, besides thermogravimetric and conductivity data. The geometry in the equilibrium was calculated by the density functional theory and the electronic spectrum by the time-dependent. The experimental and theoretical results in good agreement have defined an octahedral geometry with two isocyanide neighbours. The π→π* intraligand electronic transition was not observed for cis-isomers in the near-IR spectral region.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Emprego da fluorescência de raios X por dispersão de energia para o mapeamento de troncos de árvores em Campinas, São Paulo

Dendrochemistry is based on the determination of elements retained in tree rings, which can be useful to characterize environmental occurrences. This work shows elemental mappings obtained by EDXRF of the cross section of a tree stem. The tree is originated from a polluted area in Campinas, São Paulo. Some profiles, as the sulfur one, show variations that can be attributed to external contributions, whereas the silicon one can be inferred to a protection defense natural mechanism. Besides being simultaneous and multielementar, the main advantages here are its performance through a non-destructive sample treatment and the ease of operation of XRF equipments.

Desenvolvimento e caracterização de nanocápsulas de poli (L-lactídeo) contendo benzocaína

In this paper we describe the preparation poly (L-lactide) (PLA) nanocapsules as a drug delivery system for the local anesthetic benzocaine. The characterization and in vitro release properties of the system were investigated. The characterization results showed a polydispersity index of 0.14, an average diameter of 190.1± 3 nm, zeta potential of -38.5 mV and an entrapment efficiency of 73%. The release profile of Benzocaine loaded in PLA nanocapsules showed a significant different behavior than that of the pure anesthetic in solution. This study is important to characterize a drug release system using benzocaine for application in pain treatment.

Tecnologia de nanocristais em fármacos

The use of poorly water soluble molecules in pharmaceutical area has grown. Since these molecules exhibit low oral bioavailability, they are not used in intravenous administrations. Therefore, it is necessary to develop their new formulations with the aim to increase their oral bioavailabilities as to enable intravenous applications. One of the few possibilities in achieving this is a nanonization process that can produce crystals smaller than 1 μm by high pressure homogenization and without use of organic solvents. This mini-review describes technical aspects of the nanocrystal production, morphological aspects (polymorphisms), the market relevance of the nanocrystals products that are already in clinical phase or at the market, as well as, perspectives for the near future.