X-Ray diffraction investigations of concentrated aqueous solutions of calcium halides

Concentrated aqueous solutions of calcium chloride and calcium bromide have been investigated by X-ray diffraction. In the diffraction patterns of aqueous chloride solutions of different concentrations, a maximum of intensity is observed in the region 0.6–1.1 Å⁻¹, while in the investigated aqueous bromide solution no maximum is observed in that region. This pre-peak suggests the existence of positional correlations in solution beyond direct contact. The interpretation is similar to the one proposed by the authors in previous investigations, and is supported by the calculations based on ad hoc molecular models. The influence of the anion is discussed.     

Effect of process parameters on production of a biopolymer by Rhizobium sp.

The production of biopolymers by a Rhizobium strain was studied under batch and bioreactor conditions. The best viscosity levels were obtained under low mannitol concentrations as well as low agitation and aeration conditions. Infrared spectra indicated the presence of chemical groups characteristic of microbially produced biopolymers, including C=O and O-acetyl groups. Thermogravimetric analysis showed the characteristic degradation profiles of the exopolysaccharide produced (T _onset=290°C). The experimental design showed that a low substrate concentration (10.0 g/L), and low aeration (0.2 vvm) and agitation (200 rpm) levels should be used. The maximum yield of the process was a Yp/s (g/g) of 0.19±0.1, obtained under optimized conditions.     

Determination of uranium and impurities in Portuguese yellow-cakes

A method is described for separation of impurities in uranium yellow cakes from Urgeiriça (Portugal). The trace metals are separated and concentrated by solvent extraction from 6M nitric acid into 100% TBP. The raffinate is then analysed directly by flame spectrometry. Uranium is determined gravimetrically after stripping of the organic phase. The method is fast and economic, and the results are in good agreement with those obtained by specific methods for each element after prior separation of uranium by precipitation or solvent extraction with various solvents.     

Electrophoretic human leukocyte antigen HLA-DQA1 DNA typing after polymerase chain reaction amplification.

An electrophoretic method (sodium dodecyl sulfate-polyacrylamide gel electrophoresis) is described which permits the identification of human leukocyte antigen HLA-DQA1 types and subtypes without using allele-specific oligonucleotide probes and dot-blot methodology. The procedure can be used in miniaturized gels in combination with automated electrophoretic systems. The PhastSystem is particularly recommended since temperature control is essential. HLA-DQA1*01 and DQA1*0301 can be distinguished in homoduplexes and DQA1*01 subtypes, DQA1*0201 and DQA1*0401 in heteroduplexes (in only 5 h including DNA extraction and PCR amplification). Additional variations to those recognized using commercially available dot-blot methods can be provided since this procedure permits the identification of single base-pair substitutions. In addition, this method is faster and less expensive than commercial methods.     

Effect of storage of soil at 4°C on the microbial activity studied by microcalorimetry

The effect of the storage of soils on their microbial activity has been studied using a microcalorimetric method. Soil samples were kept in closed polyethene bags at 4°C during 3–6 months. Results show changes in the slope of the differentP?t curves recorded from the samples stored at 4°C. This fact strongly suggest the existence of changes of the microbial activity of soil as the heat evolution is a direct measurement of the cells metabolic activity. The value of the Peak-time (time in which the microcalorimetric signal reaches the maximum value) is related with the microbial density of soil samples. This parameter was affected by the time of storage increasing with time. The total heat evolutionQ(t), of the soil samples amended with glucose calculated from the area limited by the Power-Time curves, also decreases with the time of storage. The soil that had been stored for 6 months before experiments, showed the lowest valu ofQ(t).     

A new HPLC-DAD-MS/MS method for the simultaneous determination of major compounds in the crude extract of Lychnophora salicifolia Mart. (Brazilian arnicão) leaves: Application to chemical variability evaluation

Lychnophora salicifolia Mart., which occurs in the Brazilian Cerrado in the states of Bahia and Minas Gerais as well as in the southeast of the state of Goiás, is the most widely distributed and also the most polymorphic species of the genus. This plant is popularly known to have anti-inflammatory and analgesic activities. In this work, we have studied the variation in terms of polar metabolites of ninety-three Lychnophora salicifolia Mart. specimens collected from different regions of the Brazilian Cerrado. Identification of the constituents of this mixture was carried out by analysis of the UV spectra and MS data after chromatographic separation. Twenty substances were identified, including chlorogenic acid derivatives, a flavonoid C-glucoside, and other sesquiterpenes. The analytical method was validated, and the reliability and credibility of the results was ensured for the purposes of this study. The concentration range required for analysis of content variability within the analyzed group of specimens was covered with appropriate values of limits of detection and quantitation, as well as satisfactory precision and recovery. A quantitative variability was observed among specimens collected from the same location, but on average they were similar from a chemical viewpoint. In relation to the study involving specimens from different locations, there were both qualitative and quantitative differences among plants collected from different regions of Brazil. Statistical analysis revealed that there is a correlation between geographical localization and polar metabolites profile for specimens collected from different locations. This is evidence that the pattern of metabolites concentration depends on the geographical distribution of the specimens.     

Study of doubly charged alkaline earth metal and 3-azidopropionitrile complexes by electrospray ionization mass spectrometry

The present work describes a study of the complexation of calcium and magnesium by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of calcium and magnesium salts of the type CaX2 and MgX2 (where X = Cl or NO3) in water and methanol/water. The complexes detected were mainly double positively charged, with various stoichiometries not depending on the solvent, since water and 3-azidopropionitrile were always the main ligands. Solvation with methanol was not observed unlike in a previous study of complexation of nickel and cobalt by 3-azidopropionitrile. The complex ions [M(II)Az4(H2O)](2+), [M(II)Az5](2+) (where M = Ca and Mg) are the most abundant for both metals, and both counter ions. Tandem mass spectrometric (MS/MS) analysis showed that, under collision-induced dissociation (CID) conditions, the most important processes occurring were loss of neutral ligands and the replacement of 3-azidopropionitrile by water. A complex species containing reduced alkaline earth metal was due to radical loss, resulting from homolytic cleavage in the azide ligand. Some terminal ions, in the fragmentation sequences, point to the nitrile group as the coordination site in the 3-azidopropionitrile. Density functional theory (DFT) calculations confirmed this coordination site and proved that 3-azidopropionitrile behaves as a monodentate ligand in the systems under study. Moreover, the theoretical study proved that the presence of water ligand introduces stability through a hydrogen bond established between the water molecule and one nitrogen atom of the azido group. In addition, the strong dipole moment of 3-azidopropionitrile (4.76 D), which is mainly related to presence of the nitrile group, favors the stabilization of the metal-ligand complexes through charge-dipole interactions and the coordination of the metal to the nitrile group.     

Study of pyrolysis kinetic of green corn husk

In this paper, it was suggested the use of green corn husk, which is a biomass from agro-industry, as an alternative source of energy through its pyrolysis. Green corn husk characterization was done through immediate and elemental analysis of its components: cellulose, hemicelluloses, and lignin. It was also measured its higher calorific value. The pyrolysis study of green corn husk was done by the isoconversion and the Master plots method. Thermogravimetric plots were obtained at heating rates of 5, 10, 15, and 20 °C min^?1. The pyrolysis kinetics parameters were studied through the Flynn–Wall–Ozawa (FWO), Kissinger, and Friedman models. The Master plots method was used to determine the pyrolysis reaction order. The results of the reaction energy activation were found to be in the range 105.21–157.46 kJ mol^?1 by the FWO method, 150.50 kJ mol^?1 by the Kissinger method, and ranged 120.66–163.81 kJ mol^?1 by the Friedman method. The Master plots method showed a three-way-transport diffusional kinetics for the biomass de-volatilization process. The higher calorific value found for green corn husk was 16.14 MJ kg^?1. The simulation showed correlation between the experimental data and the proposed model for conversion values up to 0.8.