Density and Sound Velocity Studies of Aqueous Solutions of Tetradecyltrimethylammonium Nitrate at Different Temperatures

The density and ultrasound velocity of aqueous solutions of tetradecyltrimethylammonium nitrate were measured in the temperature range of 15 to 35°C in 5°C intervals. The concentration range covered the premicellar and micellar regimes. By assuming a pseudophase separation model for the micellar system, we applied the densitometric data to estimate the apparent molar volumes and the apparent thermal expansibility coefficients of the surfactant in monomeric and micellar forms. Ultrasound velocity and density data enabled us to estimate the isentropic compressibility of the surfactant in both forms. The results are compared with relevant literature data for alkyltrimethylammonium bromides.     

Time-resolved laser-induced plasma spectrometry for determination of minor elements in steelmaking process samples

A pulsed Nd:YAG laser operating on the fourth (266 nm) and second (532 nm) harmonics has been used to generate plasmas on the target surface in air at atmospheric pressure. The influence of wavelength on quantitative analysis of 4 minor elements in stainless steel samples (Si, Ti, Nb and Mo) was investigated. Stainless steel samples with different elemental concentrations were prepared and analyzed by laser-induced plasma spectrometry (LIPS). The effect of laser wavelength on analytical figures of merit (calibration curves, correlation coefficients, linear dynamic ranges, analytical precision, and accuracy values) was found to be negligible when internal standardization (an Fe line) and time-resolved laser-induced plasma are employed. For both wavelengths, the calibration curves presented a good linearity and an acceptable linear dynamic range in the concentration interval investigated. For the four elements studied, limits of detection lower than 150 microg g(-1) were achieved. To evaluate the influence of wavelength on precision and accuracy, a set of fifteen high-alloyed steel samples from different stages of steelmaking process have been analyzed. Finally, the long-term stability of the analytical measurements for Mo with 532 nm wavelength has been discussed. RSD values were lower than 5.3% for the elements studied.     

The electrophilic reactions of pentacyanonitrosylferrate(II) with hydrazine and substituted derivatives. Catalytic reduction of nitrite and theoretical prediction of eta(1)-, eta(2)-N(2)O bound intermediates

The electrophilic reactivity of the pentacyanonitrosylferrate(II) ion, [Fe(CN)(5)NO](2)(-), toward hydrazine (Hz) and substituted hydrazines (MeHz, 1,1-Me(2)Hz, and 1,2-Me(2)Hz) has been studied by means of stoichiometric and kinetic experiments (pH 6-10). The reaction of Hz led to N(2)O and NH(3), with similar paths for MeHz and 1,1-Me(2)Hz, which form the corresponding amines. A parallel path has been found for MeHz, leading to N(2)O, N(2), and MeOH. The reaction of 1,2-Me(2)Hz follows a different route, characterized by azomethane formation (MeNNMe), full reduction of nitrosyl to NH(3), and intermediate detection of [Fe(CN)(5)NO](3)(-). In the above reactions, [Fe(CN)(5)H(2)O](3)(-) was always a product, allowing the system to proceed catalytically for nitrite reduction, an issue relevant in relation to the behavior of the nitrite and nitric oxide reductase enzymes. The mechanism comprises initial reversible adduct formation through the binding of the nucleophile to the N-atom of nitrosyl. The adducts decompose through OH(-) attack giving the final products, without intermediate detection. Rate constants for the adduct-formation steps (k = 0.43 M(-)(1) s(-)(1), 25 degrees C for Hz) decrease with methylation by about an order of magnitude. Among the different systems studied, one-, two-, and multielectron reductions of bound NO(+) are analyzed comparatively, with consideration of the role of NO, HNO (nitroxyl), and hydroxylamine as bound intermediates. A DFT study (B3LYP) of the reaction profile allows one to characterize intermediates in the potential hypersurface. These are the initial adducts, as well as their decomposition products, the eta(1)- and eta(2)-linkage isomers of N(2)O.     

Isolation of water-soluble organic matter from atmospheric aerosol

The development of a solid phase extraction (SPE) method is presented, which is capable of isolating approx. 60% of the water-soluble organic compounds from aerosol samples. The aqueous extracts of the filter samples were acidified then passed through an SPE column. Four silica-based and two polymeric reversed phase columns were tested and similar recoveries of the organic carbon were found. The isolated organic matter was nearly free from inorganic ions, which are major constituents of atmospheric aerosol. This fraction accounted for a major part of the UV absorption above 250 nm and fluorescence activity of the aerosol extract. The precision of the method was tested by performing three parallel sample preparations with Oasis HLB columns. It was found that the relative standard deviation of the carbon content of the isolated organic matter was better than 7%, which indicated the reliability of the method. In the atmospheric aerosol research the newly developed sample preparation method facilitates the physical and chemical characterisation of water-soluble organic compounds without the interference of inorganic constituents.     

Performance of SuSi: a method for generating atomistic models of amorphous polymers based on a random search of energy minima

The performance of a recently developed method to generate representative atomistic models of amorphous polymers has been investigated. This method, which is denoted SuSi, can be defined as a random generator of energy minima. The effects produced by different parameters used to define the size of the system and the characteristics of the generation algorithm have been examined. Calculations have been performed on poly(L,D-lactic) acid (rho = 1.25 g/cm3) and nylon 6 (rho = 1.084 g/cm(3)), which are important commercial polymers.     

Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 1. Preparation,dissociations, and energetics of 2-hydroxyoxolan-2-yl radical,neutral isomers,and cations

Collisional neutralization of several isomeric C(4)H(7)O(2) cations is used to generate radicals that share some structural features with transient species that are thought to be produced by radiolysis of 2-deoxyribose. The title 2-hydroxyoxolan-2-yl radical (1) undergoes nearly complete dissociation when produced by femtosecond electron transfer from thermal organic electron donors dimethyl disulfide and N,N-dimethylaniline in the gas phase. Product analysis, isotope labeling ((2)H and (18)O), and potential energy surface mapping by ab initio calculations at the G2(MP2) and B3-PMP2 levels of theory and in combination with Rice-Ramsperger-Kassel-Marcus (RRKM) kinetic calculations are used to assign the major and some minor pathways for 1 dissociations. The major (approximately 90%) pathway is initiated by cleavage of the ring C-5[bond]O bond in 1 and proceeds to form ethylene and *CH(2)COOH as main products, whereas loss of a hydrogen atom forms 4-hexenoic acid as a minor product. Loss of the OH hydrogen atom forming butyrolactone (2, approximately 9%) and cleavage of the C-3[bond]C-4 bonds (<1%) in 1 are other minor pathways. The major source of excitation in 1 is by Franck-Condon effects that cause substantial differences between the adiabatic and vertical ionization of 1 (5.40 and 6.89 eV, respectively) and vertical recombination in the precursor ion 1(+) (4.46 eV). (+)NR(+) mass spectra distinguish radical 1 from isomeric radicals 2-oxo-(1H)oxolanium (3), 1,3-dioxan-2-yl (9), and 1,3-dioxan-4-yl (10) that were generated separately from their corresponding ion precursors.     

New considerations about the separation and quantification of antimony species by ion chromatography-hydride generation atomic fluorescence spectrometry

A new method for the speciation of inorganic [Sb(III) and Sb(V)] and organic (Me3SbCl2) antimony species by using a polystyrene-divinylbenzene-based anion-exchange HPLC column (Hamilton PRP-X100) coupled to hydride generation atomic fluorescence spectrometry (HG-AFS) is presented. Several mobile phases were tested for the baseline separation of these three antimony species, investigating in detail experimental parameters such as concentration and pH. The best efficiency and resolution was achieved by using a gradient elution between diammonium tartrate 250 mmol l(-1) pH 5.5 (A) and KOH 20 mmol l(-1) pH 12 (B). The gradient programme used was 100% B for 1.5 min, decreasing to 0% B in 0.1 min and maintained the elution with 100% A for 5.5 min. Analysis time was less than 7 min. Equilibration of the column with the complexing mobile phase was found to be critical in order to avoid Sb(III) double peak formation. Dilution in diammonium tartrate medium was necessary in order to avoid Sb(III) oxidation at microg l(-1) concentration level. Detection limits of 0.06 microg l(-1) for Sb(V), 0.09 microg l(-1) for Me3SbCl2 and 0.04 microg l(-1) for Sb(III) as well as repeatability and reproducibility better than 5% R.S.D. (n = 10) and 9% R.S.D. (n = 30) (for 1 and 5 microg l(-1) of Sb(V) and Sb(III) and 5 and 10 microg l(-1) of Me3SbCl2) were obtained. Accuracy and recovery studies were carried out by analysing one river freshwater sample and two water certified reference materials. The proposed methodology can be considered reliable and straightforward for antimony speciation in fresh water samples.     

Spectrofluorimetric and isotachophoretic determination of maprotiline in human blood serum

Maprotiline determination in blood serum samples was investigated by the use of both capillary isotachophoresis and spectrofluorimetric techniques. The analyte had to be enriched before determination and extraction with n-heptane was used for this purpose. The preliminary separation enabled the determination of maprotiline in blood serum at therapeutic concentration levels.     

Electroviscous Effect in Dilute Suspensions of Alumina

A study on the electroviscous effect of alumina suspensions has been made. At the low volume fraction of the particles studied here only a first-order effect was detected. Ubbelohde-type capillary viscometers have been used. A simple method to determine the hydrodynamic constant k(1) has been proposed. The experimental primary electroviscous coefficients corresponding to different electrolyte concentrations have been compared with two different theoretical approachs (I. G. Watterson, and L. R. White, J. Chem. Soc. Faraday Trans. 2 77, 1115 (1981); F. J. Rubio-Hernández, E. Ruiz-Reina, and A. I. Gómez-Merino, J. Colloid Interface Sci. 206, 334 (1998)) and the results suggest that the presence of a dynamic Stern layer plays a certain role in this effect. Copyright 2000 Academic Press.     

Optimization of culture medium and conditions for penicillin acylase production by Streptomyces lavendulae ATCC 13664

The culture medium for Streptomyces lavendulae ATCC 13664 was optimized on a shake-flask scale by using a statistical factorial design for enhanced production of penicillin acylase. This extracellular enzyme recently has been reported to be a penicillin K acylase, presenting also high hydrolytic activity against penicillin V and other natural aliphatic penicillins such as penicillin K, penicillin F, and penicillin dihydroF. The factorial design indicated that the main factors that positively affect penicillin acylase production by S. lavendulae were the concentration of yeast extract and the presence of oligoelements in the fermentation medium, whereas the presence of olive oil in the medium had no effect on enzyme production. An initial concentration of 2.5% (w/v) yeast extract and 3 microg/mL of CuSO4 x 5H2O was found to be best for acylase production. In such optimized culture medium, fermentation of the microorganism yielded 289 IU/L of enzyme in 72 h when employing a volume medium/volume flask ratio of 0.4 and a 300-rpm shaking speed. The presence of copper, alone and in combination with other metals, stimulated biomass as well as penicillin acylase production. The time course of penicillin acylase production was also studied in the optimized medium and conditions. Enzyme production showed catabolite repression by different carbon sources such as glucose, lactose, citrate, glycerol, and glycine.