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971.
López-García I Merino Meroño B Campillo N Hernández-Córdoba M 《Analytical and bioanalytical chemistry》2002,373(1-2):98-102
Two manifolds were assessed for the purpose of determining both the total chromium content and that present as a soluble form in industrial effluents by flow injection flame atomic absorption spectrometry (FI-FAAS). To determine the chromium content in the soluble fraction the samples were used without additional treatment, a 0.45 microm filter being included in the FI system. To determine the total chromium content, the samples were acidified with nitric acid 20% (v/v) and heated for 30 s in a microwave oven (temperatures of about 70 degrees C were reached). The problem posed by the very different concentration range in which total and soluble chromium are present was overcome by using programmed flow rate methodology and by only partially emptying the sample loop. A personal computer controlled both the rotation speed of a peristaltic pump and the volume of sample injected into the system, thus obtaining the dispersion degree required. Using the manifold proposed, the chromium content in the soluble fraction can be determined in the 0.5-20 microg mL(-1) range using a 10 microg mL(-1) single standard for calibration. To determine the total chromium content, a calibration line in the 20-200 microg mL(-1) range was obtained using a single 50 microg mL(-1) chromium standard solution. The reliability of the semi-automatic devices was verified by comparing the results obtained with those found by treating the samples and using both FAAS in a conventional way and a spectrophotometric method using diphenylcarbazide at the 95% confidence level (ANOVA test). The proposed procedures showed a RSD lower than +/-3%. 相似文献
972.
Andrés J Moliner V Safont VS Domingo LR Picher MT 《The Journal of organic chemistry》1996,61(22):7777-7783
As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling. 相似文献
973.
Jenö Kóbor Ferenc Fülöp M. Sami El-Gharib Gábor Bernáth 《Journal of heterocyclic chemistry》1984,21(1):149-153
A large number of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones were prepared by the reaction of 1-(ethoxycarbonylmethyl)-6,7-dialkoxy-1,2,3,4-tetrahydroisoquinolines with iminoethers. Reaction of the corresponding isoquinoline-1-acetic acid derivatives with iminoethers led to the formation of N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides. In the hydrolysis of the prepared 4-substituted-pyrimido[6,1-a]isoquinolin-2-ones, the corresponding N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides were obtained. While reduction of the 4-phenyl derivative resulted in the corresponding 1,3,4,6,7,11b-hexahydropyrimidinone. The steric structures of the tetrahydro- and hexahydropyrimido[6,1-a]isoquinolines were determined by nmr spectroscopy. 相似文献
974.
An extraction-AAS method of determination of Co, Ni, and Mn in metallurgical copper materials containing considerable amounts ofCu, Fe, Pb, Zn, and Al has been developed. Good selectivity of group separation of Co, Ni, and Mn has been achieved by (a) the use of tetrabutylammonium bromide to improve extractability of HTTA complexes by ion-pair formation, and (b) the masking of major elements with sodium thiosulphate and sulphosalicylic acid. The extracts are stable for at least 3 weeks. 相似文献
975.
Marián Kucharík František Šimko Vladimír Danielik Miroslav Boča Roman Vasiljev 《Monatshefte für Chemie / Chemical Monthly》2007,138(12):1211-1215
Summary. The phase diagram of the system Na3AlF6–NaVO3 was determined by means of thermal analysis. The system is a simple binary eutectic one. The eutectic point was estimated
at x(NaVO3) = 0.975 and t
eut = 617°C. The XRD patterns of samples after thermal analysis revealed the presence of cryolite and NaVO3 only supporting the above assumption of a simple eutectic binary system. 相似文献
976.
García G Rodríguez JL Lacconi GI Pastor E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8773-8780
In the present paper, a systematic electrochemical investigation on thiourea (TU) electrooxidation was developed on polycrystalline and (111) single-crystal gold electrodes in 0.1 M perchloric acid. The combination of cyclic voltammetry with in situ Fourier transform infrared spectroscopy (FTIRS) and differential electrochemical mass spectrometry techniques have allowed the nature of the species formed during the electroadsorption and electrooxidation of TU to be established. FTIRS experiments were performed in D2O to clean up the region of the H2O bending around 1600 cm(-1). It was concluded that TU adsorbs tilted on the surface in the 0.05-0.40 VRHE potential range. A dual-path reaction mechanism was evidenced in the oxidation process. The first pathway takes place from adsorbed TU at E > 0.40 VRHE and implies the formation of [Au(I)-(TU)2]+, which is oxidized to NH2CN and S0 at E > 0.80 VRHE. In a following oxidation step at E > 1.20 V, N2, CO2, and HSO4-/SO4(2-) were produced. The second parallel reaction occurs from TU in solution at E > 0.50 VRHE to form (TU)2(2+). All these species were characterized from the spectroscopic experiments. Similar results were obtained for both surfaces. 相似文献
977.
Summary Using the X-ray crystal structure of the human topoisomerase I (top1) – DNA cleavable complex and the Sybyl software package, we have developed a general model for the ternary cleavable complex formed with four protoberberine alkaloids differing in the substitution on the terminal phenyl rings and covering a broad range of the top1-poisoning activities. This model has the drug intercalated with its planar chromophore between the −1 and +1 base pairs flanking the cleavage site, with the nonplanar portion pointing into the minor groove. The ternary complexes were geometry-optimized and relative interaction energies, computed by using the Tripos force field, were found to rank in correct order the biological potency of the compounds; in addition, the model is also consistent with the top1-poisoning inactivity of berberine, a major prototype of the protoberberine alkaloids. The model might serve as a rational basis for elaboration of the most active compound as a lead structure, in order to develop more potent top1 poisons as next generation anti-cancer drugs. 相似文献
978.
Zuev V. V. de Vekki D. A. Kuchaev A. E. Vorob’ev M. V. Skvortsov N. K. 《Russian Journal of General Chemistry》2004,74(11):1679-1685
Hydrosilylation of p-substituted acetophenones XC6H4COCH3 (X = H, Me, MeO, HO, F, Cl, NO2) with 1,1,3,3-tetramethyldisiloxane in the presence of rhodium and platinum complexes was studied. The Pt(II) complexes are less active but more selective catalysts of hydrosilylation of acetophenones. Six new 1-(1-arylethoxy)-1,1,3,3-tetramethyldisiloxanes were prepared.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1804–1811.Original Russian Text Copyright © 2004 by Zuev, de Vekki, Kuchaev, Vorobev, Skvortsov.This revised version was published online in April 2005 with a corrected cover date. 相似文献
979.
I.?S.?TerekhovaEmail author a?A.?Yu.?Manakov V.?V.?Feklistov Yu.?A.?Dyadin V.?YU.?Komarov D.?Yu.?Naumov 《Journal of inclusion phenomena and macrocyclic chemistry》2005,52(3-4):207-211
X-ray powder diffraction studies were performed of the polyhydrates, formed at positive temperature in swelled grains of carboxylic cation-exchange resins in the form of tetraisoamylammonium (cross-linked tetraisoamylammonium polyacrylates, differing in the degree of cross-linking: 1, 2 and 3%). It was shown that the polyhydrates exist as the crystalline phase under specific conditions, determined earlier by DTA technique. Diffraction patterns of the samples, recorded at the temperature +3 ± 1 °C, indicate that the polyhydrates crystallize in hexagonal symmetry, the unit cell parameters are close to a=12.25 Å, c=12.72 Å and do not depend significantly upon the degree of cross-linking. The suppositions were made concerning the size of hydrate crystallites, formed in the swelled grains of the studied resins.This revised version was published online in July 2005 with a corrected issue number. 相似文献
980.
A cationic exchanger paper is used to retain analytes in solution and, after drying, to analyze directly by measuring the UV-Vis absorbance of the paper. The method was applied to determination of iron using its known 1,10-phenanthroline complex. Using 100 ml of sample the applicable concentration range was between 1.0 and 10.0 ng/ml with a detection limit of 0.2 ng/ml and a RSD around 2%. The method was applied to determination of iron total in snow, human serum and wine. 相似文献