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961.
A new software-controlled volume-based system for sample introduction in process flow injection analysis was developed. By using a multi-syringe burette coupled with one or two additional commutation valves, the multi-commuted injection of precise sample volumes was accomplished. Characteristics and performance of the injection system were studied by injecting an indicator in a buffered carrier. Three configurations were implemented in order to achieve two different tasks: the single injection of a sample in a two- or three-channels manifold, and the dual injection into different streams. The two channel flow system using the single injection was applied to the determination of free acidity in diluted samples containing high levels of iron(III), by employing the single point titration methodology. The precipitation of ferric hydroxide was prevented using the ammonium and sodium salts of oxalate and acetate as buffer titrant. Methyl Red was employed as indicator. The procedure allows determination of acid concentration in solutions with a Fe(III)/H+ molar ratio up to 0.2. Samples with higher Fe(III)/H+ molar ratios were spiked with a known strong acid at dilution. The three-channel configuration was applied to the determination of ferric ions, using, as reagent, a merging mixture of sulfuric acid and potassium thiocyanate. The double injection system was implemented in series in a single (three-channel) manifold in such a way that a different injection volume and a changed reagent were used for each analyte. It was applied to the separated or sequential determination of free acidity and ferric ions. In this configuration, iron(III) was determined using 0.5-0.7% (w/v) sodium salicylate solution as reagent. The systems can operate at up to 100, 84 and 78 injections per hour, respectively. Determinations on synthetic and process samples compared well with the reference values and procedures. Recoveries of 95-102% with a maximum RSD value of 5.4% were found for acidity. The respective values obtained for iron determinations were 96-105% and 4.3%. 相似文献
962.
The free radical polymerization of ethyl acrylate was investigated in benzene and dimethyl formamide solutions at 50°. The effects of initiator and monomer concentration were studied over a wide range. The overall rate of polymerization was proportional to (initiator concentration) but not to the concentration of the monomer. We attempted to interpret this solvent effect on the basis of (i) the diffusion theory, (ii) the theory of charge transfer complexes and (iii) the theory of hot radicals. Our experimental results could only be explained quantitatively in terms of hot radicals. 相似文献
963.
Haoshuang Gu Yongming Hu Hao Wang Xiangrong Yang Zhenglong Hu Ying Yuan Jin You 《Journal of Sol-Gel Science and Technology》2007,42(3):293-297
Single crystalline nanowires of lead titanate (PbTiO3) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure
and optical properties of PbTiO3 nanowires were investigated. The PbTiO3 nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO3 with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm.
The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy
(XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition
of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed
at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies
are responsible for the light emission of PbTiO3 nanowires. 相似文献
964.
Mátyás Milen László Hazai Pál Kolonits György Kalaus Lajos Szabó Ágnes Gömöry Csaba Szántay 《Central European Journal of Chemistry》2005,3(1):118-136
Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected.
Dedicated to Professor Károly Lempert on his 80th birthday. 相似文献
965.
Emtenäs H Carlsson M Pinkner JS Hultgren SJ Almqvist F 《Organic & biomolecular chemistry》2003,1(8):1308-1314
Optically active bicyclic beta-lactams were synthesized, starting from 2-H-delta 2-thiazolines and Meldrum's acid derivatives. Several methods to accomplish an ester hydrolysis without damaging the beta-lactam framework were investigated. A rapid CsOH saponification of the beta-lactam methyl esters was developed and protonation of the Cs-carboxylates by Amberlite (IR-120 H+) afforded a series of bicyclic beta-lactam carboxylic acids. Moreover, a convenient method for the synthesis of 2-H-delta 2-thiazolinecarboxylic acid methyl ester 2 was developed. Bicyclic beta-lactam carboxylic acids 7a-g and aldehydes 4a-d were screened for their affinity to the bacterial periplasmic chaperone PapD using a surface plasmon resonance technique. beta-Lactams substituted with large acyl substitutents showed better binding to the chaperone than the native C-terminal peptide PapG 8, demonstrating that bicyclic beta-lactams constitute a new class of potential bacterial chaperone inhibitors. 相似文献
966.
Bernardi A Potenza D Capelli AM García-Herrero A Cañada FJ Jiménez-Barbero J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4598-4612
As a step to delineate a strategy of ligand design for cholera toxin (CT), NMR studies were performed on several mimics of the GM1 ganglioside oligosaccharide. The conformation of these analogues was investigated first in solution and then upon binding to cholera toxin by transferred nuclear Overhauser effect (TR-NOE) measurements. It was demonstrated that CT selects a conformation similar to the global minima of the free saccharides from the ensemble of presented conformations. No evidence of major conformational distortions was obtained, but one or two of the available conformers of the hydroxyacid side chain appear to be selected in the bound state. The NMR data were interpreted with the aid of computer models, generated and analyzed by using a combination of different approaches (MacroModels' MC/EM and MC/SD, Autodock, and GRID). Analysis of the NMR data supported by computational studies allowed us to interpret the experimental observations and to derive workable models of the ligand:toxin complexes. These models suggest that the higher affinity of the (R)-lactic acid derivative 3 may stem from lipophilic interactions with a hydrophobic area in the toxin binding site located in the vicinity of the sialic acid side chain binding region of the CT:GM1 complex, and formed by the side chain of Ile-58 and Lys-34. Thus, the models obtained have allowed us to make useful design suggestions for the improvement of ligand affinity. 相似文献
967.
Tanskanen H Khriachtchev L Lundell J Räsänen M 《The Journal of chemical physics》2004,121(17):8291-8298
We investigate the formation mechanism of HXeCCXeH in a Xe matrix. Our experimental results show that the HXeCCXeH molecules are formed in the secondary reactions involving HXeCC radicals. The experimental data on the formation of HXeCCXeH is fully explained based on the model involving the HXeCC+Xe+H-->HXeCCXeH reaction. This reaction is the first case when a noble-gas hydride molecule is formed from another noble-gas molecule. In addition, we investigate the (12)C/(13)C isotope effect on the vibrational properties of organo-noble-gas hydrides (HKrCCH, HXeCCH, HXeCC, and HXeCCXeH) in noble-gas matrixes. The present experimental results and ab initio calculations on carbon isotope shifts of the vibrational modes support the previous assignments of these molecules. Upon (12)C to (13)C isotope substitution, we observed a pronounced effect on the H-Kr stretching mode of HKrCCH (downshift of 1.0-3.6 cm(-1), depending on the matrix site) and a small anomalous shift (+0.1 cm(-1)) of the H-Xe stretching mode of HXeCCH and HXeCCXeH. 相似文献
968.
This paper proposes a quick, novel method for tin determination in organotin chemicals by slurry nebulization inductively coupled plasma atomic emission (ICP-AES) spectrometry. The method was tested by the measurement of five organotin carboxylate complexes of known composition for obtaining simple stoichiometric data. The slurries were prepared by first dissolving the organotins in an adequate solvent (methanol, pyridine or acetone) well miscible with water and then adding this solution drop-by-drop to a 0.005% TX-100 tenzide solution while maintaining intensive mixing. Dynamic laser light scattering experiments showed that the average equivalent particle size in the resulting slurry was ≈0.3 μm for all samples and solvents. Under suitable ICP-AES measuring conditions, the signal recoveries were found to be between 101.8 and 106.6%, which allowed direct nebulization and calibration against aqueous solutions. Typically, 70 μg l−1 detection limit and 1–5% relative S.D. on five replicates can be achieved by the described method. 相似文献
969.
Thermodynamics and crystallization kinetics of the hydrothermal synthesis of Na4Ti4Si3O10 (NaTS) were systemically studied by both experiments and model simulation. Experimental results showed that the curve of
crystallinity with time was a characteristic signmoid in the shape that indicated the crystallization of Na4Ti4Si3O10 was a typical spontaneous nucleation process on the laboratory scale. Crystallization of NaTS belongs to the liquid-liquid
transformation mechanism and the reaction is endothermic (ΔH = 15.3 kJ/mol). A mathematic model of crystallization kinetics was developed to simulate the synthesis of NaTS. Runge-Kutta
and simplex methods were adopted to solve the partial differential equations. Model results fitted well with the experimental
data and showed that the synthesis process belongs to spontaneous nucleation and crystal growth. Moreover, the very small
crystal growth constant (5.6·10−7) and gel dissolution constant (7.0·10−7) indicate they are the rate-limiting steps of the whole synthesis process. 相似文献
970.
Complex systems of paramagnetic centres existing in demineralised flame coal (71.4 wt% C), medium-rank coal (85.6 wt% C) and
anthracite (94.9 wt% C) were analysed by electron paramagnetic resonance spectroscopy (EPR). Different groups of paramagnetic
centres were searched in macerals (exinite, vitrinite, inertinite) of coals with carbon contents of 73.8 wt% C and 85.6 wt%
C. Experimental EPR spectra were fitted by different superposition of theoretical lines. Total concentration of paramagnetic
centres both in coal and macerals increases with carbon content in the sample. Total concentration of paramagnetic centres
in macerals increases from exinite to inertinite. Four groups of paramagnetic centres were found in medium-rank coal, and
only two groups exist in flame coal and anthracite. The EPR spectrum of medium-rank coal is a superposition of two broad and
two narrow lines. Both broad and narrow, and two narrow lines were measured in EPR spectra of flame coal and anthracite, respectively.
Two types of paramagnetic centres with broad lines and one group with narrow lines exist in exinite and vitrinite from medium-rank
coal. Two narrow components were observed in EPR spectra of its inertinite. Two different broad electron paramagnetic resonance
signals were detected for macerals from low-coalificated coal. Paramagnetic centres systems of medium-rank coal samples reveal
the most complex character. Broad EPR lines were not observed for the higher coalificated samples, i.e., anthracite and inertinite
from medium-rank coal. Narrow lines do not occur in EPR spectra of low-coalificated macerals. Strong dipolar interactions
and fast spin-lattice relaxation processes are characteristic for paramagnetic centres with broad lines. Strong exchange interactions
and short spin-lattice relaxation time were measured for paramagnetic centres with the narrowest EPR signals. 相似文献