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151.
A simple technique is described for the routine simultaneous capillary electrophoretic determination of 6 cations in wine. Separation was achieved on a fused silica capillary column with a UV-Cat-1, alpha-hydroxysobutyric acid and 18-crown-6-ether buffer at pH 4.5 and indirect UV detection at 214 nm. The content of magnesium, sodium, potassium, calcium, manganese, and lithium was determined. The method is quantitative, with recoveries in the 92-102% range, and linear over more than one order of magnitude. The precision is better than 2.5-3.4%. The method is sensible, with detection limits between 0.01 and 0.06 mg/L. Twenty-five red wines with a Certified Brand of Origin from Galicia (north-western Spain) were analyzed by the proposed method. Various wines showed very similar electrophoretic profiles, but significant quantitative differences were observed. 相似文献
152.
We have produced recombinant gamma-chain variant fibrinogens, gamma308K, gamma308I, and gamma308A simultaneously with wild-type fibrinogen, gamma-308N, by genetic protein engineering using Chinese hamster ovary cells. Although all three variant fibrinogens are a result of a single amino acid substitution, the aberrant gamma-chains of gamma308K and gamma308I fibrinogens migrated faster than gamma308N. Furthermore, plasmic digestion profiles were examined in the presence of 5 mM ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) or 1 mM CaCl2. In the presence of EGTA, the three variant fibrinogens were digested into D1 and D2 fragments slightly faster than wild type. In addition, the D2 fragment derived from gamma308K was further digested into D3 by plasmin much faster than that from gamma308N. These data suggest that cleavage of gamma356Lys-gamma357Ala bond by plasmin in gamma308K, gamma308I, and gamma308A is slightly accelerated and the gamma302Lys-gamma303Phe bond is cleaved by plasmin rapidly in only the gamma308K variant. Furthermore, the substitution of Lys for gamma308Asn results in the generation of a new plasmin cleavage site between gamma308Lys and gamma309Gly in the presence of EGTA. In conclusion, a substitution at residue gamma308Asn may cause a conformational change in the gammachain of fragment D affecting polymerization and plasmin cleavage. 相似文献
153.
Isomer-selective infrared photodissociation (IRPD) spectra are obtained for the first time for protonated polyfunctional aromatic molecules isolated in the gas phase. IRPD spectra of the oxonium and fluoronium isomers of protonated para-fluorophenol (C6H6FO+) were separately obtained by monitoring resonant photo-induced H2O and HF loss, respectively. Analysis of the F-H, O-H, and C-H stretch wave numbers provides valuable spectroscopic information on the chemical properties of these reactive intermediates, in particular on the substitution effects of functional groups. 相似文献
154.
Zhou Q Liu X Zhao Y Jia N Liu L Yan M Jiang Z 《Chemical communications (Cambridge, England)》2005,(39):4941-4942
Single crystal tin nano-rod arrays were fabricated by the electrodeposition method when amphiphilic triblock copolymer P123 was used as a soft template at a concentration much lower than that for forming a liquid crystalline phase. 相似文献
155.
Nagaoka Y Inoue H el-Koussi N Tomioka K 《Chemical communications (Cambridge, England)》2002,(2):122-123
Upon treatment with lithium diisopropylamide achiral and chiral alpha,beta,psi,omega-unsaturated bisphosphine oxides underwent lithiation-conjugate addition tandem cyclization to afford the corresponding endo-alpha,beta-unsaturated cyclic bisphosphine oxides; sequential stereoselective reduction of the cyclized bisphosphine oxide gave the corresponding trans- and cis-bisphosphines that were successfully applicable in a catalytic asymmetric hydrogenation as chiral bisphosphine ligands. 相似文献
156.
[H+]在0.01~0.70mol?L-1范围内,离子强度为1.00mol?L-1,[Fe(III)]>>[配体]、[H+]>>[配体]的条件下,研究了Fe(III)与2,3-二羟基苯磺酸钠(Tiron)的配位反应.发现当[H+]≤3.00×10-2mol?L-1时,[Fe(III)]2对反应速率有明显的贡献.求得了相关反应的动力学参数,从而揭示了FeOH2+和FeOH24+与Tiron配位的解离反应途径及FeOH32+的缔合反应机制,并提出了该配位反应的可能机理. 相似文献
157.
Kar S Chanda N Mobin SM Urbanos FA Niemeyer M Puranik VG Jimenez-Aparicio R Lahiri GK 《Inorganic chemistry》2005,44(5):1571-1579
The reaction of cis-Ru(acac)2(CH3CN)2 (acac = acetylacetonate) with 2,2'-dipyridylamine (L) in ethanolic medium resulted in facile one-pot synthesis of stable [(acac)2RuIII(L)]ClO4 ([1]ClO4), trans-[(acac)2RuII(L)2] (2), trans-[(acac)2RuIII)L)2]ClO4 ([2]ClO4), and cis-[(acac)2RuII(L)2] (3). The bivalent congener 1 was generated via electrochemical reduction of [1]ClO4. Although in [1]+ the dipyridylamine ligand (L) is bonded to the metal ion in usual bidentate fashion, in 2/[2]+ and 3, the unusual monodentate binding mode of L has been preferentially stabilized. Moreover, in 2/[2]+ and 3, two such monodentate L's have been oriented in the trans- and cis-configurations, respectively. The binding mode of L and the isomeric geometries of the complexes were established by their single-crystal X-ray structures. The redox stability of the Ru(II) state follows the order 1 < 2 < 3. In contrast to the magnetic moment obtained for [1]ClO4, mu = 1.84 muB at 298 K, typical for low-spin Ru(III) species, the compound [2]ClO4 exhibited an anomalous magnetic moment of 2.71 muB at 300 K in the solid state. The variable-temperature magnetic measurements showed a pronounced decrease of the magnetic moment with the temperature, and that dropped to 1.59 muB at 3 K. The experimental data can be fitted satisfactorily using eq 2 that considered nonquenched spin-orbit coupling and Weiss constant in addition to the temperature-independent paramagnetism. [1]ClO4 and [2]ClO4 displayed rhombic and axial EPR spectra, respectively, in both the solid and the solution states at 77 K. 相似文献
158.
In the present paper, we describe a microfluidics-based sensing system for nonelectroactive anions under negative separation electric field by mounting a single carbon fiber disk working electrode (WE) in the end part of a poly(dimethylsiloxane) microchannel. In contrast to work in a positive separation electric field described in our previous paper (Anal. Chem. 2004, 76, 6902-6907), here the electrochemical reduction reaction at the WE is not coupled with the separation high-voltage (HV) system, whereas the electrochemical oxidation reaction at the WE is coupled with the separation HV system. The electroactive indicator is the carbon fiber WE itself but not dissolved oxygen. This provides a convenient and sensitive means for the determination of nonelectroactive anions by amperometry. The influences of separation voltage, detection potential, and the distance between the WE and the separation channel outlet on the response of the detector have been investigated. The present detection mode is successfully used to electrochemically detect F-, Cl-, SO4(2-), CH3COO-, H2PO4-. Based on the preliminary results, a detection limit of 2 microM and a dynamic range up to three orders of magnitude for Cl- could be achieved. 相似文献
159.
160.
Solid-phase microextraction (SPME) with a disposable ionic liquid (IL) coating was developed for headspace extraction of benzene, toluene, ethylbenzene, and xylenes (BTEX) in paints. The SPME fiber was coated with IL prior to every extraction, then the analytes were extracted and desorbed on the injection port of gas chromatography, and finally the IL coating on the fiber was washed out with solvents. The coating and washing out of IL from the fiber can be finished in a few minutes. This disposable IL-coated fiber was applied to determine BTEX in water-soluble paints with results in good agreement with that obtained by using commercially available SPME fibers. For all the four studied paints samples, the benzene contents were under the detection limits, but relatively high contents of toluene, ethylbenzene and xylenes (56-271 microg g(-1)) were detected with spiked recoveries in the range of 70-114%. Compared to the widely used commercially available SPME fibers, this proposed disposable IL-coated fiber has much lower cost per determination, comparable reproducibility (RSD < 11%), and no carryover between each determination. Considering that IL possess good extractability for various organic compounds and metals ions, and that task-specific IL can be designed and synthesized for selective extraction of target analytes, this disposable IL coating SPME might has great potential in sample preparation. 相似文献