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991.
The modern theory of polarization in extended insulators is applied to one-dimensional models for conjugated polymers and charge transfer salts. Closed expressions for the dependence of the polarization on the site and bond energy alternations are presented for uncorrelated models, and results from exact real-space diagonalization are obtained for correlated models. Changes in polarization induced by lattice phonons or molecular vibrations are directly related to the intensity of infrared bands in the far and mid-IR, respectively. We model intensities by introducing linear electron-vibration coupling and show that coupling to delocalized electrons generates a combination band consisting of a lattice phonon and a molecular vibration. The displaced dipole operator is defined on a real-space basis allowing for the finite field calculation of linear polarizability in finite size systems with periodic boundary conditions. Size-consistency arguments are used to demonstrate that the resulting polarizability becomes exact in the thermodynamic limit, and numerical calculations demonstrate that this approach leads to reliable results that converge rapidly to the thermodynamic limit. 相似文献
992.
Ruiz-Medina A Ortega-Barrales P Fernández-de Córdova ML Molina-Díaz A 《Journal of AOAC International》2002,85(2):369-374
A simple, rapid, inexpensive, and automated flow-through solid-phase spectroscopic sensing device is proposed for the sequential determination of 2 vitamins: thiamine and ascorbic acid. The vitamins are concentrated on ion-exchange gels, thiamine on Sephadex SP C-25, and ascorbic acid on Sephadex QAE A-25; both solid supports are packed in 2 different flow cells. The absorbance is monitored directly on the solid phase with a double-beam spectrophotometer at 250 nm, without derivatization or additional elution. With the use of 2 carrier/self-eluting solutions (0.1 5M sodium acetate/acetic acid and 0.18M citric acid/K2HPO4) and a sample volume of 1000 microL, the sensor responds linearly in the range of 0.5-15 and 3-50 microg/mL with detection limits of 0.14 and 0.36 microg/mL for thiamine and ascorbic acid, respectively. When the method was applied to synthetic samples and pharmaceutical preparations, precise and accurate values were obtained. 相似文献
993.
It is shown that the process of resonant double electron capture in high energy He2++He collisions can be approximately described by a sum over products of one-electron CDW amplitudes. The summation coefficients are determined by stationary ground-state calculations with CI wavefunctions. Total and differential cross sections are calculated and compared with experimental values. 相似文献
994.
J. Forstén 《Accreditation and quality assurance》1998,3(7):285-288
This article mainly focuses on the testing of products, materials, etc., but the general principles are applicable in a broader
perspective. Quality of testing should be judged based on fitness for purpose. This judgement includes both objective and
subjective elements. The possibility to make decisions and other professional judgements based on test results alone is discussed
and compared with the decisions and judgements being made through the certification and inspection process. Quality, including
the uncertainty of the test results, depends on many factors, and in order to make necessary improvements in the testing procedures
based on the customers' needs, the right issues should be addressed. The question arises as to whether, in laboratories' quality
systems and in the accreditation and certification process, attention is really paid to those factors that are crucial to
obtaining reliable results. 相似文献
995.
Justicia J Rosales A Buñuel E Oller-López JL Valdivia M Haïdour A Oltra JE Barrero AF Cárdenas DJ Cuerva JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1778-1788
The titanocene-catalyzed cascade cyclization of epoxypolyenes, which are easily prepared from commercially available polyprenoids, has proven to be a useful procedure for the synthesis of C(10), C(15), C(20), and C(30) terpenoids, including monocyclic, bicyclic, and tricyclic natural products. Both theoretical and experimental evidence suggests that this cyclization takes place in a nonconcerted fashion via discrete carbon-centered radicals. Nevertheless, the termination step of the process seems to be subjected to a kind of water-dependent control, which is unusual in free-radical chemistry. The catalytic cycle is based on the use of the novel combination Me(3)SiCl/2,4,6-collidine to regenerate the titanocene catalyst. In practice this procedure has several advantages: it takes place at room temperature under mild conditions compatible with different functional groups, uses inexpensive reagents, and its end step can easily be controlled to give exocyclic double bonds by simply excluding water from the medium. 相似文献
996.
A study of method robustness for arsenic speciation in drinking water samples by anion exchange HPLC-ICP-MS 总被引:2,自引:0,他引:2
Day JA Montes-Bayón M Vonderheide AP Caruso JA 《Analytical and bioanalytical chemistry》2002,373(7):664-668
Regulating arsenic species in drinking waters is a reasonable objective, since the various species have different toxicological impacts. However, developing robust and sensitive speciation methods is mandatory prior to any such regulations. Numerous arsenic speciation publications exist, but the question of robustness or ruggedness for a regulatory method has not been fully explored. The present work illustrates the use of anion exchange chromatography coupled to ICP-MS with a commercially available "speciation kit" option. The mobile phase containing 2 mM NaH(2)PO(4) and 0.2 mM EDTA at pH 6 allowed adequate separation of four As species (As(III), As(V), MMAA, DMAA) in less than 10 min. The analytical performance characteristics studied, including method detection limits (lower than 100 ng L(-1) for all the species evaluated), proved the suitability of the method to fulfill the current regulation. Other parameters evaluated such as laboratory fortified blanks, spiked recoveries, and reproducibility over a certain period of time produced adequate results. The samples analyzed were taken from water utilities in different areas of the United States and were provided by the U.S. EPA. The data suggests the speciation setup performs to U.S. EPA specifications but sample treatment and chemistry are also important factors for achieving good recoveries for samples spiked with As(III) as arsenite and As(V) as arsenate. 相似文献
997.
A sequential injection system based on the ABTS (2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulphonic-acid) methodology was developed. The proposed method, incorporating a mixing chamber in the side port of the selection valve, was evaluated to measure the total antioxidant activity of several beverages and foods.The ABTS+ is generated by oxidation of ABTS with potassium persulfate and is reduced in presence of hydrogen-donating antioxidants converting into a colourless product. The applicability of the developed method was tested by measurement of the antioxidant activity of pure compounds as well as by analysing complex food and beverage samples. The antioxidant activity was presented as l(+) ascorbic acid equivalence. The values obtained by this methodology were not significantly different from the results obtained by the original spectrophotometric ABTS assay. For most of the studied antioxidants, antioxidant activity varied with pH and dilution. The proposed SIA system is suitable for screening direct or diluted total antioxidant activity of pure compounds or food samples. 相似文献
998.
Barluenga J Diéguez A Rodríguez F Flórez J Fañanás FJ 《Journal of the American Chemical Society》2002,124(31):9056-9057
Eight-membered carbocycles with up to five new stereogenic centers are enantioselectively obtained following a one-pot procedure that involves the coupling of three components: an alkenyl Fischer carbene complex, a ketone enolate, and allyl lithium. 相似文献
999.
The Through Oven Transfer Adsorption Desorption (TOTAD) interface is used to directly introduce large volumes of water (1 mL or more) into a capillary gas chromatograph. The TOTAD interface is a greatly modified programmed temperature vaporizer injector incorporating changes that affect the pneumatics, sample introduction, solvent elimination, and operation mode. The system can easily be automated. The technique is applied to the analysis of pesticide residue in standard solutions and real water samples from the Ebro River (northeastern Spain). The speed of sample introduction was 1 mL/min, and the solvent elimination was almost complete. A nitrogen phosphorous detector is used, and the relative standard deviation varied from 5.7% to 11.7% for the absolute peak areas. The sensitivity achieved by introducing 1 mL of the sample is sufficient for most pesticide-residue analyses in water. The limits of detection ranged from 0.5 to 8.1 ng/L. 相似文献
1000.
Assignment of Saharan dust sources to episodes in Hungarian atmosphere by PIXE and TOMS observations
E. Koltay I. Borbély-Kiss Zs. Kertész Á. Z. Kiss Gy. Szabó 《Journal of Radioanalytical and Nuclear Chemistry》2006,267(2):449-459
Summary Thirty-seven episodes of dust intrusion were observed between February 12, 1991 and August 31, 2000 in the Hungarian atmosphere
and found to be of Saharan origin. They have been assigned to typical source areas in Northern Africa selected by systematic
investigations related to the Mediterranean Basin. Elemental concentrations and regional signatures deduced from PIXE analysis,
total suspended particle mass, and black carbon mass have been measured on dust samples collected in Debrecen, Hungary. These
data combined with Aerosol Index data, and dust plume axes obtained from TOMS data from NASA satellites were used for assigning
the most probable source areas of the dust transported to the sampling site. Our data and conclusions are in accordance with
other published investigations on the predominant role of Saharan dust emission in building up the aerosol load of the global
atmosphere. 相似文献