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231.
The guanidinium salt of the new heteropolymolybdate 11-molybdobismuthophosphate Gua6PBiMo11O40 (11-MBP) was synthesized, characterized and used as a reagent for batch spectrophotometric (SP) and sequential injection determination of ascorbic acid (AsA). When compared to other Keggin's heteropolyanions, the reduction of 11-MBP with AsA is both fast and maximal within a pH range of 1.6-2.0. The stoichiometry of the reaction was determined using molar ratio and continuous variation methods and was shown to be 1:1. The molar absorptivity of the reduced form of 11-MBP was 6.0 × 103 L mol−1 cm−1 at 720 nm. The reaction is also specific for AsA. Only cysteine, hydroquinone and hydroxyacids were found to interfere with the reaction, while no interference was observed with the common reducing agents, including reducing sugars, catecholamines, nitrite, sulfite and iron(II) ions. Batch SP and sequential injection analysis (SIA) systems were developed for the determination of AsA, with calibration ranges of the SP methods at 2 × 10−6-8 × 10−5 M for a 10 mm cell and 5 × 10−7-3 × 10−5 M for a 50 mm cell and a limit of detection at 3 × 10−7 M. The linear range of the SIA method was 6 × 10−6-5 × 10−4 M, with a detection limit of 2 × 10−6 M and a sample throughput of 15 h−1. The proposed methods were successfully used for the determination of AsA in both pharmaceuticals and fruit juices, and the results were consistent with those provided by the 2,6-dichlorophenolindophenol method. 相似文献
232.
Kharchenko A Vladimirov G Heeren RM Nikolaev EN 《Journal of the American Society for Mass Spectrometry》2012,23(5):977-987
The orbital trap mass analyzer provides a number of unique analytical features along with inevitable limitations as an electrostatic
instrument operating in high space charge regimes resulting in systematic measured frequency errors as an effect of stored
ion clouds on the trap field and each other effect of non-ideal machining the trap electrodes, effect of injection slot, effect
of real versus theoretical trap dimensions, etc. This paper deals with determining the influence of the space charge effect
and imperfection of the electrostatic field on the motion of ion ensembles in the orbital trap. We examine effects of theoretically
modeled non-harmonicity of the electrostatic potential and the number of confined ions on stability of coherent ion motion
in the trap that determines the frequency shifts of axial ion oscillation. Three different Orbitrap geometries were considered:
geometry close to preproduction Orbitrap, close to standard Orbitrap, close to high field Orbitrap. Frequency shifts for m/z = 500 and for charge state +23 of cytochrome c isotopic cluster particles with 104 {10^4} -6*106 {10^6} elemental charges in the trap were considered. Refined spectra were calculated using the filter diagonalization method proposed
by Mandelshtam et al. and applied to mass spectrometry by O’Connor and Aizikov. 相似文献
233.
Boll I Jentzsch E Krämer R Mokhir A 《Chemical communications (Cambridge, England)》2006,(32):3447-3449
The reaction of ester hydrolysis catalysed by a DNA duplex in a sequence specific fashion has been developed, which is the fastest and most high yielding in comparison with the known reactions of this type. 相似文献
234.
The three-dimensional reference interaction site model with the closure relation by Kovalenko and Hirata (3D-RISM-KH) in combination with the density functional theory (DFT) method has been implemented in the Amsterdam density functional (ADF) software package. The analytical first derivatives of the free energy with respect to displacements of the solute nuclear coordinates have also been developed. This enables study of chemical reactions, including reaction coordinates and transition state search, with the molecular solvation described from the first principles. The method yields all of the features available by using other solvation approaches, for instance infrared spectra of solvated molecules. To evaluate the accuracy of the present method, test calculations have been carried out for a number of small molecules, including four glycine conformers, a set of small organic compounds, and carbon nanotubes of various lengths in aqueous solution. Our predictions for the solvation free energy agree well with other approaches as well as experiment. This new development makes it possible to calculate at modest computational cost the electronic properties and molecular solvation structure of a solute molecule in a given molecular liquid or mixture from the first principles. 相似文献
235.
236.
Andriy Panasyuk 《Annals of Global Analysis and Geometry》2008,33(1):1-10
For a quite general class of Lie algebras with a nontrivial ideal we derive a formula for the index generalizing the Raïs formula for the index of semidirect products. The method of proof of our formula is based on the so-called “symplectic reduction by stages” scheme. 相似文献
237.
By condensation of 5-phenyl-1,3-cyclohexanedione with 6-quinolylamine and aldehydes of aromatic, heterocyclic, and cyclohexene series new 12-aryl(heteryl, cyclohexenyl)-9-phenyl-8,9,10,12-tetrahydro-7H-benzo[b][4,7]phenanthrolin-11-ones were prepared. The presence of diastereomers in the target reaction products was determined by 1H NMR spectroscopy.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 742–748.Original Russian Text Copyright © 2005 by Gusak, Tereshko, Kozlov. 相似文献
238.
Natalya S. Andryushina Oleksandr L. Stroyuk Igor B. Yanchuk Andriy V. Yefanov 《Colloid and polymer science》2014,292(2):539-546
Evolution of the hydrodynamic size d HD of colloidal graphene oxide (GO) sheets in water induced by the photochemical GO reduction by UV light was studied by the dynamic light scattering spectroscopy. An increase of d HD at an initial stage of the photoreduction is caused by partial photoelimination of the functional groups of GO and breaking of the hydrogen bonds between the fragments of the GO particles resulting in the sheets' unfolding. At deeper photoreduction, a decrease of d HD is observed as a result of ππ stacking interaction between the aromatic areas of GO particles and crumpling of the GO sheets. Variations of pH affect strongly the d HD of the photoreduced GO. At pH lowering from 6–7 to 2–3, a drastic growth of d HD and the sheets' aggregation are observed, caused by the protonation of the carboxyl groups. At pH elevation to 11–12, on the contrary, a decrease of d HD is observed, which is more pronounced the longer the photochemical GO reduction. The observation reflects crumpling/scrolling of the the GO sheets to minimize the contact area between the aromatic components of the photoreduced GO particles and the dispersive medium. The changes of the photoreduced GO particle size in basic media were found to be reversible. 相似文献
239.
Martin Burdel Jana Šandrejová Ioseph S. Balogh Andriy Vishnikin Vasil Andruch 《Journal of separation science》2013,36(5):932-938
Three modes of liquid–liquid based microextraction techniques – namely auxiliary solvent‐assisted dispersive liquid–liquid microextraction, auxiliary solvent‐assisted dispersive liquid–liquid microextraction with low‐solvent consumption, and ultrasound‐assisted emulsification microextraction – were compared. Picric acid was used as the model analyte. The determination is based on the reaction of picric acid with Astra Phloxine reagent to produce an ion associate easily extractable by various organic solvents, followed by spectrophotometric detection at 558 nm. Each of the compared procedures has both advantages and disadvantages. The main benefit of ultrasound‐assisted emulsification microextraction is that no hazardous chlorinated extraction solvents and no dispersive solvent are necessary. Therefore, this procedure was selected for validation. Under optimized experimental conditions (pH 3, 7 × 10?5 mol/L of Astra Phloxine, and 100 μL of toluene), the calibration plot was linear in the range of 0.02–0.14 mg/L and the LOD was 7 μg/L of picric acid. The developed procedure was applied to the analysis of spiked water samples. 相似文献
240.
Re-examination of the mercury-rich regions of the Ca-Hg and Sr-Hg phase diagrams has shown that the phases previously identified as "AHg 3.6" should be reformulated as A(11-x) Hg(54+x) (A = Ca, Sr). The crystal structures for representative members of these A 11- x Hg 54+ x phases were determined from single-crystal X-ray diffraction data (Pearson symbol hP65, space group P6; a = 13.389(1) A, c = 9.615(1) A for Ca(10.92(2))Hg(54.08) (x = 0.08(2)); a = 13.602(2) A, c = 9.818(1) A for Sr(10.48(4))Hg(54.52) ( x = 0.52(4))) and confirmed by powder Rietveld refinements ( R B = 0.020 for Ca(10.7(2))Hg(54.3) and 0.014 for Sr(10.7(3))Hg(54.3)). Diverse coordination polyhedra surround the A (CN14-16, multiply capped pentagonal or hexagonal prisms as well as Friauf polyhedra) and Hg atoms (CN11-13, pentacapped trigonal prisms and icosahedra). Partial disorder of Hg into one of the A sites accounts for the nonstoichiometry in the A(11-x)Hg(54+ x) phases. If this disordered A site is completely occupied by Hg atoms, the composition is constrained to a maximum of x = 2 in A(11-x)Hg(54+ x), corresponding to a small homogeneity range of "A(0.14-0.17)Hg(0.86-0.83)"; the true homogeneity range is likely narrower. The structure can be regarded as being built up from a stacking of triangular nets with hexagonal voids that are filled with single atoms or various clusters. In particular, the presence of triangular Hg 3 clusters in ordered orientations distinguishes this structure from that of the related Gd 14Ag 51-type structure, in which triangular Ag 3 clusters are in disordered orientations. Band structure calculations reveal a small degree of electron transfer from the A to Hg atoms, supporting the presence of a partially anionic mercuride substructure. 相似文献