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211.
A new analytical method for the determination of uric acid (UA) by the perturbation of UA on the Belousov-Zhabotinsky oscillating reaction is proposed. The method is based on the linear relationship between the changes in the oscillating period and the concentration of UA. The calibration curve is linear over the range of 2.0 × 10−5 to 5.0 × 10−4 M, with a detecting limit of 3.28 × 10−6 M. The method features good precision (R.S.D.: 3.59%) and excellent throughput (10 samples h−1). The possible mechanism of the perturbation of UA on the oscillating reaction is discussed. 相似文献
212.
An enzymatic assay for glucose based on the use of the fluorescent probe for hydrogen peroxide, europium(III) tetracycline (EuTc), is described. The weakly fluorescent EuTc and enzymatically generated H2O2 form a strongly fluorescent complex (EuTc–H2O2) whose fluorescence decay profile is significantly different. Since the decay time of EuTc–H2O2 is in the microseconds time domain, fluorescence can be detected in the time-resolved mode, thus enabling substantial reduction of background fluorescence. The scheme represents the first H2O2-based time-resolved fluorescence assay for glucose not requiring the presence of a peroxidase. The time-resolved assay (with a delay time of 60 s and using endpoint detection) enables glucose to be determined at levels as low as 2.2 mol L–1, with a dynamic range of 2.2–100 mol L–1. The method also was adapted to a kinetic assay in order to cover higher glucose levels (mmol L–1 range). The latter was validated by analyzing spiked serum samples and gave a good linear relationship for glucose levels from 2.5 to 55.5 mmol L–1. Noteworthy features of the assay include easy accessibility of the probe, large Stokes shift, a line-like fluorescence peaking at 616 nm, stability towards oxygen, a working pH of approximately 7, and its suitability for both kinetic and endpoint determination. 相似文献
213.
A series of trinuclear metal clusters MS4(M'PPh3)2(M'PPh3) (M = Mo, W; M' = Cu, Ag, Au) have been studied using the density functional theory (DFT) method. The static polarizabilities and hyperpolarizabilities of the model clusters have been calculated using the finite-field (F-F) method. The model clusters, divided into two groups, are alike in the structure of two fragments of rhombic units M-(mu-S)2-M' (M = Mo, W; M' = Cu, Ag, Au), perpendicular to each other, which are joined by sharing the bridge metal M. It is the charge transfer from one of these moieties to the other in these characteristic sulfido-transitional metal cores that is responsible for the polarizabilities and hyperpolarizabilities. This kind of electronic delocalization, different from that of the planar pi-system, is interesting and warrants further investigation. The structural effects on properties are important. In these models, considerable third-order nonlinearities are exhibited. The element substitution effect of Mo and W is weak, while that of Cu and Ag is relatively substantial. An overall order is gamma xxxx(Mo-Ag) > gamma xxxx(W-Ag) > gamma xxxx(Mo-Au) > gamma xxxx(W-Au) > gamma xxxx (Mo-Cu) > gamma xxxx(W-Cu) and gamma av(Mo-Ag) approximately gamma av(W-Ag) > gamma av(Mo-Au) approximately gamma av(W-Au) approximately gamma av (Mo-Cu) approximately gamma av(W-Cu). 相似文献
214.
Zhi-En Lin 《Journal of solid state chemistry》2006,179(3):723-728
A new layered cobalt-zinc phosphite, Co(H2O)4Zn4(HPO3)6·C2N2H10 has been synthesized in the presence of ethylenediamine as the structure-directing agent. The compound crystallizes in the monoclinic system, space group Cc (No. 9), a=18.2090(8), b=9.9264(7), c=15.4080(7) Å, β=114.098(4)°, V=2542.3(2) Å3, Z=4, R=0.0323, wR=0.0846. The structure consists of ZnO4 tetrahedra, CoO6 octahedra and HPO3 pseudopyramids through their vertices forming bimetallic phosphite layers parallel to the ab plane. Organic cations, which reside between the inorganic layers, are mobile and can be exchanged by NH4+ cations without the collapse of the framework. 相似文献
215.
Lin CS Zhang RQ Lee ST Elstner M Frauenheim T Wan LJ 《The journal of physical chemistry. B》2005,109(29):14183-14188
The assembly of small water clusters (H2O)n, n = 1-6, on a graphite surface is studied using a density functional tight-binding method complemented with an empirical van der Waals force correction, with confirmation using second-order M?ller-Plesset perturbation theory. It is shown that the optimized geometry of the water hexamer may change its original structure to an isoenergy one when interacting with a graphite surface in some specific orientation, while the smaller water cluster will maintain its cyclic or linear configurations (for the water dimer). The binding energy of water clusters interacting with graphite is dependent on the number of water molecules that form hydrogen bonds, but is independent of the water cluster size. These physically adsorbed water clusters show little change in their IR peak position and leave an almost perfect graphite surface. 相似文献
216.
The stereochemistry of the hydrogenation of 4-tert-butylmethylenecyclohexane (1) and the use of D2 or D2/H2 mixtures in place of H2 furnishes evidence that hydrogenations using the catalyst precursor [Rh(DIPHOS)(COD)]+BF
4
−
proceed via more than one mechanism. This evidence includes the effect of changes in pressure and added triethylamine upon
the kinetics and isomerization of 1, as well as the distribution of the added deuterium in the products of the reaction of 1 or norbornene with either D2 or H2/D2 mixtures. That an alkene necessarily causes the equilibration of H2/D2 mixtures, although it need not involve any of the alkenes’s hydrogen atoms (e.g., norbornene), provides a clue to the process
by which the mononuclear mechanism proposed by Halpern, which is dominant near one atmosphere of H2, merges into another with increasing pressure. It has been proposed that the cationic complex [Rh(DIPHOS)S2]+ is transformed in the presence of an alkene and hydrogen into a binuclear hydrido complex, such as those described by Sivak
and Muetterties (1979) and Fryzuk (1982), which represent a far more active catalyst than its mononuclear precursor. Such
an intermediate should readily catalyze the H2-D2 equilibration and the isomerization of an alkene in the presence of D2 without necessarily introducing deuterium into the product.
Published in Russian in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 88–97.
Deceased.
The text was submitted by the authors in English.
This work was conducted at the University of Arkansas. 相似文献
217.
In earlier work we nave described and partially characterized two histone kinases from regenerating rat liver and other tissues which catalyze the transfer of the γ-phosphoryl group from ATP to histones. The histone phosphates thus formed were observed to be acid-labile and base-stable. In the present study we report on the specificity of one of these enzymes, namely, the kinase which is optimally active at pH 9. This enzyme appears to be relatively specific for the two histidine residues of histone H4. These histidines occur at positions 18 and 75, and both are phosphorylated. However, when regenerating rat liver was the source of enzyme, the product was 1-phosphohistidine, whereas the enzyme from Walker-256 carcinosarcoma catalyzed the formation of 3-phosphohistidine. 相似文献
218.
2-Substituted homophthalimides 2a-c were reduced regioselectively with sodium borobydride to carbinol-lactam intermediates 3a-c , which were dehydrated, followed by hydrogenation, to give 1-oxo-tetrabydroisoquinolines or 3,4-dihydroisoquinolin-1(2H)ones 5a-c . The isomeric 3-oxo-tetrahydro-isoquinolines or 1,4-dihydroisoquinolin-3(2H)-ones 8a-i were obtained in satisfactory yields via heating 3-isochromanone ( 6 ) with the corresponding amines 7a-i in the presence of aluminum chloride. 相似文献
219.
8,8"-Biflavonoidsareantw0rtantclass0fbiflavonoids.Asasystematicresearchofthe8,8"-biflav0noids,wehavepreviouslyreportedthestudyonthereactionof2'-hydroxychaloneswithl2-H2SO4-DMSOsystem.'InthispaPer,thesynthesisof5,5",7,7',-tetTameth0xy-8,8"-biflavonela2,4,4",7,7"-tetramethoxy-8,8"-biflavone1b',4',4",,5,5,',7,7"-hexamethoxy-8,8"-biflav0ne1c4and4,4"-dibenZyl0xy-5,5",7,7"-tetramothoxy-8,8"-biflavoneldisreported.ThesyntheticmethodisshownintheSchemebelow.2-Hydroxyacet0phenonescondensedwithsubsti… 相似文献
220.
A general strategy is proposed to assign aliphatic side-chain resonances of large 13C,15N-labeled proteins without deuteration, using 4D 13C,15N-edited NOESY and MQ-(H)CCH-TOCSY experiments on the basis of prior assignments of backbone and 13Cbeta resonances. The strategy has been tested on a 214 residue protein (DdCAD-1) and applied to a chain-selectively 13C,15N-labeled hemoglobin (65 kDa). About 96 and 80% aliphatic side-chain spins in DdCAD-1 and hemoglobin have been assigned, respectively. The strategy proposed here will be very useful for the structure determination and dynamics characterization of large proteins by NMR. 相似文献