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1.
Unexpected benzimidazole ring formation from a quinoneimide species in the presence of ammonium acetate as supporting electrolyte used in the coupling of electrochemistry with mass spectrometry
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Multiply-connected monolayered cyclofusene (MMC) is a fused hexacyclic system with an exterior region and at least two interior empty regions called holes, as in figure 1. Each hexacyle has either: (a) two edges belonging to an exterior boundary and at least one hole, or (b)
two edges belonging to boundaries of at least two holes. Let G be the graph of a given MMC. We show that G is equitable if and only if the set of vertices belonging to three hexacycles is equitable. 相似文献
4.
Marty W. DeGroot Chhatra Khadka Harald Rösner John F. Corrigan 《Journal of Cluster Science》2006,17(1):97-110
The thermolysis of the zinc trimethylsilylchalcogenolate complexes (N,N′-tmeda)Zn(ESiMe3)2 (E = S, 1; E = Se, 2) and (3,5-Me2-C5H3N)2Zn(ESiMe3)2 (E = S, 3; E = Se, 4) has been investigated. Solid-state thermal decomposition of complexes 1–4 above 250°C results in the formation of hexagonal ZnS and cubic ZnSe, respectively, via the liberation of TMEDA (1–2) or 3,5-lutidine (3–4) and E(SiMe3)2. Solid-state or solution thermolysis of these complexes up to 200°C produces nanocrystalline ZnS and ZnSe materials whose surface is protected by either coordinated TMEDA or 3,5-lutidine ligands. The progress of the step-wise solid-state decomposition of these complexes was monitored by thermogravimetric and single differential thermal analysis and volatile decomposition products in both solution and solid-state experiments were identified by GC/MS.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement. 相似文献
5.
Eric Cancès Renaud Keriven François Lodier Andreas Savin 《Theoretical chemistry accounts》2004,111(2-6):373-380
Efficient formulas for computing the probabilities of finding exactly electrons in an arbitrarily chosen volume 3 for Hartree–Fock wavefunctions are presented. These formulas allow the use of shape optimization techniques, such as level set methods, for optimizing with respect to various criteria involving such probabilities. The criterion defined as the difference between the Hartree–Fock and the independent-particle model probabilities of finding electrons in stresses the quantum effects due to the Pauli principle. We have implemented a 2D level set method for optimizing this criterion in order to study spatial separation of electron pairs in linear molecules. The method is described and the illustrative example of the BH molecule is reported.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
6.
Mixing liquids at the micro-scale is difficult because the low Reynolds numbers in microchannels and in microreactors prohibit the use of conventional mixing techniques based on mechanical actuators and induce turbulence. Static mixers can be used to solve this mixing problem. This paper presents micromixers with geometries very close to conventional large-scale static mixers used in the chemical and food-processing industry. Two kinds of geometries have been studied. The first type is composed of a series of stationary rigid elements that form intersecting channels to split, rearrange and combine component streams. The second type is composed of a series of short helix elements arranged in pairs, each pair comprised of a right-handed and left-handed element arranged alternately in a pipe. Micromixers of both types have been designed by CAD and manufactured with the integral microstereolithography process, a new microfabrication technique that allows the manufacturing of complex three-dimensional objects in polymers. The realized mixers have been tested experimentally. Numerical simulations of these micromixers using the computational fluid dynamics (CFD) program FLUENT are used to evaluate the mixing efficiency. With a low pressure drop and good mixing efficiency these truly three-dimensional micromixers can be used for mixing of reactants or liquids containing cells in many microTAS applications. 相似文献
7.
An amperometric sensor for the detection of ethanol has been designed. The sensing layer consists of alcohol dehydrogenase (ADH), NADH oxidase and NAD+-dextran, entrapped together in a matrix of poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ). Measurements have been carried out at a low oxidizing potential (equivalent to 250 mV vs. SCE) to detect hexacyanoferrate(II), thus avoiding interferences due to presence of oxidizable compounds in real samples. The influence of the amount of polymer, enzymes and coenzyme in the sensing layer on the sensor sensitivity, linear range and operational stability has been studied. The sensitivity was close to 2 mA 1 mol−1, with a linear range 3 × 10−7 −2 × 10−4M and a response time <2 min. Good operational stability was observed, allowing more than 40 reproducible assays without NAD+ addition. Alcoholic beverages were analysed with the use of sensor and the results showed good correlation with those obtained using a standard spectrophotometric procedure. 相似文献
8.
[reaction: see text] The use of hydroxamic acids as templates for Lewis acid catalyzed enantioselective Diels-Alder reactions has been examined. A very simple chiral Lewis acid, prepared by mixing optically pure binaphthol with 3 equiv of trimethylaluminum, catalyzes the [4 + 2] cycloaddition of N-hydroxy-N-phenylacrylamide with cyclopentadiene at 0 degrees C in high yield (>96%) and with a fairly good level of enantioselectivity (91% ee). Facile conversion of the products to the corresponding alcohols or aldehydes makes the hydroxamic acid intermediates particularly useful. 相似文献
9.
Jeanty G Wojciechowska A Marty JL Trojanowicz M 《Analytical and bioanalytical chemistry》2002,373(8):691-695
Determination of the organophosphorus pesticides paraoxon, chlorpyrifos oxon, and malaoxon has been performed by a method based on inhibition of acetylcholinesterase (AChE) and amperometric detection in a flow-injection system with enzymes obtained from the electric eel (eeAChE) and Drosophila melanogaster (dmAChE) and immobilized on the surface of platinum electrode within a layer of poly(vinyl alcohol) bearing styrylpyridinium groups. dmAChE is more sensitive than eeAChE to inhibition by chlorpyrifos oxon and paraoxon. The sensitivity difference was largest for chlorpyrifos oxon (detection limit approx. 17 times lower), and practically none for malaoxon. Determination of the analytes in spiked river water samples by use of the dmAChE biosensor resulted in recoveries from 50 to 90 % for chlorpyrifos oxon at levels of 20 to 40 nmol L(-1), 50 to 100 % for paraoxon at 0.6 to 0.8 micro mol L(-1), and 140 to 190 % for malaoxon at 0.6 to 1.2 micro mol L(-1). 相似文献
10.
Azide anation and racemization of optically pure mer-exo(H)- and mer-endo(H)-[Co(OH)(dien)(dapo)]2+ ( A and B (X = OH), resp.; dien = N-(2-aminoethyl)ethane-1,2-diamine; dapo = 1,3-diaminopropan-2-ol) involve the same symmetrical pentacoordinate intermediate as the base hydrolyses of the corresponding mer-exo(H)- and mer-endo(H)-[CoX(dien)(dapo)]2+ species A and B , respectively, where X = Cl, Br, or N3. The kinetic parameters of the anation process are fully compatible with the independently measured competition ratio. The rate data reveal that substitution of OH? is unexpectedly fast, viz. it is not consistent with the usual sequence Br? > Cl? > H2O > N > OH?. This behavior is interpreted on the basis of an internal conjugate base mechanism which involves an amino-hydroxo/aminato-aqua tautomerism, viz. the reaction is actually an OH? -catalyzed substitution of [CoH2O(dien)(dapo)]3+ where deprotonation occurs effectively at the secondary-amine site NH of dien. 相似文献