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21.
Thermal decomposition of RDX from reactive molecular dynamics 总被引:1,自引:0,他引:1
Strachan A Kober EM van Duin AC Oxgaard J Goddard WA 《The Journal of chemical physics》2005,122(5):54502
We use the recently developed reactive force field ReaxFF with molecular dynamics to study thermal induced chemistry in RDX [cyclic-[CH(2)N(NO(2))](3)] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition that increases with decreasing density and shows an Arrhenius temperature dependence. These characteristic timescales are in reasonable quantitative agreement with experimental measurements in a similar energetic material, HMX [cyclic-[CH(2)N(NO(2))](4)]. Our simulations show that the equilibrium population of CO and CO(2) (as well as their time evolution) depend strongly of density: at low density almost all carbon atoms form CO molecules; as the density increases larger aggregates of carbon appear leading to a C deficient gas phase and the appearance of CO(2) molecules. The equilibrium populations of N(2) and H(2)O are more insensitive with respect to density and form in the early stages of the decomposition process with similar timescales. 相似文献
22.
Alejandro Marcó Ramón Compañó Roser Rubio Pilar Domènech Albert Palangues Miguel Maestro 《Mikrochimica acta》2002,140(1-2):131-139
Four inter-comparison exercises on organic elemental analysis were carried out between 1997 and 2001 by the Department of
Analytical Chemistry of the University of Barcelona, together with the Microanalysis Service and the Institute of the Marine
Sciences, which both belong to the CSIC in Barcelona, and the University of A Coru?a. More than sixty laboratories participated
in these exercises. Here we describe the design and characteristics of the trials, the samples and the homogeneity tests applied.
We report the results obtained for the analysis of carbon, hydrogen, nitrogen, sulphur and oxygen, their statistical analysis,
and the most relevant aspects of the technical discussion meetings.
Received December 20, 2001; accepted March 18, 2002; published online July 22, 2002 相似文献
23.
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
24.
Baeza A Nájera C Sansano JM Saá JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(13):3849-3862
The enantioselective synthesis of cyanohydrin O‐phosphates by using in situ generated bifunctional catalysts (R)‐ or (S)‐3,3′‐bis(diethylaminomethyl)‐1,1′‐binaphthol–aluminium chloride (binolam–AlCl) is reported. The reaction, which can be described as an overall cyano‐O‐phosphorylation of aldehydes, has a wide scope and applicability. Evidence is also provided, including ab initio and DFT calculations, in support of supported by the Lewis acid/Brønsted base (LABB) dual role of the catalyst in inducing first the key enantioselective hydrocyanation, which is then followed by O‐phosphorylation. A brief screening of the synthetic usefulness of the resulting cyanohydrin O‐phosphates unveiles some interesting applications. Among them, chemoselective hydrolysis, reduction and palladium‐catalysed nucleophilic allyl substitution, thereby leading to enantiomerically enriched α‐O‐phosphorylated α‐hydroxy esters, β‐amino alcohols and γ‐cyanoallyl alcohols, respectively. Naturally occurring (?)‐tembamide and (?)‐aegeline are synthesised accordingly. 相似文献
25.
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
26.
Alexander V. Gusakov Arkady P. Sinitsyn Alejandro G. Berlin Nonna N. Popova Alexander V. Markov Oleg N. Okunev Dmitry F. Tikhomirov Mark Emalfarb 《Applied biochemistry and biotechnology》1998,75(2-3):279-293
A model microassay system was developed to measure indigo backstaining on cotton fabrics in the presence of enzymes on a small
laboratory scale. Backstaining indexes for 11 cellulase samples were measured, and the enzymes were ranked from lower to higher
backstaining. Two multienzyme cellulase preparations were separated into fractions using chromatofocusing on a Mono P column.
Adsorption ability and backstaining properties of purified enzyme fractions were studied. Evidence was obtained that protein
adsorption on cotton fabrics is a crucial parameter causing backstaining (both for crude cellulase samples and purified enzyme
components). 相似文献
27.
A glassy carbon electrode was modified with an electropolymerized film of 1‐naphthylamine in aqueous solution. The electrocatalytic properties of this modified electrode (ME) were investigated using ascorbic acid (AA) as probe molecule. The electrochemical behavior of AA in buffer solution was examined by voltammetry and amperometry. The results showed that the ME exhibited good electrocatalytic activity towards the oxidation of AA, as a consequence, it can be used as amperometric sensor of this analyte in a flow injection system with good sensitivity. Calibration curves were linear over the concentration range 0.05–1.50 mM with a phosphate buffer solution pH 3 as the carrier, the detection limit was 1 ppm (S/N=3). The methods were applied to the determination of AA in beverages and pharmaceutical products. A good correlation with a reference method was attained. 相似文献
28.
Alvarez-Lueje A Valenzuela C Squella JA Núñez-Vergara LJ 《Journal of AOAC International》2005,88(6):1631-1636
In this work, a liquid chromatography stability-indicating method was developed and applied to study the hydrolytic behavior of simvastatin in different pH values and temperatures. The selected chromatographic conditions were a C18 column; acetonitrile-28 mM phosphate buffer solution, pH 4 (65 + 35) as the mobile phase; 251 degrees C column temperature; and flow rate 1 mL/min. The developed method exhibited an adequate repeatability and reproducibility (coefficient of variation 0.54 and 0.74%, respectively) and a recovery higher than 98%. Furthermore, the detection and quantification limits were 9.1 x 10(-7) and 2.8 x 10(-6) M, respectively. The degradation of simvastatin fitted to pseudo-first order kinetics. The degradation was pH dependent, being much higher at alkaline pH than at acid pH. Activation energy, kinetic rate constants (k) at different temperatures, the half life (t1/2) and the time for 10% degradation to occur (t90) values are also reported. 相似文献
29.
Barluenga J Fernández MA Aznar F Valdés C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2276-2283
A novel approach for the synthesis of the important indole ring is described. Indoles are obtained from o-bromoanilines and alkenyl halides in a Pd-catalyzed cascade process that involves an alkenyl amination followed by an intramolecular Heck reaction. The overall process represents the first example of the participation of alkenyl amination reactions in Pd-catalyzed cascade reactions. Initially, the relative reactivity of aryl and alkenyl bromides and chlorides towards Pd-catalyzed amination was investigated. Competition experiments were carried out in the presence of primary and secondary amines, and these revealed the reactivity order alkenyl bromides > aryl bromides > alkenyl chlorides > aryl chlorides, as well as very high chemoselectivity; the more reactive halide was always favored. Thereafter, optimized reaction conditions for the sequential alkenyl amination/Heck cyclization to give indoles were investigated with the model reaction of o-bromoaniline with alpha-bromostyrene. An extensive screening of ligands, bases, and reaction conditions revealed that the [Pd2(dba)3]/DavePhos, NaOtBu, toluene combination at 100 degrees C were the optimized reaction conditions to carry out the cascade process (dba=dibenzylideneacetone, DavePhos=2-dicyclohexylphosphino-2'-N,N-dimethylaminobiphenyl). The reaction proceeds with aryl, alkyl, and functionalized substitutents in both starting reactants. The cyclization was also studied with N-substituted o-bromoanilines (which would give rise to N-substituted indoles); however, in this case, indole formation occurred only with 1-substituted-2-bromoalkenes. Finally, the application of this methodology to o-chloroanilines required further optimization. Although the catalyst based on DavePhos failed to promote the cascade process, a catalytic combination based on [Pd2(dba)3]/X-Phos promoted the formation of the indole ring also from the less reactive chloroanilines. 相似文献
30.
Crespo A Martí MA Estrin DA Roitberg AE 《Journal of the American Chemical Society》2005,127(19):6940-6941
A novel technique for computing free energy profiles in enzymatic reactions using the multiple steering molecular dynamics approach in the context of an efficient QM-MM density functional scheme is presented. The conversion reaction of chorismate to prephenate catalyzed by the Bacillus subtilis enzyme chorismate mutase has been chosen as an illustrative example. 相似文献