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151.
William H. Donovan 《Structural chemistry》1995,6(4-5):243-254
Ab initio and semiempirical molecular orbital calculations have been applied to study the concerted and stepwise isotopic scrambling mechanisms of 2-chloroethyl methyl sulfide in the gas phase and in aqueous solution. The calculations reveal the structural details of the reactants, transition structures, and intermediates involved in this reaction and provide relative energy estimates. The concerted mechanism is found to be competitive with the stepwise mechanism in the gas phase, but the stepwise mechanism is favored in aqueous solution as no true transition structure for the concerted mechanism could be found using the solvation models. A combined approach of evaluating solvation energies with the generalized-Bom-plus-surface-tensions SM
x
solvation models of Cramer and Truhlar at ab initio optimized geometries is found to deliver the best agreement with experimentally determined reaction barriers. Together with the recent experimental results of McManus and co-workers, the present study provides insights into the controlling factors involved in the elementary reaction steps of sulfur mustards and a solid foundation for investigations into more complex reactions of related compounds. 相似文献
152.
ZHANG Shu-dong KONG Xiang-he ZHU Xiang-jun WANG Yan JIANG Su-rong 《高等学校化学研究》2006,22(5):621-625
IntroductionReactions of metal ions with neutral molecules orclusters produce a variety of metal complex ions andother new series of cluster ions including cations andanions.The laser ablation-molecular beam(LA-MB)method has marked its relevance in the st… 相似文献
153.
Lj.?Radonji 《Journal of Thermal Analysis and Calorimetry》2005,79(3):487-492
Summary The subject of this study was to investigate the effect of fluoride ions addition on the temperature of sol gel mullite formation based on the hypotheses that the presence of fluoride ions can decrease the temperature of mullite formation (in respect to common 980°C, in sol-gel processing). Polymeric sols were prepared by mixing TEOS and aluminum nitrate nanohydrate and by adding fluoride ions (from 2 to 5 mass%). DTA, TG, XRD and SEM were used for characterisation of mullite gel and crystalline mullite. The experimental results confirmed that the addition of fluoride ions decrease the temperature of mullite formation up to 890°C for the fluorine concentration of 3.5 mass%. Experimental results showed that the temperature of mullite formation is not a simple function of the fluoride ion content. The mechanism of fluorine effect was discussed in terms of the gelling process, gel structure and the phase separation before the mullite formation. 相似文献
154.
Yuri Vlasov 《Mikrochimica acta》1991,104(1-6):363-377
MOSFET-sensors can be considered as membrane-oxide-semiconductor field-effect transistors. MOSFETs can be divided into ISFETs, GasFETs, BioFETs, these sensors being sensitive to ion, gas, biomolecules respectively and there is also a possibility to fabricate MOSFET reference electrode (RefFET). The development and theoretical treatment of various type of MOSFET-sensors are presented in this paper. 相似文献
155.
Al3Ti1B1RE细化剂对罐用铝材的细化效果及稀土的作用 总被引:6,自引:0,他引:6
采用XRD,OM,SEM,EDAX等探讨了一种新型Al3Ti1B1RE中间合金细化剂对罐用铝材的细化效果及RE的作用。结果表明,该细化剂对罐用铝材的细化效果优于进口和国产Al3Ti1B,且具有长效性,达6h后仍未见明显衰退,明显提高了该材料的强度和塑性;其细化效果及稳定性好的主要原因是:RE可降低铝液的表面能,增加铝液对细化核心(如TiAl3,TiB2)的润湿性,既充分发挥了异质形核作用,又防止了TiB2聚集沉淀倾向;RE也极易在结晶前沿富集造成成分过冷,阻碍了α-Al晶粒生长,并促进其在细化核心上形核;此外RE还兼有一定的净化、细化和变质作用,尤其是净化作用提高了该细化剂的冶金质量。 相似文献
156.
Photochromism of two bispyrryl-substituted ethenes, 2, 3-bis-(1-p-methoxyphenyl-5-phenyl-2-methyl-3-pyrryl)-2-butene (BPE1) and 2,3-bis(1-p-bromophenyl-4-phenyl-2-methyl-3-pyrryl)-2-butene (BPE2), was studied by laser flash photolysis technique. The results indicate that photocyclization of these compounds proceeds mainly via the excited triplet state, and the cis-trans isomerization proceeds mainly via the excited singlet state. After UV laser pulse irradiation, both photocylization and cis-trans isomerization of BPEl occur, but photocydization is the main reaction. On the other hand, laser photolysis of BPE2 leads mainly to photocydization. The effects of the substituents on the photochromic mechanism are also discussed. 相似文献
157.
利用热力学循环方法,通过pK和有关电化学数据的测定,首次得到了NAD(P)H的辅酶模型物(BNAH)按不机理还原质子化N-芳基芴亚胺的各基元步骤的自由能变化,结合得到的同位素标纪结果,从热力学趋动力的角度区分了氢负离子的转移机理。 相似文献
158.
电热蒸发进样—等离子体原子发射光谱中钒和钛的蒸发机理研究 总被引:1,自引:0,他引:1
自1974年Nixon报道钽丝电热蒸发作为ICP-AES进样技术以来,这一技术已引起了人们的极大兴趣,受到越来越广泛的重视。电热蒸发(ETV)-ICP-AES是一种将蒸发和激发分步进行的联用技术。石墨是目前普遍使用的蒸发器材料。然而,在高温下某些元素和石墨材料可以发生碳化反应,形成热稳定的碳化物,使分析物蒸发不完全或根本不蒸发,从而影响分析结果的灵敏度和准确性。为了解决这一问题,我们曾提出了以聚四氟乙烯(PTFE)悬浮体为氟化剂,氟化辅助ETV-ICP-AES直接测定粉煤标样中钒和钛的新方法,其检出限 相似文献
159.
160.
For the first time the isomerization of 1,3,2-diazaphospholidine-2-sclenide dervatives in refluxing benzene in the presence of trace water was observed. The structures of isomerized products were determined by IR, ^1H NMR,^31P NMR, elemental analysis and X-ray crystallography. The mechanism of isomerization was also proposed. 相似文献