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A method for calculating the number of rotamers of a linear alkane and of the number of rotamers with a given number of gauche conformations along the chain as a function of the total number of atoms in the chain, using general equations, is presented. A graphical method for generating individual rotamers was applied to the homologs up to decane, which has 1134 rotamers. The steric energies calculated by molecular mechanics (MM2 force field) were used as measures of the heat of formation for the coiled conformations relative to the anti conformer for each molecule, whereas the statistical entropy differences were calculated for classes of coiled rotamers grouped by the number of gauche bonds and steric energy. The free energy values calculated from these components show that already at 400 K hexane exists preferentially in conformations containing gauche bonds. For larger chains the free energy advantage for the coiled chains increases very steeply. The implications for the question of reactions of linear alkanes occurring on the surface or inside the channels of small- and medium-pore zeolites are briefly examined. 相似文献
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The fragmentation patterns of 3-methyl-2-butyl trifluoroacetate and 2-methyl-2-butyl trifluoroacetate were investigated by GC/MS/MS, with electron impact and collision-induced dissociation, on regular and isotope-labeled (deuterium and 18O) esters. The atoms found in various fragments could be traced back to specific positions in the parent molecules. In this way, molecular rearrangements potentially occurring during the formation of esters by trifluoroacetolysis of 3-methyl-2-butyl p-toluenesulfonate or trifluoroacetic acid addition to various 2-methylbutenes could be shown. Rearrangements also occurred during the fragmentation, particularly during the expulsion of the small fragments CO, C2H4 and F2CO. For the decompositions of oxygen-containing ions these rearrangements were highly specific. By contrast, alkyl cations lead to fragments that are fully scrambled (statistical label distribution). Alkene radical cations ([CnH2n]+ ˙) fragment to daughter ions that are extensively, but less than statistically scrambled. Hydrogen scrambling may also occur in fluoroalkyl cation fragments. 相似文献
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Three of the main oxygen-containing fragments resulting from 3-methyl-2-butyl trifluoroacetate (11) had been identified previously as the 1-triflnoroacetoxyethyl cation (m/z 141, 12, product of simple cleavage), and the products of single (m/z 142) and double hydrogen transfer (m/z 143, protonated ethyl trifluoroacetate). Collisionally activated dissociation of m/z 142 and the isotopomers resulting from 11-2-d, 11-1-d3, 11-5,6-d6, and 11-18O2 has established that m/z 142 is the oxygen protonated 1-trifluoroacetoxyethyl free radical (17) formed by hydrogen shift irom a γ-methyl group to oxygen in the molecular ion, rather than in a complex (18) between 12 and the 2-propyl free radical, as expected based on a mechanistic model existing in the literature. The second hydrogen transferred originates in the other γ-methyl group; its migration may occur, but does not have to, in the complex between 17 and a molecule of propene, prior to dissociation of the two fragments. Collision-activated dissociation has now shown that the m/z 140 ion observed in the spectrum is the molecular ion of vinyl trifluoroacetate, possibly formed by a hydrogen transfer from 12 to the 2-propyl radical in the complex 18. The hydrogen migration to oxygen exhibits no isotope effect, whereas the transfers to carbon atoms exhibit small primary and α secondary kinetic isotope effects. Exclusive migration of the tertiary hydrogen from C(3) occurs in the formation of 2-methylbutene cation radical (m/z 70) from the molecular ion. The hydrocarbon ion fragments and the heteroatom-containing fragments are formed from 11 by disjoint pathways. 相似文献
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赵惠昌 《南京理工大学学报(自然科学版)》1998,22(6):489-491
该文以国外某舰炮弹药无线电近炸引信为例,分析研究了该无线电近炸引信炮口安全保险距离有关的参量,通过对火药燃烧时间和电路延迟时间的计算推出了几种不同情况下该无线电近炸引信炮口保险距离,分析计算方法具有普遍性。 相似文献
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用^1H—NMR测定纤维素的摩尔取代度 总被引:1,自引:0,他引:1
用^1H-NMR测定羟丙基纤维素的摩尔取代度,根据纤维素在DCl中水解后的^1H-NMR谱峰面积来计算MS值。同时还应用铬酸氧化蒸馏法测定了羟丙基纤维素的MS值,以及利用MS与羟丙基含量的关系得到MS值,可以发现NMR的方法是可行的。 相似文献
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Boualem Alleche Vicenţiu D. Rădulescu 《Journal of Optimization Theory and Applications》2017,175(1):39-58
In this paper, we introduce some concepts of convexity and semicontinuity for real set-valued mappings similar to those of real single-valued mappings. Then, we obtain different results on the existence of solutions of set-valued equilibrium problems generalizing in a common way several old ones for both single-valued and set-valued equilibrium problems. Applications to Browder variational inclusions, with weakened conditions on the involved set-valued operator, are given. 相似文献
10.
Monica Roşiu 《复变函数与椭圆型方程》2015,60(2):181-190
We extend the notion and basic properties of quadratic differential divisors to a Klein surface, using the corresponding form’s divisors from the double cover of the Klein surface. 相似文献