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81.
Rees B. Rankin 《Surface science》2005,574(1):L1
Plane wave density functional theory has been employed to analyze the structure of alanine adlayers on the Cu(1 1 0) surface. Alanine forms (3 × 2) adlayers on Cu(1 1 0) that are closely related to the structures of glycine on the same surface. There is essentially no energy difference between the most stable racemic and enantiopure alanine adlayers. This observation implies that adsorption of racemic alanine on Cu(1 1 0) will result in a pseudoracemate adlayer. 相似文献
82.
The cation distribution in spinel-related titanium-substituted lithium ferrite, Li0.5+0.5xFe2.5−1.5xTixO4 has been explored using interatomic potential and ab initio calculations. The results suggest that the cation distribution with Ti4+ substituting for Fe3+ on octahedral B sites and excess Li+ substituting for Fe3+ on tetrahedral A sites is stabilised by the formation of clusters of two octahedrally coordinated Ti4+ ions and one tetrahedrally coordinated Li+ ion linked through a common oxygen. 相似文献
83.
The signals of a single-pulse echo (SE) generated on nonresonant excitation of an inhomogeneously broadened two-level system by a radio-frequency pulse (RFP), against the background of which a magnetic video pulse (MVP) of certain length has been switched on, have been described analytically. It is established that under the conditions of such excitation several SE signals are formed whose generation moments are determined by the duration and amplitudes of the RFP and MVP. The amplitudes of some of these signals depend on the Rabi frequency according to a quadratic law, and the amplitudes of others depend on this frequency according to a biquadratic law. It has been established that the mechanism underlying the appearance of these signals is associated with zero beats arising as a result of superposition of the magnetization fluctuations at variable frequencies and at a frequency of detuning from resonance. It is shown that in the limiting case, where the RFP duration considerably exceeds the duration of the MVP or is comparable with it, the number of SE signals decreases to two. Theoretical results on the formation of SE and the dependence of the amplitude of these signals on the MVP amplitude agree with the experimental data on NMR pulsed signals in ferromagnetic materials. 相似文献
84.
明确从地胆草中分离得到的两对牦牛儿内酯型的立体异构体即地胆草种内酯(scabertopin)、异地胆草种内酯(isoscabertopin)、异去氧地胆草内酯(isodeoxyelephantopin)和去氧地胆草内酯(deoxyelephantopin)的C-2相对构型;方法 NOESY技术,并结合这4个化合物的1H NMR,13C NMR,HMQC谱;结果 两对立体异构体的NOESY谱有明显差异;结论 通过分析NOESY谱,找寻H-1相关信息,若发现H-1与H-8,H-9β和14-CH3有NOE相关,可以判断化合物的C-2为α构型,若H-1与H-5,H-7,H-3α及H-9α之间有NOE相关,则化合物的C-2为β构型. 相似文献
85.
Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature. 相似文献
86.
《Magnetic resonance in chemistry : MRC》2003,41(9):731-734
An NMR study of one new and several known abietane diterpenes isolated from the roots of Aegiphila lhotzkyana is described. In addition to 1D NMR, several 2D shift‐correlated NMR pulse sequences (1H–1H‐COSY, NOESY, HMQC and HMBC) were used to establish all the structures, and unambiguously perform the 1H and 13C chemical shift assignments of the new natural diterpene and three derivatives, the NMR data for which have not been reported previously. Revision of current data assignment for teuvincenone H is also suggested. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
87.
John M. Brown 《Journal of organometallic chemistry》2004,689(24):4006-4015
An overview of the contribution of NMR to the development of our understanding of homogeneous catalysis is presented, with an emphasis on work from the author’s research group. 相似文献
88.
Homogeneously prepared tosylcelluloses (TC) with degrees of substitution (DS) of DSTos 0.1–1.8 were used as intermediates for the synthesis of methylaminocelluloses (MAC) by nucleophilic substitution with methylamine. TC with DSTos up to 1.1 were shown to be valuable intermediates for selective synthesis of MAC with DSMA varying from 0.1 to approximately 1. No nucleophilic substitution was observed at higher DSTos. At the chosen reaction conditions (60 °C, 48 h) residual tosyl moieties remained unchanged and little hydrolysis took place. The samples obtained were characterized by means of elemental analysis, FTIR and 13C CP/MAS NMR spectroscopy. 13C CP/MAS NMR spectroscopy was found to be an efficient tool for quantification of DSMA. Furthermore, the swelling behaviour in water was investigated and preliminary tests concerning the bilirubin adsorption capacity of MAC were carried out. 相似文献
89.
One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
90.
XPS measurement revealed that the original state of TiO2 was changed to Ti2O3 and TiO by ion bombardment. TiO2 decreased and Ti2O3 increased at the initial stage. TiO increased at a later stage than Ti2O3. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO2 to Ti2O3 and from Ti2O3 to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO2 to Ti2O3 is about ten times larger than that from Ti2O3 to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment. 相似文献