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131.
Marko D. Mihovilovic Bernhard Müller Markus Spina Arjumand I. Durrani Peter Stanetty Georg Dazinger Karl Kirchner 《Monatshefte für Chemie / Chemical Monthly》2006,137(6):785-794
Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was
observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established
by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful
enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones
produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids. 相似文献
132.
ZhengBin Zhang Chunying Liu Peifeng Li Zhenzhen Wu Cai Lin Huawei Huang Lei Xing Liansheng Liu 《Frontiers of Chemistry in China》2006,1(1):86-97
Many food algae and red tide algae were cultivated in the f/2 medium, and the nitric oxide (NO) concentration of the medium
and the cell density were determined. The experiments on algae were conducted when different concentrations of NO were added
into the medium using two methods. The results show that low concentrations of NO were self-produced by marine algae during
the exponential growth period and were about nmol/L level. But at the end of the period, i.e., 2 or 3 days before the cell
density reaches the maximum, an NO peak appeared, with the NO concentration reaching 10 nmol/L. The NO threshold concentration
exists according to the influence of exogenous NO on the marine phytoplankton growth. One type is the threshold concentration
that can promote algae growth, and its value is between 10 and 1 nmol level, or even lower. The other type can inhibit the
phytoplankton growth, which is about μmol level or higher. The results indicate that red tide algae are far more sensitive
to NO than are food algae. The fundamental experimental outcome above may provide a new clue for red tide chemical forecast
by inspecting the NO change. 相似文献
133.
Alfred Wünsche 《Annalen der Physik》1992,504(3):181-197
The eigenvalue problem for arbitrary linear combinations kα + μα? of a boson annihilation operator α and a boson creation operator α? is solved. It is shown that these operators possess nondegenerate eigenstates to arbitrary complex eigenvalues. The expansion of these eigenstates into the basic set of number states | n >, (n = 0, 1, 2, …), is found. The eigenstates are normalizable and are therefore states of a Hilbert space for | ζ | < 1 with ζ ? μ/k and represent in this case squeezed coherent states of minimal uncertainty product. They can be considered as states of a rigged Hilbert space for | ζ | ? 1. A completeness relation for these states is derived that generalizes the completeness relation for the coherent states | α 〉. Furthermore, it is shown that there exists a dual orthogonality in the entire set of these states and a connected dual completeness of the eigenstates on widely arbitrary paths over the complex plane of eigenvalues. This duality goes over into a selfduality of the eigenstates of the hermitian operators kα + k* α? to real eigenvalues. The usually as nonexistent considered eigenstates of the boson creation operator α? are obtained by a limiting procedure. They belong to the most singular case among the considered general class of eigenstates with ζ ? μ/k as a parameter. 相似文献
134.
J. P. S. Farinha J. M. G. Martinho H. Xu M. A. Winnik R. P. Quirk 《Journal of Polymer Science.Polymer Physics》1994,32(9):1635-1642
Cyclization of a polystyrene chain (Mn = 10,600; Mw/Mn = 1.09) both ends labeled with 4-(1-pyrenyl)butanoamide groups was studied in cyclohexane between 25 and 95°C. The amide groups (peptide bonds) at both ends can form an intrachain hydrogen bond between the amide hydrogen at one chain end and the carbonyl oxygen at the other. The presence of two sets of conformers, random coils, and chains cyclized through hydrogen bonding, complicates the data analysis. The pyrene excimer kinetics of this polymer is well described by a model composed of two monomers (hydrogen bonded and nonbonded chains) and one excimer, in equilibrium. The cyclization rate constant for hydrogen-bonded chains is larger than the one for nonhydrogen-bonded chains. The pyrene excimer binding energy (ca. 1.6 kcal/mol) is lower than the published value for nonhydrogen-bonded chains (~ 9 kcal/mol), suggesting that intrachain hydrogen bonding hinders the stabilization of the excimer. © 1994 John Wiley & Sons, Inc. 相似文献
135.
Michelle J. S. Spencer Andrew Hung Ian K. Snook Irene Yarovsky 《Surface science》2003,540(2-3):420-430
The adsorption of atomic S on the Fe(1 1 0) surface is examined using density functional theory (DFT). Three different adsorption sites are considered, including the atop, hollow and bridge sites and the S is adsorbed at a quarter monolayer coverage in a p(2 × 2) arrangement. The hollow site is found to be the most stable, followed by the bridge and atop sites. At all three sites, S adsorption results in relatively minor surface reconstruction, with the most significant being that for the hollow site, with lateral displacements of 0.09 Å. Comparisons between S-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the S. At the hollow site, the presence of S causes an increase in the surface Fe d-orbital density of states between 4 and 5 eV. However, S adsorption has no significant effect on the structure and magnetic properties of the lower substrate layers. 相似文献
136.
HCHO-(DL-苹果酸)-BrO-3-Mn2+-H2SO4体系化学振荡反应动力学研究 总被引:1,自引:0,他引:1
研究了HCHO参与下的(DL-苹果酸)-BrO-3-Mn2+-H2SO4化学振荡反应体系的非线性动力学行为,考察了该体系中各反应物的初始浓度范围及主要影响因素. 结果表明,在5.0×10-5~1.0×10-2 mol·L-1范围内, HCHO对振荡反应的诱导期和周期有较大影响,且HCHO浓度的对数lnc(HCHO)与诱导期倒数的对数ln(1/tin)及周期倒数的对数ln(1/tp)均存在线性关系. 诱导期和周期的表观活化参数分别为70.87,55.71 kJ·mol-1. 另外还对HCHO参与下的可能振荡反应机理进行了探讨. 相似文献
137.
提出了一种利用简并Ⅴ型三能级原子与相干态光场(大失谐条件下)Raman相互作用实现类自旋的腔场Greenberger-Home-Zeilinger(即GHZ)态的新方案。 相似文献
138.
采用基于相对论平均场的耦合常数解析延拓方法研究球形核的单粒子共振态.具体计算了Zr同位素链中巨晕核的核芯核122Zr阈值附近的中子共振态的能量、宽度和波函数,其结果同相应的散射相移法的结果一致. Using analytic continuation in the coupling constant (ACCC) method within the framework of the self-consistent relativistic mean field (RMF) theory, the energies, widths and wave functions for single-particle resonant states close to the continuum threshold are evaluated. Predictions are also compared with corresponding results obtained by the scattering phase shift method. 相似文献
139.
140.
Reduction of tetranuclear heterometallic complex Mo2Mg2 was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex
[MoVIO2Mg(MeOH)2(OMe)4]2 and a partially reduced MoV complex are in good agreement with experimental data. The reduced MoIII complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with
release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of
the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008. 相似文献