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211.
Solid-phase methodology has been rapidly and extensively applied to the preparation of small organic molecules recently1. It might be argued that selenoxide syn-elimination provided the principal impetus for the development of organoselenium chemistry. In addition, the required selenoxides are readily available from the oxidation of the corresponding selenides, which in turn can be prepared by the reaction of selenium-stabilized carbanions with various electrophilic substrates2. However, or… 相似文献
212.
组件式设计常被用地人工髋关节,钴络钼合金(Co-Cr-Mo)与钛合金(Ti-6Al-4V)的压配最常用,本文应用电化学方法研究了静态条件下两种合金的电偶腐蚀行为,浸泡实验表明,钴络钼合金为阳极,但电偶电流与其维钝电流相近,并无明显加速度腐蚀效应,钛合金为阴极,受到保护,失重及金相观察结果显示,在45天的浸泡实验周期内,未发现腐蚀痕迹,混合电位理论和电位处于两种合金的钝化电位区,电偶电流为合金的维钝 相似文献
213.
Geometries and stabilization energies of various simple H-bonded complexes (water dimer, hydrogen fluoride dimer, formamide
dimer, formic acid dimer) have been determined by a gradient optimization that eliminates the basis set superposition error
(BSSE) by the counterpoise (CP) method in each gradient cycle as well as by the standard gradient optimization. Both optimization
methods lead to different potential energy surfaces (PES). The difference depends on the theoretical level used and is larger
if correlation energy is considered. Intermolecular distances from the CP-corrected PES are consistently longer, and this
difference might be significant (∼0.1 ?); also angular characteristics determined from both surfaces differ significantly.
Different geometries were obtained even when passing to larger basis sets (aug-cc-pVDZ). The standard optimization procedure
can result in a completely wrong structure. For example, the “quasi-linear” structure of the (HF)2 (global minimum) does not exist at the standard MP2/ 6-31G** PES (where only cyclic structure was detected) and is found
only at the CP-corrected PES. Stabilization energies obtained from the CP-corrected PES are always larger than these from
the standard PES where the BSSE is added only a posteriori for the final optimized structure; both energies converge only
when passing to a larger basis set (aug-cc-pVDZ).
Received: 11 March 1998 / Accepted: 19 June 1998 / Published online: 4 September 1998
RID="
ID=" <E6>Acknowledgements.</E6> The project was supported by the Grant Agency of the Czech Republic (Grant No. 203/98/1166).
RID="
ID=" <E5>Correspondence to</E5>: P. Hobza 相似文献
214.
Toshiaki Sunazuka Masaki Handa Tatsuya Shirahata Kazuhiko Otoguro Satoshi ōmura 《Tetrahedron》2004,60(36):7845-7859
In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins. 相似文献
215.
Michael Ruck 《无机化学与普通化学杂志》1994,620(10):1832-1836
Preparation and Crystal Structure of the First Polymeric Phosphorus Selenide catena-(P4Se4)x Catena-(P4Se4)x was prepared in crystalline form from the elements using iodine as a catalyst, and characterized by means of X-ray diffraction and IR spectroscopy. Single-crystal investigations (space group P21/c, a = 1 119.2(3), b = 728.2(2), c = 1 142.5(3) pm, β = 115.91(2)°, V = 837.5(7) · 106 pm3) revealed parallel chains of P4Se3 hetero-norbornane units linked via Se atoms. Thus, being the first phosphorus selenide which does not contain discrete molecules, catena-(P4Se4)x can be regarded as a polymeric form of α-P4Se4 or as a crystalline modification of vitrous phosphorus selenide. 相似文献
216.
Sodium-dicyclohexyl- 18-crown-6 complex cation was used as carrier for the uphill transport of zinc as Zn(SCN)42? complex anion. By using L-cysteine as a metal ion acceptor in the receiving phase at the optimized pH of 7.6, the amount of zinc transport through the liquid membrane after 90 min was 97.2 ± 1.0%. The selectivity and efficiency of zinc transport from aqueous solutions containing equimolar mixtures of Ag+, Cd2+ Co2+, Cu2+, Fe2+, Ni2+, Pb2+, Pd2+, Sr2+, Bi3+, Cr3+ and Fe3+ ions was investigated. In the presence of NH2OH.HCl as a suitable masking agent in the source phase, the interfering effect of Cu2+ and Pb2+ ions was diminished drastically. 相似文献
217.
The proton affinity on each of the possible sites in the antitumor 2‐(4‐aminophenyl)benzazoles has been calculated at the B3LYP/6‐311G** level of theory in the gas phase and in solution. The N3‐site of protonation is found to be strongly favored over the NH2‐site for the studied compounds both in gas phase and in solution. The stability of N3‐protonated species is explained by the resonance interaction of the NH2‐group with the heterocyclic ring. The potential energy surface (PES) for the protonation process was studied at the density functional theory (DFT)/B3LYP/6‐311++G** level of theory. Solvent effects on the PES were also examined using two models: Onsager self‐consistent field and polarizable continuum model (PCM). © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
218.
The formation and properties of the products of the radiation-induced chemical reduction of silver ions in aqueous solutions containing sodium polyacrylate were investigated. The absorption spectra of these species exhibit a band at 290 mn and a band in the visible region. The latter shifts from 470 nm to -800 nm with time or after the addition of silver ions. The species obtained (clusterites) arc linear silver clusters bound to the carboxyl groups of the ion exchanger. The red shift of the visible band is due to the increase in their size. The mechanism of the formation and the structure of the clusterites are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1429–1435, June, 1996. 相似文献
219.
M. Schubert-Zsilavecz D. Gusterhuber W. Likussar G. Färber 《Monatshefte für Chemie / Chemical Monthly》1994,125(6-7):735-742
Summary Regio-, stereo- and siteselectivity of the cycloadditions of trimethylbenzonitrile oxide with 2H-3,4-Dihydro-1,4-benzoxazin-6(8aH)-ones have been investigated. The structures of the obtained products were elucidated by means of homonuclear NOE difference spectroscopy and HMQC and HMBC spectra. The structure of 6-Benzyl-9a-methoxy-3-mesityl-9b-methyl-7,8,9a,9b-tetrahydro-3aH-1,2-oxazolo-[4,5-h]1,4-benzoxazin-4(6H)-on5 was elucidated from a single crystal X-ray structure analysis at ambient temperature: C27H30N2O4, M=446.55g/mol, monoclinic, P21/c,a=10.372 (34) Å,b=11.908 (21) Å,c=20.040 (34) Å, =97.16 (17)°,V=2455.8 (1.9)Å3,Z=4,d
c=1.208g/cm3, =0.08mm–1,R=0.0546.Dedicated to Prof. Ott with best wishes for his 70th birthday 相似文献
220.
The effect of the addition of a second metals such as Zn and Ni on the calcinaton and reduction of alumina, magnesia and silicasupported iron catalysis with total iron loading of 5wt% is investigated by Mössbauer spectroscopy. It is shown that the reducibility of supported α-Fe2O3 is gradually increased by adding the second metal. The values of the magnetic hyperfine field obtained from Mössbauer spectra for the Zn or Ni-added α-Fe2O3 or Fe catalysts decreased with increasing second metal loading. 相似文献