首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   66篇
  免费   2篇
化学   58篇
晶体学   2篇
物理学   8篇
  2021年   1篇
  2017年   1篇
  2015年   1篇
  2014年   2篇
  2013年   2篇
  2012年   3篇
  2011年   8篇
  2010年   3篇
  2009年   1篇
  2008年   2篇
  2007年   3篇
  2006年   6篇
  2005年   3篇
  2004年   6篇
  2003年   7篇
  2002年   6篇
  2001年   4篇
  2000年   1篇
  1998年   2篇
  1996年   1篇
  1993年   1篇
  1992年   1篇
  1989年   1篇
  1979年   1篇
  1973年   1篇
排序方式: 共有68条查询结果,搜索用时 359 毫秒
31.
The conformation and vibrational properties of 2-methoxy-1,2-diphenylethanone (MDPE) are investigated in the gas phase and in organic solvents. Ab initio calculations carried out at the B3LYP/6-31G(d) level demonstrate that three stable conformers having cisoid, skewed and transoid structures are present in the gas phase. In the gas phase, the conformers are separated by a low energy barrier and their relative energies do not differ by more than 7.2 kJ mol (-1) Like in crystalline MDPE 'Acta Crystallogr. Sect. C 44 (1988) 894', weak CH...O hydrogen bonds are present in the cisoid conformation. The IR and Raman spectra of solid MDPE are discussed. Several vibrational modes are split in organic solvents. A comparison between the theoretical data and the experimental dipole moments indicates that two conformers are present in solution, the population of the cisoid form increasing with the permittivity of the medium.  相似文献   
32.
33.
34.
The structures of iminium salts formed from diarylprolinol or imidazolidinone derivatives and α,β‐unsaturated aldehydes have been studied by X‐ray powder diffraction (Fig. 1), single‐crystal X‐ray analyses (Table 1), NMR spectroscopy (Tables 2 and 3, Figs. 2–7), and DFT calculations (Helv. Chim. Acta 2009 , 92, 1, 1225, 2010 , 93, 1; Angew. Chem., Int. Ed. 2009 , 48, 3065). Almost all iminium salts of this type exist in solution as diastereoisomeric mixtures with (E)‐ and (Z)‐configured +NC bond geometries. In this study, (E)/(Z) ratios ranging from 88 : 12 up to 98 : 2 (Tables 2 and 3) and (E)/(Z) interconversions (Figs. 2–7) were observed. Furthermore, the relative rates, at which the (E)‐ and (Z)‐isomers are formed from ammonium salts and α,β‐unsaturated aldehydes, were found to differ from the (E)/(Z) equilibrium ratio in at least two cases (Figs. 4 and 5, a, and Fig. 6, a); more (Z)‐isomer is formed kinetically than corresponding to its equilibrium fraction. Given that the enantiomeric product ratios observed in reactions mediated by organocatalysts of this type are often ≥99 : 1, the (E)‐iminium‐ion intermediates are proposed to react with nucleophiles faster than the (Z)‐isomers (Scheme 5 and Fig. 8). Possible reasons for the higher reactivity of (E)‐iminium ions (Figs. 8 and 9) and for the kinetic preference of (Z)‐iminium‐ion formation are discussed (Scheme 4). The results of related density functional theory (DFT) calculations are also reported (Figs. 10–13 and Table 4).  相似文献   
35.
The efficient asymmetric total synthesis of (?)‐oseltamivir, an antiviral reagent, has been accomplished by using two “one‐pot” reaction sequences, with excellent overall yield (60 %) and only one required purification by column chromatography. The first one‐pot reaction sequence consists of a diphenylprolinol silyl ether mediated asymmetric Michael reaction, a domino Michael reaction/Horner–Wadsworth–Emmons reaction combined with retro‐aldol/Horner–Wadsworth–Emmons reaction and retro Michael reactions, a thiol Michael reaction, and a base‐catalyzed isomerization. Six reactions can be successfully conducted in the second one‐pot reaction sequence; these are deprotection of a tert‐butyl ester and its conversion into an acyl chloride then an acyl azide, Curtius rearrangement, amide formation, reduction of a nitro group into an amine, and a retro Michael reaction of a thiol moiety. A column‐free synthesis of (?)‐oseltamivir has also been established.  相似文献   
36.
We proposed and developed a new solid immersion mirror (SIM) for near-field optical data storage. The SIM has some advantages, especially in manufacturing, because its shape is similar to a general plano-convex lens. Making an aperture of about 130 nm in diameter just on the focus area of the SIM, a bit-data recording onto a photochromic thin film was carried out. Minimum diameter of the written marks was estimated to be 180nm. We also demonstrated readout experiments where a recorded medium was rotating and a gap between the SIM and the disk was controlled with capacitance sensing. This is the first result of reading with a rotating disk using an SIM containing a small aperture.This paper was originally presented at the 10th Optical Near Field Workshop, which was held on June 27-28, 2001 at Osaka University, organized by the Optical Near Field Group, the Optical Society of Japan, an affiliate of the Japan Society of Applied Physics.  相似文献   
37.
Magnetic nanoparticles (MNPs) have many potential biomedical applications. Improvements in their magnetic properties and solubility are necessary for these applications to realize their full potential. In this study, MNPs in the form of raspberry-like magnetite (Fe(3)O(4)) nanoparticle clusters, consisting of tiny Fe(3)O(4) particles with a diameter of approximately 20 nm, were prepared under hydrothermal conditions at 200 °C in the presence of 3,4-dihydroxyhydroxysinnamic acid (DHCA). The primary particles were connected by DHCA molecules to form the clusters, which were well dispersed in water media because a COOH group from DHCA appeared on their surfaces. The cluster size could be tuned from 50 to 400 nm without changing the primary particle size by controlling the reaction time. Therefore, all prepared clusters displayed superparamagnetic properties at room temperature. In addition, the sensitivity of Fe(3)O(4) to an external magnetic field could also be controlled by the cluster size.  相似文献   
38.
The reactions of α,β‐unsaturated aldehydes with cyclopentadiene in the presence of diarylprolinol silyl ethers as catalyst proceed via iminium cations as intermediates, and can be divided into two types; one involving a Michael‐type reaction (type A) and one involving a cycloaddition (type B). Diphenylprolinol silyl ethers and trifluoromethyl‐substituted diarylprolinol silyl ethers, which are widely used proline‐type organocatalysts, have been investigated in this study. As the LUMO of the iminium ion derived from trifluoromethyl‐substituted diarylprolinol silyl ether is lower in energy than that derived from diphenylprolinol silyl ether, as supported by ab initio calculations, the trifluoromethyl‐substituted catalyst is more reactive in a type B reaction. The iminium ion from an α,β‐unsaturated aldehyde is generated more quickly with diphenylprolinol silyl ether than with the trifluoromethyl‐substituted diarylprolinol silyl ether. When the generation of the iminium ion is the rate‐determining step, the diphenylprolinol silyl ether catalyst is the more reactive. Because acid accelerates the generation of iminium ions and reduces the generation of anionic nucleophiles in the Michael‐type reaction (type A), it is necessary to select the appropriate acid for specific reactions. In general, diphenylprolinol silyl ether is a superior catalyst for type A reactions, whereas the trifluoromethyl‐substituted diarylprolinol silyl ether catalyst is preferred for type B reactions.  相似文献   
39.
We propose a semiempirical procedure for the estimation of the rate constants for hydrogen atom abstraction reactions of OH radicals with haloalkanes and haloethers. Our procedure is derived from the collision theory based kinetic equation, which was originally proposed by Heicklen (Int. J. Chem. Kinet. 1981, 13 , 651). This equation provides the estimates for the rate constants of hydrogen abstraction from the C? H bond dissociation enthalpy for each potential hydrogen atom abstraction site. We reparameterized the equation and then applied this procedure to a series of haloalkane and haloether molecules. The results obtained from the new equations are found to be quite satisfactory. In addition, we also report highly reliable calculated values of the C? H bond dissociation enthalpies for six environmentally important haloether molecules (CH2FOCH2F, CHF2CF2OCH2CF3, CF3CH2OCH2CF3, CF3CF2CH2OCHF2, CHF2OCF2CHFCl, and CHF2OCHClCF3). © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 130–138, 2003  相似文献   
40.
The pressure-dependent energetic and mechanical stabilities of simple cubic carbon were studied using first-principles calculations. The enthalpies of graphite, diamond, BC8, and simple cubic carbon were calculated, and it was found that simple cubic carbon was the most energetically stable polytype above 2700 GPa. Elastic constants were calculated as a function of pressure. Simple cubic carbon was mechanically unstable below 400 GPa, but became mechanically stable above 400 GPa. Our calculated results also indicated that the bulk module of simple cubic carbon increased linearly with increasing pressure.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号