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   337篇
  免费   12篇
  国内免费   1篇
化学   250篇
晶体学   12篇
力学   7篇
数学   42篇
物理学   39篇
  2024年   1篇
  2023年   1篇
  2022年   6篇
  2021年   20篇
  2020年   9篇
  2019年   9篇
  2018年   12篇
  2017年   8篇
  2016年   14篇
  2015年   7篇
  2014年   13篇
  2013年   26篇
  2012年   27篇
  2011年   28篇
  2010年   22篇
  2009年   8篇
  2008年   18篇
  2007年   14篇
  2006年   14篇
  2005年   20篇
  2004年   13篇
  2003年   10篇
  2002年   5篇
  2001年   4篇
  2000年   4篇
  1999年   6篇
  1998年   2篇
  1997年   1篇
  1996年   5篇
  1995年   2篇
  1994年   4篇
  1993年   2篇
  1990年   2篇
  1986年   3篇
  1984年   1篇
  1983年   2篇
  1982年   2篇
  1979年   1篇
  1973年   1篇
  1971年   1篇
  1954年   2篇
排序方式: 共有350条查询结果,搜索用时 15 毫秒
1.
An efficient synthesis of vinyl-[1-13C]pyruvate has been reported, from which 13C hyperpolarized (HP) ethyl-[1-13C]pyruvate has been obtained by means of ParaHydrogen Induced Polarization (PHIP). Due to the intrinsic lability of pyruvate, which leads quickly to degradation of the reaction mixture even under mild reaction conditions, the vinyl-ester has been synthesized through the intermediacy of a more stable ketal derivative. 13C and 1H hyperpolarizations of ethyl-[1-13C]pyruvate, hydrogenated using ParaHydrogen, have been compared to those observed on the more widely used allyl-derivative. It has been demonstrated that the spin order transfer from ParaHydrogen protons to 13C, is more efficient on the ethyl than on the allyl-esterdue to the larger J-couplings involved. The main requirements needed for the biological application of this HP product have been met, i. e. an aqueous solution of the product at high concentration (40 mM) with a good 13C polarization level (4.8 %) has been obtained. The in vitro metabolic transformation of the HP ethyl-[1-13C]pyruvate, catalyzed by an esterase, has been observed. This substrate appears to be a good candidate for in vivo metabolic investigations using PHIP hyperpolarized probes.  相似文献   
2.
In this paper, we give a partial classification of commutative spaces of Heisenberg type. Several classification results were known previously. In order to avoid complicated technical details, we restrict ourselves to saturated commutative spaces. Our results are presented in Table II.  相似文献   
3.
We have obtained new semiconductor materials with microheterojunctions by substitution of surface cadmium ions in CdS by Cu(I), Cu(II), and Bi(III) ions. We have shown that the photocatalytic activity of their dispersions in the reaction of evolution of H2 from alcohol-water mixtures is considerably higher than in the original cadmium sulfide.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 3, pp. 270–274, May–June, 1993.We would like to acknowledge Academician V. D. Pokhodenko of the Academy of Sciences of Ukraine for drawing our attention to the prospects for investigation of complex photocatalytic systems based on semiconductors with different types of conductivity.  相似文献   
4.
The crystal structure of the molecular complex of C-undecylcalix[4]resorcinarene with dioxane has been determined by X-ray analysis. The asymmetric unit contains one host and four guest molecules. The calix[4]resorcinarene moiety adopts a bowl conformation with C4v symmetry. Four undecyl chains are axially oriented. Calix molecules are packed in a bowl-to-bowl fashion with alternating hydrophilic and hydrophobic layers. One of the hydrophilic dioxane molecules is located at the rim of the calix moiety and is hydrogen bonded to the other one. There is no interaction to attract, or direct the dioxane molecule into the interior of the cavity. There is an exo complex formed. The dioxane molecules – located in the hydrophobic part – are highly disordered.  相似文献   
5.
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands.  相似文献   
6.
The electrochemical production and doping of soluble, as well as the physicochemical properties of a soluble electrically conducting polymer based on 3-methyl-4-phenylthiophene were studied.Translated from Teoreticheskaya i Éxperimental'naya Khimiya, Vol. 29, No. 2, pp. 143–148, March–April, 1993.The authors would like to express gratitude to the State Committee of the Ukraine on questions of science and technology for financial support for this work within the framework of the State Scientific and Technical Program 7.1. Materials for Electronic Technology, as well as to V. P. Kandilenko and V. Ya. Chernov for aid in recording the fluorescence spectra of the P3M4PT films.  相似文献   
7.
The possibility of photocatalysis of hydrogen production from aqueous alcohol mixtures by heterostructures of cadmium sulfide with dyes under the action of light with >600 nm was shown. A probable mechanism of the sensitization is proposed on the basis of an examination of the spectral, photochemical, and electrochemical data obtained.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 6, pp. 370–374, November–December, 1995.The authors are grateful to S. V. Shinkorenko for providing the dyes that they synthesized for the first time.  相似文献   
8.
Two newly identified supramolecular structures arise from self-assembly of the macrocyclic 1,5,9,18,22,26- hexaaza[11.11]-p-cyclophane salts with o-nitrophenol (C28H50N6)4+·4(C6H4NO2O) (1) and with HCl (C28H52N6)6+·6Cl-·4H2O (2). In both cases two-dimensional supramolecular sheets are formed.  相似文献   
9.
The title salt, [Zn(C2N2H8)3]2[CdI4]I2, conventionally abbreviated [Zn(en)3]2[CdI4]I2, where en is ethyl­enediamine, contains discrete [Zn(en)3]2+ cations and [CdI4]2− anions with distorted octa­hedral and nearly tetra­hedral geometries, respectively, as well as uncoordinated I ions. The cation and the free I anion lie on twofold rotation axes and the [CdI4]2− anion lies on a axis in the space group I2d. The structure exhibits numerous weak inter‐ionic hydrogen bonds of two types, viz. N—H⋯I(free ion) and N—H⋯I([CdI4]2−), which support the resulting three‐dimensional framework.  相似文献   
10.
Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, methyl 4,6-O-benzylidene-α-d-glucopyranoside, 1,2-O-cyclohexylidene-α-d-glucofuranose, methyl α-d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH-DMSO, t-BuOK-DMSO). The complete vinylation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and methyl α-d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH-THF as well.  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