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   3168篇
  免费   161篇
  国内免费   12篇
化学   2591篇
晶体学   44篇
力学   53篇
数学   341篇
物理学   312篇
  2023年   21篇
  2022年   43篇
  2021年   41篇
  2020年   44篇
  2019年   58篇
  2018年   40篇
  2017年   25篇
  2016年   90篇
  2015年   111篇
  2014年   113篇
  2013年   190篇
  2012年   233篇
  2011年   257篇
  2010年   119篇
  2009年   141篇
  2008年   215篇
  2007年   210篇
  2006年   207篇
  2005年   183篇
  2004年   148篇
  2003年   123篇
  2002年   135篇
  2001年   51篇
  2000年   31篇
  1999年   43篇
  1998年   24篇
  1997年   31篇
  1996年   39篇
  1995年   29篇
  1994年   27篇
  1993年   22篇
  1992年   23篇
  1991年   20篇
  1990年   21篇
  1989年   18篇
  1988年   13篇
  1987年   14篇
  1986年   19篇
  1985年   17篇
  1984年   12篇
  1983年   16篇
  1982年   15篇
  1981年   6篇
  1980年   15篇
  1979年   12篇
  1978年   10篇
  1977年   12篇
  1976年   9篇
  1975年   6篇
  1974年   8篇
排序方式: 共有3341条查询结果,搜索用时 9 毫秒
1.
The accumulation of pathological prion protein is used as a diagnostic marker for transmissible spongiform encephalopathies. According to European Union (EU) regulations cattle older than 30 months of age (Germany, France, Italy, and Spain by national law >24 months) and slaughtered for human consumption must be tested by using rapid tests for bovine spongiform encephalopathy (BSE). Likewise fallen stock and clinically affected animals must be tested. This article gives a short overview of the incidence of BSE in Europe. The diagnostic hierarchy, i.e., the officially approved methodology for the confirmation of suspect rapid test cases, and the organization of the numerous laboratories involved in this large-scale testing for BSE are described. Special emphasis is given to necessary quality control measures currently in place for BSE rapid testing laboratories and to measures intended to assure a consistent performance of the commercially available rapid test kits.Presented at BERM-9—Ninth International Symposium on Biological and Environmental Reference Materials, 15–19 June 2003, Berlin, Germany.  相似文献   
2.
Crystals of the title compound are orthorhombic, Pca21;a=27.586(4),b=10.509(3),c=11.080(2) Å,V=3212(1) Å3,Z=8. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by full-matrix least squares to a finalR value of 0.055 using 2043 reflections. One of the two independent molecules in the asymmetric unit is disordered. The disorder is manifested mainly between the oxygen atom and one sulfur atom and is caused by opposite enantiomers occupying corresponding positions in different unit cells. The endocyclic torsion angles in both independent molecules are very similar but the disposition of the heteroatoms on the twist-boat framework is different in the two molecules. Site occupancy of the two models on this framework in the disordered molecule is in the ratio 2179 with the smaller proportion being very similar to the ordered molecule and the remainder similar to that found in the normal molecule oftrans-4-chloro-2,4,6-tris(trichloromethyl)-1-oxa-3,5-dithian (Irving and Irving, 1988).  相似文献   
3.
The study deals with the analysis of diffusion and mass transfer modelling during pervaporation in a true ternary system involving a polar liquid mixture (ETBE/EtOH) and a polar block copolymer (polyurethaneimide or PUI). A survey of methods of pervaporative transfer modelling in ternary systems is first developed. From differential permeation experiments carried out with both pure liquids, it appears that both permeants obey a Fickian law. Moreover, the diffusional behaviour is consistent with Long's model, which has thus been assumed for the related ternary system. An extension of the Brun's model is then derived, which takes into account the diffusion coupling as well the significant deviation from sorption ideality. From a practical point of view, the calculated values of fluxes show generally good agreement with the experimental results, although a small deviation occurs for mixtures of low ethanol content. Diffusion coefficients of both pure solvents corresponding to transient or steady state are compared. A very good agreement is found for the aprotic permeant (ETBE). whereas the diffusion coefficient of ethanol in transient state is only the quarter of the value corresponding to steady state. The results are discussed in comparison with related investigations in the literature, involving specific liquid-polymer interactions.  相似文献   
4.
In neutral DMF, ellipticinium cations 9 R—E+H—2 CH3 undergo a reversible 1 e addition (standard potential ca. ?1.35 V) to yield a neutral radical which rapidly dimerizes (dimerization rate constant ca. 107 mol?1 1 s?1). In basic DMF or in the presence of superoxide anion, the corresponding conjugated bases undergo a reversible 1 e addition accompanied by a fast and reversible proton addition (standard potential at pHDMF 0 ca. ?0.52 V) to yield the same neutral radical. R being H, OCH3 or OH, there is no effect of the substituent at the C-9 position on the electrochemical process.  相似文献   
5.
The X-ray structure of a 1:1 Cu/O(2) adduct revealed side-on (eta(2)) O(2) coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)-(O(2)(2-)) resonance form, and provided insights into the key bonding interactions. Reaction of a 1:1 adduct supported by a slightly different beta-diketiminate ligand with Cu(I) reagents resulted in the formation of novel asymmetric bis(mu-oxo) complexes that were identified by EPR, UV-vis, and Raman spectroscopy, as well as by an X-ray structure in one instance.  相似文献   
6.
7.
Abstract— Pulmonary macrophages obtained from neonatal rats contain approximately four times the activity of cyanide resistant superoxide dismutase and catalase compared with the cells from adult animals. The activity is highest immediately after birth and diminishes with age until the minimum level is reached at approximately 3 weeks of age. Superimposed upon this change in basal activity is the capability of neonatal cells to synthesize additional cyanide resistant superoxide dismutase and catalase when either the animals or isolated pulmonary macrophages are exposed to 95–100% oxygen. The inductive effect begins at 2–3 days after birth, peaks at 10 days, and disappears at approximately 15 days after birth. In contrast to adult rats, neonatal rats are extremely resistant to the toxic effects of oxygen. If, however, the oxygen mediated increase in both enzymes is prevented or the maximum effective pulmonary macrophage number is diminished in test animals, these animals become vulnerable to toxic effects of oxygen exposure, observed by gross and histologic examination of lung tissue, in a manner similar to adult animals. These data indicate that both cyanide-resistant superoxide dismutase and catalase may be part of the endogenous defense mechanisms which provide neonatal rats with an exceptional resistance to oxygen toxicity.  相似文献   
8.
Heterodienetricarbonyliron complexes react with ligands ( L = PMe2Ph, P(OMe)3 or P(OPh)3) to give the adducts (enone)Fe(CO)3L with the ethylenic double bond coordinated only to the iron(0). Electron-releasing and low-steric effects of L make the reaction which is specific for enones easier compared to that for dienes. PMe2Ph allows enone exchange and P(OPh)3 promotes carbonyl elimination. Ligand influence is shown by infrared spectroscopy and by the shielding of ethylenic protons in NMR spectroscopy.  相似文献   
9.
A non-aqueous capillary electrophoresis (NACE) method coupled to indirect absorbance detection has been developed for the separation of the three positional isomers of monosulfated fucose. The optimized electrolyte was composed of 12 mM ethanolamine, 2 mM trimesic acid buffer in a methanol-ethanol (1:1, v/v) mixture. As the retained electrolyte entails no separating agent other than the pH buffer, the NACE separation of the positional isomers has been ascribed mainly to selective ion-pairing with the electrolyte counter-ion and the possibility of a selective solvation effect in the alcohol mixture. In the absence of pure isomeric standards, peak identification was completed by MS and NMR spectroscopy and selective enzymatic desulfation. This method should be of interest for the structure elucidation of monosulfated fucose-based polysaccharides and for the screening of sulfoesterase of unknown activity.  相似文献   
10.
Ab initio SCF computations on the intrinsic preferences of the H+, CH 3 + and C2H 5 + cations towards the two principal sites of protonation or alkylation on cytosine, N3 or O2, show that this preference undergoes a continuous modification with the increase in size and complexity of the cation. N3 is the preferred site of fixation of H+, O2 the preferred site of C2H 5 + , while CH 3 + has no marked preference. The exchange repulsion term of the binding energy appears responsible for the preference of C2H 5 + for O2.This work was supported by the Ligue Francaise contre le Cancer and the National Foundation for Cancer Research (USA)  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