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   20486篇
  免费   600篇
  国内免费   354篇
化学   13126篇
晶体学   119篇
力学   614篇
综合类   30篇
数学   2908篇
物理学   4643篇
  2022年   190篇
  2021年   241篇
  2020年   237篇
  2019年   252篇
  2018年   254篇
  2017年   217篇
  2016年   478篇
  2015年   437篇
  2014年   529篇
  2013年   1030篇
  2012年   946篇
  2011年   1079篇
  2010年   743篇
  2009年   722篇
  2008年   978篇
  2007年   1011篇
  2006年   887篇
  2005年   869篇
  2004年   836篇
  2003年   808篇
  2002年   892篇
  2001年   544篇
  2000年   500篇
  1999年   361篇
  1998年   280篇
  1997年   265篇
  1996年   295篇
  1995年   287篇
  1994年   291篇
  1993年   229篇
  1992年   218篇
  1991年   232篇
  1990年   237篇
  1989年   198篇
  1988年   177篇
  1987年   177篇
  1986年   162篇
  1985年   297篇
  1984年   315篇
  1983年   210篇
  1982年   261篇
  1981年   201篇
  1980年   228篇
  1979年   195篇
  1978年   188篇
  1977年   218篇
  1976年   197篇
  1975年   159篇
  1974年   154篇
  1973年   147篇
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
31.
5-vinylisoxazole     
Cycloaddition of fulminic acid to 1-butyn-3-ol gave a mixture of 5-α-hydroxyethylisoxazole (I) and 4-α-hydroxyethylisoxazole (II) in the ratio 9:1. By the dehydration of 1, 5-vinylisoxazole (III) was obtained. Compound III has also been prepared by cyclization of 4-penten-2-ynal as well as its diethylacetal with hydroxylamine hydrochloride; in both instances no isomers have been obtained. Compound III spontaneously polymerizes even at room temperature yielding a polymer still containing isoxazole rings.  相似文献   
32.
The use of corticosteroids in combination with other hormonal substances has long been known to result in increased mass gain with bovines. Practice has demonstrated, however, that even the single use of a glucocorticoid may result in growth promoting effects. In addition to the popular dexamethasone, more recently other corticosteroids have also been misused for fattening purposes. The first part of this study deals with the detection of two of them, namely betamethasone and triamcinolone acetonide. Betamethasone was administered orally to a cow at a dose of 50 mg d-1 for 5 d, then later the same cow was injected intramuscularly with a dose of 50 mg of betamethasone dipropionate. Excretion in urine and faeces was followed with both HPLC-enzyme immunoassay and a previously described method based on negative chemical ionization mass spectrometry (NCI-MS) after oxidation. For the triamcinolone acetonide study a cow was treated with 50 mg d-1 of the drug during a 7 d period. Excretion in faeces was followed with GC-NCI-MS. As triamcinolone acetonide is resistant to the previously described oxidation procedure, however, a hydrolysis step had to be introduced prior to oxidation. In addition to this specific modification necessary for triamcinolone acetonide, in a subsequent part of this study the original oxidation procedure with pyridinium chlorochromate was re-investigated especially to shorten the procedure. With the introduction of potassium dichromate the reaction time could be decreased from 3 h to 10 min.  相似文献   
33.
A method for the determination of sulphur in fly ash by instrumental proton activation analysis using the34S/p,n/34mCl reaction was developed. The 2128.5 keV and 3305.0 keV -rays of34mCl /t=32.0 min/ were measured on a Ge/Li/ -spectrometer, shielded with a lead absorber to attenuate low energy -rays. Irradiation and measuring conditions were optimized. The detection limit for instrumental analysis is 0.3 to 1 mg g–1 and the standard deviation is cca. 4% for a typical sample.  相似文献   
34.
To obtain the intrinsic acidity constant of a carboxylic ion-exchanger, we propose a method of graphical double extrapolation. The results for an ion-exchanger made of polyvinyl alcohol grafted with acrylic acid are close to those published for the corresponding linear polyacid.  相似文献   
35.
A novel generally applicable synthesis of coumarins from phenolic substrates utilizing ring-closing metathesis is described. This sequence involves O-allylation of phenols followed by ortho-Claisen rearrangement, subsequent based-induced isomerization affording 2-(1-propenyl)phenols, acylation with acryloyl chloride, and finally ring-closing metathesis (RCM) with Grubbs’ second generation catalyst.  相似文献   
36.
Résumé Les auteurs ont étudié le comportement chromatographique sur plusieurs phases stationnaires polaires et non polaires de composés cyclopropaniques stéréoisomêres: où R=H ou CH3 et X=CH, COOCH3 ou CH2OH. Les résultats sont interprétés en fonction de la configuration de X par rapport à , de la nature électronique de X et de l'orientation du phényle par rapport au plan du cyclopropane.
Relationship between chemical structure and retention. VII. Cyclopropane compounds
Summary The chromatographic behaviour, on several polar and non polar phases, of stereoisomeric cyclopropanes has been studied R=H or CH3 and X=CN, COOCH3, CH2OH. The results are interpreted in terms of the X versus configuration, the electronic nature of X and the orientation of the phenyl ring in relation to plane of the cyclopropane ring.
  相似文献   
37.
In an attempt to rationalize a synthesis of penicillin analogs modified at C(3), we have isolated the 3R(β)-carbinolamide derivative 4a. The trityl substituent on N(6′) seems to be responsible for the inversion of configuration which occurs at C(3) during the acid hydrolysis of the isocyanate intermediate. An hydrogen bond is formed on the β-face of the bell-shaped bicyclic skeleton between the N(6′)-nitrogen lone pair and the C(3) hydroxyl group. On standing, the carbinolamide analog slowly isomerizes to its expanded bicyclic isomer 4b , but the starting material may be easily recovered by treatment with acid. The postulated intermediate during isomerization, i.e., the open aldehyde form, does not accumulate. Substitutions of the hydroxyl group at C(3) lead to a variety of compounds with the biologically active 3S(α) configuration. These may be used to study the importance of the carboxyl group of penicillins in their interaction with β-lactamases at the molecular level.  相似文献   
38.
The isolation of (2S,1'S,2'S)-2-(2'-carboxycyclopropyl)glycine (CCG I, 2) from Blighia sapida (Akee) was achieved through column chromatography on deactivated silica gel followed by ion-exchange chromatography. A HPLC method has also been devised in order to assess the purity of the isolated product.  相似文献   
39.
The thermolysis of compounds of the type Cp2VR (R = aryl) in the solid state has been studied. A distinct increase in thermal stability is observed upon substitution of the ortho-position of the aryl group. Thermal decomposition occurs with formation of RH, Cp2 V, a vanadocene homologue with the group R substituted in one of the Cp rings and, probably, a vanadocene homologue with two substituted Cp rings. It is shown that the abstraction of the hydrogen atom from the cyclopentadienyl ring, necessary for the formation of RH, is an intermolecular process, whereas the substitution of the aryl group in the Cp ring is intramolecular. A decomposition mechanism is proposed in which the group R is transferred from the vanadium atom to the C5H5 ring of the same molecule by interaction with an aryl group of another molecule. The thermal decomposition of Cp2VR is compared with that of the analogous titanium compounds.  相似文献   
40.
An efficient method for the preparation of crystalline α-hydroxy previtamin D3 is described. Also the stereoselective reduction of 1-keto previtamin 9 is discussed; it was observed that with aluminum hydride 7 is the most abundant product. This stands in contrast with previously reported LiAlH4 and NaBH4 mediated reductions.  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