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   1469篇
  免费   25篇
  国内免费   1篇
化学   943篇
晶体学   16篇
力学   12篇
数学   304篇
物理学   220篇
  2021年   20篇
  2020年   13篇
  2019年   15篇
  2018年   22篇
  2017年   28篇
  2016年   34篇
  2015年   34篇
  2014年   31篇
  2013年   101篇
  2012年   52篇
  2011年   71篇
  2010年   36篇
  2009年   36篇
  2008年   56篇
  2007年   48篇
  2006年   62篇
  2005年   44篇
  2004年   50篇
  2003年   48篇
  2002年   47篇
  2001年   25篇
  2000年   28篇
  1999年   27篇
  1998年   29篇
  1997年   18篇
  1996年   23篇
  1995年   12篇
  1994年   20篇
  1993年   17篇
  1992年   16篇
  1991年   24篇
  1990年   23篇
  1989年   16篇
  1988年   25篇
  1987年   20篇
  1986年   17篇
  1985年   32篇
  1984年   32篇
  1983年   13篇
  1982年   20篇
  1981年   24篇
  1980年   14篇
  1979年   18篇
  1978年   12篇
  1977年   12篇
  1976年   17篇
  1975年   17篇
  1974年   15篇
  1973年   21篇
  1972年   8篇
排序方式: 共有1495条查询结果,搜索用时 140 毫秒
11.
A selective and sensitive flow-injection system for the determination of myo-inositol (hexahydroxycyclohexane) is described. Inositol dehydrogenase, IDH, lactate dehydrogenase, LDH, and lactate oxidase, LOD, are co-immobilized on porous glass and used in a packed-bed enzyme reactor. myo-Inositol reacts to produce an equivalent amount of hydrogen peroxide, which oxidizes hexacyanoferrate(II) to hexacyanoferrate(III) in a second reactor containing immobilized peroxidase. The hexacyanoferrate(III) is then detected amperometrically at 0 mV vs. SCE in a flow-through detector. The system responds linearly to injected samples of myo-inositol (25 μl) in the concentration range 1–300 μM. The maximum throughput was 90 samples per hour. The IDH/LDH/LOD reactor was stable for at least 5 weeks.  相似文献   
12.
This is one in a series of papers studying measures of information in the so-called mixed theory of information (i.e. considering the events as well as their probabilities) on the open domain (i.e. without empty sets and zero probabilities). In this paper we find all-recursive, 3-semisymmetric inset entropies on the open domain. We do this by solving the fundamental equation of inset information of degree () on the open domain.Dedicated to Professor János Aczél on his 60th birthday.  相似文献   
13.
We have studied the adsorption on a platinum (Pt) catalyst of two compounds utilizable as a chiral basic catalyst and a chiral modifier, dihydrocinchonidine (DHCD), and a new cinchona alkaloid derivative containing a bulky group, the Ph3SiO-DHCD molecule. The method of choice was the detection by electrospray ionization (ESI) ion-trap tandem mass spectrometry (MS/MS) of hydrogen/deuterium (H/D) exchange at room temperature, in tetrahydrofuran, at a D2 pressure of 1 bar. Based on the ESI-MS/MS spectrum of the new compound, we propose a mechanism for the formation of the silatropylium cation containing a Si-O bond. From the fragmentation pattern of Ph3SiO-DHCD it was confirmed that ESI-ion-trap MS/MS can be used to study the adsorption processes of complicated carbon compounds by investigating their H/D exchange reactions. In the case of Ph3SiO-DHCD, the results demonstrate that H/D exchange takes place mainly on the quinoline skeleton. However, the strong pi-bonded adsorption of the quinoline skeleton parallel with the imaginary plane of Pt is not preferred because the bulky Ph3Si group inhibits the multiple pi-bonded adsorption of the Ph3SiO-DHCD. Because of this hindrance the molecule was adsorbed tilted via the nonbonding electron pair of the N atom and C2' atom of the quinoline skeleton; consequently, mainly alkaloid-d1 and alkaloid-d2 are formed.  相似文献   
14.
The reaction of the isothiourea derivative 2 with methylaminc or pyrrolidine resulted in guanidines 3a-3b . Using hydrazine under the same conditions the tetrazole derivative 4 was obtained. On reacting 2 with piperidine, morpholine, methylhydrazine, phenylhydrazine, hydroxylamine or sodium hydroxide, cycliza-tion took place leading to the novel 4-cyanimino-1,2,3,4,6,7,12,12b-octahydro-3,12b-ethanopyrim-ido[1′,6′:1,2]pyrido[3,4-b]indole ( 5 ). Some structural aspects of 5 and other model compounds were analysed mainly by 13C nmr spectroscopy.  相似文献   
15.
The catalytic activity of BeO for the double bond shift of 1-pentene has been investigated. The maximum activity was exhibited by samples calcined at 1173 K. The effect of pyridine, CO2 and CCl4 on the activity was also studied. Lewis acid-base site pairs appear to be active for the isomerization.
BeO 1- . , 1173 . , CO2 CCl4 . - .
  相似文献   
16.
JPC – Journal of Planar Chromatography – Modern TLC - The chemical composition of the oils of four thyme (Lamiaceae) chemotypes (Thymus vulgaris L., Thymus serpyllum L., Thymus x...  相似文献   
17.
Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected. Dedicated to Professor Károly Lempert on his 80th birthday.  相似文献   
18.
The molecular structure of 1,3,5-tris (trimethylstannyl) benzene has been determined by gas-phase electron diffraction. The C — C bond length is in good agreement with that in benzene. In agreement with the somewhat electron-releasing character of the substituents, the endocyclic bond angles at the substituents are somewhat smaller than 120°. The mean value of Sn — C bond lengths is greater than that in tetraphenyltin and tetramethyltin. The SnMe3 groups appear freely rotating around the Caryl — Sn bonds. The following bond lengths (r g) and bond angles were determined: (Sn — C)mean 2.150 ± 0.007 Å, C — C 1.399 ± 0.005 Å, (C — H)mean 1.105 ± 0.006 Å, < C — C(Sn) — C 117.7 ± 1.7º, < Caryl — Sn — Cmethyl 106.7 ± 0.7º < Sn — C — H 111.5 ± 0.9º.  相似文献   
19.
The Cyclopropa[c]chromenes 14 , trans-and cis- 15 , trans-and cis- 16 and 17 rearrange on heating > 200° in N, N-diethylaniline to give 2-alkyl-2H-chromenes 7, 8, 21, 22. The rate determining step of this rearrangement is the ‘homoelectrocyclic’ ring opening of the cyclopro-pa[c]chromenes to give ω-allyl-quinomethanes of type 4. These intermediates show fast [1,5s] and [1,7a] H-shifts, followed by electrocyclic ring closure. Deuterium labelling experiments are in agreement with this mechanism. The remarkable dependence of the rates of rearrangement with respect to the stereochemistry of the cyclopropa[c]chromenes (cf. table 2) suggests that in the first step only one of the two possible disrotatory modes of ring opening is involved.  相似文献   
20.
The reaction takes place on Cd-containing Lewis sites, whereas the irreversible adsorption and condensation of product acetaldehyde on acidic OH groups of Cd-X, FAU catalyst results in deactivation. Preadsorbed ammonia moderates the deactivation, because it reacts with acetylene, and pyridine homologues are formed which block the accessible OH groups. Since in divalent cationic forms of clinoptilolite no OH groups are generated, Cd-clinoptilolite proved to be a catalyst of permanent activity.
, Cd, — OH FAU, Cd-X. , .. , OH . OH, Cd- .
  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