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   4303篇
  免费   176篇
  国内免费   24篇
化学   2913篇
晶体学   34篇
力学   180篇
数学   414篇
物理学   962篇
  2024年   16篇
  2023年   39篇
  2022年   204篇
  2021年   206篇
  2020年   153篇
  2019年   141篇
  2018年   170篇
  2017年   123篇
  2016年   182篇
  2015年   161篇
  2014年   167篇
  2013年   321篇
  2012年   273篇
  2011年   291篇
  2010年   163篇
  2009年   147篇
  2008年   156篇
  2007年   178篇
  2006年   135篇
  2005年   142篇
  2004年   95篇
  2003年   85篇
  2002年   71篇
  2001年   72篇
  2000年   52篇
  1999年   59篇
  1998年   27篇
  1997年   27篇
  1996年   43篇
  1995年   40篇
  1994年   27篇
  1993年   32篇
  1992年   33篇
  1991年   40篇
  1990年   20篇
  1989年   20篇
  1988年   29篇
  1987年   26篇
  1986年   26篇
  1985年   38篇
  1984年   24篇
  1983年   23篇
  1982年   22篇
  1981年   11篇
  1980年   28篇
  1979年   21篇
  1978年   27篇
  1977年   27篇
  1976年   18篇
  1973年   11篇
排序方式: 共有4503条查询结果,搜索用时 203 毫秒
111.
A new flavonol glycoside, isorhamnetin 3-O-beta-D-apiofuranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-galactopyranoside, and the known diglycoside, isorhamnetin 3-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-galactopyranoside were isolated from the aerial parts of Astragalus vulneraria. Characterization of the two compounds was done by spectroscopic methods (1D and 2D NMR, and FAB-MS).  相似文献   
112.
The cyclizations of two structurally similar 2-oxo-5-hexenyl-type radicals have been investigated by ab initio and density functional (UB3LYP/6-31+G**//UHF/6-31G* and UB3LYP/6-31G*//UB3LYP/6-31G*) calculations. The origin of apparently contradictory reports of 6-endo and 5-exo cyclizations is determined. Kinetic control favors 6-endo cyclization, while thermodynamic control gives 5-exo cyclization, and the observation of different products from different research groups arises from the difference in experimental conditions used by the two groups. The outcome of a new cyclization reaction was predicted by using these theoretical techniques. Kinetic control is predicted to yield exclusively the products of 6-endo cyclization, while thermodynamic control would lead to an approximately equal mixture of one 6-endo and one 5-exo cyclized product. Experimental studies revealed that the reaction yields only the products of 6-endo cyclization through kinetic control.  相似文献   
113.
A novel kinetic method for the determination of trace amounts of Co(II) has been developed. The proposed method based on the catalytic effect of Co(II) on the oxidation of xylenol orange tetra sodium salt by H2O2 in the presence of cationic surfactant (N‐dodecylpyridinium chloride). Co(II) at μg.mL?1 was determined spectrophotometrically by measuring the decrease in the absorbance of xylenol orange at 577 nm by the differential method. The method is precise, selective, and sensitive. The detection limit of the procedure was 0.058 μg.mL?1. The relative standard deviation for the replicate determination (n = 6) of 0.7 μg.mL?1 was 1.285%. The results compared satisfactorily with those of atomic absorption spectrometry. The method was successful for the analysis of Co(II) in veterinary and synthetic samples.  相似文献   
114.
Ru/SiO2 catalysts prepared by reduction of supported RuCl3·xH2O are active in gas-phase hydroformylation of propylene at low pressure (ca. 0.3 MPa) of H2+CO+C3H6 mixtured and show unexpectedly high selectivity towards unbranched oxo-products. Data concerning the effect of electronic state and dispersity of Ru on their catalytic behavior have been obtained.
Ru/SiO2, RuCl3·xH2O, (0,3 ) - . .
  相似文献   
115.
The ultraviolet spectra of Na2 and K2 molecules have been investigated. These studies were made in absorption in the second order of a 3.4 m Ebert Spectrograph with a reciprocal dispersion of 2.6 Å/mm. A number of new bands in the spectra of both the molecules not previously reported have been observed. Computer methods have been used to calculate the term values and to evaluate molecular constants.  相似文献   
116.
117.
Two new oleanane triterpenes; 2alpha,3alpha,24-trihydroxyolean-12-ene-28,30-dioic acid ([structure: see text]) and 2alpha,3alpha,24,28-tetrahydroxyolean-12-ene ([structure: see text]) have been isolated from the roots of Atropa acuminata. Anti-oxidant p-hydroxyphenethyl trans-ferulate ([structure: see text]), beta-sitosterol-3-O-beta-D-glucopyranoside ([structure: see text]) and oleanolic acid ([structure: see text]) have also been reported for the first time from this species. The structures were determined by spectroscopic studies including 2D-NMR.  相似文献   
118.
M. M. Taqui Khan 《Polyhedron》1983,2(12):1247-1260
Dichlorotetrakis(dimethylsulphoxide)ruthenium(II) reacts with AsPh3 AsMePh2, AsMe2Ph and SbPh3 in ethanolic hydrochloric acid solution to yield the complexes RuCl2(DMSO)2(AsPh3)2, RuCl2(DMSO) L2 (L = AsMePh2, AsMe2Ph, SbPh3) respectively. The treatment of ruthenium(II) blue solution with AsMePh2, AsMe2Ph and SbPh3 in alcohol resulted in the formation of the complexes; RuCl2L3 (L = AsMePh2, AsMe2Ph and SbPh2), respectively. The reaction of RuCl2(DMSO)4 with the bidentate ligands 1,2 bis (diphenylarsino)methane (DPAM), 1,2 bis(diphenylarsino)ethane (DPAE) and 1,2 bis (diphenylphosphino)methane (DPPM). 1,2 bis(diphenylphosphino)ethane (DPPE), in ethanol gave the complexes RuCl2(DPAM)2, RuCl2(DPAE)2, RuCl2 (DPPM)2 RuCl2(DPPE)2, respectively. The complexes thus obtained undergo reaction with carbon monoxide, hydrogen, molecular nitrogen and nitric oxide to yield a variety of mixed ligand complexes.  相似文献   
119.
A new phase of ‘organic-inorganic’ composite system, polypyrrole polyantimonic acid, prepared by mixing the inorganic precipitate of hydrated antimony oxide with organic conducting polymer i.e., polypyrrole, providing a novel granular form hybrid cation-exchanger suitable for column operation with better chemical and thermal stability, good ion-exchange capacity, reproducibility and selectivity for heavy metals. The physicochemical properties of this material were studied using elemental analyses, AAS, SEM, XRD, FTIR and simultaneous TGA-DTA studies. Ion-exchange capacity, pH-titrations, elution and distribution behavior were also carried out to characterize the material. Distribution studies revealed the cation-exchange material to be highly selective for Hg(II) and its selectivity was performed by achieving some important binary separations like Hg2+-Zn2+, Hg2+-Ni2+, Hg2+-Cu2+, Hg2+-Fe3+, Hg2+-Cd2+, Hg2+-Mg2+ etc. on its column. Using this electroactive composite material, a new heterogeneous precipitate based selective ion-sensitive membrane electrode was fabricated for the determination of Hg(II) ions in solutions. The membrane electrode is mechanically stable, with a quick response time, and can be operated within a wide pH range. The selectivity coefficients for different cations determined by mixed solution method were found to be less than unity The electrode was also found to be satisfactory in electrometric titrations.  相似文献   
120.
The kinetics of the oxidation of cyclohexanol by molecular O2 catalyzed by Ru(III) and Ru(III)-EDTA complexes has been investigated by oxygen absorption method in the pH range 1.75–3.00 at 30°C (=0.1M KNO3) in a 11 ethanol-water medium. In both cases the reaction was found to be first order with respect to substrate and catalyst concentration. The rate was found to decrease with the decrease of pH in case of Ru(III)-EDTA complex. Ethanol is not oxidized under the reaction conditions. A possible mechanism for the catalytic oxidation of cyclohexanol is proposed.
O2, Ru(III) Ru(III)-EDTA, pH 1,75–3,00 30°C (=0,1M KNO3) - (11). . pH Ru(III)-EDTA. . .
  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