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   2290篇
  免费   84篇
  国内免费   22篇
化学   1305篇
晶体学   11篇
力学   72篇
数学   253篇
物理学   327篇
无线电   428篇
  2023年   8篇
  2022年   88篇
  2021年   87篇
  2020年   85篇
  2019年   76篇
  2018年   77篇
  2017年   71篇
  2016年   134篇
  2015年   58篇
  2014年   75篇
  2013年   192篇
  2012年   133篇
  2011年   117篇
  2010年   98篇
  2009年   87篇
  2008年   93篇
  2007年   88篇
  2006年   93篇
  2005年   67篇
  2004年   60篇
  2003年   54篇
  2002年   52篇
  2001年   36篇
  2000年   42篇
  1999年   33篇
  1998年   34篇
  1997年   32篇
  1996年   29篇
  1995年   15篇
  1994年   20篇
  1993年   17篇
  1992年   19篇
  1991年   14篇
  1990年   9篇
  1989年   12篇
  1988年   10篇
  1987年   7篇
  1986年   10篇
  1985年   19篇
  1984年   14篇
  1983年   19篇
  1982年   12篇
  1981年   13篇
  1980年   11篇
  1979年   7篇
  1978年   11篇
  1976年   6篇
  1975年   10篇
  1974年   7篇
  1973年   6篇
排序方式: 共有2396条查询结果,搜索用时 937 毫秒
991.
Based on dipole moment measurements, a study was made of the keto-enol equilibria of five alpha substituted benzoylacetanilide derivatives in two non-polar and one polar solvents at 30°C. The enol mole fractions of the compounds investigated were determined by analysis of their ultraviolet spectra. The same type of study was extended to salicylanilide for its resemblance to the enol tautomer of these compounds. A deduction of the most probable configurations of the keto and enol forms was tentatively made through a comparison between the dipole moments of some suggested configurations for these forms of benzoylacetanilide and those measured in benzene for the alpha methyl benzoylacetanilide and salicylanilide, respectively. These inferred configurations were used to calculate the dipole moments of both tautomers of the other compounds, and consequently, the dipole moment values of their tautomeric mixtures in dioxane and chloroform. A comparison between the dipole moment values of their tautomeric mixtures in dioxane and chloroform. A comparison between the dipole moment values calculated in this way and those measured indicated a solute-solvent interaction with dioxane, which chloroform behaved as a non-interacting solvent.  相似文献   
992.
The highly chemo- and enantioselective organocatalytic [C+NC+CC] coupling process between aldehydes, dialkyl 2-aminomalonates and α,β-unsaturated aldehydes is presented. The reaction gives access to highly functionalized pyrrolidine derivatives in good yields with >10:1 dr and 90-98% ee.  相似文献   
993.
Simple methods are described for the determination of ethambutol in pharmaceutical preparations. They are based on the reaction of the drug with copper phosphate suspension in a borate buffer of pH 9.2, whereby a blue 11 water-soluble copper-ethambutol complex is quantitatively formed. Four portions of the reaction solution are used for (i) measurement of copper by atomic-absorption spectrometry at 324.7 nm; (ii) potentiometric titration with EDTA with use of a solid-state copper ion-selective electrode; (iii) visual titration with EDTA (copper-PAN indicator); and (iv) spectrophotometric measurement of the copper-ethambutol complex at 640 nm. The results obtained are in good agreement and are better than those of the British Pharmacopoeia (BP) method.  相似文献   
994.
Various mushroom species have been analyzed for their elemental composition (i.e., Al, B, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, P, Sr and Zn) by means of ICP-AES. The accuracy of the measurements was confirmed by analyzing a series of the same samples by short time activation analysis. The data were evaluated statistically including the values of137Cs. The results denote that the distribution of these elements and their correlation of these elements and their correlation coefficients are highly distinctive for each mushroom species. K, Na and P were found to correlate negatively with137Cs in most species. Suillus grevillei and Cantharellus cibarius show high Be values (0.27 and 0.30 g g–1, respectively), while Pb was high in Suillus grevillei (16.3 g g–1) and Amanita rubescens (9.3 g g–1). Higher levels of Cd were found in Rozites caperata and Russula vesca with a mean of 9.2 and 16.1 g g–1, respectively. Cluster analysis was applied to classify these samples according to their botanical species using their elemental composition. The concentrations of Al, Cr, Mn, Na and137Cs have no influence on the classification of these samples.  相似文献   
995.
Rapid potentiometric methods were given for determination of some sulfide and chromate pigments in pure as well as adulterated samples. The methods are based on oxidation of S2? or Cr3+ with known excess of KBrOs3 to the corresponding (S ↓) or Cr6?. Oxidation of trivalent chromium proceeds only toward completion in presence of a catalyst such as Co2+. Sulfide oxidation needs gradual liberation of H2S—which can be achieved by dropwise additions of the acid—together with the presence of excessive amount of water, in order to obtain accurate results excess oxidant was subsequently reduced with SO2 to produce Br? that can be titrated against Hg(I). The potential breaks are quite sharp for accurate determination of the equivalent points.  相似文献   
996.
铜及其配合物在生物体系中的作用   总被引:8,自引:0,他引:8  
自人类有历史记载以来,铜及其配合物即用作药物。铜是人体必需的金属元素。人体的正常代谢过程需要它们,但无法体内合成,因此,需要每天从饮食摄取和吸收。生物药学家和研究者以极大的努力彻底地了解铜及其配合物在生物体系中的作用,希望获得更多地信息以利于人类疾病的预防和治疗。本综述评述了铜在组织中的分配和代谢、铜依赖酶、在病态时铜的非正常代谢、铜配合物的药疗活性和抑制氧自由基的产生。  相似文献   
997.
Telecommunication Systems - Millimeter wave (mm-wave) communication is one of the key enabling technologies for meeting the requirements of the fifth generation (5G) wireless communication systems....  相似文献   
998.
The T—silyl functionalized diamine‐bis(ether‐phosphine)ruthenium(II) complexes 1a(T ° ) — 1g(T ° ) (Scheme 1) were sol‐gel processed in the presence of different amounts of the co‐condensation agents CH3Si(OMe)3 (Me—T ° ) and (MeO)2SiMe—(CH2)6—MeSi(OMe)2 (D ° —C6—D ° ) to produce a library of the interphase catalysts X1a — X1c , X2a — X2g , and X3a — X3g . Due to the remarkable electronic and steric effects of the co‐ligands on the catalytic activity of such complexes, a series of aliphatic and aromatic diamines was selected. The new polymers were investigated by multinuclear CP/MAS solid‐state NMR spectroscopy as well as by EXAFS, EDX, SEM, and BET methods. Selected interphase catalysts show high activities and selectivities in the hydrogenation of trans‐4‐phenyl‐3‐butene‐2‐one.  相似文献   
999.
A novel vic-dioxime, 1,2 dihydroxyimino-1-p-tolyl-3-aza-6-morpholine heptane (LH2) was prepared by reacting anti-p-tolylchloroglyoxime with 4-(3-aminopropyl)morpholine in absolute THF. Mononuclear complexes with a metal–ligand ratio of 1:2 were prepared using CoII, CuII and NiII salts. The ligand and its complexes were characterized by elemental analyses, FT-IR, u.v.–vis., 1H- and 13C-n.m.r. spectra, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.), and by cyclic voltammetry.  相似文献   
1000.
A sensitive and highly selective spectrophotometric method is described for the determination of cyanide. It is based on a reaction of cyanide with aquacyanocobyrinic acid heptamethyl ester (ACCbs) reagent (orange color) at pH 9.5 to give dicyanocobester (DCCbs) (violet color). The increase of the absorption bands of the reaction product at 368 and 580 nm and the decrease of the reagent band at 353 nm are linearly proportional to the cyanide concentration. The method is used in static mode for determining cyanide over the concentration range 0.04-1.20 μg ml−1 with a detection limit of 0.02 μg ml−1 and for hydrodynamic analysis of 0.4-5.2 μg ml−1 cyanide. Application for batch and flow injection monitoring of cyanide in electroplating wastewater samples gives results agree within ± 1.2% with those obtained by the standard potentiometry using the cyanide ion selective electrode. The method is practically free from interferences by PO43−, NO3, NO2, SO42−, F, Cl, Br, I, S2− and SCN ions and gives results with average recoveries of 97.6-99.2%. Advantages offered by using ACCbs as a chromogen for cyanide assay are: (i) high selectivity and sensitivity of the coordination site of the reagent towards cyanide ion; (ii) fast reaction, since legation takes place at the axial position of the reagent; (iii) good solubility and stability of the reagent in aqueous solutions over a wide pH range; (iv) high stability of the reagent (ACCbs) and the colored complex product (DCCbs) and (v) possible absorbance measurements at three different wavelengths.  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