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   38832篇
  免费   7038篇
  国内免费   4924篇
化学   29000篇
晶体学   484篇
力学   2202篇
综合类   246篇
数学   4157篇
物理学   14705篇
  2024年   92篇
  2023年   730篇
  2022年   1070篇
  2021年   1370篇
  2020年   1605篇
  2019年   1674篇
  2018年   1390篇
  2017年   1278篇
  2016年   1927篇
  2015年   1909篇
  2014年   2408篇
  2013年   3000篇
  2012年   3653篇
  2011年   3707篇
  2010年   2505篇
  2009年   2437篇
  2008年   2717篇
  2007年   2370篇
  2006年   2190篇
  2005年   1839篇
  2004年   1472篇
  2003年   1123篇
  2002年   1171篇
  2001年   927篇
  2000年   730篇
  1999年   762篇
  1998年   660篇
  1997年   614篇
  1996年   586篇
  1995年   494篇
  1994年   421篇
  1993年   332篇
  1992年   323篇
  1991年   268篇
  1990年   249篇
  1989年   178篇
  1988年   124篇
  1987年   94篇
  1986年   121篇
  1985年   87篇
  1984年   43篇
  1983年   51篇
  1982年   32篇
  1981年   25篇
  1980年   9篇
  1979年   3篇
  1977年   3篇
  1975年   2篇
  1957年   4篇
  1936年   7篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
981.
The voltammetric behavior of uric acid was studied at a single-walled carbon nanotube (SWNT) modified gold electrode. Uric acid can effectively accumulate at this electrode and produce an anodic peak at about 0.45 V (vs. SCE) in pH 5.0 sodium acetate buffer solutions (HAc-NaAc). The experimental parameters, such as solution pH, accumulation time, and amount of SWNT, were optimized for determination. Under the optimum conditions, the anodic peak current is linear to the uric acid concentration over the range of 1.0×10−7 M to 2.5×10−5 M with a correlation coefficient of 0.998. The detection limit was 5.0×10−8 M for 60 s accumulation. The electrode could be easily regenerated and exhibited good stability. A 5.0×10−6 M uric acid solution was measured ten times using the same electrode, and the relative standard deviation of the peak current was 1.3%. This method was successfully applied to the determination of uric acid in human urine samples, and the recovery was 97–99%. The feasibility for simultaneous determination of xanthine, ascorbic acid and uric acid was discussed. These species did not interfere with each other in a certain concentration range. The influence of some surfactants on the anodic peak was also examined.  相似文献   
982.
Wang XS  Zhao H  Qu ZR  Ye Q  Zhang J  Xiong RG  You XZ  Fun HK 《Inorganic chemistry》2003,42(19):5786-5788
The reaction of Cu(I)(CH(3)CN)(4)BF(4) with 4-pyridylacrylic acid (4-HPYA) affords an unprecedented 8-fold interpenetrating diamondoid-like coordination polymer network [Cu(I)(3)(4-PYA)(2)(H(2)O)(BF(4)) ] (1) with a Cu(+)(4)(CO(2))(4) cluster as connecting node. The interpenetration in metal coordination polymers is the highest degree ever found within diamondoid nets containing a cluster as connecting note. Its fluorescent property was also reported.  相似文献   
983.
An ionic liquid (i.e., 1‐butyl‐3‐methylimidazolium hexafluorophosphate, BMIMPF6)‐single‐walled carbon nanotube (SWNT) gel modified glassy carbon electrode (BMIMPF6‐SWNT/GCE) is fabricated. At it the voltammetric behavior and determination of p‐nitroaniline (PNA) is explored. PNA can exhibit a sensitive cathodic peak at ?0.70 V (vs. SCE) in pH 7.0 phosphate buffer solution on the electrode, resulting from the irreversible reduction of PNA. Under the optimized conditions, the peak current is linear to PNA concentration over the range of 1.0×10?8–7.0×10?6 M, and the detection limit is 8.0×10?9 M. The electrode can be regenerated by successive potential scan in a blank solution for about 5 times and exhibits good reproducibility. Meanwhile, the feasibility to determine other nitroaromatic compounds (NACs) with the modified electrode is also tested. It is found that the NACs studied (i.e., p‐nitroaniline, p‐nitrophenol, o‐nitrophenol, m‐nitrophenol, p‐nitrobenzoic acid, and nitrobenzene) can all cause sensitive cathodic peaks under the conditions, but their peak potentials and peak currents are different to some extent. Their peak currents and concentrations show linear relationships in concentration ranges with about 3 orders of magnitude. The detection limits are 8.0×10?9 M for p‐nitroaniline, 2.0×10?9 M for p‐nitrophenol, 5.0×10?9 M for o‐nitrophenol, 5.0×10?9 M for m‐nitrophenol, 2.0×10?8 M for p‐nitrobenzoic acid and 8.0×10?9 M for nitrobenzene respectively. The BMIMPF6‐SWNT/GCE is applied to the determination of NACs in lake water.  相似文献   
984.
Gui-Ling Zhao 《Tetrahedron》2005,61(30):7277-7288
This paper describes several highly efficient DABCO-catalyzed aza-Michael addition reactions of hydrazones to activated olefins. In most cases, these aza-Michael addition reactions gave the corresponding products in high yields under mild conditions. The plausible reaction mechanism is discussed on the basis of deuterium labeling experiments. Upon treatment with HCl, the corresponding cyclized products can be obtained in high yields from the Michael addition products.  相似文献   
985.
With the accomplishment of Human Genome Project (HGP), single nucleotide polymorphism (SNP) and mutation detection in human genome are becom-ing a new researching focus. These researches can help us to understand the phenotype diversity of indi-vidual, disease susceptibility and drug resistance of different colonies. Traditional method used for muta-tion detection is slab gel electrophoresis, which re-mains labor-intensive and time-consuming because of the requirement of radioactivity or te…  相似文献   
986.
A glassy carbon electrode (GCE) was modified with electropolymerized films of amidosulfonic acid in pH 7.0 phosphate buffer solution (PBS) by cyclic voltammetry (CV). The modified electrode showed an excellent electrocatalytical effect on the oxidation of dopamine (DA). In pH 7.0 PBS, the anodic peak current increased linearly with the concentration of DA in the range of 5.0×10–7 1.0×10–4moldm–3, with a correlation coefficient of 0.9932, and a detection limit (S/N=3) of 1.0× 10–7moldm–3. The relative standard deviation of 10 successive scans was 2.5% for 1.0×10–6moldm–3 DA. The interference of ascorbic acid (AA) with the determination of DA could be eliminated because of the very distinct attracting interaction between DA cations and the negatively poly(amidosulfonic acid) film in pH 7.0 PBS. The proposed method exhibited good recovery and reproducibility.  相似文献   
987.
邻位吡啶自由基多通道分解反应的动力学和反应机理研究   总被引:1,自引:0,他引:1  
Utilizing Gaussian94 program package, all species involved in decomposition reactions of o-pyridyl radical were optimized fully at B3LYP/6-311++G^** level. Intrinsic reaction coordinate calculations were employed to confirm the connections of the transition states and products, and transition states were ascertained by the number of imaginary frequency (0 or 1). The reaction mechanism was elucidated by the vibrational mode analysis and electronic population analysis, and the reaction rate constants were calculated with transition state theory.  相似文献   
988.
Reactions of the substituted 2‐formyl chromones with aroylhydrazines gave corresponding 2‐(aroylhydrazonomethylidyne) chromones. Then 2‐(3′‐acetyl‐5′‐aryl‐2′,3′‐dihydro‐1′,3′,4′‐oxadiazol‐2′‐yl) chromones were prepared by these 2‐(aroylhydrazonomethylidyne) chromones under refluxing with Ac2O. All target compounds were characterized through elemental analysis and IR, 1H NMR, MS.  相似文献   
989.
A flow injection (FI) method with a biamperometric detector, based on the biamperometry for an irreversible redox couple, is described for the determination of phenols in environmental wastewater. The method relies on coupling of the oxidation of phenols at one platinum-wire electrode with the reduction of MnO4- at another platinum wire electrode to enable biamperometric detection with an applied potential difference of 0 V. The linear dynamic range for the dependence of current on phenol concentration was from 1.0 x 10(-6) to 1.0 x 10(-4) mol L(-1), with a detection limit of 4.0 x 10(-7) mol L(-1) (signal-to-noise ratio, S/N=3). In comparison with the 4-aminoantipyrine (4-AAP) standard method and the 3-methyl-2-benzothiazoline hydrazone (MBTH) method the proposed method can be used to detect many para-substituted phenols that do not react with 4-AAP and MBTH, and response factors are higher for most of the phenols tested. The method, which is simple, economic, and rapid (180 samples h(-1)), has been applied to the analysis of four wastewater samples. The results obtained were compared with those from 4-AAP method. The recoveries obtained by adding phenol standards to samples ranged from 94.3 to 105.2% with a standard deviation of 3.6%.  相似文献   
990.
Two-photon excitation studies of hypocrellins for photodynamic therapy   总被引:8,自引:0,他引:8  
The photophysical and photochemical properties of hypocrellins (HA and HB) are examined with two-photon excitations at 800 nm using femtosecond pulses from a Ti:sapphire laser. The two-photon excited fluorescence spectra of HA and HB are very similar to those obtained by one-photon excitation, which may indicate that the two-photon induced photodynamic processes of hypocrellins are similar to one-photon induced photodynamic processes. The two-photon excitation cross sections of HA and HB are measured at 800 nm as about 34.8 x 10(-50) cm(4) s/photon and 21.3 x 10(-50) cm(4) s/photon, respectively. The large two-photon cross sections of both HA and HB, suggest that the hypocrellins can be potential two-photon phototherapeutic agents. As an example for two-photon photodynamic therapy of hypocrellins, we also further examine the cell-damaging effects of HA upon two-photon illumination. Our preliminary results of cell viability test indicate hypocrellins can effectively damage the Hela cells under two-photon illumination.  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