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   34801篇
  免费   5969篇
  国内免费   4875篇
化学   25469篇
晶体学   520篇
力学   2014篇
综合类   441篇
数学   3938篇
物理学   13263篇
  2024年   30篇
  2023年   709篇
  2022年   850篇
  2021年   1197篇
  2020年   1495篇
  2019年   1414篇
  2018年   1178篇
  2017年   1206篇
  2016年   1676篇
  2015年   1623篇
  2014年   2030篇
  2013年   2595篇
  2012年   3161篇
  2011年   3188篇
  2010年   2313篇
  2009年   2230篇
  2008年   2468篇
  2007年   2212篇
  2006年   2102篇
  2005年   1688篇
  2004年   1319篇
  2003年   1081篇
  2002年   960篇
  2001年   814篇
  2000年   731篇
  1999年   773篇
  1998年   657篇
  1997年   538篇
  1996年   504篇
  1995年   465篇
  1994年   422篇
  1993年   377篇
  1992年   311篇
  1991年   274篇
  1990年   273篇
  1989年   189篇
  1988年   137篇
  1987年   93篇
  1986年   111篇
  1985年   77篇
  1984年   40篇
  1983年   44篇
  1982年   39篇
  1981年   22篇
  1980年   9篇
  1979年   7篇
  1976年   2篇
  1975年   2篇
  1959年   2篇
  1957年   4篇
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
991.
Fan C  Gao Q  Zhu D  Wagner G  Li G 《The Analyst》2001,126(7):1086-1089
Hemoglobin was incorporated in a montmorillonite membrane. Electrochemical and spectroscopic studies revealed that the electron transfer reactivity and peroxidase activity of the protein were both enhanced. Nevertheless, its structure was still maintained native-like in the membrane. An unmediated hydrogen peroxide biosensor was accordingly prepared. The calibration plot of this H202 sensor was linear in the range of 1.0 x 10(-6)-6.0 x 10(-4) mol L(-1). The relative standard deviation was 3.1% for six successive determinations at a concentration of 1.0 x 10(-4) mol L(-1). The detection limit was 6.0 x 10(-7) mol L(-1). Possible interferences in real sample analyses are discussed.  相似文献   
992.
1-三甲硅氧基膦酸酯是一类具有显著生物活性的有机硅磷化合物。具有药效长、毒性低等特点,采用含P—O—Si键的亚磷酸酯与羰基化合物反应的方法进行合成,反应条件温和,产率比较高,但需要先制备化学性质活泼的含硅基亚磷酸酯,而且反应要在惰性气体下进行,实施有所不便。本文直接采用三烷基亚磷酸酯(1)、α、β-不饱和醛(2)与三甲基氯硅烷进  相似文献   
993.
Cu-Mg/Al复合氧化物催化碳颗粒物燃烧性能的研究   总被引:5,自引:0,他引:5  
恒定二价与三价阳离子比为3(nM2+/nM3+=3),采用共沉淀法制备不同Cu含量的系列水滑石前驱物, 800 ℃焙烧4 h形成复合氧化物(CuO质量百分数分别为0%、5%、10%、15%、20%、30%、40%)用作柴油车排放碳颗粒物燃烧的催化剂,并采用XRD、BET、TG-DSC、FT-IR、TPR等表征手段研究了Cu、Mg含量对材料前驱物物化性能的影响及对其衍生复合氧化物催化碳颗粒物燃烧性能的影响.结果表明,Cu、Mg含量对材料的热稳定性、比表面和催化氧化活性有显著的影响. Mg有助于提高催化剂的热稳定性; Cu含量增加,催化剂比表面下降,但比表面不是影响催化剂活性的主要因素. CuO含量为15%时,催化剂具有最好的催化活性和稳定性,碳颗粒物的起燃温度(T10)和半转化温度(T50)分别为336 ℃和409 ℃.在CuO含量≤30%时可以形成结构完整的水滑石前驱物, CuO含量为40%时出现Cu(OH)2杂相; CuO含量< 20%时,经高温焙烧可得到均匀的复合氧化物, CuO含量≥20%时出现CuO偏析. TPR结果表明焙烧温度和复合氧化物的组成决定了材料的可还原性能.  相似文献   
994.
Xue J  Wu J  Guo Z 《Organic letters》2004,6(9):1365-1368
[reaction: see text] A new one-step reaction has been developed for converting 4-azido-4-deoxy-d-galactoside into 4-deoxy-d-erythro-hexos-3-ulose by phosphoramidites and tetrazole. It is proposed that the new reaction proceeds via an intramolecular Staudinger reaction of the phosphite intermediate and a tetrazole-catalyzed elimination reaction of the resultant phosphorimidate. Tetrazole appears to be playing a unique role by acting as a bifunctional catalyst to facilitate the elimination reaction.  相似文献   
995.
Anilinium is strongly adsorbed at monolayers of the phospholipid L-alpha-dimyristoylphosphatidic acid (DMPA) and hexadecanesulfonic acid (HDSA) at the air-water interface, and undergoes chemical polymerisation under conditions where bulk polymerisation does not occur.  相似文献   
996.
Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry (APCI-LC/MS) has been used for identification of the epimers of hydroxy, methoxy and methoxylactone allomers of chlorophyll a (13(2)-HO-chl a, 13(2)-MeO-chl a and 15(1)-MeO-lact-chl a), the hydroxy allomer of bacteriochlorophyll a (13(2)-HO-bchl a) and the hydroxy and methoxylactone allomers of bacterioviridin a (13(2)-HO-bvir a and 15(1)-MeO-lact-bvir a). The APCI mass spectra show that facile fragmentations involve the methoxyl or hydroxyl groups at the C-13(2) or C-15(1) chiral centres. Losses involving the C-13(2) or C-15(1) hydroxyl or methoxyl groups occur more easily from the S-epimer than from the R-epimer due to the greater relief of the steric strain associated with interaction with the bulky C-17 substituent. The differences in mass spectrometric fragmentation can be used as a diagnostic tool for the assignment of the stereochemical configuration at the C-13(2) or C-15(1) chiral centres.  相似文献   
997.
Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2) containing salicyl fluorones (THBF), Pb(CMC)2-THBF were synthesized by the sol-gel method, using sodium carboxymethyl cellulose (NaCMC) as precursor and Pb2+ as precipitant. Pb(CMC)2-THBF can emit the intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. And EDTA can chelate Pb2+ in Pb(CMC)2-THBF, causing it to decompose into aqueous soluble components PbY2-, CMC- and THBF, which can react with Ag+ to form Ag(CMC)2-THBF, causing the decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace silver by SS-RTP quenching method was established. The linear range of this method is 8.0-40.0 fg spot(-1) (20.0-100.0 pg ml(-1)), with a detection limit (LD) of 2.2 fg spot(-1) (corresponding to a concentration range of 5.5 x 10(-13) g ml(-1)), and the regression equation of working curve is DeltaI(p) = 12.56 + 0.5527C(Ag+) (fg spot(-1), 0.4 microl spot(-1)), n = 8, r = 0.9992. This method has been applied to the determination of trace silver in human hair and tea sample with satisfactory results. The mechanism of SS-RTP emission is also discussed.  相似文献   
998.
An in situ photochemical fluorescence probe method for the determination of DNA with sodium 9,10-anthraquinone-2-sulfonate (AQS) as a photochemical fluorescence probe was developed. It was based on the conversion of AQS into an intensively fluorescent product by irradiating with UV radiation. The photochemical reaction is retarded by DNA. The determination can be carried out by measuring the fluorescence intensity at a fixed time. The calibration graph was linear in the range 0–80 ng ml−1 calf thymus (CT) DNA (r = 0.9991), the limit of detection was 3.2 ng ml−1 CT DNA (n = 9). The kinetic behaviour of the photochemical reaction and the effects of experimental conditions were investigated and discussed in detail. The results of absorption spectra and competitive binding experiments suggested the interaction between AQS and DNA to be intercalative.  相似文献   
999.
用金属钾、金属钠以及氢氧化钠水溶液等方法制备聚苯乙烯负载聚乙二醇,结果表明,采用金属钾比金属钢具有更好的接枝效果,并能使反应在较低的温度下较快进行。在氢氧化钠溶液中添加少量相转移剂,如Bu4NBr,接枝效果也有所提高。以聚苯乙烯负载聚乙二醇和KI一起为催化剂,研究了溶剂、温度等因素对CO2与环氧丙烷合成碳酸亚丙酯催化活性的影响。结果表明,以甲醇为溶剂催化活性较高。研究还表明,聚苯乙烯负载聚乙二醇具有较好的热稳定性,可以在150℃下重复使用至少5次。  相似文献   
1000.
IntroductionDimethyl carbonate(DMC) is known to be a novelbuilding block in organic synthesis. As an environmen-tally benign compound and a unique intermediate,DMC has attracted much attention[1,2]. Among the va-rious methods for synthesizing DMC, the tra…  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