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   14420篇
  免费   2785篇
  国内免费   1795篇
化学   10628篇
晶体学   228篇
力学   836篇
综合类   141篇
数学   1554篇
物理学   5613篇
  2024年   60篇
  2023年   403篇
  2022年   659篇
  2021年   768篇
  2020年   751篇
  2019年   702篇
  2018年   600篇
  2017年   523篇
  2016年   744篇
  2015年   878篇
  2014年   973篇
  2013年   1119篇
  2012年   1348篇
  2011年   1338篇
  2010年   886篇
  2009年   923篇
  2008年   1004篇
  2007年   843篇
  2006年   765篇
  2005年   600篇
  2004年   468篇
  2003年   370篇
  2002年   342篇
  2001年   257篇
  2000年   236篇
  1999年   224篇
  1998年   197篇
  1997年   160篇
  1996年   153篇
  1995年   125篇
  1994年   93篇
  1993年   75篇
  1992年   68篇
  1991年   48篇
  1990年   40篇
  1989年   36篇
  1988年   34篇
  1987年   35篇
  1986年   32篇
  1985年   24篇
  1984年   25篇
  1983年   7篇
  1982年   6篇
  1981年   5篇
  1980年   11篇
  1979年   5篇
  1976年   9篇
  1971年   3篇
  1966年   3篇
  1957年   3篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
61.
Wang CH  Chen SM  Wang CM 《The Analyst》2002,127(11):1507-1511
The anodic polymerization of 3-aminophthalhydrazide (luminol) and iron(II) tris 5-aminophenanthroline (Fe(phen-NH2)3(2+)) has been reported in this paper. A bilayer electrode was developed based on these polymers and the ITO conductive glass (denoted ITO[Fe(phen-NH2)3(2+)]luminol electrode). This electrode emitted light (lambdaem: 430 nm) as it was brought into contact with H2O2. At pH 10, the resulting electrochemiluminescence (ECL) showed a linear relationship with the concentration of H2O2 in the range of 10 microM(-1) mM. This bilayer electrode also showed an application potential for the detection of glucose after being further modified with glucose oxidase (denoted ITO[Fe(phen-NH2)3(2+)]luminol]GOx electrode). Although the resulting ECL decayed more rapidly in concentrated glucose solutions (e.g., I M) because of the consumption of luminol during use, the decay became less severe in diluted glucose solutions (e.g., 10 mM). According to the flow injection analysis, a linear relationship existed between the ECL and the concentration of glucose from 10(-5)-10(-3) M at pH 9. The detection limit could reach a level of 5 x 10(-5) M at this pH.  相似文献   
62.
Zhang X  Liao Y  Qian R  Wang H  Guo Y 《Organic letters》2005,7(18):3877-3880
Reaction solutions of selectfluor (1) with triphenylethylene (4a) and tetraphenylethylene (4b) were monitored by ESI-MS and ESI-MS/MS. Detection and characterization of the key radical cationic intermediates 5a.+ and 5b.+) fully supports the SET mechanism in electrophilic fluorination as depicted above. [reaction: see text]  相似文献   
63.
利用正交法对丁苯橡胶(SBR)/聚丙撑碳酸酯(PPC)共混弹性体进行配方设计,得到了一个具有良好综合性能的配方。并通过方差分析得出PPC含量和马来酸酐(MA)用量是影响弹性体拉伸性能的最显著因素。  相似文献   
64.
Wu Y  Hu B  Peng T  Liao Z  Jiang Z 《Talanta》2001,55(4):841-845
Based on gaseous compound introduction as 1-phenyl-3-methyl-4-benzoylpyrazolone[5](PMBP) chelate of aluminum by electrothermal vaporization in ICP-AES, a method for determination of trace aluminum was developed. Trace aluminum was vaporized at temperature of 1000 degrees C, and the vaporization behavior of aluminum chelate was detailedly investigated. Under the optimum conditions, the detection limit of aluminum was 0.6 ng ml(-1), and the relative standard deviation for 0.1 mug ml(-1) aluminum was 4.7% (n=8). The proposed method was applied to the determination of trace aluminum in rice flour reference materials, and the results well agreed with the reference values.  相似文献   
65.
A novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H2O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H2O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py.  相似文献   
66.
1 INTRODUCTION Nonlinear optics (NLO) is at the forefront of cur- rent researches because of its importance in provi- ding the key functions of frequency shifting, optical modulation, optical switching, optical logic and op- tical memory for the emerging …  相似文献   
67.
提出了一个基于局部组成概念上的核磁共振模型. 利用该模型和以前别人提出的局部组成型粘度方程, 成功地同时关联属于传递性质的粘度数据和属于波谱性质的核磁共振化学位移数据,关联所得到化学位移的平均绝对偏差小于0.0072,粘度的平均绝对偏差小于0.0006 mPa•s,结果表明提出的局部组成模型是合理的.  相似文献   
68.
氮化铁催化剂的制备及其苯胺催化加氢性能   总被引:4,自引:0,他引:4  
用α-Fe2O3与氨气程序升温还原方法制备出不同温度氮气的氮化铁系列催化剂。通过XRD测试对氮化过程中的晶相转变进行了分析。在中压反应装置上考察了氮化铁系列催化剂上苯胺加氢活性以及反应条件对苯胺加氢反应活性的影响。结果表明,在700℃氮化制香的氮化铁催化剂显示有较高的苯胺加氢活性,在氢压为3.0MPa,温度为250℃,n(H2)/n(oil)=18,液体空速(WHSV)为0.3h^-1时,该催化剂  相似文献   
69.
Diels-Alder reactions of six o-benzoquinones with dimethyl acetylenedicarboxylate has been examined. The yields of adducts vary with the natures of the o-benzoquinones, 3,4-Di-n-propyl-(1c), 3,6-di-n-propyl (1d). 3. 4-diallyl-(1e) and 3, 6-diallyl-o-benzoquinone (1f) are found to give bicyclic a-diketones exclusively without the formation of 1,4-dioxine derivatives, the yields ranging from 20 to 70%. In the case of 4, 5-dimethoxy-o-benzoquinone, dimethyl 4, 5-dimethoxyphthalate is produced in 42% yield, presumably derived from the decomposition of the corresponding initially formed α-diketone. 3, 6-Di-n-propyl-4, 5-dimethoxy-o-benzoquinone deteriorates without addition to dimethyl acetylenedicarboxylate upon heating. The additions of o-benzoquinones 1c , 1d and 1f to phenylacetylene are also studied. The yields of adducts, α-diketones, range from 23% to 82%.  相似文献   
70.
A novel and convenient route for the synthesis of biologically potent and rare L-hexose derivatives from D-glucose is described. Conversion of diacetone-alpha-D-glucose (14) into 1,2:3,5-di-O-isopropylidene-beta-L-idofuranose (19) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6-di-O-isopropylidene-beta-L-idofuranose (27), which underwent regioselective epimerization at the C3 position to give the L-talo- and 3-functionalized L-idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6-anhydro-beta-L-idopyranose (35) in excellent yield, which was successfully transformed into the corresponding L-allo, L-altro, L-gulo, and L-ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6-anhydro-beta-L-hexopyranoses as valuable building blocks to the syntheses of 4-methylcoumarin-7-yl-alpha-L-iduronic acid and the disaccharide moieties of bleomycin A(2) as well as heparan sulfate are highlighted.  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