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   55944篇
  免费   9141篇
  国内免费   5922篇
化学   39638篇
晶体学   692篇
力学   3213篇
综合类   343篇
数学   6267篇
物理学   20854篇
  2024年   185篇
  2023年   1150篇
  2022年   2137篇
  2021年   2244篇
  2020年   2356篇
  2019年   2246篇
  2018年   1912篇
  2017年   1847篇
  2016年   2728篇
  2015年   2786篇
  2014年   3253篇
  2013年   4166篇
  2012年   5115篇
  2011年   5035篇
  2010年   3499篇
  2009年   3292篇
  2008年   3559篇
  2007年   3132篇
  2006年   2809篇
  2005年   2429篇
  2004年   1847篇
  2003年   1486篇
  2002年   1380篇
  2001年   1079篇
  2000年   938篇
  1999年   1086篇
  1998年   890篇
  1997年   830篇
  1996年   820篇
  1995年   754篇
  1994年   639篇
  1993年   533篇
  1992年   449篇
  1991年   409篇
  1990年   347篇
  1989年   250篇
  1988年   183篇
  1987年   174篇
  1986年   166篇
  1985年   150篇
  1984年   95篇
  1983年   98篇
  1982年   60篇
  1981年   42篇
  1980年   54篇
  1978年   31篇
  1977年   66篇
  1976年   38篇
  1975年   39篇
  1973年   22篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
951.
抗坏血酸-铁(Ⅱ)络合反应在薄层色谱板上的吸收光谱   总被引:1,自引:0,他引:1  
本文利用薄层色谱板上吸收光谱研究了抗坏血酸与铁(Ⅱ)离子在不同pH值和不同配比溶液中络合反应情况,并对抗坏血酿-铁(Ⅱ)螯合物的结构进行了探讨。  相似文献   
952.
随着油田深部调剖应用的不断推广,以及环保要求的提高,适用于深部调剖调驱体系的低污染有机锆交联剂逐渐受到关注。以ZrOCl2·8H2O、乳酸、乙二胺、硫脲为原料,制备了有机锆交联剂和HPAM-锆交联凝胶,其结构和性能经SEM和岩心驱替装置表征。并利用正交实验法优化了制备条件。结果表明:制备有机锆交联剂的最佳条件为:氧氯化锆、乳酸、乙二胺及硫脲的质量比为7.8/1/6.7/5,反应温度为70 ℃,反应时间为3 h。交联温度为60 ℃,HPAM浓度为2 g·L-1、聚锆比为30/1时,聚合物凝胶成胶强度达到24968 mPa·s,成胶时间约8 h,凝胶体系可维持90 d不破胶。在级差为3.9的双管驱替岩心实验中,两管的岩心分流率均接近50%,剖面改善率达到66.77%。  相似文献   
953.
Metal–organic frameworks constructed from multiple (≥3) components often exhibit dramatically increased structural complexity compared to their 2 component (1 metal, 1 linker) counterparts, such as multiple chemically unique pore environments and a plurality of diverse molecular diffusion pathways. This inherent complexity can be advantageous for gas separation applications. Here, we report two isoreticular multicomponent MOFs, bMOF-200 (4 components; Cu, Zn, adeninate, pyrazolate) and bMOF-201 (3 components; Zn, adeninate, pyrazolate). We describe their structures, which contain 3 unique interconnected pore environments, and we use Kohn–Sham density functional theory (DFT) along with the climbing image nudged elastic band (CI-NEB) method to predict potential H2/CO2 separation ability of bMOF-200. We examine the H2/CO2 separation performance using both column breakthrough and membrane permeation studies. bMOF-200 membranes exhibit a H2/CO2 separation factor of 7.9. The pore space of bMOF-201 is significantly different than bMOF-200, and one molecular diffusion pathway is occluded by coordinating charge-balancing formate and acetate anions. A consequence of this structural difference is reduced permeability to both H2 and CO2 and a significantly improved H2/CO2 separation factor of 22.2 compared to bMOF-200, which makes bMOF-201 membranes competitive with some of the best performing MOF membranes in terms of H2/CO2 separations.

Tailorable multicomponent MOFs and MOF membranes for efficient H2/CO2 separation.  相似文献   
954.
董玉林  杨孔章 《催化学报》1994,15(3):225-228
2,6—二甲基吡啶在Y型分子筛的Bronsted和Lewis酸中心上的吸附动力学董玉林,杨孔章(山东大学胶体与界面化学研究所,济南250100)关键词Y型分子筛,酸中心,Lewis酸中心,2,6—二甲基吡啶,吸附动力学沸石分子筛是一类固体酸催化剂,在...  相似文献   
955.
The influence of natural organic matter (NOM) constituents on contaminant distribution coefficients was evaluated by determining the Koc values of aromatic and aliphatic organic compounds (solutes) with clays modified with both aromatic- and aliphatic-rich organic constituents. The studied compounds consisted of naphthalene, phenanthrene, n-pentane, and 2,3,4-trimethylmethane; the solid samples comprised two clays with little organic content, kaolinite and Ca-montmorillonite. Two aliphatic surfactants and three aromatic dyes, sorbed to the clays, served as reference NOM constituents. For solutes of comparable water solubilities, the organic-carbon normalized distribution coefficients (Koc) of the aliphatic solutes between sorbed aliphatic organic matter and aqueous solution slightly exceed those of the aromatic solutes. By contrast, the aromatic solutes exhibited higher Koc values than did the aliphatic compounds with sorbed aromatic-rich organic matter. The difference in Koc values could be attributed to either comparable solubility parameters or the difference in the chemical structure between nonionic organic solutes and specific components of the simulated NOM. The much higher Koc values observed for the aromatic solutes indicate that the NOM composition is a major factor determining the NOC environmental distribution.  相似文献   
956.
We describe the two-dimensional (2D) assemblies of N,N'-dialkyl-substituted quinacridone derivatives on highly orientated pyrolytic graphite observed by scanning tunneling microscopy, and focus our discussion on whether the supramolecular organization can be modulated by the coadsorption of dicarboxylic acids. Our experiments have demonstrated that the quinacridone derivatives can form different 2D nanostructures when coadsorbed with dicarboxylic acids of different length at the liquid/graphite interface. Interestingly, N,N'-dihexadecyl-substituted quinacridone derivative alternately takes two different conformations in two columns for its coadsorption with pentadecanedioic acid and form a gridlike structure. It is shown that a cooperative effect of different interactions can be modulated by introducing guest molecule, leading to formation of different self-assembled nanostructures.  相似文献   
957.
High-quality CdSxSe1-x nanobelts of variable composition (0 相似文献   
958.
Zhang S  Huang F  Cao X  Yang P  Zhang W  Jin L 《The Analyst》2002,127(4):485-489
Microdialysis sampling coupled with liquid chromatography-electrochemical detection (LC-ED) was developed and applied to determine the interaction of thiopurine (TP) with bovine serum albumin (BSA). A nickel hexacyanoferrate (NiHCNFe) modified electrode was fabricated and used as the working electrode in LC-ED for the determination of TP. Cyclic voltammetric experiments demonstrate that this chemically modified electrode (CME) can effectively catalyze the electrooxidation of TP. The mechanism of the catalytic oxidation of TP at the CME involves an 'EC' process. In the LC-ED, the CME also shows good stability and reproducibility for the determination of TP. The limit of detection is 5.0 x 10(-7) mol l(-1) for 6-TP with a signal-to-noise ratio of 3. The utility of microdialysis as a quantitative sampling technique for in vitro studies of drug-protein interactions was studied. The microdialysis experiments were performed in phosphate buffer solution (pH 7.4) containing different molar ratios of the drug and protein at 37 degrees C. The collected microdialysis sample with unbound TP was analyzed at the NiHCNFe CME in the LC-ED. The relative recovery of TP determined in vitro is 18.3% at a perfusion rate of 1.0 microl min(-1) and the RSD is about 2.1%. The association constant and the number of binding sites on a BSA molecule calculated with the Scatchard equation are 3.72 x 10(-3) (1 mol(-1)) and 1.51, respectively. This method provides a fast, sensitive and simple technique for the study of drug-protein interactions.  相似文献   
959.
合成了10种甲基二环己基锡-O,O-二烃基二硫代磷酸酯,利用IR,NMR,MS及元素分析确证了化合物的结构,生物活性测试结果表明,这类化合物具有较高的杀螨和除草活性。  相似文献   
960.
The synthesis, dual fluorescence, and fluoroionophoric behavior of two donor-sigma spacer-acceptor (D-s-A) compounds, trans-4-(N,N-bis(2-pyridyl)amino)methylstilbene (1H) and trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-cyanostilbene (1CN), are reported and compared to that of trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-(N,N-dimethylamino)stilbene (1DPA). To gain insights into the dual fluorescence properties for 1H and 1CN in polar but not in nonpolar solvents, model compounds resulting from a replacement of the stilbene group by alkyl (2R) or xylyl (2X) groups or from a replacement of the dipyridylamino (dpa) group by dianisoleamino (3AA), diethylamino (3EE), methylanilino (3MP), or diphenylamino (3PP) groups also have been investigated. In addition to 1H and 1CN, all four compounds of 3 display dual fluorescence. The locally excited (LE) fluorescence mainly results from the stilbene group and the ICT fluorescence from the through-bond interactions between the amino donor and the stilbene acceptors. In the presence of transition metal ions such as Zn(II), Ni(II), Cu(II), and Cd(II), the ICT processes are switched from dpa (D) --> stilbene (A) in 1H and 1CN to stilbene (D) --> dpa/metal ion (A) in their complexes. Whereas the ICT states for the complexes are generally nonfluorescent, an exception was found for the case of 1H/Zn(II). As a result, substituent-dependent fluoroionophoric behavior has been demonstrated by 1H, 1CN, and 1DPA in response to Zn(II).  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