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   105398篇
  免费   18079篇
  国内免费   10087篇
化学   71235篇
晶体学   1218篇
力学   6922篇
综合类   533篇
数学   11928篇
物理学   41728篇
  2024年   369篇
  2023年   2133篇
  2022年   3645篇
  2021年   3875篇
  2020年   4250篇
  2019年   4137篇
  2018年   3551篇
  2017年   3286篇
  2016年   5185篇
  2015年   4950篇
  2014年   6025篇
  2013年   7783篇
  2012年   9428篇
  2011年   9756篇
  2010年   6440篇
  2009年   6156篇
  2008年   6534篇
  2007年   5996篇
  2006年   5478篇
  2005年   4596篇
  2004年   3399篇
  2003年   2669篇
  2002年   2414篇
  2001年   1980篇
  2000年   1767篇
  1999年   2075篇
  1998年   1846篇
  1997年   1720篇
  1996年   1890篇
  1995年   1502篇
  1994年   1459篇
  1993年   1167篇
  1992年   1069篇
  1991年   986篇
  1990年   792篇
  1989年   565篇
  1988年   464篇
  1987年   382篇
  1986年   374篇
  1985年   318篇
  1984年   241篇
  1983年   154篇
  1982年   142篇
  1981年   106篇
  1980年   76篇
  1979年   44篇
  1978年   34篇
  1976年   36篇
  1975年   33篇
  1974年   45篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A series of heat energy storage microcapsules was prepared using melamine-formaldehyde resin as the shell material and the mechanical properties of the shell were investigated. A phase change material whose melting point was 24 °C was used as core and the quantity of heat involved in phase transition was 225.5 J/g. Average diameter of the microcapsules varied from 5 to 10 μm, and the globular surface was smooth and compact. The mechanical properties of the shell were evaluated by observing the surface morphological structure change after application of pressure by means of scanning electron microscopy. When the mass ratio of the core and shell material is 3:1, a yield point of about 1.1×105 Pa was found and when the compression was increased beyond this point the microcapsules showed plastic behavior. This has been attributed to the cross-link density and to the high degree of reaction of the shell material. Different yield points subsequently reflected differences in the mechanical behavior. It was also found that the mechanical intensity of double-shell microcapsules was better than that of single shelled ones.  相似文献   
992.
Volumetric H2-uptake measurements on an Mo2N (79 m2g–1) sample reduced at 673 K have been carried out and the uptake isotherms in the temperature range of 308–623 K have been determined. Both the total and reversible hydrogen uptake increased with the uptake temperature. The irreversible hydrogen uptake increased abruptly when the uptake temperature was raised up to 423 K. The maximum of irreversible hydrogen uptake was measured at 473 K. The HIR/Mo ratio calculated from the uptakes obtained in the temperature range of 308–623 K varies in the range of 0.0010–0.0202. One possible mechanism for hydrogen adsorption is proposed to be heterolytic dissociation on Mo-N paris, in which the molybdenum atoms are in unsaturated coordination.  相似文献   
993.
本文报导的方法是在南京大学高鸿教授研究的K_3Fe(CN)_6示波极谱滴定法(在PH8的K_2HPO_4—KH_2PO_4—KBr底液中,用0.04660mol/LK_3Fe(CN)_6标准溶液对纯抗坏血酸测定)的基础上,考虑到L—抗坏血酸(以下简称V_e)在碱性、中性介质中稳定性差,如用于V_e含量很微的果蔬测定,对结果影响大。本文改为H_2C_2O_4—KBr的酸性介质作底液,用  相似文献   
994.
The photoelectron spectrum of the title compound is reported and assigned by correlation with the photoelectron spectra of related molecules.  相似文献   
995.
The concerted mechanism of phosphate-catalyzed proton exchange in N,N'-dimethylurea has been studied. Kinetic data were measured using the technigue of NMR line-shape analysis. A significant kinetic isotope effect was observed for the concerted proton transfer in N,N'-dimethylurea and is attributed to the tunnelling effect.  相似文献   
996.
A mild, efficient and convenient extraction method of using 2-mercaptoethanol contained extractant solution combined with an incubator shaker for determination of mercury species in biological samples by HPLC–ICP-MS has been developed. The effects of the concentration of 2-mercaptoethanol, the composition of the extractant solution and the shaking time on the efficiency of mercury extraction were evaluated. The optimization experiments indicated that the quantitative extraction of mercury species from biological samples could be achieved by using 0.1% (v/v) HCl, 0.1% (v/v) 2-mercapoethanol and 0.15% (m/v) KCl extractant solution in an incubator shaker for shaking overnight (about 12 h) at room temperature. The established method was validated by analysis of various biological certified reference materials, including NRCC DOLT-3 (dogfish liver), IAEA 436 (tuna fish), IAEA MA-B-3/TM (garfish filet), IAEA MA-M-2/TM (mussel tissue), GBW 08193 (bovine liver) and GBW 08572 (prawn). The analytical results of the reference materials were in good agreement with the certified or reference values of both methyl and total mercury, indicating that no distinguishable transformation between mercury species had occurred during the extraction and determination procedures. The limit of detection (LOD) for methyl (CH3Hg+) and inorganic mercury (Hg2+) by the method are both as 0.2 μg L−1. The relative standard deviation (R.S.D.s) for CH3Hg+ and Hg2+ are 3.0% and 5.8%, respectively. The advantages of the developed extraction method are that (1) it is easy to operate in HPLC–ICP-MS for mercury species determination since the extracted solution can be directly injected into the HPLC column without pH adjustment and (2) the memory effect of mercury in the ICP-MS measurement system can be reduced.  相似文献   
997.
Chemical shifts of the alcohol and DMF protons in DMF–alcohol mixtures with the mole fraction of alcohol are reported in order to study the hydrogen bond interaction present in the mixtures. The densities of DMF–methanol mixture at 22°C are also measured. Excess volumes and excess chemical shifts are correlated by the Redlich–Kister equation. The relation between excess volumes and excess chemical shifts in the mixtures is discussed. It is found that the maximum excess chemical shifts E(CHO-OH) and E(CH3-OH) are positioned at about mole fraction methanol = 0.57 for the DMF–methanol system, as is V E. The results show that the NMR spectral method offers a valuable approach to similar future studies of interactions in mixtures.  相似文献   
998.
Targeting cell surface receptors with ligand-conjugated nanocrystals   总被引:9,自引:0,他引:9  
To explore the potential for use of ligand-conjugated nanocrystals to target cell surface receptors, ion channels, and transporters, we explored the ability of serotonin-labeled CdSe nanocrystals (SNACs) to interact with antidepressant-sensitive, human and Drosophila serotonin transporters (hSERT, dSERT) expressed in HeLa and HEK-293 cells. Unlike unconjugated nanocrystals, SNACs were found to dose-dependently inhibit transport of radiolabeled serotonin by hSERT and dSERT, with an estimated half-maximal activity (EC(50)) of 33 (dSERT) and 99 microM (hSERT). When serotonin was conjugated to the nanocrystal through a linker arm (LSNACs), the EC(50) for hSERT was determined to be 115 microM. Electrophysiology measurements indicated that LSNACs did not elicit currents from the serotonin-3 (5HT(3)) receptor but did produce currents when exposed to the transporter, which are similar to those elicited by antagonists. Moreover, fluorescent LSNACs were found to label SERT-transfected cells but did not label either nontransfected cells or transfected cells coincubated with the high-affinity SERT antagonist paroxetine. These findings support further consideration of ligand-conjugated nanocrystals as versatile probes of membrane proteins in living cells.  相似文献   
999.
Wang XP  Pan JH  Li WH  Zhang Y 《Talanta》2001,54(5):805-810
The interaction of cyclodextrins with meso- Tetrakis (4-N-trimethylaminobenzyl) porphyrin (TAPP) in 0.1 mol l(-1) phosphate buffer (pH 7.0, 20 degrees C) has been studied by polarography. The TAPP can form the 1:1 inclusion complex with Sulfobutylether-beta-cyclodextrin (SBE-beta-CD) and1:2 inclusion complexes with other four cyclodextrins. A new expression, which is used to calculate the inclusion constant for1:2 inclusion complex by polarography, has been educed and testified firstly in this paper. Furthermore, the inclusion abilities of different kinds of cyclodextrins are compared. The result shows the inclusion ability of anionic cyclodextrin SBE-beta-CD with cationic porphyrin TAPP is very strong. It suggests that the charge attraction between CDs and TAPP plays an important role in the inclusion procedure except for the hydrophobic effect. The inclusion formation of anionic cyclodextrins with drugs can increase released rate of drugs at high pH; therefore, the suparmolecular data for the controlled release of the drugs that owned the similar properties as hematoporphyrin have been offered by polarography in this paper.  相似文献   
1000.
在四氟硼酸银存在下,分别以硫醚、硫醇、硫酚或过硫醚为原料与碘甲烷反应制备了相应的甲基锍盐。用1HNMR和13CNMR表征产物的结构并提出了反应的机理。  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