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   68982篇
  免费   15097篇
  国内免费   6937篇
化学   65125篇
晶体学   841篇
力学   2441篇
综合类   609篇
数学   5846篇
物理学   16154篇
  2024年   74篇
  2023年   660篇
  2022年   912篇
  2021年   1322篇
  2020年   2503篇
  2019年   3797篇
  2018年   2128篇
  2017年   1853篇
  2016年   4837篇
  2015年   5082篇
  2014年   5204篇
  2013年   6523篇
  2012年   5858篇
  2011年   5359篇
  2010年   5001篇
  2009年   4930篇
  2008年   4767篇
  2007年   3983篇
  2006年   3535篇
  2005年   3368篇
  2004年   2784篇
  2003年   2469篇
  2002年   3167篇
  2001年   2272篇
  2000年   2126篇
  1999年   1184篇
  1998年   686篇
  1997年   642篇
  1996年   648篇
  1995年   513篇
  1994年   527篇
  1993年   396篇
  1992年   344篇
  1991年   299篇
  1990年   220篇
  1989年   180篇
  1988年   151篇
  1987年   127篇
  1986年   120篇
  1985年   108篇
  1984年   67篇
  1983年   59篇
  1982年   47篇
  1981年   34篇
  1980年   35篇
  1979年   26篇
  1978年   10篇
  1977年   10篇
  1975年   10篇
  1973年   10篇
排序方式: 共有10000条查询结果,搜索用时 296 毫秒
991.
Ge-132对小鼠H22肝癌移植瘤的实验研究证明:1.Ge-132对H22肝癌移植瘤有一定的抑制作用,300mg/kg体重剂量抑瘤率达到36.19%;2.增强机体的抗氧化作用,抑制脂质的过氧化物水平;3.促进免疫功能,当Ge-132和环磷酰胺联合使用时,可抵抗环磷酰胺的免疫抑制作用,而且并不减弱其抑制瘤作用。  相似文献   
992.
993.
Two new alkaloids, i.e., (2,3‐dihydro‐1‐oxo‐1H‐pyrrolo[1,2‐a]pyrrol‐7‐yl)methyl (2S*,3S*)‐3‐[(β‐D ‐glucopyranosyl)oxy]‐2‐hydroxy‐2‐(1‐methylethyl)butanoate ( 1 ) and 1,2‐dihydro‐8‐methoxy‐2‐oxoquinoline‐4‐carboxylic acid ( 2 ), were isolated from the alcoholic extract of the whole plant of Cynoglossum gansuense, together with twelve known compounds Their structures were characterized by means of spectroscopic methods, especially by 1H‐, 13C‐, and 2D‐NMR, as well as by HR‐MS experiments and comparison with literature data.  相似文献   
994.
Highly ordered rod-like large-pore periodic mesoporous organosilica (PMO) was successfully synthesized at low acid concentration with the assistance of inorganic salt using triblock copolymer P123 as a template. The roles of inorganic salt and acidity in the production of highly ordered mesostructure and the morphology control of PMOs were investigated. It was found that the inorganic salt can significantly widen the range of the synthesis parameters to produce highly ordered 2D hexagonal pore structure of p6mm symmetry. However, the uniform rod-like PMOs can only be synthesized in a narrow range of acid and salt concentrations, which were sensitive to induction time. The adsorption of lysozyme on PMO was studied at different pH values in comparison with adsorption on pure silica material under controlled morphology and pore structure. It was found that the adsorption capacity of lysozyme on the PMO was lower than that on pure SBA-15 silica material and the adsorption amounts are larger at pH 9.6 than at 7.0 for both materials. The results show that the electrostatic interaction between lysozyme and PMO/SBA-15 surface is more dominant than the hydrophobic forces and the interaction of neighboring lysozyme molecules also plays an important role.  相似文献   
995.
The in vitro adsorption kinetics of lung surfactant at air-water interfaces is affected by both the composition of the surfactant preparations and the conditions under which the assessment is conducted. Relevant experimental conditions are surfactant concentration, temperature, subphase pH, electrolyte concentration, humidity, and gas composition of the atmosphere exposed to the interface. The effect of humidity on the adsorption kinetics of a therapeutic lung surfactant preparation, bovine lipid extract surfactant (BLES), was studied by measuring the dynamic surface tension (DST). Axisymmetric drop shape analysis (ADSA) was used in conjunction with three different experimental methodologies, i.e., captive bubble (CB), pendant drop (PD), and constrained sessile drop (CSD), to measure the DST. The experimental results obtained from these three methodologies show that for 100% relative humidity (RH) at 37 degrees C the rate of adsorption of BLES at an air-water interface is substantially slower than for low humidity. It is also found that there is a difference in the rate of surface tension decrease measured from the PD and CB/CSD methods. These experimental results agree well with an adsorption model that considers the combined effects of entropic force, electrostatic interaction, and gravity. These findings have implications for the development and evaluation of new formulations for surfactant replacement therapy.  相似文献   
996.
Bacterial aromatic polyketides are pharmacologically important natural products. A critical parameter that dictates product structure is the carbon chain length of the polyketide backbone. Systematic manipulation of polyketide chain length represents a major unmet challenge in natural product biosynthesis. Polyketide chain elongation is catalyzed by a heterodimeric ketosynthase. In contrast to homodimeric ketosynthases found in fatty acid synthases, the active site cysteine is absent from the one subunit of this heterodimer. The precise role of this catalytically silent subunit has been debated over the past decade. We demonstrate here that this subunit is the primary determinant of polyketide chain length, thereby validating its designation as chain length factor. Using structure-based mutagenesis, we identified key residues in the chain length factor that could be manipulated to convert an octaketide synthase into a decaketide synthase and vice versa. These results should lead to novel strategies for the engineered biosynthesis of hitherto unidentified polyketide scaffolds.  相似文献   
997.
Self-assembled monolayers (SAMs) of functionalized azobenzene thiols (RAzoCnSH, n=3-6 for R=H, abbreviated as AzoCnSH; and n=4 for R=CH(3)CONH, abbreviated as aaAzoC4SH) on different substrates RAzoCnSz.sbnd;z.sfnc;S (S represents substrates of vacuum-deposited gold (Au), silver foil (Ag), HNO(3) etched silver foil (EAg), and silver mirror (mAg)) have been studied by SERS in the near-infrared region. SERS of the SAMs on EAg and/or mAg exhibit SERS effects that vary with etching time and/or deposition time. The most appropriate time is 5 s for etching in 1:1 HNO(3) and 40 s for deposition in 0.1 M Ag(NH(3))(2)NO(3). Further, a layer of Ag mirror was conveniently deposited on the top of the SAMs on different substrates, yielding a more efficient SERS-active system possessing a "sandwiched" structure of mAgz.sfnc;RAzoCnS-z.sfnc;S. An appropriate surface roughness is required for the strongest SERS effect. Scanning electron microscopy (SEM) indicates that there exist a large number of projects around 100 nm on the surface showing the strongest SERS effect. When the surface roughness is decreased or increased, the SERS effect decreases sharply. The relationship between the SERS effect and the structural nature was investigated and showed that the enhancement factor decays exponentially with increasing in distances of the azobenzene group from the underlying substrate or the overlying silver mirror. This result reveals that the SERS effect may be the result of the electromagnetic coupling effect between two metal layers.  相似文献   
998.
In the title compound, [Fe(C17H14P)2]2[Sb4Cl16]·C2H6O, the Fe atoms lie on inversion centres and the pairs of cyclopentadienyl rings are consequently in a fully staggered conformation. The centrosymmetric anionic clusters formed by [Sb4Cl16]4? are surrounded by the cations and are held together by weak C—H?Cl interactions. These formations stack along the a axis to form columns, and the columns are interconnected by another weak C—H?Cl interaction along the b axis.  相似文献   
999.
From the changes in energy band, density of state (DOS) and electronic structure calculated by the DFT/B3LYP method, the conductivity of carbon doped boron‐nitride nanotube (BNNT), which is formed by C‐C bond substituting B‐N bond, was discussed. The results indicate that the substitution will strengthen the conductivity of the tube, and its semi‐conductivity might be adjusted by controlling the substitution.  相似文献   
1000.
This investigation conducted reaction channels of weakly bound complexes CO2…HF, CO2…HF…NH3, CO2…HF…NH2CH3, CO2…HF…NH(CH3)2, and CO2…HF…N(CH3)3 systems, using the Gaussian 98 package at the B3LYP/6‐311++G(3df,2pd) level. The syn‐fluoroformic acid or syn‐fluoroformic acid plus NH3 or amine conformers are more stable than the related anti‐fluoroformic acid or anti‐fluoroformic acid plus NH3 or amine conformers. However, the above‐mentioned weakly bound complexes are more stable than both the related syn‐ and anti‐type fluoroformic acid or acid plus NH3 or amine conformers and their related decomposed into CO2 + HF or CO2 + NHR3F (R?H, CH3) combined molecular systems. Five reaction channels of the weakly bound complexes exist. Each channel includes weakly bound complexes and their related above‐mentioned systems. Moreover, each reaction channel contains two transition states. The transition state between the weakly bound complex and anti‐fluoroformic acid type structure (T13) is significantly higher than that of internal rotation (T23) between syn‐ and anti‐FCO2H (or FCO2H…NR3) structures. However, the above‐mentioned T13 can significantly decrease its energy by adding the third molecule NH3 or NR3 (R?H or CH3). The more CH3 that is substituted in NR3 of the reaction channel, the lower the activation energy of the transition state in the system is affected. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005  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