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   8632篇
  免费   1706篇
  国内免费   1046篇
化学   6514篇
晶体学   96篇
力学   419篇
综合类   96篇
数学   864篇
物理学   3395篇
  2024年   23篇
  2023年   185篇
  2022年   240篇
  2021年   336篇
  2020年   418篇
  2019年   464篇
  2018年   368篇
  2017年   331篇
  2016年   493篇
  2015年   479篇
  2014年   564篇
  2013年   685篇
  2012年   867篇
  2011年   831篇
  2010年   614篇
  2009年   513篇
  2008年   582篇
  2007年   548篇
  2006年   435篇
  2005年   343篇
  2004年   248篇
  2003年   228篇
  2002年   269篇
  2001年   249篇
  2000年   140篇
  1999年   181篇
  1998年   125篇
  1997年   88篇
  1996年   84篇
  1995年   61篇
  1994年   62篇
  1993年   63篇
  1992年   50篇
  1991年   50篇
  1990年   41篇
  1989年   35篇
  1988年   23篇
  1987年   18篇
  1986年   12篇
  1985年   12篇
  1984年   6篇
  1983年   8篇
  1982年   3篇
  1981年   3篇
  1980年   2篇
  1979年   1篇
  1959年   2篇
  1936年   1篇
排序方式: 共有10000条查询结果,搜索用时 375 毫秒
991.
通过对多种频率转换方案的深入对比分析,设计了一套兼容多波长及多脉宽高效输出的频率转换系统。采用"Ⅱ+Ⅱ"类双晶体级联的方式,可以实现"偏振失配"三倍频和Ⅱ类双晶体正交级联二倍频两种模式间的快速切换。通过数值模拟程序优化了晶体构型,结果表明,当两块晶体厚度均为10mm时,可以兼顾低功率长脉冲和高功率短脉冲对效率和稳定性的需求。  相似文献   
992.
For the first time, a diffusive gradients in thin films (DGT) device using molecularly imprinted polymer (MIP) as the binding agent and nylon membrane (NM) as the diffusive layer (NM-MIP-DGT) has been developed for sampling 4-chlorophenol (4-CP) in water. The MIP was prepared by precipitation polymerization with methacrylic acid as monomer and ethyleneglycoldimethacrylate as cross-linker. The diffusion coefficient of 4-CP through NM was obtained to be 0.788 ± 0.040 μ cm2 s−1 by diffusion cell method. The ratio was 1.01 ± 0.05 (mean ± standard deviation) for the concentration of 4-CP sampled by NM-MIP-DGT and analyzed by HPLC method to the total concentration of 4-CP in the synthetic solution where free 4-CP species dominated. The results showed that NM-MIP-DGT could sample 4-CP in synthetic solution accurately. The performance of NM-MIP-DGT for sampling 4-CP was independent of pH in the range of 3–7 and ionic strength in the range of 0.0001–0.1 mol L−1 NaCl solution. The concentration of free form of 4-CP sampled by NM-MIP-DGT decreased with the increasing concentration of dissolved organic carbon in different water samples due to the electrostatic interaction of natural organic compounds with 4-CP. 1.8 mg L−1 of the free form of 4-CP was determined by HPLC which was sampled by NM-MIP-DGT in an intermediate untreated industrial effluent. The NM-MIP-DGT can be a potential passive tool for sampling the free form of 4-CP in water.  相似文献   
993.
Herba Epimedii (Epimedium) is a kind of tonic herb, widely used in China. Epimedin A is a major component of Herba Epimedii with bioactivities. Analysis of the metabolic profile in vivo plays a pivotal role in understanding how traditional Chinese medicine works. And the metabolites of epimedin A might influence the effects of Herba Epimedii. Moreover, the metabolic routes of epimedin A provide an important basis for safety evaluation. Until now, little has been known about the metabolism of epimedin A. The current study was designed to characterize the metabolic pathways of epimedin A in vivo. The metabolites in rat plasma, bile, feces, and urine were identified by UPLC/Q–TOF–MS analysis. A total of 27 metabolites from epimedin A were detected or tentatively identified. The major metabolic processes were hydrolysis, hydrogenation, hydroxylation, dehydrogenation, demethylation, and conjugation with glucuronic acid and different sugars. The present study revealed the metabolic pathways of epimedin A in rat for the first time, and epimedin A could undergo extensive phase I and phase II metabolism in rat. These findings would provide an important basis for the further study and clinical application of epimedin A. In addition, the results of this work have shown the feasibility of the UPLC/Q–TOF–MS approach for rapid and reliable characterization of metabolites.  相似文献   
994.
Two new tirucallane‐type triterpenoids, (24Z)‐tirucalla‐7,24‐diene‐3β,11β,26‐triol ( 1 ) and (3S,24R)‐tirucall‐7‐ene‐3,24,25‐triol ( 2 ), along with the known compound celastrol ( 3 ), were isolated from the root barks of Celastrus stylosus Wall . The structures of 1 – 3 were established by spectroscopic methods, including extensive 2D NMR and MS analyses. It is the first report on tirucallane‐type triterpenoids from the genus Celastrus and may be of vital chemotaxonomic significance.  相似文献   
995.
N-Alkoxymethylation of heterocyclic compounds with diethyl phosphite via cleavage of P-O bond was investigated and a series of N3-ethoxymethylated heterocyclic compounds were synthesized. A mechanism in which diethyl phosphite acts as an efficient surrogate of ethanol was proposed and supported by several evidences.  相似文献   
996.
The Biginelli 3,4-dihydropyrimidin-2(1H)-one was converted to various C2-multifunctionalized pyrimidines via the dehydrogenation and Mitsunobu reaction using amines, alcohols, phenols and carboxylic acids as nucleophiles. A possible mechanism was also proposed to rationalize the formation of products.  相似文献   
997.
998.
Tris(N-methylbenzimidazol-2-ylmethyl)amine (Mentb) and its two complexes, [Mn(Mentb)(DMF)(H2O)](pic)2 1 and [Zn(Mentb)(pic)](pic) 2 (pic = picrate), have been synthesized and characterized by physico-chemical and spectroscopic methods. Single crystal X-ray diffraction revealed that the two complexes have different structures. In complex 1, the coordination sphere around Mn(II) is distorted octahedral, whereas in complex 2 the coordination sphere around Zn(II) is distorted trigonal bipyramidal. The DNA-binding properties of the free ligand and its two complexes have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that the ligand and its two complexes bind to DNA via an intercalation binding mode, and their binding affinity for DNA follows the order 1 > 2 > ligand.  相似文献   
999.
Two decades ago, it has been observed experimentally that hydrogels immersed in a bath solution swells or shrinks under external stimulations (Ric?ka et al., Macromolecules 17:2916?C2921, 1984). Recently, this fact has received renewed interest, since understanding the precise mechanisms underlying that kind of behavior has the potential to tailor most sensitive drug delivery systems based on hydrogels (Segalman and Witkowski, Mater Sci Eng C 2:243?C249, 1995). Here we contribute to a precise understanding of the mechanisms responsible for the hydrogels?? swelling kinetics as well as dynamics by proposing for the first time a model approach that can resolve the inherent short-range correlation effects along the hydrogel?Csolution interface jointly with the long-range ionic transport fields. To that end, we investigate the swelling dynamics of hydrogels, which is a moving boundary problem, by a phase field model, which couples the Nernst?CPlanck equation for the concentration of mobile ions, Poisson equation for the electric potential, mechanical equation for the displacement, and an equation for the phase field variable. Simulation for two-dimensional case reveals that under the chemical stimulation, the hydrogel will swell or shrink if the concentration of mobile ions inside bath solution decreases or increases. This is in agreement with the experimental results qualitatively and validates our new model approach.  相似文献   
1000.
A new Schiff base ligand N-(2-hydroxylacetophenone)-3-oxapentane-1,5-diamine (HL) and its Ni complex, [Ni2(L)2(NO3)2], have been synthesized and characterized by physicochemical and spectroscopic methods. The X-ray crystal structure of [Ni2(L)2(NO3)2] shows it to be a dinuclear 2:2 complex, in which each Ni(II) atom is in a distorted octahedral geometry. The two Ni(II) atoms are dibridged by two phenoxo ligands, forming a Ni2O2 parallelogram-type moiety. The interactions between free HL and the complex with calf thymus DNA have been investigated, and the binding constant and linear Stern–Volmer quenching constant suggest that the two compounds bind to DNA via the intercalation mode. The binding affinity of the complex was higher than that of HL. Antioxidant assays in vitro showed that the Ni(II) complex possesses significant antioxidant activity.  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