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   5431篇
  免费   185篇
  国内免费   24篇
化学   4172篇
晶体学   47篇
力学   79篇
数学   351篇
物理学   991篇
  2023年   24篇
  2022年   21篇
  2021年   44篇
  2020年   65篇
  2019年   97篇
  2018年   55篇
  2017年   48篇
  2016年   108篇
  2015年   92篇
  2014年   131篇
  2013年   284篇
  2012年   318篇
  2011年   397篇
  2010年   209篇
  2009年   240篇
  2008年   393篇
  2007年   381篇
  2006年   430篇
  2005年   366篇
  2004年   341篇
  2003年   271篇
  2002年   225篇
  2001年   64篇
  2000年   49篇
  1999年   35篇
  1998年   41篇
  1997年   56篇
  1996年   55篇
  1995年   43篇
  1994年   34篇
  1993年   49篇
  1992年   30篇
  1991年   33篇
  1990年   20篇
  1989年   18篇
  1988年   28篇
  1987年   29篇
  1986年   40篇
  1985年   58篇
  1984年   49篇
  1983年   20篇
  1982年   49篇
  1981年   53篇
  1980年   43篇
  1979年   43篇
  1978年   33篇
  1977年   27篇
  1976年   25篇
  1975年   17篇
  1973年   18篇
排序方式: 共有5640条查询结果,搜索用时 15 毫秒
1.
BIT Numerical Mathematics - Linear and nonlinear evolution equations have been formulated to address problems in various fields of science and technology. Recently, methods using an exponential...  相似文献   
2.
Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.  相似文献   
3.
An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties.  相似文献   
4.
Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies.  相似文献   
5.
Most CdTe photoanodes and photocathodes show positive and negative photocurrent onset potentials for water oxidation and reduction, respectively, and are thus unable to drive photoelectrochemical (PEC) water splitting without external applied biases. Herein, the activity of a CdTe photoanode having an internal p‐n junction during PEC water oxidation was enhanced by applying a CdCl2 annealing treatment together with surface modifications. The resulting CdTe photoanode generated photocurrents of 1.8 and 5.4 mA cm?2 at 0.6 and 1.2 VRHE, respectively, with a photoanodic current onset potential of 0.22 VRHE under simulated sunlight (AM 1.5G). The CdCl2 annealing increased the grain sizes and lowered the density of grain boundaries, allowing more efficient charge separation. Consequently, a two‐electrode tandem PEC cell comprising a CdTe‐based photoanode and photocathode split water without any external bias at a solar‐to‐hydrogen conversion efficiency of 0.51 % at the beginning of the reaction.  相似文献   
6.
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark.  相似文献   
7.
Surface‐diffusion‐induced spontaneous Ga incorporation process is demonstrated in ZnO nanowires grown on GaN substrate. Crucially, contrasting distributions of Ga atoms in axial and radial directions are experimentally observed. Ga atoms uniformly distribute along the ~10 μm long ZnO nanowire and show a rapidly gradient distribution in the radial direction, which is attributed substantially to the difference between surface and volume diffusion. The understanding on the incorporation process can potentially modulate doping and properties in semiconductor nanomaterials.

  相似文献   

8.
A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at ?80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In 29Si NMR spectrum in [D8]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a [2+3] cycloadduct, respectively. The silanone remains intact in [D8]toluene below ?80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3‐silyl migration at higher temperatures.  相似文献   
9.
LaTaON2 is a photocatalyst with intense visible light absorption up to 650 nm, but exhibits low H2 evolution activity owing to uncontrolled facets and high defect densities. In this work, core–shell‐structured plate‐like LaKNaTaO5/LaTaON2 was synthesized by nitriding a layered perovskite‐type LaKNaTaO5. The volatilization of K and Na species during the nitridation promoted the rapid transformation of LaKNaTaO5 into LaTaON2 along [010] direction with the plate‐like shape retained. This yielded high‐quality LaTaON2 shells exposing (010) facets on the lattice‐matched LaKNaTaO5 cores. After loading with a Rh co‐catalyst, LaKNaTaO5/LaTaON2 showed photocatalytic H2 evolution activity four times greater than that obtained from conventional irregular‐shaped LaTaON2 powders and utilized visible light up to 620 nm. This work provides a novel strategy yielding oxynitrides with well‐defined facets and low defect densities by selecting lattice‐matched oxide precursors containing volatile components.  相似文献   
10.
In order to gain new insights into the effect of the π–π stacking interaction of the indole ring with the CuII–phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a CuII complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized CuII complex exhibited the π–π stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the π–π stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized CuII complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical–indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the π–π stacking interaction.  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