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   61862篇
  免费   6038篇
  国内免费   4篇
化学   61891篇
晶体学   68篇
力学   2080篇
数学   2649篇
物理学   1216篇
  2024年   376篇
  2023年   4177篇
  2022年   2451篇
  2021年   3967篇
  2020年   6469篇
  2019年   4071篇
  2018年   2278篇
  2017年   605篇
  2016年   5574篇
  2015年   5543篇
  2014年   4943篇
  2013年   5147篇
  2012年   3217篇
  2011年   1053篇
  2010年   3411篇
  2009年   3368篇
  2008年   1052篇
  2007年   777篇
  2006年   138篇
  2005年   112篇
  2004年   95篇
  2003年   84篇
  1997年   92篇
  1995年   143篇
  1994年   87篇
  1993年   212篇
  1992年   100篇
  1988年   118篇
  1987年   101篇
  1985年   127篇
  1984年   112篇
  1983年   101篇
  1982年   134篇
  1981年   158篇
  1980年   198篇
  1979年   186篇
  1978年   190篇
  1977年   309篇
  1976年   363篇
  1975年   460篇
  1974年   471篇
  1973年   285篇
  1972年   369篇
  1971年   355篇
  1970年   541篇
  1969年   413篇
  1968年   482篇
  1967年   116篇
  1966年   89篇
  1963年   112篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
191.
192.
193.
The chemical mechanism of the precipitation of lead titanium peroxohydroxide particles in a solution of nitrilotriacetate (NTA) complexes of lead and titanium peroxo-hydroxide is envisioned as the interaction between cations of lead hydroxide and anions of polymeric titanium peroxo-hydroxide.  相似文献   
194.
195.
    
A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross-coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross-coupling partners without the need of co-catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.  相似文献   
196.
By transplanting identity elements into E. coli tRNAfMet, we have engineered an orthogonal initiator tRNA (itRNATy2) that is a substrate for Methanocaldococcus jannaschii TyrRS. We demonstrate that itRNATy2 can initiate translation in vivo with aromatic non-canonical amino acids (ncAAs) bearing diverse sidechains. Although the initial system suffered from low yields, deleting redundant copies of tRNAfMet from the genome afforded an E. coli strain in which the efficiency of non-canonical initiation equals elongation. With this improved system we produced a protein containing two distinct ncAAs at the first and second positions, an initial step towards producing completely unnatural polypeptides in vivo. This work provides a valuable tool to synthetic biology and demonstrates remarkable versatility of the E. coli translational machinery for initiation with ncAAs in vivo.  相似文献   
197.
    
Boron-containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron-containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B2(OH)xO(3−x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM-22 isomorphously substituted with boron (B-MWW). Using 11B solid-state NMR spectroscopy, we show that the majority of boron species in B-MWW exist as isolated BO3 units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B-MWW for ODH of propane falsifies the hypothesis that site-isolated BO3 units are the active site in boron-based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium-based catalysts and provides an important piece of the mechanistic puzzle.  相似文献   
198.
Metal–organic frameworks (MOFs) with long-term stability and reversible high water uptake properties can be ideal candidates for water harvesting and indoor humidity control. Now, a mesoporous and highly stable MOF, BIT-66 is presented that has indoor humidity control capability and a photocatalytic bacteriostatic effect. BIT-66 (V3(O)3(H2O)(BTB)2), possesses prominent moisture tunability in the range of 45–60 % RH and a water uptake and working capacity of 71 and 55 wt %, respectively, showing good recyclability and excellent performance in water adsorption–desorption cycles. Importantly, this MOF demonstrates a unique photocatalytic bacteriostatic behavior under visible light, which can effectively ameliorate the bacteria and/or mold breeding problem in water adsorbing materials.  相似文献   
199.
Enantiospecific intramolecular Suzuki–Miyaura-type coupling with α-(2-halobenzoylamino)benzylboronic esters to give 3-substituted isoindolinones is achieved by using copper catalysts with 2,2′-bipyridine-based achiral ligands. Enantioenriched α-aminobenzylboron reactants bearing a hydrogen atom at the boron-bound stereogenic carbons undergo stereoinvertive coupling in the presence of a 6-phenyl-2,2′-bipyridine ligand with high enantiospecificity. α-Aminobenzylboronates bearing fully substituted boron-bound stereogenic centers also gave the 3,3-disubstituted isoindolinones with stereospecific stereochemical inversion in the presence of simple 2,2′-bipyridine as a ligand.  相似文献   
200.
    
Herein, we report a theoretical and experimental study of the water-gas shift (WGS) reaction on Ir1/FeOx single-atom catalysts. Water dissociates to OH* on the Ir1 single atom and H* on the first-neighbour O atom bonded with a Fe site. The adsorbed CO on Ir1 reacts with another adjacent O atom to produce CO2, yielding an oxygen vacancy (Ovac). Then, the formation of H2 becomes feasible due to migration of H from adsorbed OH* toward Ir1 and its subsequent reaction with another H*. The interaction of Ir1 and the second-neighbouring Fe species demonstrates a new WGS pathway featured by electron transfer at the active site from Fe3+−O⋅⋅⋅Ir2+−Ovac to Fe2+−Ovac⋅⋅⋅Ir3+−O with the involvement of Ovac. The redox mechanism for WGS reaction through a dual metal active site (DMAS) is different from the conventional associative mechanism with the formation of formate or carboxyl intermediates. The proposed new reaction mechanism is corroborated by the experimental results with Ir1/FeOx for sequential production of CO2 and H2.  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