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   9545篇
  免费   791篇
  国内免费   777篇
化学   6063篇
晶体学   140篇
力学   526篇
综合类   56篇
数学   1168篇
物理学   3160篇
  2025年   14篇
  2024年   108篇
  2023年   217篇
  2022年   344篇
  2021年   359篇
  2020年   383篇
  2019年   403篇
  2018年   270篇
  2017年   286篇
  2016年   434篇
  2015年   429篇
  2014年   568篇
  2013年   608篇
  2012年   786篇
  2011年   780篇
  2010年   514篇
  2009年   459篇
  2008年   524篇
  2007年   404篇
  2006年   414篇
  2005年   381篇
  2004年   341篇
  2003年   247篇
  2002年   234篇
  2001年   193篇
  2000年   129篇
  1999年   196篇
  1998年   139篇
  1997年   99篇
  1996年   120篇
  1995年   120篇
  1994年   103篇
  1993年   62篇
  1992年   57篇
  1991年   66篇
  1990年   78篇
  1989年   51篇
  1988年   39篇
  1987年   26篇
  1986年   31篇
  1985年   17篇
  1984年   19篇
  1983年   14篇
  1982年   11篇
  1981年   13篇
  1979年   3篇
  1976年   3篇
  1974年   2篇
  1973年   2篇
  1928年   2篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
111.
    
1,2‐Bisphosphines have been identified as one class of important and powerful chiral ligands in asymmetric catalysis with transition metals. Herein, a copper(I)‐catalyzed asymmetric hydrophosphination of α,β‐unsaturated phosphine sulfides was developed with the assistance of “soft–soft” interaction between copper(I)‐catalyst and the phosphine sulfide moiety, which afforded 1,2‐bisphosphine derivatives with diversified electronic nature and steric hindrance in high to excellent yields with high to excellent enantioselectivity. Moreover, the challenging catalytic asymmetric hydrophosphination/protonation reaction was achieved with excellent enantioselectivity. Strikingly, the dynamic kinetic resolution of racemic diarylphosphines was also successfully carried out with high to excellent diastereo‐ and enantioselectivities. Interestingly, the nucleophilic copper(I)‐diphenylphosphide species was characterized by 31P NMR spectrum and mass spectrum. At last, three products were transformed to chiral 1,2‐bisphosphines, which were employed as ligands in Rh‐catalyzed asymmetric hydrogenation of α‐amino‐α,β‐unsaturated ester. The α‐amino acid derivative was produced in high enantioselectivity, which demonstrated the utility of the present methodology.  相似文献   
112.
    
We have demonstrated B2pin2 as superior deoxidizing agent for the reductive deoxygenation of quinol derivatives under basic conditions. A wide range of highly functionalized phenols were obtained in good yields including a complex drug molecule, which revealed the high functional group tolerance of this protocol.  相似文献   
113.
    
A simple solvent ligation effect was successfully used to disrupt the growth of a model compound, Fe[(OH)(O3P(CH2)2CO2H)]?H2O (MIL‐37), into an extended 2D structure by replacing water with dimethylformamide (DMF) as the solvent during the synthesis. Owing to the lack of ?OH group, which provides the corner‐sharing (binding) oxygen atoms for the octahedra, an amorphous and porous structure is formed. When Fe3+ is partially replaced by Ni2+, the amorphous structure remains and the resultant binary metal catalyst displays excellent photocatalytic oxygen evolution activity with almost 100 % yield achieved under visible light irradiation using [Ru(bpy)3]2+ as the photosensitizer. This study opens up new possibilities of using the simple solvent effect to synthesize high surface area metal phosphonates for catalytic and other applications.  相似文献   
114.
千金子油理化性质及其脂肪酸和挥发油成分分析   总被引:1,自引:0,他引:1  
对千金子油理化性质进行了系统的分析测试,并利用气相色谱法分析了千金子油脂肪酸及千金子挥发油,结果表明,千金子油中油酸含量最高占78.158%,其次是软脂酸、硬脂酸,分别为8.513%和5.523%;千金子挥发油中油酸、亚油酸和油酸-2-丙三醇酯含量较高,分别为17.747%,15.852%和13.196%.  相似文献   
115.
The new title compound is prepared from a mixture of AgGaSe2 (obtained from the elements at 900 °C, 2 d) and CsI in the molar ratio 1:2 (silica tube, Ar, 800 °C, 48 h).  相似文献   
116.
Autoimmune diseases are characterized by the presence of autoantibodies in serum of affected patients. The heterogeneity of autoimmune relevant antigens creates a variety of different antibodies, which requires a simultaneous detection mode. For this reason, we developed a tool for parallelized, label-free, optical detection that accomplishes the characterization of multiple antigen–antibody interactions within a single measurement on a timescale of minutes. Using 11-aminoundecyltrimethoxysilane, we were able to immobilize proteinogenic antigens as well as an amino-functionalized cardiolipin on a glass surface. Assay conditions were optimized for serum measurements with a single spot antigen chip on a single spot 1-λ detection system. Minimized background signal allows a differentiation between patients and healthy controls with a good sensitivity and specificity. Applying polarized imaging reflectometric interference spectroscopy, we evaluated samples from three APS patients and three control subjects for this proof-of-principle and already obtained good results for β2-glycoprotein I and cardiolipin.  相似文献   
117.
Dong  Sheng  Zhang  Kai  Liu  Xiang  Yin  Qingwu  Yip  Hin-Lap  Huang  Fei  Cao  Yong 《中国科学:化学(英文版)》2019,62(1):67-73
An organic-inorganic hybrid cathode interfacial layer(CIL) was developed by doping ZnO with the naphthalene-diimide based derivative NDI-PFNBr. It was found the resulting organic-inorganic hybrid CIL showed apparently improved conductivity and could act as an effective cathode interlayer to modify indium tin oxide(ITO) transparent electrodes. As a result, by employing the blend of PTB7-Th:PC71BM as the photoactive layer, the inverted polymer solar cells(PSCs) exhibited a remarkable enhancement of power conversion efficiency(PCE) from 8.52% for the control device to 10.04% for the device fabricated with the hybrid CIL. Moreover, all device parameters were simultaneously improved by using this hybrid CIL. The improved open-circuit voltage(VOC) was attributed to the reduced work function of the ITO cathode, whereas the enhancements in fill factor(FF) and short-circuit current density(JSC) were assigned to the increased conductivity and more effective charge extraction and collection at interface. Encouragingly, when the thickness of the hybrid CIL was increased to 80 nm, the resulting device could still keep a PCE of 8.81%, exhibiting less thickness dependence. Considering these advantages, 16 and 93 cm2large-area PSCs modules were successfully fabricated from the hybrid CIL by using doctor-blade coating techniques and yielded a remarkable PCE of8.05% and 4.49%, respectively. These results indicated that the hybrid CIL could be a promising candidate to serve as the cathode interlayer for high-performance large-area inverted PSCs.  相似文献   
118.
The title compounds, dimethylammonium 2‐{4‐[1‐(4‐carboxymethoxyphenyl)‐1‐methylethyl]phenoxy}acetate, C2H8N+·C19H19O6, (I), and 2,2′‐[isopropylidenebis(p‐phenyleneoxy)]diacetic acid–4,4′‐bipyridine (1/1), C19H20O6·C10H8N2, (II), are 1:1 adducts of 2,2′‐[isopropylidenebis(p‐phenyleneoxy)]diacetic acid (H2L) with dimethylammonium or 4,4′‐bipyridine. The component ions in (I) are linked by N—H...O, O—H...O and C—H...O hydrogen bonds into continuous two‐dimensional layers parallel to the (001) plane. Adjacent layers are stacked via C—H...O hydrogen bonds into a three‐dimensional network with an –ABAB– alternation of the two‐dimensional layers. In (II), two H2L molecules, one bipy molecule and two half bipy molecules are linked by O—H...N hydrogen bonds into one‐dimensional chains and rectanglar‐shaped rings. They are assembled viaπ–π stacking interactions and C—H...O hydrogen bonds into an intriguing zero‐dimensional plus one‐dimensional poly(pseudo)rotaxane motif.  相似文献   
119.
The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal-air battery devices. Herein, an efficient liquid exfoliation strategy was designed for producing silk-like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn-air batteries. Because of the unique silk-like morphology and interface nanocrystal structure, they can catalyze the oxygen evolution reaction (OER) efficiently with a low overpotential of 233 mV at j = 10 mA cm?2. This is an improvement from the recently reported catalysts in 1.0 M KOH. Meanwhile, the oxygen reduction reaction (ORR) activity of the silk-like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half-wave potential of 640 mV. In addition, the reversible oxygen electrode activity of the silk-like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V, based on the potential of the OER and ORR. Further, the homemade rechargeable Zn-air batteries using FeS2/NiS2 hybrid nanocrystals as the air-cathode displayed a high open-circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h. The solid Zn-air batteries exhibited an excellent rechargeable performance for 15 h. This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.  相似文献   
120.
Stable complexes : An extremely air‐stable μ2‐hydroxy‐bridged binuclear hafonocene perfluorooctanesulfoante complex shows high catalytic efficiency in Lewis acid‐catalyzed reactions, such as esterification, Friedel–Crafts acylation, the Mukaiyama aldol reation, and the allylation of aldehyde (see scheme).

  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