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   47636篇
  免费   9313篇
  国内免费   2375篇
化学   48057篇
晶体学   467篇
力学   973篇
综合类   75篇
数学   3379篇
物理学   6373篇
  2023年   220篇
  2022年   423篇
  2021年   545篇
  2020年   1621篇
  2019年   2900篇
  2018年   1311篇
  2017年   967篇
  2016年   3766篇
  2015年   3930篇
  2014年   3885篇
  2013年   4716篇
  2012年   3781篇
  2011年   3074篇
  2010年   3421篇
  2009年   3399篇
  2008年   2989篇
  2007年   2368篇
  2006年   1988篇
  2005年   2062篇
  2004年   1842篇
  2003年   1677篇
  2002年   2319篇
  2001年   1653篇
  2000年   1482篇
  1999年   543篇
  1998年   202篇
  1997年   170篇
  1996年   191篇
  1995年   138篇
  1994年   161篇
  1993年   139篇
  1992年   125篇
  1991年   106篇
  1990年   116篇
  1989年   88篇
  1988年   94篇
  1987年   62篇
  1986年   71篇
  1985年   100篇
  1984年   71篇
  1983年   70篇
  1982年   49篇
  1981年   46篇
  1980年   47篇
  1979年   35篇
  1977年   37篇
  1976年   38篇
  1975年   34篇
  1974年   48篇
  1973年   44篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
992.
For the first time, hydroxypropyl-β-cyclodextrin (HP-β-CD) has been brought in to include 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) in order to enhance inhibition efficiency of PBTCA, which leads a new approach to study oil–gas field corrosion inhibition in the process of acid treatment. Based on the host–guest inclusion reaction, the inclusion complex of PBTCA with HP-β-CD has been prepared in the laboratory. UV–Vis absorption spectrum was applied to study the inclusion behavior of PBTCA with HP-β-CD. The results revealed that PBTCA with HP-β-CD can form a 1:1 stoichiometry inclusion complex. The 1:1 inclusion complex synthesized by using lyophilization was further characterized by Fourier transform infrared spectroscopy. Besides, inhibition effect of the inclusion complex on the corrosion inhibition of Q235 carbon steel has been investigated in 0.1 M sulfuric acid (H2SO4) solution using potentiodynamic polarization, electrochemical impedance spectroscopy techniques and scanning electron microscopy (SEM). It was found that the presence of the inclusion complex better achieved the anti-corrosion property in aggressive medium than was the case with alone PBTCA and the highest inhibition efficiency of the inclusion complex over 90 % was obtained, which are suggestive of the active effect of the inclusion complex for improving inhibition efficiency of PBTCA. Meanwhile, the results obtained from SEM further showed that the inclusion complex acts as a more efficient corrosion inhibitor for Q235 carbon steel in H2SO4 medium.  相似文献   
993.

New retinoyl sugar derivatives of 13‐cis‐retinoic acid were synthesized in three ways in this paper in order to enhance pharmacal effects, especially antiproliferative activities of 13‐cis‐retinoic acid. Their structures were confirmed by IR, 1H‐NMR, 13C‐NMR, and MS spectra and their antiproliferative activities were determined in vitro using human cancer lines. Results showed that some compounds possessed potential antitumor activities.  相似文献   
994.
995.

Highly α‐selective sialylation of sialic acid N‐phenyltrifluoroacetimidate with various galactose and lactose acceptors has been achieved by introducing the C‐5 N‐phthalyl group on the donor. The “fixed dipole effect” of the N‐phthalyl group was proposed to explain the high reactivity and α‐selectivity. The microfluidic system was applied to the present α‐sialylation, which is amenable to large‐scale synthesis. The N‐phthalyl group was removed by treatment with methylhydrazine acetate, for which protocol can be readily applied to the synthesis of a variety of sialic acid‐containing oligosaccharides.   相似文献   
996.
Effectively enhancing the enantioselectivity is a persistent challenge in heterogeneous asymmetric catalysis. Here, the validity of a layered double hydroxides (LDH) nanosheet as an efficient planar substituent to enhance the enantioselectivity has been investigated theoretically; first in vanadium‐catalyzed asymmetric epoxidation of allylic alcohols, and then in zinc‐catalyzed direct asymmetric aldol addition. The computational predication is further confirmed experimentally in zinc‐catalyzed direct asymmetric aldol addition by controlling the location of catalytic sites.  相似文献   
997.
998.
The band structure of multicomponent semiconductor photocatalysts, as well as their reactivity distinction under different wavelengths of light, is still unclear. BiOBr, which is a typical multicomponent semiconductor, may have two possible valence‐band structures, that is, two discrete valence bands constructed respectively from O 2p and Br 4p orbitals, or one valence band derived from the hybridization of these orbitals. In this work, aqueous photocatalytic hydroxylation is applied as the probe reaction to investigate the nature and reactions of photogenerated holes in BiOBr. Three organic compounds (microcystin‐LR, aniline, and benzoic acid) with different oxidation potentials were selected as substrates. Isotope labeling (H218O as the solvent) was used to determine the source of the O atom in the hydroxyl group of the products, which distinguishes the contribution of different hydroxylation pathways. Furthermore, a spin‐trapping ESR method was used to quantify the reactive oxygen species (.OH and .OOH) formed in the reaction system. The different isotope abundances of the hydroxyl O atom of the products formed, as well as the reverse trend of the .OH/.OOH ratio with the oxidative resistance of the substrate under UV and visible irradiation, reveal that BiOBr has two separate valence bands, which have different oxidation ability and respond to UV and visible light, respectively. This study shows that the band structure of semiconductor photocatalysts can be reliably analyzed with an isotope labeling method.  相似文献   
999.
The extent of charge delocalization and of conjugation in oligofurans and oligothiophenes was studied by using mixed valence systems comprising oligofurans and oligothiophenes capped at both ends by ferrocenyl redox units. Using electrochemical, spectral, and computational tools, we find strong charge delocalization in ferrocene‐capped oligofurans which was stronger than in the corresponding oligothiophene systems. Spectroscopic studies suggest that the electronic coupling integral (Hab) is roughly 30–50 % greater for oligofuran‐bridged systems, indicating better energy matching between ferrocene units and oligofurans. The distance decay constant (damping factor), β, is similar for oligofurans (0.066 A?1) and oligothiophenes (0.070 A?1), which suggests a similar extent of delocalization in the bridge, despite the higher HOMO–LUMO gap in oligofurans. Computational studies indicate a slightly larger extent of delocalization in furan‐bridged systems compared with thiophene‐bridged systems, which is consistent with oligofurans being significantly more rigid and less aromatic than oligothiophenes. High charge delocalization in oligofurans, combined with the previously reported strong fluorescence, high mobility, and high rigidity of oligofuran‐based materials makes them attractive candidates for organic electronic applications.  相似文献   
1000.
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