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   5124篇
  免费   214篇
  国内免费   24篇
化学   3828篇
晶体学   43篇
力学   57篇
数学   383篇
物理学   1051篇
  2024年   23篇
  2023年   39篇
  2022年   93篇
  2021年   139篇
  2020年   152篇
  2019年   133篇
  2018年   82篇
  2017年   65篇
  2016年   226篇
  2015年   151篇
  2014年   219篇
  2013年   307篇
  2012年   400篇
  2011年   449篇
  2010年   232篇
  2009年   215篇
  2008年   329篇
  2007年   305篇
  2006年   251篇
  2005年   248篇
  2004年   272篇
  2003年   179篇
  2002年   186篇
  2001年   71篇
  2000年   88篇
  1999年   46篇
  1998年   33篇
  1997年   27篇
  1996年   42篇
  1995年   35篇
  1994年   22篇
  1993年   26篇
  1992年   43篇
  1991年   21篇
  1990年   10篇
  1989年   12篇
  1988年   10篇
  1987年   10篇
  1986年   12篇
  1985年   22篇
  1984年   13篇
  1982年   11篇
  1981年   12篇
  1980年   11篇
  1979年   10篇
  1977年   16篇
  1976年   7篇
  1975年   8篇
  1974年   12篇
  1968年   6篇
排序方式: 共有5362条查询结果,搜索用时 15 毫秒
61.
A completely “green” synthetic approach has been developed for the reduction and stabilization of Pt nanoparticles followed by self-assembly into nanowires in an aqueous β-d-glucose solution. Hydrothermal treatment initiated the reduction of Pt(IV) ions dispersed in a pH 8.0 β-d-glucose solution. The Pt nanoparticles were stabilized with oxidized glucose molecules. The Pt nanoparticles continued growing into nanowires followed by transformation into cubic nanocrystals with a rough needle surface. Evidence from TEM and FT-IR spectra reveal that carboxylate groups, which are generated by the oxidation of β-d-glucose, strongly interact with and stabilize the surface of these Pt nanostructures.  相似文献   
62.
Oxidative stress has been implicated in mediation of vascular disorders. Earlier study showed that the exposure of vascular smooth muscle cells (VSMC) to pervanadate (hydrogen peroxide plus orthovanadate) resulted in the accumulation of [3H]phosphatidylbutanol. In this study, the effect of pervanadate on the activation of p38 mitogen-activated protein kinase (p38 MAPK) was studied in the VSMC. Pervanadate treatment activated p38 MAPK in a dose-and time-dependent manner. Interestingly, specific inhibition of p38 MAPK with SB203580 attenuated pervanadate-induced PLD activation. This correlates with the finding that expression of dominant negative mutants of MKK3/6 inhibited the PLD activation. SB203580 pretreatment also inhibited other cellular stressors (i.e. high osmolarity and UV light)-induced PLD activation. The possible correlationship of p38 MAPK activation with PKC was examined since PKC is reported to be involved in the pervanadate-induced PLD activation. Calphostin C, a PKC inhibitor, suppressed pervanadate-induced p38 MAPK and PLD activation in a dose-dependent manner. These results suggest that PKC-p38 MAPK may represent an upstream pathway of PLD in the signal transduction of cellular stress.  相似文献   
63.
[reaction: see text] Beta-lactones are useful synthetic intermediates allowing access to a number of functional arrays. In this report, enantiomerically pure 4-trichloromethyl-2-oxetanone is shown to be a versatile amino acid synthon leading to a variety of gamma-substituted alpha-amino acid precursors. The utility of this methodology was demonstrated by the concise synthesis of a protected homoserine equivalent, alpha-azidobutyro lactone, and a naturally occurring alpha-amino acid from the seeds of Blighia unijugata.  相似文献   
64.
Applied Biochemistry and Biotechnology - The production of nisin by batch culture of Lactococcus lactis ATCC 11454 in MRS broth (pH 6.5), as treated in 30 assays, that were set up by a fractional...  相似文献   
65.
Mesoporous TiO2 nanocrystalline film was formed on fluorine‐doped tin oxide electrode (TiO2/FTO) and gold nanoparticles (NPs) of different sizes were loaded onto the surface with the loading amount kept constant (Au/TiO2/FTO). Visible‐light irradiation (λ>430 nm) of the Au/TiO2/FTO photoanode in a photoelectrochemical cell with the structure of photoanode|0.1 m NaClO4 aqueous solution|Ag/AgCl (reference electrode)|glassy carbon (cathode) leads to the oxidation of water to oxygen (O2). We show that the visible‐light activity of the Au/TiO2/FTO anode increases with a decrease in Au particle size (d) at 2.9≤d≤11.9 nm due to the enhancement of the charge separation and increasing photoelectrocatalytic activity.  相似文献   
66.
67.
In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p‐type doping (oxidation) of the organic semiconductor poly(3‐ hexylthiophene‐2,5‐diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near‐IR range as well as in the mid‐IR range. In the low‐oxidation regime, two absorption bands related to sub‐gap transitions appear, one in the UV/Vis range and another one in the mid‐IR range. The UV/Vis absorption gradually decreases upon further doping while the mid‐IR absorption shifts to lower energy. Additionally, electron paramagnetic resonance (EPR) measurements are performed, showing an increase of the EPR signal up to a certain doping level, which significantly decreases upon further doping. Furthermore, the absorption spectra in the UV/Vis range are analyzed in relation to the morphology (crystalline vs. amorphous) by using theoretical models. Finally, the calculated charge carriers from cyclic voltammogram are linked together with optical transitions as well as with the EPR signals upon p‐type doping. We stress that our results indicate the formation of polarons at low doping levels and the existence of bipolarons at high doping levels. The presented spectroscopic data are an experimental evidence of the formation of bipolarons in P3HT.  相似文献   
68.
69.
An in situ bimolecular reaction, in which syngas is fed with toluene as a secondary reactant (hereafter Tol in situ methylation), was studied over bifunctional catalysts comprised of methanol synthesis catalyst and H-ZSM-5 in a fixed-bed down-flow reactor at 460 psig. When physically mixed with H-ZSM-5 to form bifunctional catalysts, CrZ_HZ (Cr2O3/ZnO + HZSM-5) catalyst showed much higher activity than CZA_HZ (CuO/ZnO/Al2O3 + H-ZSM-5) in the Tol in situ methylation, while CrZ catalyst exhibited substantially lower activity than CZA in methanol synthesis. CO conversion to methanol in the Tol in situ methylation was estimated by Bz in situ methylation. The CO conversion to methanol was calculated to be in the range of 11–27 %, while that in methanol synthesis over CrZ was about 5 % at most due to chemical equilibrium limitation. By employing a silicalite-coated H-ZSM-5 (Sil/HZ) in bifunctional catalyst, xylene selectivity and para-xylene yield were much improved in the Tol in situ methylation.  相似文献   
70.
Dimethyl carbonate (DMC) was synthesized via transesterification of ethylene carbonate and methanol with ionic liquid catalysts. For this reaction, 1,4-diazobicyclo[2.2.2]octane (DABCO), [Choline]OH, and [BMIM]Cl were used as a homogeneous catalyst, and hydrotalcite, [DABCO]OH@MCF, [DABCO]Cl@MCF, and DABCO/MCF were used as a heterogeneous catalyst. To support the ionic liquids, mesoporous cellular foam (MCF) was prepared and characterized by SEM, TEM and BET surface area analyzer. The average cell and window sizes of the prepared MCF were 34.4 and 21.3 nm, respectively. The prepared MCF had a well structured three-dimensional structure. Among the homogeneous catalysts used, DABCO showed the highest DMC yield about 84 %, and among the heterogeneous catalysts, [DABCO]OH@MCF showed the highest DMC yield about 77 %. In the reusability test of the used catalysts, there was only 8 % point decrease in DMC yield with [DABCO]OH@MCF, whereas 58 percent point decrease in DMC yield with DABCO/MCF after four times recycling tests. The effects of an anion on the catalytic activity were investigated. The optimum reaction condition for DMC synthesis was also investigated with [DABCO]OH@MCF catalyst.  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