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   10865篇
  免费   443篇
  国内免费   69篇
化学   7549篇
晶体学   110篇
力学   316篇
数学   956篇
物理学   2446篇
  2023年   60篇
  2022年   217篇
  2021年   261篇
  2020年   202篇
  2019年   200篇
  2018年   200篇
  2017年   176篇
  2016年   364篇
  2015年   315篇
  2014年   421篇
  2013年   729篇
  2012年   852篇
  2011年   946篇
  2010年   563篇
  2009年   457篇
  2008年   698篇
  2007年   671篇
  2006年   600篇
  2005年   556篇
  2004年   475篇
  2003年   391篇
  2002年   408篇
  2001年   237篇
  2000年   198篇
  1999年   145篇
  1998年   81篇
  1997年   90篇
  1996年   107篇
  1995年   89篇
  1994年   84篇
  1993年   60篇
  1992年   63篇
  1991年   54篇
  1990年   53篇
  1989年   40篇
  1988年   27篇
  1987年   16篇
  1986年   11篇
  1985年   33篇
  1984年   22篇
  1983年   17篇
  1982年   20篇
  1981年   19篇
  1980年   14篇
  1979年   16篇
  1978年   16篇
  1977年   13篇
  1976年   13篇
  1975年   13篇
  1972年   10篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
251.
We developed an effective isolation method of magnesium lithospermate B from Salviae miltiorrhizae Radix and found for the first time that magnesium lithospermate B shows strong in vitro inhibition (IC50=0.04 microM) of aldose reductase (AR), 2.5 times than that of clinically used epalrestat (IC50=0.1 microM) and accumulation of fibronectin dose dependently.  相似文献   
252.
A three-step one-pot synthesis of fenestranes from a readily available enyne and an alkyne diester has been carried out with cobalt nanoparticles and palladium(II) as catalysts.  相似文献   
253.
General methods for combining multiple, independent measurements for minimized uncertainty are presented. Although the methods are general, the presentation is motivated by the reduction of heat exchanger performance data. It is demonstrated that the prevalent practice of using the arithmetic mean of two measured heat transfer rates for the evaluation of heat exchanger performance, which is widely adopted in the literature and used in engineering standards, does not always lead to reduced experimental uncertainty and very rarely—if ever—leads to a minimized experimental uncertainty. For the case of averaging two redundant measurements, simple criteria are developed to determine whether using the arithmetic mean or a single measurement yields a smaller absolute or relative uncertainty. Then, more general methods are proposed in the form of weighted-linear averages, in which the weight factors are determined to minimize the combined uncertainty. The methods are generally applicable to averaging any number of redundant measurements with varying uncertainties.  相似文献   
254.
The effect of alcohol washing on the anatase-rutile transition of precipitated titanium oxide was investigated using X-ray powder diffraction, Fourier-transform IR spectroscopy, and thermogravimetry. Alcohol (butanol) rinsing accelerated the anatase-rutile transition of precipitated titanium oxide powder so that the onset temperature of transition decreased drastically from 800 degrees C for water-washed powder to 550 degrees C for alcohol-rinsed powder. Alternation of transition kinetics and mechanisms by rinsing media could be confirmed from the analysis of temperature and time dependence of rutile content. The attributability of the chemical state of anatase after crystallization, which contained H(2)O, OH, and organic residues, to the change of transition kinetics with alcohol rinsing will be discussed. Two mechanisms, the effect of residual organics and/or H(2)O(OH), could be suggested on the basis of analysis of the difference between chemical states of water-washed anatase and alcohol-rinsed powder. Copyright 2000 Academic Press.  相似文献   
255.
The mechanism of [2 + 2] cycloadditions activated by visible light and catalyzed by bis-cyclometalated Rh(iii) and Ir(iii) photocatalysts was investigated, combining density functional theory calculations and spectroscopic techniques. Experimental observations show that the Rh-based photocatalyst produces excellent yield and enantioselectivity whereas the Ir-photocatalyst yields racemates. Two different mechanistic features were found to compete with each other, namely the direct photoactivation of the catalyst–substrate complex and outer-sphere triplet energy transfer. Our integrated analysis suggests that the direct photocatalysis is the inner working of the Rh-catalyzed reaction, whereas the Ir catalyst serves as a triplet sensitizer that activates cycloaddition via an outer-sphere triplet excited state energy transfer mechanism.

The mechanism of [2 + 2] cycloadditions activated by visible light and catalyzed by bis-cyclometalated Rh(iii) and Ir(iii) photocatalysts was investigated, combining density functional theory calculations and spectroscopic techniques.  相似文献   
256.
The enzyme from halophilic microorganisms often has unique properties such as organic-solvent-tolerance. In this study, a novel organic-solvent-tolerant α-amylase gene was cloned from the mild halophile Exiguobacterium sp. DAU5. The open reading frame (ORF) of the enzyme consisted of 1,545 bp and encoded 514 amino acids, the primary sequence revealed that it belongs to the glycoside hydrolase (GH) family 13. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed an AmyH monomer of 57 kDa. The enzyme exhibited maximal activity at 40 °C in pH?8.5 glycine–NaOH buffer, and the activity was strongly inhibited by Zn2+, Cu2+, and Fe2+. The α-amylase AmyH exhibited high hydrolysis activity toward soluble starch, and the major hydrolysis products were maltose, maltotriose, and maltopentaose; the AmyH could not efficiently hydrolyze oligosaccharides smaller than maltoheptaose, nor could it act on the β-1,4 or α-1,6 glucosidic bonds in xylan or pullulan, respectively. In addition, the α-amylase exhibited better tolerance to organic solvents, as it was stable in the presence of dimethylsulfoxide (DMSO), methanol, ethanol, and acetone. Base on all of these results, the enzyme could be useful for practical application in the bakery industry and in biotechnological processes that occur in the presence of organic solvents.  相似文献   
257.
LiNi1 ? y Ti y O2 (0.000 ≤ y ≤ 0.100) and LiNi0.990M0.010O2 (M = Zn, Al, and Ti) were synthesized by the combustion method. The effects of Zn, Al and Ti substitution for Ni of LiNiO2 on the electrochemical properties of LiNiO2 were investigated. LiNi0.995Ti0.005O2 has the largest first discharge capacity (188.1 mA h/g) among the Ti-substituted samples. LiNi0.990Ti0.010O2 has a relatively large first discharge capacity (185.5 mA h/g) and a relatively good cycling performance. Among LiNi0.990M0.010O2 (M = Ni, Zn, Al, and Ti), LiNiO2 has the largest discharge capacities at a rate of 0.1 C from n = 1(189.3 mA h/g) to n = 10. LiNi0.990Al0.010O2 has the lowest discharge capacities from n = 1 to n = 10, but it has the best cycling performance. LiNi0.990Zn0.010O2 showed poor crystallinity, LiNi0.990Ti0.010O2 showed high cation mixing, and LiNi0.990Al0.010O2 had good crystallinity and showed low cation mixing. Fewer occurrence of phase transitions and the least change of the ?dx/|dV| vs. voltage curve at the second cycle from the curve at the first cycle of LiNi0.990Al0.010O2 suggest that Al substitution stabilizes the structure and leads to a good cycling performance.  相似文献   
258.
Physicochemical properties of materials can be amended by altering their physical structure through different processing conditions. The present study was conducted to investigate the post-synthesis structural variations and physico-mechanical properties of bacterial cellulose (BC) sheets prepared using different drying methods. Wet BC sheets of the same origin were freeze dried (BC-FD), dried at room temperature (25 °C) (BC-DRT), and dried at elevated temperature (50 °C) (BC-DHT). FE-SEM micrographs revealed that BC-DRT and BC-DHT had a more tightly packed and compact structure than the loosely held fibrils of BC-FD. XRD analysis revealed the relative crystallinity of the BC sample to be 64.60, 59.16, and 47.20 % for BC-DHT, BC-DRT and BC-FD, respectively. The water holding capacity (WHC) of the BC-FD was higher than that of the other two samples. Four consecutive drying and rewetting cycles demonstrated that the WHC of all samples decreased with each cycle. The WHC of BC-DRT and BC-DHT was reduced to almost 0 after the first drying cycle, but the BC-FD samples were able to regain some of their WHC. The tensile strength and elongation modulus were in the order of BC-DHT > BC-DRT > BC-FD. Overall, the results of this study revealed that the post-synthetic processing conditions had a strong effect on the structure and physico-mechanical properties of BC.  相似文献   
259.
The total synthesis of (+)-valienamine and (−)-1-epi-valienamine was concisely accomplished from readily available d-glucose via a highly diastereoselective amination of chiral benzylic ether using chlorosulfonyl isocyanate, intramolecular olefin metathesis, and diastereoselective reduction of cyclic enone using l-Selectride as the key steps.  相似文献   
260.
Trisubstituted thiazoles were synthesized with excellent yields using ligand-free, palladium-catalyzed, direct 5-arylation of 2,4-disubstituted thiazole and conventional or microwave-assisted heating. The palladium-catalyzed reaction yields were significantly influenced by LiCl additive, solvent, and heating method. The reaction times were reduced dramatically by employing microwave radiation instead of conventional heating. The synthetic methods can be applied to diverse 2,4,5-trisubstituted thiazoles by varying the aryl bromide and disubstituted thiazole reactants.  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