全文获取类型
收费全文 | 31688篇 |
免费 | 4614篇 |
国内免费 | 5149篇 |
专业分类
化学 | 24172篇 |
晶体学 | 489篇 |
力学 | 1581篇 |
综合类 | 493篇 |
数学 | 3877篇 |
物理学 | 10839篇 |
出版年
2024年 | 32篇 |
2023年 | 317篇 |
2022年 | 593篇 |
2021年 | 790篇 |
2020年 | 896篇 |
2019年 | 1028篇 |
2018年 | 889篇 |
2017年 | 844篇 |
2016年 | 1323篇 |
2015年 | 1420篇 |
2014年 | 1767篇 |
2013年 | 2341篇 |
2012年 | 2583篇 |
2011年 | 2806篇 |
2010年 | 2172篇 |
2009年 | 2187篇 |
2008年 | 2526篇 |
2007年 | 2315篇 |
2006年 | 2155篇 |
2005年 | 1857篇 |
2004年 | 1606篇 |
2003年 | 1383篇 |
2002年 | 1590篇 |
2001年 | 1214篇 |
2000年 | 973篇 |
1999年 | 716篇 |
1998年 | 463篇 |
1997年 | 416篇 |
1996年 | 356篇 |
1995年 | 294篇 |
1994年 | 259篇 |
1993年 | 234篇 |
1992年 | 214篇 |
1991年 | 159篇 |
1990年 | 142篇 |
1989年 | 126篇 |
1988年 | 86篇 |
1987年 | 72篇 |
1986年 | 56篇 |
1985年 | 54篇 |
1984年 | 33篇 |
1983年 | 23篇 |
1982年 | 16篇 |
1981年 | 16篇 |
1980年 | 18篇 |
1979年 | 8篇 |
1978年 | 25篇 |
1977年 | 10篇 |
1976年 | 12篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 312 毫秒
981.
Integration of gene amplification and capillary gel electrophoresis on a polydimethylsiloxane-glass hybrid microchip 总被引:5,自引:0,他引:5
We report on the development of a hybrid polydimethylsiloxane (PDMS)-glass microchip for genetic analysis by functional integration of polymerase chain reaction (PCR) and capillary gel electrophoresis (CGE), and on related temperature control systems for PCR on a PDMS-glass hybrid microchip. The microchip was produced by molding PDMS against a microfabricated master with comparatively simple and inexpensive methods. PCR was successfully carried out on the PDMS-glass hybrid microchip with 500 bp target of lambdaDNA and the amplified gene was subsequently analyzed by CGE on the same PDMS-glass microchip. The chip could be considered as an inexpensive single-use apparatus compared to glass or silicon-made microchips for the same purpose. 相似文献
982.
Yu Mao Wenxuan Zhao Shuo Lu Lei Yu Yi Wang Yong Liang Shengyang Ni Yi Pan 《Chemical science》2020,11(19):4939
Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C–C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac)2. The photoexcitation of copper acetylides with electron-rich NEt3 as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne.Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C–C bond formation. 相似文献
983.
Chains, ladders and sheets of d metal–organic polymers generated from the flexible bipyridyl ligands
Yaqiong Gong Ruihu Wang Daqiang Yuan Weiping Su Yougui Huang Chengyang Yue Feilong Jiang Maochun Hong 《Polyhedron》2007,26(18):5309-5316
By use of the three-layer diffusion method, reactions of flexible bipyridyl ligands (4,4′-bpp or 3,3′-bpp) with M(II) salts (M = Zn, Cd) and multi-carboxylate ligands resulted in the formation of four interesting d10 metal–organic coordination polymers: [Zn(μ-4,4′-bpp)Br2]n (1), [Zn(μ-4,4′-bpp)(1,2-bdc)]n · nH2O (2), [Zn(μ-3,3′-bpp)(1,3-bdc)]n · nCH3OH · 2nH2O (3) and [Cd(μ-3,3′-bpp)(C4H2O4)]n · 3nH2O (4) (4,4′-bpp = 2,2′-bis(4-pyridylmethyleneoxy)-1,1′-biphenylene; 3,3′-bpp = 2,2 ′-bis(3-pyridylmethyleneoxy)-1,1′-biphenylene; bdc=benzenedicarboxylate, C4H4O4 = fumaric acid). Complex 1 has a 2D sheet structure consisting of two unusual zigzag Zn(II) chains which are nearly perpendicular to each other. Complex 2 is comprised of two-leg ladders, in which [Zn(4,4′-bpp)] chains serve as the side rails and 1,2-bdc ligands serve as the cross rungs. In complex 3, every two 1,3-bdc ligands connect the neighbouring Zn(II)-3,3′-bpp dimetallic rings in η1 coordination modes into an interesting chain structure. Complex 4 consists of an anionic macrocycle-containing cadmium dicarboxylate sheets that are separated by 3,3′-bpp. These d10 metal complexes exhibit high thermal stabilities and strong luminescence efficiencies. 相似文献
984.
Bound and resonance states of HO(2) are calculated quantum mechanically using both the Lanczos homogeneous filter diagonalization method and the real Chebyshev filter diagonalization method for nonzero total angular momentum J=6 and 10, using a parallel computing strategy. For bound states, agreement between the two methods is quite satisfactory; for resonances, while the energies are in good agreement, the widths are in general agreement. The quantum nonzero-J specific unimolecular dissociation rates for HO(2) are also calculated. 相似文献
985.
The cyclodextrins(CDs) are a class of cyclic oligosaccharides made up of six(a), seven(a)or more [a-(1,4)-linked] D-glucopyranose units, and shaped like truncated cones with primary and secondary hydroxyl groups crowning the narrower rim and wider rim respectively. As they have a hydrophobic cavity of appropriate dimension, they can bind with various guest moleculars, such as hydrocarbon, cyclohexane, aromatic compounds, to form inclusion complexes. The cyclodextins inclusion complexation has been considered an ideal model mimicking the enzyme-substrate interaction and a lot of effect has been devoted to it. In this paper, we report our investigation on the inclusion complexation behavior of a-cyclodextrin(a-CD) with diphenyl compounds in order to further explore the molecular recongnition mechanism of 2:1 inclusion complexation of a-CD with aromatic compounds.Figure 1: Possible structures of the inclusion compounds.The inclusion complexation behavior of a-CD with sym-diphenyl-urea, sym-diphenyl-thiourea and diphenyl kotone as respective guest moleclars was studied by ultraviolet spectrometric titrations.The absorption spectral changes observed for the compounds in the absence and presence of a-CD are used to draw the corresponding Benesi-Hildebrand plots and caculate the complex stability constant value (Ks) for the inclusion compounds.The 2:1 inclusion complexations show higher binding constants by cooperative binding of one guest molecular in the closely two hydrophobic cyclodextrin cavites as compared with 1:1 inclusion complexations.The highest value observed for sym-diphenyl-urea could be due to the formation of a hydrogen bond between the carbonyl group and the hydrogen in the hydroxyl group of CD and this is not possible with sym-tiphenyl-thiourea. The lowest value observed for diphenyl kotone indicate the hydrophobic interaction is one of the binding force of cyclodextrin inclusion complex. 相似文献
986.
PEMFC催化剂的研究:自制抗CO中毒Pt-Ru/C电催化剂的性质 总被引:4,自引:0,他引:4
用胶体法制备了抗CO中毒PEMFC阳极Pt-Ru/C电催化剂(标记为THYT-2),对 比研究了THYT-2与Johnson Matthey (JM)公司同类品牌Pt-Ru/C催化剂的电化学及 其它物理化学性能。结果表明,THYT-2电催化剂在甲醇燃料电池和CO/H_2(Φ_ (CO) = 1 * 10~(-4))的氢氧燃料电池中的电催化行为与JM催化剂相当,但THYT- 2在低浓度CO氢气燃料中的电池性能更好。两种催化剂的其它物理化学性质具有类 似性:XPS分析结果表明THYT-2和JM催化剂 中都有三种不同价态的Pt存在:即金 属态Pt(0)、氧化态Pt(II)和Pt(IV)。HRTEM测试结果表明两种催化剂的粒径处在2 ~3 mn左右,这可能是它们拥有良好电化学性能的主要原因之一。本文还对催化剂 中Pt与Ru组分的分布和相互作用进行了讨论,提出了改进Pt-Ru/C电催化剂的思路 。 相似文献
987.
Huaping Liu Guoan Cheng Ruiting Zheng Yong Zhao Changlin Liang 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):17-22
The Ni/CNT catalyst was fabricated by directly dipping carbon nanotube precursors refluxed in 4 M of nitric acid into Ni electroless plating bath, and used to synthesize new carbon nanotubes. The experimental results indicate that the duration of acid-treatment of carbon nanotubes precursors exerts a great influence on the catalysis of Ni/CNT in the synthesis of carbon nanotubes and hence the structures of the new carbon nanotubes. When the carbon nanotubes precursors were refluxed for 0.5 h in 4 M of nitric acid, bamboo-shaped carbon nanotubes (BSCNT) or Y junction carbon nanotubes in the carbon products were obtained. As the duration of acid-treatment of carbon nanotubes precursors increased to 6 h, the as-prepared Ni/CNT displayed higher activity, and the carbon nanotube products were high pure without any Y junction structure or any separation layers in hollow. 相似文献
988.
We investigate the distribution of the number of photons emitted by a single molecule undergoing a spectral diffusion process and interacting with a continuous wave laser field. The spectral diffusion is modeled based on a stochastic approach, in the spirit of the Anderson-Kubo line shape theory. Using a generating function formalism we solve the generalized optical Bloch equations and obtain an exact analytical formula for the line shape and Mandel's Q parameter. The line shape exhibits well-known behaviors, including motional narrowing when the stochastic modulation is fast and power broadening. The Mandel parameter, describing the line shape fluctuations, exhibits a transition from a quantum sub-Poissonian behavior in the fast modulation limit to a classical super-Poissonian behavior found in the slow modulation limit. Our result is applicable for weak and strong laser fields, namely, for arbitrary Rabi frequency. We show how to choose the Rabi frequency in such a way so that the quantum sub-Poissonian nature of the emission process becomes strongest. A lower bound on Q is found and simple limiting behaviors are investigated. A nontrivial behavior is obtained in the intermediate modulation limit, when the time scales for spectral diffusion and the lifetime of the excited state become similar. A comparison is made between our results and previous ones derived, based on the semiclassical generalized Wiener-Khintchine formula. 相似文献
989.
990.
Ben‐Yong Lou Yan‐Bin Huang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(4):o246-o248
4,4′‐Bipyridyl N,N′‐dioxide crystallizes with 3‐hydroxy‐2‐naphthoic acid to give a centrosymmetric three‐component adduct, C10H8N2O2·2C11H8O3, which is engineered into a two‐dimensional layer structure by two kinds of π–π interactions. Weak C—H⋯O interactions further link the two‐dimensional structure into a three‐dimensional structure. 相似文献