全文获取类型
收费全文 | 29219篇 |
免费 | 4630篇 |
国内免费 | 3114篇 |
专业分类
化学 | 21342篇 |
晶体学 | 365篇 |
力学 | 1688篇 |
综合类 | 149篇 |
数学 | 3473篇 |
物理学 | 9946篇 |
出版年
2024年 | 36篇 |
2023年 | 515篇 |
2022年 | 616篇 |
2021年 | 870篇 |
2020年 | 1100篇 |
2019年 | 1131篇 |
2018年 | 901篇 |
2017年 | 816篇 |
2016年 | 1368篇 |
2015年 | 1334篇 |
2014年 | 1550篇 |
2013年 | 2066篇 |
2012年 | 2688篇 |
2011年 | 2757篇 |
2010年 | 1851篇 |
2009年 | 1817篇 |
2008年 | 1978篇 |
2007年 | 1788篇 |
2006年 | 1667篇 |
2005年 | 1422篇 |
2004年 | 1091篇 |
2003年 | 887篇 |
2002年 | 954篇 |
2001年 | 711篇 |
2000年 | 565篇 |
1999年 | 607篇 |
1998年 | 486篇 |
1997年 | 484篇 |
1996年 | 483篇 |
1995年 | 382篇 |
1994年 | 331篇 |
1993年 | 251篇 |
1992年 | 248篇 |
1991年 | 215篇 |
1990年 | 183篇 |
1989年 | 148篇 |
1988年 | 103篇 |
1987年 | 115篇 |
1986年 | 95篇 |
1985年 | 92篇 |
1984年 | 55篇 |
1983年 | 48篇 |
1982年 | 40篇 |
1981年 | 22篇 |
1980年 | 15篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1976年 | 15篇 |
1975年 | 12篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
The hydrogen abstraction reaction of O(^3P) with Si2H6 has been studied theoretially. Two transition states of ^3A″ and ^3A′ symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 leve with 6-311G (d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200-3000K using canonical variational transition-state sheory (CVT) with small curvature tunneling effect(SCT). The calculated CVT/SCT rate constants match well with the experimental value. 相似文献
962.
963.
No K Bok JH Suh IH Kang SO Ko J Nam KC Kim JS 《The Journal of organic chemistry》2004,69(20):6938-6941
A series of novel tetrahomodioxacalix[4]biscrowns with crown-2, crown-3, crown-4, crown-5, and crown-6 units were synthesized. Conformations of each product are dependent on the base used and their conformation stabilities. All conformations were proven by NMR spectra and/or X-ray crystal structures. The 1,3-alternate homodioxacalix[4]biscrown-4 (4b) shows the best selectivity for K+, whereas the 1,3-alternate homodioxacalix[4]crown-5 (5) does for Cs+. Those selectivities are attributable to electrostatic interaction between the metal ion and the crown ring, as well as a pi-metal complexation. However, the C-1,2-alternate conformation does not take the metal ions regardless of the crown species as a result of steric hindrance from the methylene bridge of an ArCH2Ar unit. 相似文献
964.
Wang Y Liu Z Han B Huang Y Zhang J Sun D Du J 《The journal of physical chemistry. B》2005,109(25):12376-12379
We report a facile route to pattern polymer surfaces with the aid of compressed CO(2), termed the compressed-CO(2)-assisted imprint method. In this method, compressed CO(2) serves as a plasticizer for polymers (such as poly(methyl methylate) and polystyrene), which leads to a tremendous reduction in the glass transition temperature and viscosity of the polymers. Nylon fabrics and anode aluminum oxide porous membranes are used as molds, respectively, to pattern the softened polymers at relatively low temperatures, resulting in patterns at the scale of micrometers and nanometers on the surface of polymer films. The patterned structures can be tuned by changing CO(2) pressure and temperature in the imprinting process. This method is simple and environmentally benign. It also can be operated at low temperatures, for instance, ambient temperature. 相似文献
965.
The reaction of Co(NO3)2·6H2O with two equivalents of PPz (PPz = piperazine hexahydrate) and two equivalents of NH4SCN in CH3OH afforded the complex [Co(NCS)2(PPz)2(CH3OH)2]. The reaction of Ni(NO3)2·6H2O with two equivalents of PPz and four equivalents of NH4SCN in CH3OH afforded the complex [Ni(NCS)4(PPz)2]. Their IR spectra have been recorded and the structures have been determined. Crystal data for 1 : space group P&1bar;, a = 6.7208(6) Å, b = 8.4310(8) Å, c = 8.5923(8) Å, a = 77.881(2)°, β = 76.342(2)°, γ = 83.936(2)°, V = 461.75(1) Å3, Z = 1 with final residuals R1 = 0.0650 and wR2 = 0.1725. Crystal data for 2 : space group P2(1)/n, a = 7.4209(6) Å, b = 11.0231(9) Å, c = 12.317(1) Å, β = 96.642(9)°, V = 1000.9(2) Å3, Z = 2 with final residuals R1 = 0.0378 and wR2 = 0.0809. Important NCS—H‐N and O‐H—N(PPz) hydrogen‐bonding interactions in compound 1 and NCS···H‐N hydrogen‐bonding interactions and NCS—SCN interactions in compound 2 play a significant role in aligning the polymer strands in crystalline solids. 相似文献
966.
The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain. 相似文献
967.
Wei Y Guo X Shuang S Dong C Sun X Wong M 《Journal of photochemistry and photobiology. B, Biology》2005,81(3):190-194
Novel dimeric capsules are generated from the noncovalent assembly of 5, 10, 15, 20-tetrakis(4-N-ethylpyridiniurmyl)prophyrin (TEPyP) and tetracarboxyl-phenyl calix[4]arene. The self-assembly system was investigated based on UV-Vis absorption and fluorescent spectra. The factors affecting the interaction process including pH and concentration were examined in detail. The association constants between TEPyP and calix[4]arene were determined by the nonlinear least squares fit. The results showed that the basic medium is favourable to the interaction and electrostatic interaction was determinate in the processes of self-assembly process. The related mechanism was discussed. 相似文献
968.
Ya Wen TANG Shuang CAO Ling Ling ZHANG Jian Chun BAO Ping ZHOU Tian Hong LU 《中国化学快报》2006,17(12):1623-1626
The performance of the direct formic acid fuel cell (DFAFC) is considerably higher than the direct methanol fuel cell (DMFC) because of some characteristics of formic acid1. For example, formic acid is non-toxic. Formic acid has two orders of magnitude smaller crossover flux through a Nafion membrane than methanol2. In DFAFC, the concentration of formic acid can be as high as 20 mol/L, while the best concentration of methanol in DMFC is only about 2 mol/L3. Thus, the power density of … 相似文献
969.
Sun T Zhang L Wang Y Zhao S Peng B Li M Yu J 《Journal of colloid and interface science》2002,255(2):241-247
The influences of two commercial demulsifiers that have a straight chain and branch chain, respectively, on the dilational viscoelasticity of an oil-water interfacial film containing surface-active fractions from crude oil were investigated. The branch-chain demulsifier AE-121 could efficiently substitute surface-active fractions of different average molecular weights from the oil-water interface, while straight-chain SP-169 could only efficiently substitute those of large average molecular weight. It was apt to form a mix-adsorption layer with surface-active fractions of small average molecular weight. The results showed that the molecular size (or represented by average molecular weights) of the surface-active fractions was an important factor influencing the reciprocity of demulsifiers and surface-active fractions at the oil-water interface. This effect could be well explained by the difference between sizes of surface-active fraction molecules and vacancies between demulsifier molecules at the interface. The results of SDBS also proved this explanation. 相似文献
970.
ClnOPodiumpoIycePhalum(VantjCYWhetHsuancalled'DuanXielin'inChineseisusedinfolkmedicineforthetreatInentofhaemorrhagiadisease.lInordertofmdtheactivecomPounds,studiesonthechedricalconstituentsofthewholeplan,collectedatHuoShanofAnhuiprovince,werecarriedout.Fromthealcoholicextracts,wehaveisolatedanewanthraquinone,Glyceroyl-l,6,8-trihydroxy-3-methyl-9)lO-dioxo-2-anthrcenecarboxylateI(Figurel).Iwasobtainedasredneedles,mP:ll9-l2l"C.TheHR-MSdareaffordedthefor-mulaasCl9Hl6O9(Found388.O791;… 相似文献