全文获取类型
收费全文 | 19749篇 |
免费 | 539篇 |
国内免费 | 113篇 |
专业分类
化学 | 14104篇 |
晶体学 | 189篇 |
力学 | 378篇 |
综合类 | 1篇 |
数学 | 2956篇 |
物理学 | 2773篇 |
出版年
2022年 | 164篇 |
2021年 | 200篇 |
2020年 | 294篇 |
2019年 | 290篇 |
2018年 | 186篇 |
2017年 | 181篇 |
2016年 | 406篇 |
2015年 | 357篇 |
2014年 | 451篇 |
2013年 | 929篇 |
2012年 | 977篇 |
2011年 | 1268篇 |
2010年 | 619篇 |
2009年 | 524篇 |
2008年 | 1014篇 |
2007年 | 1092篇 |
2006年 | 1073篇 |
2005年 | 1038篇 |
2004年 | 881篇 |
2003年 | 745篇 |
2002年 | 732篇 |
2001年 | 250篇 |
2000年 | 254篇 |
1999年 | 230篇 |
1998年 | 223篇 |
1997年 | 259篇 |
1996年 | 284篇 |
1995年 | 227篇 |
1994年 | 212篇 |
1993年 | 244篇 |
1992年 | 203篇 |
1991年 | 185篇 |
1990年 | 163篇 |
1989年 | 141篇 |
1988年 | 140篇 |
1987年 | 158篇 |
1986年 | 135篇 |
1985年 | 202篇 |
1984年 | 249篇 |
1983年 | 178篇 |
1982年 | 220篇 |
1981年 | 241篇 |
1980年 | 180篇 |
1979年 | 181篇 |
1978年 | 214篇 |
1977年 | 159篇 |
1976年 | 157篇 |
1975年 | 150篇 |
1974年 | 165篇 |
1973年 | 140篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Stephen G. Davies Ai M. Fletcher Gesine J. Hermann Giovanna Poce Paul M. Roberts Andrew D. Smith Miles J. Sweet James E. Thomson 《Tetrahedron: Asymmetry》2010,21(13-14):1635-1648
The doubly diastereoselective conjugate addition of the antipodes of lithium N-benzyl-N-(α-methylbenzyl)amide to a range of enantiopure N-enoyl oxazolidin-2-ones has been used as a mechanistic probe to determine that the reactive conformation is the anti-s-cis form. The β-amino carbonyl products resulting from these conjugate addition reactions are useful templates for further elaboration into an α,β,α-pseudotripeptide. 相似文献
992.
Ligia Frunza Stefan Frunza Irina Zgura Traian Beica Nicoleta Gheorghe Paul Ganea Daniel Stoenescu Adrian Dinescu Andreas Schönhals 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(4):1228-1235
Composites prepared from aerosil A380 and liquid crystals (LCs) of 4-n-alkyl-4′-cyanophenyl benzoate type, with four to six carbon atoms in the alkyl chain were investigated by infrared spectroscopy. Their high silica content (of 2–7 g aerosil/1 g of LC) was given by thermogravimetric investigations and allows the observation of a rather thin LC layer on the silica particles. Several surface species onto the external surface of the grains were demonstrated. Arguments are given that monomer and dimer species are present in the bulk cyanophenyl benzoate materials while bulk-like species along with hydrogen-bonded ones coexist in the so-called surface layer of the composites. The main interaction of LC molecules with the aerosil surface is by hydrogen bonding taking place with the involvement of the cyan group. There is a contribution of ester carbonyl group to these surface interactions but this cannot be well quantified. 相似文献
993.
Anna K. Renfrew Alexander E. Egger Rosario Scopelliti Christian G. Hartinger Paul J. Dyson 《Comptes Rendus Chimie》2010,13(8-9):1144-1150
Metal complexes bearing phosphine ligands are attracting increasing attention for their applications in medicinal chemistry. In particular, organometallic ruthenium-phosphine complexes have been found to exhibit promising antitumour activity. The synthesis, anticancer activity and reactivity of a novel bis-phosphine complex, [Ru(η6-cymene)(PPh2(o-C6H4O)-κ2-P,O)(pta)]Cl (pta = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1.]decane), is presented. The complex appears to exhibit its anticancer effect via a different mechanism to other ruthenium-arene pta complexes with labile co-ligands. 相似文献
994.
995.
John Fielden Arkady Ellern Paul Kgerler 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(9):m253-m256
The Cr4O4 hetero‐cubane‐centered octachromium(III) cluster [Cr8(PhCO2)16O4] crystallizes from fluorobenzene–acetonitrile as dodeca‐μ2‐benzoato‐tetrabenzoatotetra‐μ4‐oxido‐octachromium(III) acetonitrile tetrasolvate dihydrate, [Cr8(C7H5O2)16O4]·4C2H3N·2H2O, (I). Crystals produced by this method are significantly more stable than the originally published dichloromethane pentasolvate, [Cr8(PhCO2)16O4]·5CH2Cl2 [Atkinson et al. (1999). Chem. Commun. pp. 285–286], leading to a significantly higher quality structure and allowing the production of large quantities of high‐quality nondeuterated and deuterated material suitable for inelastic neutron scattering (INS) measurements. Compound (I) reveals a higher symmetry structure in which the cluster sits on a twofold rotation axis, and is based on an asymmetric unit containing four crystallographically independent Cr positions, two oxide ligands, eight benzoate ligands, two acetonitrile solvent molecules and one disordered water molecule. All the Cr atoms are six‐coordinate, with an octahedral geometry for the inner cubane and a more highly distorted coordination environment in the outer positions. Despite the higher symmetry, the coordination geometries observed in (I) are largely similar to the dichloromethane pentasolvate structure, indicating that crystal‐packing effects have little influence on the molecular structure of [Cr8(PhCO2)16O4]. Close structural analysis reveals that the high magnetic anisotropy observed in the INS measurements is a consequence of the distorted coordination geometry of the four outer Cr atoms. 相似文献
996.
Anuva Samanta Bijan Kumar Paul Sankar Jana Nikhil Guchhait 《Photochemistry and photobiology》2010,86(5):1022-1029
The photophysical properties of 5-(4-fluorophenyl)-2-hydroxypyridine (FP2HP) at different pH and its fluorescence response toward different transition metal ions have been studied by steady-state absorption and emission spectroscopy in combination with quantum chemical calculations. Although keto-enol tautomerization is observed in the excited state, the molecule is weakly fluorescent due to the presence of electron-rich nitrogen atom and relatively electron-deficient fluorine atom, which may lead to photoinduced electron transfer process. In the presence of the transition metal ions, such as Zn2+, Cd2+, Hg2+, etc., the studied molecule exhibits changes in its absorption and emission properties. The present system shows fluorescence enhancement instead of usual quenching in presence of the transition metal ions, such as Fe2+ and Cu2+. Spectral observation leads to the interpretation that this structurally simple molecule can be effectively utilized as a chelation-enhanced fluorescence-based chemosensor for the detection of transition metal ions. The experimental findings corroborate well with theoretical calculations at Hartree–Fock level using 6-31G** and lanl2dz basis sets. 相似文献
997.
998.
999.
1000.
Facile,Template‐Free Synthesis of Stimuli‐Responsive Polymer Nanocapsules for Targeted Drug Delivery