全文获取类型
收费全文 | 6110篇 |
免费 | 147篇 |
国内免费 | 29篇 |
专业分类
化学 | 4231篇 |
晶体学 | 49篇 |
力学 | 175篇 |
数学 | 909篇 |
物理学 | 922篇 |
出版年
2021年 | 51篇 |
2020年 | 63篇 |
2019年 | 58篇 |
2018年 | 53篇 |
2017年 | 38篇 |
2016年 | 91篇 |
2015年 | 96篇 |
2014年 | 107篇 |
2013年 | 306篇 |
2012年 | 243篇 |
2011年 | 284篇 |
2010年 | 195篇 |
2009年 | 159篇 |
2008年 | 296篇 |
2007年 | 291篇 |
2006年 | 299篇 |
2005年 | 275篇 |
2004年 | 238篇 |
2003年 | 245篇 |
2002年 | 247篇 |
2001年 | 92篇 |
2000年 | 79篇 |
1999年 | 75篇 |
1998年 | 68篇 |
1997年 | 64篇 |
1996年 | 76篇 |
1995年 | 59篇 |
1994年 | 69篇 |
1993年 | 70篇 |
1992年 | 57篇 |
1991年 | 80篇 |
1990年 | 54篇 |
1989年 | 75篇 |
1988年 | 56篇 |
1987年 | 44篇 |
1986年 | 49篇 |
1985年 | 122篇 |
1984年 | 94篇 |
1983年 | 71篇 |
1982年 | 110篇 |
1981年 | 119篇 |
1980年 | 114篇 |
1979年 | 87篇 |
1978年 | 99篇 |
1977年 | 103篇 |
1976年 | 103篇 |
1975年 | 82篇 |
1974年 | 75篇 |
1973年 | 68篇 |
1972年 | 39篇 |
排序方式: 共有6286条查询结果,搜索用时 15 毫秒
981.
Derrien G Charnay C Zajac J Jones DJ Rozière J 《Chemical communications (Cambridge, England)》2008,(27):3118-3120
Copper-containing mesoporous silica spheres of size in the colloidal range with perfect conservation of pore-ordering, shape and monodispersity and high intra-pore metal dispersion were prepared via a new one-step synthesis and functionalisation route. 相似文献
982.
983.
984.
985.
986.
987.
Mishra S Jeanneau E Chermette H Daniele S Hubert-Pfalzgraf LG 《Dalton transactions (Cambridge, England : 2003)》2008,(5):620-630
The solvated yttrium iodide precursors [Y(L)(8)]I(3) (L = DMSO or DMF), prepared in situ by stirring YI(3)(Pr(i)OH)(4) in DMSO or DMF, react with CuI in the presence of NH(4)I to give ionic hetero-metallic species [Y(DMSO)(8)][Cu(2)(mu-I)I(4)] (1) and [Y(DMF)(8)][Cu(4)(mu(3)-I)(2)(mu-I)(3)I(2)] (2) in excellent yields. Re-crystallization of 1 from DMF afforded the mixed-solvate complex [Y(DMSO)(6)(DMF)(2)][CuI(3)][I] (3). Compounds 2 and 3 undergo unique crystal-to-crystal transformation via progressive substitution of DMF by water molecules in a confined, solvent-free environment. Thus, crystals of 3 transform into [Y(DMSO)(6)(H(2)O)(2)][CuI(3)][I] (4), whereas a discrete ion-pair assembly of 2 is first converted into a 1-D zig-zag structure [Y(DMF)(6)(H(2)O)(2)](3+)[Cu(7)(mu(4)-I)(3)(mu(3)-I)(2)(mu-I)(4)(I)](1infinity)(3-) (5) and finally into a 2-D sheet containing mixed-valent copper atoms, [Y(DMF)(6)(H(2)O)(3)](3+)[Cu(I)(7)Cu(II)(2)(mu(3)-I)(8)(mu-I)(6)](2infinity)(3-) (6). The bi- and tetrafurcate H-bonding between water ligands on yttrium and iodides of the Cu-I cluster plays a pivotal role in the evolution of structures 4-6. Formation of a wide range of iodocuprate structures in 1-6, from discrete mono-, di- or tetranuclear units to one- and two-dimensional extended arrays, reflects the influence of solvated yttrium cations on the nuclearity and dimensionality of Cu-I clusters. TG-DTA-MS studies and DFT calculations for these complexes have also been carried out in order to determine their thermal stability and have insight about aforesaid transformations. 相似文献
988.
Zhang X Li QS Xie Y King RB Schaefer HF 《Dalton transactions (Cambridge, England : 2003)》2008,(35):4805-4810
The cyclopentadienylchromium carbonyls Cp(2)Cr(2)(CO)(n) and Cp*(2)Cr(2)(CO)(n) (Cp = eta(5)-C(5)H(5) and Cp* = eta(5)-Me(5)C(5); n = 3, 2) have been studied by density functional theory using the B3LYP and BP86 functionals. Triplet and singlet structures are found for Cp(2)Cr(2)(CO)(3), with the triplet isomer having an apparent Cr[triple bond, length as m-dash]Cr triple bond (2.295 A by BP86) and predicted to have a lower energy than the singlet isomer having an apparent Cr[quadruple bond, length as m-dash]Cr quadruple bond (2.191 A by BP86). Quintet, septet, and singlet structures, as well as a highly spin contaminated triplet structure, were found for the dicarbonyl Cp(2)Cr(2)(CO)(2). In all of the Cp(2)Cr(2)(CO)(n) (n = 3, 2) structures the carbonyls are asymmetric semi-bridging groups, typically with differences of 0.3-0.5 A between the shortest and longest M-C distances. Very little difference was found between the structures and energetics of the corresponding Cp and Cp* derivatives. These DFT studies suggest that the reported unstable photolytic decarbonylation product of Cp*(2)Cr(2)(CO)(4), characterized only by its infrared nu(CO) frequencies, is the singlet isomer of the tricarbonyl Cp*(2)Cr(2)(CO)(3). 相似文献
989.
Paolini J Tomi P Bernardini AF Bradesi P Casanova J Kaloustian J 《Natural product research》2008,22(14):1270-1278
The composition of the essential oil of Cistus albidus (L.) obtained from plants growing wild in Provence (France) has been investigated using GC-RI (RI = retention indices), GC/MS and (13)C-NMR. Eighty-eight components were reported accounting for 81.8% of the essential oil. This essential oil was characterized by a high content of sesquiterpenes with alpha-zingiberene (12.8%), alpha-curcumene (7.7%), (E)-beta-caryophyllene (5.9%), alpha-cadinol (5.4%), alpha-bisabolol (4.1%), caryophyllene oxide (3.8%), allo-aromadendrene (3.4%), delta-cadinene (3.4%), and germacrene D (3.1%) being the main components. 相似文献
990.
5',8-Purine cyclonucleosides constitute an important class of oxidatively generated tandem lesions whose formation involves initial hydroxyl radical-mediated hydrogen atom abstraction from the 5-hydroxymethyl group of 2-deoxyribose followed by intramolecular cyclization. The present study deals with the synthesis of the 5'S diastereomer of 5',8-cyclo-2'-deoxyadenosine containing di- and tri-oligodeoxynucleotides as an attempt to delineate the conformational changes induced in the DNA fragments by the presence of a rigid modified nucleoside. For this purpose, extensive 1D and 2D NMR measurements that were completed by DFT theoretical calculations were performed. As a striking result, it was found that the covalent bond between C(5') and C(8) in the investigated purine cyclonucleoside induces an unusual West ((0)T(1)) conformation of the furanose ring. Thus it can be postulated that the rigid structure of the tandem lesion would strongly perturb the global geometry of oligonucleotides at the site of the modification and therefore affect the enzymatic activity of DNA polymerases and repair enzymes. 相似文献