全文获取类型
收费全文 | 2516篇 |
免费 | 88篇 |
国内免费 | 9篇 |
专业分类
化学 | 1677篇 |
晶体学 | 14篇 |
力学 | 93篇 |
数学 | 355篇 |
物理学 | 474篇 |
出版年
2023年 | 19篇 |
2022年 | 51篇 |
2021年 | 53篇 |
2020年 | 60篇 |
2019年 | 71篇 |
2018年 | 52篇 |
2017年 | 39篇 |
2016年 | 103篇 |
2015年 | 68篇 |
2014年 | 85篇 |
2013年 | 151篇 |
2012年 | 171篇 |
2011年 | 180篇 |
2010年 | 113篇 |
2009年 | 93篇 |
2008年 | 156篇 |
2007年 | 141篇 |
2006年 | 117篇 |
2005年 | 114篇 |
2004年 | 113篇 |
2003年 | 84篇 |
2002年 | 98篇 |
2001年 | 35篇 |
2000年 | 41篇 |
1999年 | 26篇 |
1998年 | 28篇 |
1997年 | 19篇 |
1996年 | 20篇 |
1995年 | 21篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 21篇 |
1991年 | 22篇 |
1990年 | 10篇 |
1989年 | 13篇 |
1988年 | 9篇 |
1986年 | 7篇 |
1985年 | 10篇 |
1984年 | 17篇 |
1983年 | 7篇 |
1982年 | 15篇 |
1981年 | 14篇 |
1980年 | 15篇 |
1979年 | 14篇 |
1978年 | 19篇 |
1977年 | 7篇 |
1976年 | 10篇 |
1974年 | 9篇 |
1973年 | 8篇 |
1912年 | 3篇 |
排序方式: 共有2613条查询结果,搜索用时 9 毫秒
81.
Stasch A Roesky HW Vidovic D Magull J Schmidt HG Noltemeyer M 《Inorganic chemistry》2004,43(12):3625-3630
The carbaalane halogen derivatives [(AlX)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (X = F (9), Cl (7), Br (10), I (11)) were prepared in toluene from [(AlH)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (6) and BF(3).OEt(2), BX(3) (X = Br, I), Me(3)SnF, and Me(3)SiX (X = Cl, Br, I), respectively. A partially halogenated product [(AlH)(2)(AlX)(4)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (12) (X = Cl (approximately 40%), Br (approximately 60%)) was obtained from 5 and impure BBr(3). [(AlH)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (5) was converted to [(AlX)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (X = F (13), Cl (14), Br (15), I (16)) using BF(3).OEt(2) and Me(3)SiX (X = Cl, Br, I), respectively. The X-ray single-crystal structures of 11.C(6)H(6), 12.3C(7)H(8), 13.6C(7)H(8), and 15.4C(7)H(8) were determined. Compounds 7 and 9-11 are soluble in benzene/toluene and could be well characterized by NMR spectroscopy and MS (EI) spectrometry. The results demonstrate the facile substitution of the hydridic hydrogen atoms in 5 and 6 by the halides with different reagents. 相似文献
82.
Zhu H Chai J Chandrasekhar V Roesky HW Magull J Vidovic D Schmidt HG Noltemeyer M Power PP Merrill WA 《Journal of the American Chemical Society》2004,126(31):9472-9473
The reaction of beta-diketiminated aluminum(I) monomer LAl with a large bulky azide N3Ar' (L = HC(CMeNAr)2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3) in the temperature range from -78 degrees C to room temperature affords two different isomers 2 and 3, which have been characterized by spectroscopic and X-ray structural analyses, as well as elemental analysis. The variable-temperature 1H NMR kinetic studies of this reaction indicate the existence of the monomer LAlNAr' (1) at low temperature and the thermal stability of the compounds increases in the order of 1 < 2 < 3. 相似文献
83.
Youte JJ Barbier D Al-Mourabit A Gnecco D Marazano C 《The Journal of organic chemistry》2004,69(8):2737-2740
Potassium ferricyanide oxidation of salt 1 gave isoquinolinone 7 whose treatment with Grignard reagents resulted in a high-yield formation of substituted isoquinolinium salts 5. The selectivity of the reduction of these salts to give derivatives 6 has been studied. Particularly good selectivities (82-84%) were observed when R is a benzylic group. On the basis of these results, a practical and enantioselective synthesis of the natural alkaloid (-)-argemonine is presented. 相似文献
84.
Domínguez L van Nhien AN Tomassi C Len C Postel D Marco-Contelles J 《The Journal of organic chemistry》2004,69(3):843-856
The carbanion-mediated sulfonate intramolecular cyclizations (CSIC protocols) of glyco-alpha-sulfonamidonitriles derived from readily available monosaccharides have been extensively investigated using potassium carbonate, cesium carbonate, n-BuLi, and LDA as bases. As a result, a series of enantiomerically pure spiro(4-amino-5-H-2,3-dihydroisothiazole-1,1-dioxide) derivatives have been prepared efficiently and isolated in good yield. The synthesis of these new bicyclic systems is key to accessing a novel range of aza analogues of TSAO nucleosides (ATSAOs). 相似文献
85.
Proshlyakov DA Henshaw TF Monterosso GR Ryle MJ Hausinger RP 《Journal of the American Chemical Society》2004,126(4):1022-1023
The reaction of substrate-bound taurine/alpha-ketoglutarate dioxygenase with O2 has been studied using cryogenic continuous-flow spectroscopy. Transient absorption spectra acquired at -38 degrees C show an exponential decay of a 318-nm chromophore with an apparent rate of 1.3 s-1. The observed optical changes and their kinetics are consistent with the profile of an Fe(IV) species detected recently by M?ssbauer spectroscopy (Price et al., Biochemistry 2003, 42, 7497-7508). Resonance Raman measurement upon excitation at 363.7 nm reveal at least two oxygen isotope-sensitive vibrations at 821/787 cm-1 and 583/555 cm-1 for 16O and 18O derivatives, respectively. An additional mode is likely to be obscured by an ethylene glycol vibration at 865 cm-1 and/or 1089 cm-1. The 821 cm-1 vibration is assigned to the stretching mode of Fe(IV)=O species on the basis of its frequency and isotopic shift amplitude. The 583 cm-1 band is likely to originate from an Fe-O2 precursor of the Fe(IV)=O species, although its structural details are unclear at present. 相似文献
86.
Tandem cuprate addition-Dieckmann condensation is featured in the construction of the polyketide metabolite tetracenomycin A(2). Thus, cyclization substrate 11 was treated with Gilman cuprate Me(2)CuLi to afford anthracene 12. The phenolic acetate protecting group of 12ensured its chemoselective oxidation to reveal terminal quinone 13, which intercepts the previously reported synthesis of tetracenomycin A(2). 相似文献
87.
Karine Herreyre Denis Boudreau 《Spectrochimica Acta Part B: Atomic Spectroscopy》2004,59(12):1927-1933
The spectral background from 281 to 285 nm in the laser-enhanced ionization (LEI) spectrum of aqueous samples containing easily ionized elements (EIE) at concentrations similar to those found in blood was investigated. A complex, structured spectral background was observed, which appears in the presence of Na or K, but does not match the spectral signature of either element. The same behavior was also observed for Li. It was established that this background originates from an energy transfer between laser-excited hydroxyl (OH) molecules and ground-state EIEs. The intensity of this spectral feature was found to increase with EIE concentration and applied electrode voltage. This unexpected source of spectral interference may complicate the determination of trace metals by LEI in the presence of EIEs, since it can not be prevented by simply avoiding interference from atomic lines. 相似文献
88.
Denis N. Tomilin Maxim D. Gotsko Lyubov N. Sobenina Igor A. Ushakov Boris A. Trofimov 《Tetrahedron letters》2019,60(28):1864-1867
The cycloadducts of menthofuran with acylbromoacetylenes, (3-bromo-1,6-dimethyl-5,6,7,8-tetrahydro-2H-2,4a-epoxynaphthalen-4-yl)(aryl)methanones, rearrange (CHCl3, reflux, 1 h) to 2-(2-acylethyl)benzofurans (along with the expected 2-bromo-3-hydroxy-4,7-dimethyl-5,6,7,8-tetrahydronaphthalene-1-yl)(aryl)methanones) via 2-acylethynylmenthofurans, thus indicating the exceptionally mild and rapid transfer of four hydrogens from a cyclohexane ring to a triple bond through the furan moiety in the key intermediate 2-acylethynylmenthofuran. 相似文献
89.
Feng H Ermolat'ev DS Song G Van der Eycken EV 《The Journal of organic chemistry》2012,77(11):5149-5154
A novel microwave-assisted approach for the one-pot Cu(I)-catalyzed A(3)-coupling/decarboxylative coupling (PA(2)-coupling) of a propiolic acid, an aldehyde, and an amine, resulting in the formation of diversely substituted 1,4-diamino-2-butynes,is described. It is noteworthy that this new multicomponent coupling provides an efficient access to introduce alkyl and aryl group at the 1,4-position of the 1,4-diamino-2-butynes. 相似文献
90.
He Z Zajdlik A St Denis JD Assem N Yudin AK 《Journal of the American Chemical Society》2012,134(24):9926-9929
A reaction exemplifying migration of boron-substituted carbon is described. We show that α-boroalkyl groups of transient boroalkyl acyl azide intermediates readily migrate from carbon to nitrogen. This process allows access to a new class of stable molecules, α-boryl isocyanates, from α-borylcarboxylic acid precursors. The methodology facilitates synthesis of a wide range of α-aminoboronic acid derivatives, including α,α-disubstituted analogues. 相似文献