全文获取类型
收费全文 | 2133篇 |
免费 | 50篇 |
国内免费 | 13篇 |
专业分类
化学 | 1355篇 |
晶体学 | 19篇 |
力学 | 88篇 |
数学 | 371篇 |
物理学 | 363篇 |
出版年
2022年 | 25篇 |
2021年 | 34篇 |
2020年 | 27篇 |
2019年 | 41篇 |
2018年 | 37篇 |
2017年 | 15篇 |
2016年 | 58篇 |
2015年 | 33篇 |
2014年 | 42篇 |
2013年 | 102篇 |
2012年 | 90篇 |
2011年 | 119篇 |
2010年 | 65篇 |
2009年 | 79篇 |
2008年 | 106篇 |
2007年 | 107篇 |
2006年 | 104篇 |
2005年 | 112篇 |
2004年 | 90篇 |
2003年 | 80篇 |
2002年 | 53篇 |
2001年 | 32篇 |
2000年 | 36篇 |
1999年 | 38篇 |
1998年 | 25篇 |
1997年 | 32篇 |
1996年 | 31篇 |
1995年 | 29篇 |
1994年 | 35篇 |
1993年 | 18篇 |
1992年 | 29篇 |
1991年 | 15篇 |
1990年 | 22篇 |
1989年 | 18篇 |
1988年 | 13篇 |
1987年 | 11篇 |
1986年 | 17篇 |
1985年 | 27篇 |
1984年 | 25篇 |
1983年 | 17篇 |
1982年 | 15篇 |
1981年 | 15篇 |
1980年 | 9篇 |
1979年 | 10篇 |
1978年 | 10篇 |
1977年 | 11篇 |
1976年 | 9篇 |
1975年 | 9篇 |
1974年 | 10篇 |
1888年 | 8篇 |
排序方式: 共有2196条查询结果,搜索用时 312 毫秒
61.
Baldelli E Battaglia A Bombardelli E Carenzi G Fontana G Gelmi ML Guerrini A Pocar D 《The Journal of organic chemistry》2004,69(20):6610-6616
New taxanes 15 and 18, containing the unsaturated and saturated baccatin[14,1-d]furan-2-one nucleus, respectively, were prepared starting from the readily available 13-oxo-7-Tes-baccatin III (3). Sequential formation of the enolate of 3 and reaction with ethyl glyoxylate gave the 13-oxo-7-Tes-baccatin[14,1-d]-3,4-dehydrofuran-2-one 4. The reduction of 4 can result in the formation of a mixture of compounds corresponding to 13-hydroxy alcohol 5 and 13-enol derivative 6. Both 5 and 6 were transformed into 13-oxo-7-Tes-baccatin[14,1-d]furan-2-one 8 by treatment with a base. Further reduction of 8 gave 13-hydroxy compound 9. Esterification of 6 and 9 with N,O-protected norstatine 12, followed by deprotection, gave the new promising anticancer taxanes 15 and 18, respectively. 相似文献
62.
Two new uncommon nitrogenous sesquiterpenes, 11‐ethoxy‐3‐formamidotheonellin ( 1 ) and 7‐ethoxy‐3‐formamidobisabolane‐8,10‐diene ( 2 ), together with two known related sesquiterpenes, 3‐formamidotheonellin (=theonellin formamide; 3 ) and theonellin isothiocyanate ( 4 ), were isolated from the Hainan sponge Axinyssa aff. variabilis. Their structures were determined on the basis of extensive spectroscopic analysis and by comparison of their NMR data with those of known compounds. 相似文献
63.
64.
65.
Arturo Battaglia Eleonora Baldelli Gabriele Fontana Andrea Guerrini 《Tetrahedron》2005,61(32):7727-7745
The base induced deprotonation of H-14 of 7-triethylsilyl- (7-TES-) and 7-tert-butoxycarbonyl- (7-BOC-) protected 13-oxo-baccatins gave the corresponding enolates, which were selectively aminated with electrophilic nitrogen donors, such as azodicarboxylates and tosyl azide. In particular, tosyl azide gave the corresponding 7-BOC- and 7-TES-13-oxo-14β-azido-baccatin III. Alternatively, the last compound was prepared via NaN3 induced azidation of the 13-silyl enol ether of 7-TES-13-oxo-baccatin III under oxidative (cerium ammonium nitrate) conditions. The 13-silyl enol ether was obtained in a multistep process by DBU induced silylation of 7-TES-13-oxo-baccatin III. The 7-TES-13-oxo-14β-azido-baccatin III was used as a key intermediate for the synthesis of a new family of antitumour taxanes containing amino based functional groups at the C-14 position, such as: 14β-azido, 14β-amino, 14β-amino 1, 14-carbamate, 14β-amino 1, 14-thiocarbamate, and 14β-amino N-tert-butoxycarbonyl-1,14-carbamate. 相似文献
66.
Both single crystals of VCl3(THF)3 as well as isotypic cocrystals of the composition MCl3(THF)3, M=Ti/V 1/3, undergo a topotactic reversible phase transition to a hitherto unknown low-temperature modification. The close relationship between this new structure and the room-temperature phase determined by Cottonet al. is discussed from the molecular and the intermolecular point of view: Both modifications are built up by conformationally very similar molecules which change their arrangement during the phase transition. Lattice energy calculations confirm that these two alternative arrangements correspond to minima of almost the same packing energy.Dedicated to Professor Dr. G. E. Herberich on the occasion of his 60th birthday. 相似文献
67.
68.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemical communications (Cambridge, England)》2005,(40):5115-5117
Chiral C3-symmetric trisoxazolines are highly efficient stereodirecting ligands in enantioselective Cu(II) Lewis acid catalysis which is based on the concept of a stereoelectronic hemilability of the divalent copper; in direct comparison with the analogous bisoxazoline systems they are more efficient in the enantioselective alpha-amination as well as the enantioselective Mannich reaction of prochiral beta-ketoesters. 相似文献
69.
Matthias Bauer Christoph Gastl Christoph Köppl Guido Kickelbick Helmut Bertagnolli 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):567-581
Summary. The molecular structure of the transition metal alkoxide Zr(OnBu)4 in toluene and its modification by addition of i-propanol, tetrahydrofurane, and the coordinating ligand pentane-1,3-dione (Hacac) were investigated by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy.
Zr(OnBu)4 dissolved in toluene forms dimers. It was proved that cluster size is a function of the number of added equivalents ligand.
In contrast, the addition of i-propanol or tetrahydrofurane caused no structural changes observable by EXAFS spectroscopy. A detailed discussion of the
structural models is given in terms of possible alternatives and errors within the EXAFS analysis. 相似文献
70.
The objective of this work was to evaluate the use of composite mass spectral (CMS) data from pyrolysis gas chromatography/mass spectrometry (PY–GC/MS) for lignocellulosic materials. Various forages, by-products and fiber fractions derived from them were examined as CMS by PY–GC/MS. The PY–GC/MS system consisted of a heated platinum filament, a capillary gas chromatograph and an ion trap detector (ITD) mass spectrometer operated under electron impact conditions. Mass spectra were then composited in several ways by summing all the mass spectra acquired within retention times corresponding to major product classes. CMS data were entered in a dedicated library and compared using the ITD library editor software. The usefulness of such a simple procedure for studies related to lignocellulose analysis, such as forage recognition, development of analytical methods and digestibility/maturity correlation, is discussed. 相似文献