全文获取类型
收费全文 | 570篇 |
免费 | 16篇 |
国内免费 | 6篇 |
专业分类
化学 | 342篇 |
晶体学 | 7篇 |
力学 | 7篇 |
数学 | 76篇 |
物理学 | 160篇 |
出版年
2022年 | 4篇 |
2021年 | 4篇 |
2020年 | 5篇 |
2018年 | 4篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 12篇 |
2013年 | 22篇 |
2012年 | 21篇 |
2011年 | 20篇 |
2010年 | 9篇 |
2009年 | 11篇 |
2008年 | 26篇 |
2007年 | 31篇 |
2006年 | 24篇 |
2005年 | 34篇 |
2004年 | 18篇 |
2003年 | 20篇 |
2002年 | 23篇 |
2001年 | 21篇 |
2000年 | 10篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 11篇 |
1996年 | 15篇 |
1995年 | 15篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 11篇 |
1991年 | 5篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 10篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1977年 | 7篇 |
1976年 | 4篇 |
1975年 | 7篇 |
1974年 | 10篇 |
1973年 | 6篇 |
1967年 | 3篇 |
1931年 | 3篇 |
1903年 | 4篇 |
排序方式: 共有592条查询结果,搜索用时 15 毫秒
101.
102.
In a quest to develop an effective, scalable synthesis of (+)-spongistatin 1 ( 1), we devised a concise, third-generation scalable synthesis of (+)- 7, the requisite F-ring tetrahydropyran aldehyde, employing a proline-catalyzed cross-aldol reaction. Subsequent elaboration to (+)-EF Wittig salt (+)- 3, followed by union with advanced ABCD aldehyde (-)- 4, macrolactonization and global deprotection permitted access to >1.0 g of totally synthetic (+)-spongistatin 1 ( 1). 相似文献
103.
104.
Ley SV Abad-Somovilla A Anderson JC Ayats C Bänteli R Beckmann E Boyer A Brasca MG Brice A Broughton HB Burke BJ Cleator E Craig D Denholm AA Denton RM Durand-Reville T Gobbi LB Göbel M Gray BL Grossmann RB Gutteridge CE Hahn N Harding SL Jennens DC Jennens L Lovell PJ Lovell HJ de la Puente ML Kolb HC Koot WJ Maslen SL McCusker CF Mattes A Pape AR Pinto A Santafianos D Scott JS Smith SC Somers AQ Spilling CD Stelzer F Toogood PL Turner RM Veitch GE Wood A Zumbrunn C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(34):10683-10704
We describe in full the first synthesis of the potent insect antifeedant azadirachtin through a highly convergent approach. An O-alkylation reaction is used to unite decalin ketone and propargylic mesylate fragments, after which a Claisen rearrangement constructs the central C8-C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carbon-carbon bond forming event whereby the [3.2.1] bicyclic system, present in the natural product, is generated via a 5-exo-radical cyclisation process. Finally, using knowledge gained through our early studies into the reactivity of the natural product, a series of carefully designed steps completes the synthesis of this challenging molecule. 相似文献
105.
Bagchi S Kim YS Charnley AK Smith AB Hochstrasser RM 《The journal of physical chemistry. B》2007,111(11):3010-3018
The linear infrared and two-dimensional infrared (2D IR) spectra in the amide-I region of N-acetyl tryptophan methyl amide (NATMA) in solvents of varying polarity are reported. The two amide-I transitions have been assigned unambiguously by using 13C isotopic substitution of the carbonyl group. The amide unit at the amino end shows a lower transition frequency in CH2Cl2 and methanol, while the acetyl end has a lower transition frequency in D2O. Multiple conformers exist in CH2Cl2 and methanol, but only one conformer is evident in D2O. The 2D IR cross peaks from the intermode coupling yield off-diagonal anharmonicities 2.5 +/- 0.5, 3.25 +/- 0.5, and 3.0 +/- 0.5 cm(-1) in CH2Cl2, methanol, and D2O, respectively, which by simple matrix diagonalization yield the coupling constants 8.0 +/- 0.5, 8.0 +/- 1.0, and 5.5 +/- 1.0 cm(-1). The major conformer in CH2Cl2 corresponds to a C7 structure, in agreement with that found in the gas phase [Dian, B. C.; Longarte, A.; Mercier, S.; Evans, D. A.; Wales, D. J.; Zwier, T. S. J. Chem. Phys. 2002, 117, 10688-10702] with intramolecular hydrogen bonding between the acetyl end C=O and the amino end N-H. The backbone dihedral angles (phi, psi) are determined to be in the ranges of (-55 +/- 5 degrees , 30 +/- 5 degrees ), (120 +/- 10 degrees , -20 +/- 10 degrees ), and (+/-160 +/- 10 degrees , +/-75 +/- 10 degrees ) in CH2Cl2, methanol, and D2O, respectively. 相似文献
106.
A highly convergent synthesis of (-)-okilactomycin is described. Key reactions of this synthesis include a strategy-level diastereoselective oxy-Cope rearrangement/oxidation sequence, a Petasis-Ferrier union/rearrangement tactic, and an efficient RCM reaction to construct the 13-membered macrocyclic ring. 相似文献
107.
The emission of radiation from an accelerated charge is analyzed. It is foundthat at zero velocity, the radiation emitted from the charge imparts no countermomentum to the emitting charge, and no radiation reaction force is created bythe radiation. A reaction force is created by the stress force that exists in thecurved electric field of the charge, and the work done in overcoming this forceis the source of the energy carried by the radiation. 相似文献
108.
109.
110.
Moon G. Kim Yimin Wu Larry W. Amos 《Journal of polymer science. Part A, Polymer chemistry》1997,35(15):3275-3285
A wood adhesive-type phenol–formaldehyde (PF) resol resin synthesized with a typical formaldehyde to phenol mol ratio of 2.10 was thoroughly cured and studied by the solid-state crosspolarization/magic angle spinning 13C nuclear magnetic resonance (CP/MAS NMR) spectroscopy. The methylene group/phenol mol ratio values found were between 1.35 and 1.46, close to the value of a completely cured PF polymer structure. The amount of formaldehyde emitted during resin curing was very small. Other formaldehyde-derived groups determined from CP/MAS NMR spectra and relatively high levels of oxidation products of formaldehyde determined from water extracts of cured resin raised the total formaldehyde-derived groups/phenol mol ratio value to close to that of the synthesis mol ratio. Technological implications of these findings are discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3275–3285, 1997 相似文献