全文获取类型
收费全文 | 1897篇 |
免费 | 42篇 |
国内免费 | 9篇 |
专业分类
化学 | 1402篇 |
晶体学 | 23篇 |
力学 | 43篇 |
数学 | 121篇 |
物理学 | 359篇 |
出版年
2024年 | 6篇 |
2023年 | 14篇 |
2022年 | 20篇 |
2021年 | 72篇 |
2020年 | 37篇 |
2019年 | 39篇 |
2018年 | 63篇 |
2017年 | 37篇 |
2016年 | 89篇 |
2015年 | 65篇 |
2014年 | 94篇 |
2013年 | 132篇 |
2012年 | 116篇 |
2011年 | 208篇 |
2010年 | 103篇 |
2009年 | 92篇 |
2008年 | 78篇 |
2007年 | 88篇 |
2006年 | 92篇 |
2005年 | 107篇 |
2004年 | 91篇 |
2003年 | 61篇 |
2002年 | 37篇 |
2001年 | 17篇 |
2000年 | 17篇 |
1999年 | 24篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 12篇 |
1995年 | 9篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 12篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 11篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1972年 | 7篇 |
1971年 | 5篇 |
排序方式: 共有1948条查询结果,搜索用时 15 毫秒
51.
Z. Iqbal 《Chemical physics letters》1976,40(1):41-44
The phase changes in polycrystalline ammonium nitrate and its fully deuterated analogue have been studied by Raman scattering. The phase V and IV transition was found to be associated with the softening and intensity decrease of a NO3? librational mode. The Raman line-width data suggest that the VII to V phase transition involves a change in the degree of orientational order of the ions without incurring a change in lattice structure. 相似文献
52.
Ashraf Ghanem Author Vitae 《Tetrahedron》2007,63(8):1721-1754
Over the last few years, there has been a dramatic increase in the number of publications in the field of lipase-catalyzed reactions performed in common organic solvents, ionic liquids or even non-conventional solvents. A fairly large percentage of these publications have emerged from organic chemists who have recognized the potential of biocatalysis as a viable and popular technique in organic synthesis. Considerable research has shown that reactions catalyzed by enzymes are more selective and efficiently performed than many of their analogues in the organic chemistry laboratory. This review article focuses on some of the recent developments in the rapidly growing field of lipase-catalyzed asymmetric access to enantiomerically pure/enriched compounds. The literature search is dated back to the last five years and covers some comprehensive examples. 相似文献
53.
The present paper describes the synthesis of 5‐azido‐6‐ketones (14) and 6‐hydroxy‐5‐ketone (20) from Hajos Wiechert ketone as chiral building blocks for cephalostatin analogues. The synthesis of symmetric cephalostatin analogue from 6‐hydroxy‐5‐ketone has also been reported. The characterization of the each synthesized compounds was carried out by IR, 1H‐NMR, 13C‐NMR and High resolution Mass Spectrometry. 相似文献
54.
Hersh WH Xu P Simpson CK Grob J Bickford B Hamdani MS Wood T Rheingold AL 《The Journal of organic chemistry》2004,69(6):2153-2163
Reaction of the N-toluenesulfonyl derivatives of (S)-alanine, phenylalanine, and valine (4-6) with PhPCl(2) gave in high yield the 4-methyl, benzyl, and isopropyl derivatives (7-9) of 2-phenyl-1-p-toluenesulfonyl-1,3,2-oxazaphospholidin-5-one. The ratios of the (2S,4S)/(2R,4S) diastereomers (cis/trans isomers) were 1:1, 2:1, and 10:1 for the methyl, benzyl, and isopropyl derivatives 7a,b, 8a,b, and 9a,b, respectively. For 7a,b, both isomers could be crystallized, but for the others only the major isomers were isolable. The X-ray crystal structure of 9a shows that the isopropyl and phenyl groups are mutually cis and that the tolyl moiety is oriented s-trans to both the isopropyl and phenyl groups. Reaction of 6 with Cl(2)PCH(2)CH(2)PCl(2) (10) gave a 56:38:7 mixture of the cis/cis, cis/trans, and trans/trans diphosphorus heterocycles 11a-c. The major isomer could be crystallized and isolated free of the other diastereomers. Reaction of 6 with EtPCl(2) gave a 6:1 mixture of cis/trans isomers of the ethyl-substituted heterocycles 12a,b as an inseparable oil but allowed confirmation of the structure of 11a. Slow epimerization at phosphorus may occur by inversion but more likely by ring opening/closure, since 7b, 9a, and 11a give rise upon standing in solution to mixtures containing starting material and 7a, 9b, and 11b, respectively, along with the free amino acid derivatives 4 and 6. The NMR spectra, and in particular the coupling constants between the alpha-hydrogen atom of the amino acid moiety and phosphorus, were used to establish the identities of the cis and trans isomers. Reaction of 9a with (THF)W(CO)(5) gave the phosphorus-ligated adduct (9a)W(CO)(5) (13), and the IR spectrum of this complex shows that 9a is a strongly electron-withdrawing ligand. The geometry of the sulfonamide moiety is discussed in detail, as are the (1)H NMR coupling constants. The data are consistent with the presence of little steric interaction between the cis isopropyl and phosphorus substituent in 9a, 11a, and 12a and orientation of the tolyl moiety s-cis to the isopropyl group in 9b, 12b, and 13. 相似文献
55.
M. Salman Y. Girault N Balbi L. Elegant 《Journal of Thermal Analysis and Calorimetry》1991,37(10):2389-2394
The attack by formic acid on the nitrogen electron pairs of N,N,N,N-tetramethylethylenediamine leads to the stoichiometric salt or to many other complexes with different molar fractions. Physical and thermodynamic parameters of two adducts, obtained by calorimetric study, are discussed in terms of their use as potential phase change materials in thermal energy storage because of their large heat of fusion between 288 and 333 K.
Zusammenfassung Bei der Einwirkung von Ameisensäure auf die Elektronenpaare von N,N,N,N-Tetramethylethylendiamin entsteht ein stöchiometrisches Salz oder mehrere andere Komplexe mit unterschiedlichem Molenbruch. Es werden physikalische und thermodynamische Parameter zweier bei der kalorimetrischen Untersuchung erhaltenen Addukte hinsichtlich ihrer Verwendung als potentielle Phasenwechselsubstanzen bei der thermischen Energiespeicherung diskutiert, da sie im Bereich 288–333 K eine große Schmelz-wärme besitzen.相似文献
56.
57.
Our own work on steroid compounds with defined conformation as chiral model compounds for investigations of chemo-, regio- and stereoselectivity of metal-mediated new reactions is reviewed. Reactions with nickelacycles, (π-allyl)zirconoxycarbene complexes, iron tricarbonyl complexes of dienes and 1-azadienes, the Ru-catalyzed synthesis of 1,3-dihydropyrrol-2-ones from 1-azadienes, the Pd-catalyzed cyclopropanation of 1-azadienes, syntheses with cuprio steroids, copper complexes of amino alcohol derivatives and the copper-mediated hydroxylation of nonactivated C-H bonds with molecular oxygen are discussed. 相似文献
58.
Some new N‐glycosides of 4‐(2‐phenylethyl)‐5‐pyridyl‐1,2,4‐triazole‐3‐thiones were synthesised by the coupling reaction of halo sugar with 4,5‐disubstituted 3H‐1,2,4‐triazole‐3‐thiones in the presence of mercuric cyanide and dry nitromethane as solvent, followed by deprotection using dry ammonia in methanol. All of the above compounds were fully characterized by means of infrared, 1H NMR spectroscopy, mass spectroscopy and elemental analysis. 相似文献
59.
ViqarUddin Ahmad MuhammadAthar Abbasi Muhammad Zubair Naheed Fatima Umar Farooq M.Iqbal Choudhary 《Helvetica chimica acta》2004,87(1):67-72
Phytochemical investigation of Symplocos racemosa resulted in the isolation of two new glycosides, symploracemoside ( 1 ) and symplomoside ( 2 ), which are structurally related to the reported benzoylsalireposide ( 3 ) and salireposide ( 4 ). The structure elucidation of the isolated compounds was based primarily on 1D‐ and 2D‐NMR analysis, including COSY, NOESY, HMQC, and HMBC correlations. These glycosides showed inhibitory activity against snake‐venom phosphodiesterase I. 相似文献
60.
Salman R. Salman Gazi A. W. Derwish Sabri M. H. Al-Marsoumi 《Journal of inclusion phenomena and macrocyclic chemistry》1995,23(3):175-179
The intermolecular charge transfer complexes (CT) of two crown ethers (CE), viz, B15C5 and DB18C6 (as donors), and tetracyanoethylene (TCNE), as acceptor, were studied in the UV-visible region in dichloroethane (DCE), at 298.2 K. The sequence of addition of the cation was varied in the case of B15C5 such that in one system the sequence was (CE+Cation)+TCNE and in the other (CE+TCNE)+cation. These two systems were found to be non-interchangeable, even under reflux conditions, giving differentK
c
values which were explained as being due to the different geometries of the CE. For the first sequence, the values most affected depended on the fit of the metal cation with the ether cavity, thus in B15C5, Na+ showed the greatest effect, while for DB18C6 it was K+. 相似文献