全文获取类型
收费全文 | 1304篇 |
免费 | 34篇 |
国内免费 | 5篇 |
专业分类
化学 | 860篇 |
晶体学 | 9篇 |
力学 | 39篇 |
数学 | 184篇 |
物理学 | 251篇 |
出版年
2023年 | 5篇 |
2022年 | 11篇 |
2021年 | 14篇 |
2020年 | 13篇 |
2019年 | 16篇 |
2018年 | 16篇 |
2017年 | 6篇 |
2016年 | 41篇 |
2015年 | 30篇 |
2014年 | 28篇 |
2013年 | 70篇 |
2012年 | 88篇 |
2011年 | 108篇 |
2010年 | 56篇 |
2009年 | 48篇 |
2008年 | 78篇 |
2007年 | 72篇 |
2006年 | 78篇 |
2005年 | 70篇 |
2004年 | 70篇 |
2003年 | 44篇 |
2002年 | 50篇 |
2001年 | 16篇 |
2000年 | 15篇 |
1999年 | 18篇 |
1998年 | 12篇 |
1997年 | 21篇 |
1996年 | 16篇 |
1995年 | 6篇 |
1994年 | 10篇 |
1993年 | 10篇 |
1992年 | 14篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1986年 | 11篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 13篇 |
1982年 | 12篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 11篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 10篇 |
1973年 | 9篇 |
1972年 | 9篇 |
1971年 | 4篇 |
排序方式: 共有1343条查询结果,搜索用时 15 毫秒
51.
52.
Can one join both ends of a helix? A helical aromatic oligoamide was macrocyclized into a saddle-shaped bifunctional clip molecule that self-assembles into discrete circular dodecamers in the solid state and shows great potential for binding aromatic acid guests in solution. The cyclization step requires that the helix is only partly denatured in the reaction medium. 相似文献
53.
Muñoz-Hernández MA Montiel-Palma V Huitrón-Rattinger E Cortés-Llamas S Tiempos-Flores N Grevy JM Silvestru C Power P 《Dalton transactions (Cambridge, England : 2003)》2005,(1):193-199
Dichloro and chloromethyl Ga(III) complexes of general formulae [XClGa-eta2-{R2P(E)NP(E'R'2-E,E'}](X = Cl, R, R'= Ph, E, E'= O (1), S (2), Se (3); R = Ph, R'= OEt, E = O, E'= S (4); R = Me, R'= Ph, E, E'= S (5) and X = Me, E, E'= O (6), S (7), Se (8)) were synthesised by either metathesis reactions between GaCl3 and the potassium salt of the ligand (X = Cl) or by methane eliminations from in situ prepared GaMe2Cl and the protonated ligands LH (X = Me). Redistribution reaction of (3) in either CDCl3 or THF afforded the solvent-free tetracoordinate gallium spirocycle cation [Ga-{eta2-{Ph2P(Se)NP(Se)Ph2-Se,Se'})2]+ (9+). The molecular structures of complexes 2, 4, 5, 7 and 9(+) show non-planar gallacycle rings. 相似文献
54.
55.
F. Baros M. Bouchy A. Bouchy J. Y. Jezequel J. C. Andre 《Reaction Kinetics and Catalysis Letters》1990,41(1):89-95
The superposition principle which is commonly used to solve the Smoluchowsky equation can be proved to be unreliable by elementary calculations applied to a particular example. But the practical kinetic consequences are small and usually hidden whithin experimental errors.
, , , , . , .相似文献
56.
The diastereoselective addition of Ph(2)PH to the chiral ortho-substituted eta(6)-benzaldimine complexes (eta(6)-o-X-C(6)H(4)CH=NAr)Cr(CO)(3) (1, X = MeO, Ar = p-C(6)H(4)OMe; 2, X = Cl, Ar = Ph) leads to the formation of the corresponding chiral aminophosphines (alpha-P,N) Ph(2)P-CH(Ar(1))-NHAr(2) (3, Ar(1) = o-C(6)H(4)(OCH(3))[Cr(CO)(3)], Ar(2) = p-C(6)H(4)OCH(3); 4, Ar(1) = o-C(6)H(4)Cl[Cr(CO)(3)], Ar(2) = Ph) in equilibrium with the starting materials. The uncomplexed benzaldimine (o-ClC(6)H(4)CH=NPh), 2', analogously produces an equilibrium amount of the corresponding aminophosphine Ph(2)P-CH(Ar(1))-NHAr(2) (4', Ar(1) = o-C(6)H(4)Cl, Ar(2) = Ph). Depending on the equilibrium constant, the subsequent addition of (1)/(2) equiv of [RhCl(COD)](2) (COD = 1,5-cyclooctadiene) leads to either Ph(2)PH oxidative addition in the case of 3 or to the corresponding [RhCl(COD)(alpha-P,N)] complexes [RhCl(COD)(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)] (5) and [RhCl(COD)(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)] (5') in the cases of the aminophosphines 4 and 4'. The addition of the latter ligands, as racemic mixtures, to (1)/(4) equiv of [Rh(CO)(2)Cl](2) leads to the [RhCl(CO)(alpha-P,N)(2)] complexes [RhCO(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)(2)Cl] (7) or [RhCO(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)(2)Cl] (7') as mixtures of (R(C),S(C))/(S(C),R(C)) and (R(C),R(C))/(S(C),S(C)) diastereomers. The rhodium complexes 5 and 7' have been fully characterized by IR and (31)P NMR spectroscopies and X-ray crystallography. These compounds exhibit intramolecular Rh-Cl.H-N interactions in the solid state and in solution. The stability of the new rhodium complexes has been studied under different CO pressures. Under 1 atm of CO, 5 is converted to an unstable complex [RhCl(CO)(2)(alpha-P,N)], 6, which undergoes ligand redistribution leading to 7 plus an unidentified complex. This reaction is inhibited under higher CO or syngas pressure, as confirmed by the observation of the same catalytic activity in hydroformylation when styrene was added to a catalytic mixture that was either freshly prepared or left standing for 20 h under high CO pressure. 相似文献
57.
Brian Mckittrick Amedeo Failli Robert J. Steffan Richard M. Soll Philip Hughes Jean Schmid Andre A. Asselin C. C. Shaw R. Noureldin G. Gavin 《Journal of heterocyclic chemistry》1990,27(7):2151-2163
Three practical synthetic entries of functionalized 6-fluoro-7-substituted indole derivatives were developed in connection with the preparation of 7-fluoro-8-substituted-1,3,4,9-tetrahydropyrano[3,4-b]indole-1-acetic acid derivatives 11 . The first route, which permits group modification about position 8 of the pyranoindole skeleton, employs 2-bromo-3-fluoroaniline ( 18 ) as a key intermediate, the preparation of which was achieved by either a novel ortho metalation of 15 or via the intermediacy of 22 . The second route utilizes 32 to append a terminally functionalized three carbon side chain onto the indole template and in addition leads to 43 from 40 . The third route to the 7-fluoro-8-substituted-pyranoindole skeleton complements route two in that the synthetic pathway exploits 32 in a nucleophilic fashion to construct a terminally functionalized two carbon appendage onto the indole nucleus. 相似文献
58.
Ahmad Sarakbi Zeynep AydogmusAngela Dago Dominique MertensJean-Yves Dewert Jean-Michel Kauffmann 《Analytica chimica acta》2013
Liquid chromatography coupled to a silver electrode based flow-through amperometric detector (LC-EC-Ag) was developed for the determination of aminothiols in white wines. The C18 reversed phase LC system operated in the isocratic mode at 0.7 mL min−1 and used an acidic mobile phase composed of formic acid, EDTA, sodium nitrate, sodium hydroxide, and methanol 1% (v/v) at pH 4.5. The working electrode operated at 0.08 V vs Ag/AgCl, 3 M KCl and its manual cleaning was realized once a month by smoothing on a polishing cloth. The analyzed aminothiols were resolved and eluted within 4 min, and all standard curves were linear in the range 2 × 10−7–2 × 10−5 M. The analyzed wine samples needed no preparation other than dilution with the mobile phase. The concentration of cysteine (CYS), homocysteine (HCYS), glutathione (GSH) and N-acetylcysteine (NAC) in bottled white wines, determined by the method of standard addition, was found to be in the low μM range (0.2–2 mg L−1) depending on the wine type and its age. 相似文献
59.
60.
Let {X n , n ≥ 1} be a sequence of negatively associated random variables. The aim of this paper is to establish some limit theorems of negatively associated sequence, which include the L p -convergence theorem and Marcinkiewicz–Zygmund strong law of large numbers. Furthermore, we consider the strong law of sums of order statistics, which are sampled from negatively associated random variables. 相似文献