全文获取类型
收费全文 | 4736篇 |
免费 | 124篇 |
国内免费 | 16篇 |
专业分类
化学 | 3013篇 |
晶体学 | 16篇 |
力学 | 241篇 |
数学 | 808篇 |
物理学 | 798篇 |
出版年
2023年 | 50篇 |
2022年 | 140篇 |
2021年 | 136篇 |
2020年 | 109篇 |
2019年 | 99篇 |
2018年 | 82篇 |
2017年 | 93篇 |
2016年 | 186篇 |
2015年 | 145篇 |
2014年 | 143篇 |
2013年 | 253篇 |
2012年 | 272篇 |
2011年 | 298篇 |
2010年 | 176篇 |
2009年 | 155篇 |
2008年 | 286篇 |
2007年 | 276篇 |
2006年 | 230篇 |
2005年 | 251篇 |
2004年 | 172篇 |
2003年 | 159篇 |
2002年 | 122篇 |
2001年 | 50篇 |
2000年 | 51篇 |
1999年 | 46篇 |
1998年 | 33篇 |
1997年 | 33篇 |
1996年 | 55篇 |
1995年 | 46篇 |
1994年 | 41篇 |
1993年 | 37篇 |
1992年 | 28篇 |
1991年 | 29篇 |
1990年 | 29篇 |
1989年 | 30篇 |
1988年 | 30篇 |
1987年 | 42篇 |
1986年 | 26篇 |
1985年 | 40篇 |
1984年 | 39篇 |
1983年 | 21篇 |
1982年 | 25篇 |
1981年 | 27篇 |
1980年 | 28篇 |
1979年 | 19篇 |
1978年 | 17篇 |
1977年 | 28篇 |
1975年 | 14篇 |
1974年 | 13篇 |
1858年 | 11篇 |
排序方式: 共有4876条查询结果,搜索用时 15 毫秒
91.
Giuseppe Werber Francesco Buccheri Manlio Gentile 《Journal of heterocyclic chemistry》1977,14(7):1263-1265
The ambident nucleophilic behaviour of some 2-amino-5-H-1,3,4-thiadiazoles in alkylation, acylation and nitrosation reaction has been verified. The structures assigned to the 2-amino-1,3,4-thiadiazoles ( 1a-i ) and to the Δ2-1,3,4-thiadiazolines ( 2a-e ) agree with the spectral data. 相似文献
92.
[reaction: see text] Ytterbium triflate was shown to be an effective catalyst in promoting the synthesis of either isopropyl esters or free alpha-hydroxy-arylacetic acids from substituted aromatic glyoxals and aryl methyl ketones, respectively. The reaction to provide acids starting from differently substituted ketones was carried out by an environmentally friendly method using an aqueous medium as a solvent and giving the adducts in 78-99% yield without any further purification after the usual workup. 相似文献
93.
Attilio Citterio Anna Gentile Francesco Minisci Marco Serravalle Susanna Ventura 《Tetrahedron》1985,41(3):617-620
The homolytic decomposition of hydroxylamine-O-sulphonic acid in alcoholic solvents was investigated in the presence or absence of protonated heteroaromatic bases and Fe(II) salt. The addition of the α-hydroxyalkyl radicals to the base and their oxidation by Fe(III) salt to the corresponding alkyl cyanide were competitive processes. A redox chain process involving the amino radical cation, NH3t., is suggested and the factors affecting the yields of the homolytic substitution are discussed. 相似文献
94.
Free-energy-perturbation theory from molecular dynamics calculations has been used to obtain the DeltaG of adjoining cavities' formation in water. The DeltaGs for systems with three, five and seven cavities are compared with that of a single cavity of the same volume, and found to be in good agreement. The conditions under which the analytical formulation of the energy of cavity formation proposed by Pierotti holds are discussed. The data for a single cavity have been tabulated and can lend themselves to a simple numerical implementation in standard quantum chemical packages, which can be used when high accuracy for DeltaG(cav) is required. 相似文献
95.
Amantini D Beleggia R Fringuelli F Pizzo F Vaccaro L 《The Journal of organic chemistry》2004,69(8):2896-2898
Tetrabutylammonium fluoride (TBAF) is an efficient catalyst in the [3 + 2] cycloaddition reaction of organic nitriles 1 with trimethylsilyl azide (TMSN(3)) in solventless conditions. The corresponding 5-substituted 1H-tetrazoles 2 were obtained under mild conditions and in 80-97% yields. 相似文献
96.
Hybrid density functional theory (B3LYP) method allows the study of the role of metal ions (Li(+)) in the regioselective opening of 2,3-epoxy alcohols with lithium halides (Cl, Br, I) to the corresponding halohydrins. The theoretical results largely confirm the experimental results, especially with regards to the regioselectivity observed in the opening of the oxirane ring. The C3 halogen attack is always preferred to the C2 attack, with a significant difference in the TS structures with the reaction pathway under kinetic control. The central role of the lithium cation, linked to the oxygen atoms of the epoxy alcohol, is well documented in the reaction mechanisms presented. The energy differences between the two structures of the proposed TS appear to be ascribed to the different contribution of the X-H-O hydrogen bond between the hydroxyl groups of the reactant and the incoming halogen nucleophile. 相似文献
97.
The (17R,20S,22S,24S) C20-C29 segment of contignasterol has been stereoselectively prepared in 8 steps and 40% overall yield from (S)-carvone. Synthetic studies towards contignasterol's C/D ring functionalization/isomerization are also reported. 相似文献
98.
Chlorophyll-a was incorporated into cellulose acetate films and the triplet state decay kinetics and electron transfer from triplet to p-benzoquinone in aqueous solution was studied using laser flash photolysis and EPR. The triplet was found to decay by first order kinetics with a rate constant which was independent of Chl concentration. The triplet yield, however, was concentration dependent. These properties are due to quenching which occurs only at the singlet state level. In the presence of quinone, the triplet is quenched and, when the quinone is in an aqueous solution in contact with the film, Chl cation radical (C±) as well as the semiquinone anion radical (Q±) can be observed. The C decays by second order kinetics with a rate constant of 1.5 × 106M-1 s-1. Although triplet conversion to radicals is slightly lower in the films as compared to fluid solutions (? 3 times), the lifetimes of the radicals are greatly increased (? 103 times). 相似文献
99.
Nadia Marino Giuseppe Bruno Archimede Rotondo Giovanna Brancatelli Francesco Nicol 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):o587-o589
The title compound, C8H8NO4+·Cl−·H2O, is the chlorohydrated form of 2‐aminobenzene‐1,4‐dicarboxylic acid, the basic crystal structure of which is still not known. Molecules are linked by classical N—H⋯O, O—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds, mainly along the molecular plane, into sheets built by unusual R64(26), R64(22) and R43(22) rings. The stacking between layers is stabilized by another N—H⋯Cl hydrogen bond and by π–π interactions between aromatic rings facing each other. 相似文献
100.
Maurizio Botta Francesco De Angelis Ingeborg Grgurina Mauro Marzi Rosario Nicoletti 《Journal of heterocyclic chemistry》1985,22(4):1001-1007
The reactivity of Δ3- and Δ2-3-bromomethylcephems toward carboxylate nucleophiles has been studied. The Δ3-bromomethylcephem 1 , less reactive than the Δ2-analogue 4 , is converted in high yields into 3-acyl-oxymethyl-3-cephems 2a-d , generally with no isomerization of the double bond, only within a narrow range of conditions. In particular, the Δ3-7-aminocephalosporanic acid (7-ACA) derivative 2a has been obtained as the only product in 91% yield by treatment of 1 with triethylammonium acetate in acetic acid. The Δ2-bromomethyl-cephem 4 is easily converted into the Δ2-acyloxymethyl-cepheras 5a-d without double bond isomerization, in very high yields. 相似文献