全文获取类型
收费全文 | 2330篇 |
免费 | 92篇 |
国内免费 | 324篇 |
专业分类
化学 | 2201篇 |
晶体学 | 17篇 |
力学 | 5篇 |
综合类 | 16篇 |
数学 | 242篇 |
物理学 | 265篇 |
出版年
2024年 | 6篇 |
2023年 | 68篇 |
2022年 | 52篇 |
2021年 | 74篇 |
2020年 | 151篇 |
2019年 | 106篇 |
2018年 | 95篇 |
2017年 | 116篇 |
2016年 | 107篇 |
2015年 | 67篇 |
2014年 | 133篇 |
2013年 | 512篇 |
2012年 | 168篇 |
2011年 | 140篇 |
2010年 | 104篇 |
2009年 | 112篇 |
2008年 | 116篇 |
2007年 | 124篇 |
2006年 | 117篇 |
2005年 | 89篇 |
2004年 | 91篇 |
2003年 | 60篇 |
2002年 | 12篇 |
2001年 | 12篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 7篇 |
1995年 | 13篇 |
1994年 | 6篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有2746条查询结果,搜索用时 78 毫秒
1.
2.
《Tetrahedron letters》2019,60(24):1582-1586
Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred. 相似文献
3.
Lígia M. Rodrigues 《Tetrahedron》2004,60(40):8929-8936
Tetrapeptides containing one of a set of four different α,α-dialkyl glycines at the C-terminus were synthesized by conventional methods in solution and their conformational behavior investigated by 1H NMR spectroscopy in connection with molecular mechanics calculations. The results were consistent with conformations stabilized by a γ-turn in the case of compounds with alkyl groups larger than methyl, while the corresponding Aib derivative did not exhibit intramolecular hydrogen bonding. 相似文献
4.
Zhijun Yi Tingyu LiuQiren Zhang Yuanyuan Sun 《Journal of Electron Spectroscopy and Related Phenomena》2006
The electronic structures of PbWO4 crystals containing F type color centers with the lattice structure optimized are studied within the framework of the fully relativistic self-consistent Direc–Slater theory, using a numerically discrete variational (DV-Xα) method. The calculated results show that F and F+ centers have donor energy level in forbidden band. Their optical transition energy are 1.84 eV, 2.21 eV, respectively, which corresponds to the 680 nm, 550 nm absorption bands. It predicts that the 680 nm, 550 nm absorption bands originate form the F and F+ centers in PbWO4 crystals. 相似文献
5.
Let G(x,y) and GD(x,y) be the Green functions of rotationally invariant symmetric α-stable process in Rd and in an open set D, respectively, where 0<α<2. The inequality GD(x,y)GD(y,z)/GD(x,z)?c(G(x,y)+G(y,z)) is a very useful tool in studying (local) Schrödinger operators. When the above inequality is true with c=c(D)∈(0,∞), then we say that the 3G theorem holds in D. In this paper, we establish a generalized version of 3G theorem when D is a bounded κ-fat open set, which includes a bounded John domain. The 3G we consider is of the form GD(x,y)GD(z,w)/GD(x,w), where y may be different from z. When y=z, we recover the usual 3G. The 3G form GD(x,y)GD(z,w)/GD(x,w) appears in non-local Schrödinger operator theory. Using our generalized 3G theorem, we give a concrete class of functions belonging to the non-local Kato class, introduced by Chen and Song, on κ-fat open sets. As an application, we discuss relativistic α-stable processes (relativistic Hamiltonian when α=1) in κ-fat open sets. We identify the Martin boundary and the minimal Martin boundary with the Euclidean boundary for relativistic α-stable processes in κ-fat open sets. Furthermore, we show that relative Fatou type theorem is true for relativistic stable processes in κ-fat open sets. The main results of this paper hold for a large class of symmetric Markov processes, as are illustrated in the last section of this paper. We also discuss the generalized 3G theorem for a large class of symmetric stable Lévy processes. 相似文献
6.
Suvi T.M. Simila 《Tetrahedron letters》2006,47(17):2933-2936
A concise synthesis of the azatricyclic core structure of FR901483, a potent immunosuppressant, has been accomplished. The key elements of the approach involve a nucleophilic addition to an acyl iminium ion, a ring closing metathesis and a lactone-lactam rearrangement to provide the tricyclic structure. 相似文献
7.
A method for direct sulfenylation of aldehydes and ketones, catalyzed by a novel pyrrolidine trifluoromethanesulfonamide organocatalyst, has been developed. This process serves as an efficient and mild approach to the preparation of α-phenylthio-ketones and -aldehydes. 相似文献
8.
9.
Hans-Georg Henning Giedrius Mazunaitis 《Monatshefte für Chemie / Chemical Monthly》1992,123(1-2):93-98
Summary Irradiation of solutions of excess cyclohexene and 2-acetyl-5,5-dimethyl-1,3-cyclohexanedione (1), and 3-acetyl-1,5,5-trimethyl-2,4-pyrrolidinedione (4) results mainly in the formation of 1,5-diones2 and5. These originate from intermediate cycloadducts of cyclohexene and theexo-enols of the cyclic 1,3-diketones. The yields decrease with increasing polarity of the solvent. In solution2 and5 are in equilibrium with the cyclic hemiacetales3 and6. 相似文献
10.
Bakhtar Ullah Yuli Zhou Jingwen Chen Zongbi Bao Yiwen Yang Qiwei Yang Qilong Ren Zhiguo Zhang 《Tetrahedron letters》2019,60(4):348-351
Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N-aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experimental investigations demonstrated that thiourea acts as a radical initiator by abstracting hydroxyl radical (OH) from tert-butyl hydroperoxide (TBHP) directly instead of non-covalent hydrogen bondings (H-bondings) activation. The use of thiourea as a radical initiator offers a new avenue for innovative chemical transformations in organocatalyzed radical chemistry. 相似文献