全文获取类型
收费全文 | 1381篇 |
免费 | 29篇 |
国内免费 | 6篇 |
专业分类
化学 | 882篇 |
晶体学 | 12篇 |
力学 | 30篇 |
数学 | 196篇 |
物理学 | 296篇 |
出版年
2021年 | 8篇 |
2019年 | 8篇 |
2018年 | 12篇 |
2017年 | 6篇 |
2016年 | 17篇 |
2015年 | 20篇 |
2014年 | 24篇 |
2013年 | 52篇 |
2012年 | 46篇 |
2011年 | 77篇 |
2010年 | 54篇 |
2009年 | 51篇 |
2008年 | 78篇 |
2007年 | 74篇 |
2006年 | 58篇 |
2005年 | 81篇 |
2004年 | 66篇 |
2003年 | 59篇 |
2002年 | 50篇 |
2001年 | 18篇 |
2000年 | 25篇 |
1999年 | 13篇 |
1998年 | 20篇 |
1997年 | 15篇 |
1996年 | 21篇 |
1995年 | 18篇 |
1994年 | 20篇 |
1993年 | 11篇 |
1992年 | 11篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 19篇 |
1988年 | 6篇 |
1987年 | 9篇 |
1986年 | 10篇 |
1985年 | 20篇 |
1984年 | 18篇 |
1983年 | 12篇 |
1982年 | 23篇 |
1981年 | 26篇 |
1980年 | 23篇 |
1979年 | 20篇 |
1978年 | 22篇 |
1977年 | 24篇 |
1976年 | 14篇 |
1975年 | 13篇 |
1974年 | 11篇 |
1973年 | 15篇 |
1972年 | 6篇 |
1971年 | 5篇 |
排序方式: 共有1416条查询结果,搜索用时 31 毫秒
1.
A new asymmetric synthesis of 2-substituted chiral chromanes has been achieved. The key step is the intramolecular conjugate addition of a phenolic nucleophile on a α,β-unsaturated ester catalyzed by Cinchona alkaloids. The high ee’s obtained with cinchonine and its derivatives have been rationalized by ab initio quantum chemistry calculations of transition state structures. 相似文献
2.
Alain Estve Adeline Bail Georges Landa Ahmed Dkhissi Marie Brut Mehdi Djafari Rouhani Jan Sudor Anne-Marie Gu 《Chemical physics》2007,340(1-3):12-16
Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior. 相似文献
3.
In this Note we propose a rigorous justification of the limit constitutive law of a periodic bi-anisotropic electromagnetic structure with memory. This study is based on the periodic unfolding method, introduced by D. Cioranescu, A. Damlamian and G. Griso, and is applied on the time domain and on the frequency domain. To cite this article: A. Bossavit et al., C. R. Acad. Sci. Paris, Ser. I 338 (2004). 相似文献
4.
5.
Arielle Milliet Georges Sozzi Henri E. Audier 《Journal of mass spectrometry : JMS》1992,27(7):787-794
Radical cations derived from the ethers ROCH2CH2OR′ (R, R′ = H, CH3, C25) were studied, since β-distonic oxonium ions are often prepared from ionized ethers of glycol. The first step in the fragmentation is a 1,5-transfer of an α-hydrogen to oxygen of a terminal alkoxy group leading to a δ-distonic oxonium ion. This step is thermo-neutral and reversible in the ROCH2CH2OH radical cations and exothermic and irreversible in the dialkyl ether radical cations. Depending on R and R,′ these δ-distonic oxonium ions fragment by three reactions: the loss of an alcohol or a water molecule, the formation of a β-distonic oxonium ion ˙CH2CH2O(H)+R and a 1,4-H migration between carbon atoms. Competition between these processes is discussed. 相似文献
6.
The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pKa are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C18‐bonded packing materials, including the 5 μm Xterra‐C18 (121 Å), 5 μm Gemini‐C18 (110 Å), 5 μm Luna‐C18(2) (93 Å), 3.5 μm Extend‐C18 (80 Å), and 2.7 μm Halo‐C18 (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant WWpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pKa and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution. 相似文献
7.
Georges Griso 《Comptes Rendus Mathematique》2004,338(3):261-266
We study the asymptotic behaviour of a structure depending of two small parameters. The ratio of these two parameters plays a part in the limit problems. To cite this article: G. Griso, C. R. Acad. Sci. Paris, Ser. I 338 (2004). 相似文献
8.
Crosslinked hyaluronan gels are used in various applications where their stability is a prerequisite. The sensitivity of such gels to hyaluronidase can be determined as an index of stability by several approaches: chromatography, electrophoresis, and viscometry. We describe here a test based on the colorimetric determination of the N-acetyl-d-glucosamine released by hyaluronidase in standardized conditions. The sensitivities to bovine testicular hyaluronidase of 11 different gels used to fill skin wrinkles (Restylane; Perlane; Juvéderm 18, 24, 24HV, 30, and 30HV; Surgiderm 18, 24XP, 30, and 30XP) were compared.The method was reproducible, easy to perform, not time-consuming and allowed us to demonstrate that the sensitivity to testicular hyaluronidase was dependent on the degree of crosslinking of the gels and also on their monophasic/biphasic nature. Under our conditions, Surgiderm 30, 24XP and 30XP were the most resistant gels.We propose to retain the hyaluronidase test to predict the in situ stability of a crosslinked gel used to fill skin wrinkles. 相似文献
9.
10.
Ab initio pseudopotential SCF calculations were performed on tetrahedral X4 molecules using double-zeta basis sets with and without d functions. The inclusion of d orbitals shortens the bond lengths, stabilizes the X4 structures and intensifies the electron density inside the tetrahedron. The cubic X8 molecules, calculated without d AOs, are not predicted to be more stable than 2X4. Repulsions between parallel bonds in X8 may compensate the lack of ring strain. 相似文献