全文获取类型
收费全文 | 3257篇 |
免费 | 133篇 |
国内免费 | 9篇 |
专业分类
化学 | 2606篇 |
晶体学 | 22篇 |
力学 | 75篇 |
数学 | 312篇 |
物理学 | 384篇 |
出版年
2023年 | 29篇 |
2022年 | 21篇 |
2021年 | 135篇 |
2020年 | 98篇 |
2019年 | 110篇 |
2018年 | 66篇 |
2017年 | 66篇 |
2016年 | 139篇 |
2015年 | 93篇 |
2014年 | 103篇 |
2013年 | 170篇 |
2012年 | 221篇 |
2011年 | 237篇 |
2010年 | 129篇 |
2009年 | 128篇 |
2008年 | 190篇 |
2007年 | 167篇 |
2006年 | 142篇 |
2005年 | 172篇 |
2004年 | 125篇 |
2003年 | 134篇 |
2002年 | 84篇 |
2001年 | 63篇 |
2000年 | 41篇 |
1999年 | 35篇 |
1998年 | 25篇 |
1997年 | 28篇 |
1996年 | 47篇 |
1995年 | 37篇 |
1994年 | 41篇 |
1993年 | 33篇 |
1992年 | 19篇 |
1991年 | 18篇 |
1990年 | 15篇 |
1989年 | 19篇 |
1988年 | 16篇 |
1987年 | 16篇 |
1986年 | 20篇 |
1985年 | 18篇 |
1984年 | 11篇 |
1983年 | 9篇 |
1982年 | 17篇 |
1981年 | 20篇 |
1980年 | 9篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 12篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1974年 | 5篇 |
排序方式: 共有3399条查询结果,搜索用时 726 毫秒
1.
Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms 下载免费PDF全文
Dr. Marta E. Alberto Gaspar Pinto Prof. Nino Russo Dr. Marirosa Toscano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3736-3745
The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐CoII derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear CoII center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered. 相似文献
2.
Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells 下载免费PDF全文
Dr. Donatella Diana Anna Russomanno Dr. Lucia De Rosa Dr. Rossella Di Stasi Dr. Domenica Capasso Dr. Sonia Di Gaetano Dr. Alessandra Romanelli Dr. Luigi Russo Dr. Luca D. D'Andrea Prof. Roberto Fattorusso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):91-95
In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast 15N‐edited NMR spectroscopic experiments. To this aim, 15N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including 15N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2. 相似文献
3.
Summary We present an approximation method of a space-homogeneous transport equation which we prove is convergent. The method is very promising for numerical computation. Comparison of a numerical computation with an exact solution is given for the Master equation. 相似文献
4.
5.
On the Application of the Auxiliary Problem Principle 总被引:6,自引:0,他引:6
The auxiliary problem principle (APP) derives from a general theory on decomposition-coordination methods establishing a comprehensive framework for both one-level and two-level methods. In this paper, the results of the two-level methods of APP are specialized for an efficient application to some engineering problems. 相似文献
6.
7.
Various types of LU-factorizations for nonsingular matrices, where L is a lower triangular matrix and U is an upper triangular matrix, are defined and characterized. These types of LU-factorizations are extended to the general m × n case. The more general conditions are considered in the light of the structures of [C.R. Johnson, D.D. Olesky, P. Van den Driessche, Inherited matrix entries: LU factorizations, SIAM J. Matrix Anal. Appl. 10 (1989) 99-104]. Applications to graphs and adjacency matrices are investigated. Conditions for the product of a lower and an upper triangular matrix to be the zero matrix are also obtained. 相似文献
8.
Robert Andreu Gerard Lligadas Joan Carles Ronda Marina Galià Virginia Cádiz 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4965-4973
A new oxazolidine derivative was obtained from phenol, 2‐amino‐2‐methylpropane‐1,3‐diol and paraformaldehyde. The reaction of this novel oxazolidine diol with phenylisocyanate lead to a urethane model compound which can be polymerized thermally by oxazolidine ring opening to give a Mannich bridge structure. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (Mw ~ 400) with 4,4′‐methylenbis (cyclohexylisocyanate) (HMDI, 90% isomers mixture). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials which showed improved thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4965–4973, 2007 相似文献
9.
In this paper we report the results of a morphological and structural investigation on film properties of a soluble polydiacetylene, the poly[1,6-bis(3,6-dihexadecyl-N-carbazolyl)-2,4-hexadiyne] (polyDCHD-HS). The red films of this polymer, prepared by standard spin-coating techniques, revealed absence of linear dichroism and birefringence in contrast with the ordered mesophases detected by powder X-ray studies. In order to interpret the optical behavior of this polymer, we performed AFM and SEM studies of polyDCHD-HS films spun on hydrophylic and hydrophobic glass substrates. We found the presence of surfaces organized in rod-like particles, more regularly oriented on the hydrophylic substrate. GIXRD studies, carried out on films sufficiently thick to allow the observation of the diffraction pattern, reveled the presence of a lamellar structure with a spacing of 3.22 nm. The low intensity of the diffraction peaks and the isotropic linear optical properties of the films show that the lamellar mesophases are not extended over large areas. These findings were compared with the data obtained from AFM and SEM studies on films of two other polydiacetylenes, the poly[1-(3,6-dihexadexyl-N-carbazolyl)-6-(N-carbazolyl)-2,4-hexadyine] (polya-DCHD) and the poly[1,6-bis(3,6-dipalmitoyl-N-carbazolyl)-2,4-hexadyine] (polyDPCHD), spun on hydrophylic glass substrate. The results confirmed the presence of nodular morphologies which seem to be a general characteristic of this class of materials. The particles organization appears instead related to the chemical nature of the substituents on the carbazolyl rings. 相似文献
10.
Marina DellaGreca 《Tetrahedron》2006,62(12):2877-2882
Examination of the hydroalcoholic extract of the leaves of Aptenia cordifolia has afforded three cinnamic acid amides and two lignanamides. Structures were established on the basis of spectroscopic data, including 2D-NMR analyses. 相似文献