全文获取类型
收费全文 | 14683篇 |
免费 | 768篇 |
国内免费 | 67篇 |
专业分类
化学 | 10733篇 |
晶体学 | 41篇 |
力学 | 339篇 |
数学 | 2272篇 |
物理学 | 2133篇 |
出版年
2023年 | 117篇 |
2022年 | 165篇 |
2021年 | 248篇 |
2020年 | 343篇 |
2019年 | 367篇 |
2018年 | 181篇 |
2017年 | 197篇 |
2016年 | 519篇 |
2015年 | 574篇 |
2014年 | 587篇 |
2013年 | 803篇 |
2012年 | 1127篇 |
2011年 | 1124篇 |
2010年 | 690篇 |
2009年 | 604篇 |
2008年 | 874篇 |
2007年 | 851篇 |
2006年 | 818篇 |
2005年 | 773篇 |
2004年 | 660篇 |
2003年 | 518篇 |
2002年 | 486篇 |
2001年 | 238篇 |
2000年 | 189篇 |
1999年 | 179篇 |
1998年 | 190篇 |
1997年 | 187篇 |
1996年 | 147篇 |
1995年 | 135篇 |
1994年 | 124篇 |
1993年 | 117篇 |
1992年 | 95篇 |
1991年 | 91篇 |
1990年 | 69篇 |
1989年 | 91篇 |
1988年 | 63篇 |
1987年 | 46篇 |
1986年 | 48篇 |
1985年 | 67篇 |
1984年 | 56篇 |
1983年 | 55篇 |
1982年 | 62篇 |
1981年 | 65篇 |
1980年 | 51篇 |
1979年 | 71篇 |
1978年 | 58篇 |
1977年 | 56篇 |
1976年 | 56篇 |
1975年 | 46篇 |
1973年 | 46篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
Youte JJ Barbier D Al-Mourabit A Gnecco D Marazano C 《The Journal of organic chemistry》2004,69(8):2737-2740
Potassium ferricyanide oxidation of salt 1 gave isoquinolinone 7 whose treatment with Grignard reagents resulted in a high-yield formation of substituted isoquinolinium salts 5. The selectivity of the reduction of these salts to give derivatives 6 has been studied. Particularly good selectivities (82-84%) were observed when R is a benzylic group. On the basis of these results, a practical and enantioselective synthesis of the natural alkaloid (-)-argemonine is presented. 相似文献
982.
The addition reaction of monomeric lithium enolate (Z)-1, derived from propiophenone, to propene oxide 2, was examined to clarify the exact geometry of the transition state (TS) involved in this type of reaction. The eight possible TSs and the corresponding pathways, four leading to syn gamma-hydroxy ketone (gamma-HK) 3 and four leading to anti gamma-HK 4, were compared, using the B3LYP/6-31+G(d)//B3LYP/6-31+G(d) theory level in vacuo and in the presence of the reaction solvent (toluene/hexane). In every case, the favored pathway involves a TS where the enolate C=C and the epoxide C-C are in a gauche relationship and where the Li(+) is stabilized by some C-C and C-H sigma bonds of epoxide 2. 相似文献
983.
Huskens J Mulder A Auletta T Nijhuis CA Ludden MJ Reinhoudt DN 《Journal of the American Chemical Society》2004,126(21):6784-6797
A model has been described for interpreting the binding of multivalent molecules to interface-immobilized monovalent receptors through multiple, independent interactions. It is based on the concept of effective concentration, C(eff), which has been developed before for multivalent binding in solution and which incorporates effects of lengths and flexibilities of linkers between interacting sites. The model assumes: (i). the interactions are independent, (ii). the maximum number of interactions, p(max), is known, (iii). C(eff) is estimated from (simple) molecular models. Simulations of the thermodynamics and kinetics of multivalent host-guest binding to interfaces have been discussed, and competition with a monovalent competitor in solution has been incorporated as well. The model was successfully used to describe the binding of a divalent guest to self-assembled monolayers of a cyclodextrin host. The adsorption data of more complex guest-functionalized dendrimers, for which p(max) was not known beforehand, was interpreted as well. Finally, it has been shown that the model can aid to deconvolute contributions of multivalency and cooperativity to stability enhancements observed for the adsorption of multivalent molecules to interfaces. 相似文献
984.
Linge JP Habeck M Rieping W Nilges M 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,167(2):970-342
Indirect magnetization transfer increases the observed nuclear Overhauser enhancement (NOE) between two protons in many cases, leading to an underestimation of target distances. Wider distance bounds are necessary to account for this error. However, this leads to a loss of information and may reduce the quality of the structures generated from the inter-proton distances. Although several methods for spin diffusion correction have been published, they are often not employed to derive distance restraints. This prompted us to write a user-friendly and CPU-efficient method to correct for spin diffusion that is fully integrated in our program ambiguous restraints for iterative assignment (ARIA). ARIA thus allows automated iterative NOE assignment and structure calculation with spin diffusion corrected distances. The method relies on numerical integration of the coupled differential equations which govern relaxation by matrix squaring and sparse matrix techniques. We derive a correction factor for the distance restraints from calculated NOE volumes and inter-proton distances. To evaluate the impact of our spin diffusion correction, we tested the new calibration process extensively with data from the Pleckstrin homology (PH) domain of Mus musculus beta-spectrin. By comparing structures refined with and without spin diffusion correction, we show that spin diffusion corrected distance restraints give rise to structures of higher quality (notably fewer NOE violations and a more regular Ramachandran map). Furthermore, spin diffusion correction permits the use of tighter error bounds which improves the distinction between signal and noise in an automated NOE assignment scheme. 相似文献
985.
Panse S Dong L Burian A Carus R Schutkowski M Reimer U Schneider-Mergener J 《Molecular diversity》2004,8(3):291-299
Kinases represent one of the largest enzyme families and key regulatory proteins in the cell. Only a small subset of these enzymes has been characterised so far. We have prepared different types of phosphopeptide and peptide microarrays displaying peptides deduced from annotated human phosphorylation sites and cytoplasmic domains of all annotated human membrane proteins. This approach was enabled by fully-automated high throughput micro-scale synthesis of peptides by the SPOT technology combined with chemo-selective immobilisation on modified glass slides. The phosphopeptide microarrays displaying 2923 peptides in total have been used for the characterisation of commercially available generic anti-phosphopeptide antibodies. This enabled us to detect Abl kinase activity on a microarray with anti-phosphotyrosine antibodies yielding results comparable to those obtained from a radioactive assay. More than 13 000 peptides deposited on six glass slides were used to profile casein kinase 2 (CK2) using a radioactive assay, since no generic antibody for the reliable detection of serine or threonine phosphorylation could be identified. All previously identified substrates were detected in the microarray experiment. In order to confirm whether substrates on the microarray are substrates in solution phase assays, more than 700 peptides were synthesised and tested with CK2 in a solution phase assay. All substrates identified in the solution phase assay were also detected on the microarray. 相似文献
986.
Zou L Wang J Beleva VJ Kooijman EE Primak SV Risse J Weissflog W Jákli A Mann EK 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2772-2780
A systematic study of five different, symmetric bent-core liquid crystals in Langmuir thin films at the air/water interface is presented. Both the end chains (siloxane vs hydrocarbon) and the core (more or less amphiphilic) are varied, to allow an exploration of different possible layer structures at the interface. The characterization includes systematic surface pressure isotherms, Brewster angle microscopy, and surface potential measurements. The properties of these layers are strongly dependent on the individual type of molecule: the molecules with amphiphilic end chains lie quite flat on the surface, while the molecules with hydrophobic end chains construct multilayer structures. In both cases, the three-dimensional collapse structure is reversible. 相似文献
987.
Faller D Reinheckel T Wenzler D Hagemann S Xiao K Honerkamp J Peters C Dandekar T Timmer J 《Journal of chemical information and computer sciences》2004,44(1):168-169
Data organization and data mining represents one of the main challenges for modern high throughput technologies in pharmaceutical chemistry and medical chemistry. The presented open source documentation and analysis system provides an integrated solution (tutorial, setup protocol, sources, executables) aimed at substituting the traditionally used lab-book. The data management solution provided incorporates detailed information about the processing of the gels and the experimental conditions used and includes basic data analysis facilities which can be easily extended. The sample database and User-Interface are available free of charge under the GNU license from http://webber.physik.uni-freiburg.de/~fallerd/tutorial.htm. 相似文献
988.
Eberhard?ReimannEmail author Christian?Ettmayr 《Monatshefte für Chemie / Chemical Monthly》2004,135(8):959-972
Summary. N-Alkylation of certain angularly substituted heterocycles by C2- and C3-units provided appropriate precursors to construct stereoselectively the erythrinanone and several erythrinanone type analogues by intramolecular Friedel-Crafts acylation. The resulting aromatic ketones were catalytically reduced affording the corresponding parent frameworks including the hitherto unknown tetracyclus A-norschelhammerane. On the other hand, the stereoselective reduction of the carbonyl moiety offered a convenient approach to 11-hydroxylated erythrinanes with the natural occurring -configuration. The structures and the stereochemistry of the target compounds were proved by NMR spectroscopy.Part of PhD thesis, LMU München, D 相似文献
989.
Johannes?Winkler Ernst?Urban Christian R.?NoeEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(1):109-116
Summary. A synthesis of the amino sugar 2-amino-2,3-didesoxyribose is described. Starting from D-glucosamine, -methylfuranoside was obtained in eight steps in 20% yield. This carbohydrate is a novel building block for nucleosides and for backbone modified antisense oligonucleotides with 2–5 amide linkages. 相似文献
990.
Larsen J Rasmussen BS Hazell RG Skrydstrup T 《Chemical communications (Cambridge, England)》2004,(2):202-203
A disphosphine-palladium(0) complex capable of recognising barbiturates has been prepared. Oxidative addition studies with a barbitiurate:aryl iodide conjugate provided new Pd(ii) complexes where the positioning of the Pd-bound aryl group is controlled by the molecular recognition event. 相似文献