全文获取类型
收费全文 | 52318篇 |
免费 | 2031篇 |
国内免费 | 72篇 |
专业分类
化学 | 33466篇 |
晶体学 | 250篇 |
力学 | 1690篇 |
数学 | 8209篇 |
物理学 | 10806篇 |
出版年
2023年 | 384篇 |
2022年 | 323篇 |
2021年 | 536篇 |
2020年 | 705篇 |
2019年 | 678篇 |
2018年 | 1065篇 |
2017年 | 871篇 |
2016年 | 1601篇 |
2015年 | 1471篇 |
2014年 | 1471篇 |
2013年 | 3071篇 |
2012年 | 3563篇 |
2011年 | 3695篇 |
2010年 | 2228篇 |
2009年 | 1846篇 |
2008年 | 3116篇 |
2007年 | 3136篇 |
2006年 | 2764篇 |
2005年 | 2686篇 |
2004年 | 2298篇 |
2003年 | 1860篇 |
2002年 | 1612篇 |
2001年 | 966篇 |
2000年 | 810篇 |
1999年 | 569篇 |
1998年 | 433篇 |
1997年 | 400篇 |
1996年 | 496篇 |
1995年 | 321篇 |
1994年 | 380篇 |
1993年 | 370篇 |
1992年 | 405篇 |
1991年 | 347篇 |
1990年 | 331篇 |
1989年 | 326篇 |
1988年 | 267篇 |
1987年 | 270篇 |
1986年 | 234篇 |
1985年 | 407篇 |
1984年 | 366篇 |
1983年 | 263篇 |
1982年 | 346篇 |
1981年 | 338篇 |
1980年 | 293篇 |
1979年 | 283篇 |
1978年 | 266篇 |
1976年 | 283篇 |
1975年 | 257篇 |
1974年 | 267篇 |
1973年 | 261篇 |
排序方式: 共有10000条查询结果,搜索用时 265 毫秒
991.
Mikkelsen LM Hernáiz MJ Martín-Pastor M Skrydstrup T Jiménez-Barbero J 《Journal of the American Chemical Society》2002,124(50):14940-14951
The conformational properties of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man in solution have been carefully analyzed by a combination of NMR spectroscopy and time-averaged restrained molecular dynamics. It has been found that both the alpha-1,3- and the alpha-1,6-glycosidic linkages show a major conformational averaging. Unusual Phi ca. 60 degrees orientations for both Phi torsion angles are found. Moreover, a major conformational distinction between the natural compound and the glycomimetic affects to the behavior of the omega(16) torsion angle around the alpha-1 --> 6-linkage. Despite this increased flexibility, the C-glycosyl analogue is recognized by three mannose binding lectins, as shown by NMR (line broadening, TR-NOE, and STD) and surface plasmon resonance (SPR) methods. Moreover, a process of conformational selection takes place, so that these lectins probably bind the glycomimetic similarly to the way they recognize the natural analogue. Depending upon the architecture and extension of the binding site of the lectin, loss or gain of binding affinity with respect to the natural analogue is found. 相似文献
992.
Some polymer melts (of high viscosity ) can wet completely the surface of a non miscible, simple liquid. We discuss here the laws of spreading for a macroscopic droplet of this type, when the internal friction of the droplet dominates. We predict a droplet radius increasing liket
1/4 wheret is the spreading time, or equivalently a droplet curvature decreasing liket
–1. The droplet should be surrounded by a precursor film, which is not discussed in the present note. 相似文献
993.
An enzyme-immunoassay for the detection of the mycotoxin zearalenone by use of yolk antibodies 总被引:1,自引:0,他引:1
H. Pichler R. Krska A. Székács M. Grasserbauer 《Fresenius' Journal of Analytical Chemistry》1998,362(1):176-177
The development of an enzyme-immunoassay (ELISA) for the detection of the Fusarium mycotoxin zearalenone (ZON) is described. In contrast to the common antibody isolation from mammal serum, chicken were immunized
in order to isolate specific antibodies from the egg yolk. Five weeks after the start of the immunization a titer of 1:76 000
resulted from three injections without any adverse effects for the animals. Utilizing the indirect competitive assay format
ZON could be detected in a concentration range between 10 and 200 μg/L.
Received: 3 January 1998 / Revised: 16 March 1998 / Accepted: 20 March 1998 相似文献
994.
Péter R. Surján 《Journal of mathematical chemistry》1991,8(1):151-160
Nonlinear time-independent Schr6dinger equations arise if the model Hamiltonian depends on the wave function. This may occur if certain interactions are accounted for in an averaged manner, for example, if a moleule is embedded into a polarizable medium. Arguments are given in favor of the perturbational solution which facilitate the treatment of nonlinearity effects. Two examples are discussed: the case of a polarizable environment and the effective correction of the basis set superposition error. 相似文献
995.
Arturo Zizumbo Rosa Maria Félix-Navarro Jorge Cervantes-Jáuregui Felípe Avalos-Belmontes 《Silicon Chemistry》2005,2(5-6):265-269
Electrochemical formation of poly(phenylmethylsilane) in a divided cell containing a Teflon® neutral membrane was studied. The electrolysis of dichlorosilanes was carried out in a solution containing tetrahydrofuran + hexamethylphosphoramide as the solvent, tetrabutylammonium perchlorate as the support electrolyte and stainless steel as the cathode, with Pt and graphite as the resistant anodes or stainless steel as the sacrificial anode. Polysilanes with a number-average molecular weight in the range from 2,600 to 130,000 g/mol were obtained, depending on the conditions used. 相似文献
996.
The reversible folding of deca-alanine is chosen as a test case for characterizing a method that uses an adaptive biasing force (ABF) to escape from the minima and overcome the barriers of the free-energy landscape. This approach relies on the continuous estimation of a biasing force that yields a Hamiltonian in which no average force is exerted along the ordering parameter xi. Optimizing the parameters that control how the ABF is applied, the method is shown to be extremely effective when a nonequivocal ordering parameter can be defined to explore the folding pathway of the peptide. Starting from a beta-turn motif and restraining xi to a region of the conformational space that extends from the alpha-helical state to an ensemble of extended structures, the ABF scheme is successful in folding the peptide chain into a compact alpha helix. Sampling of this conformation is, however, marginal when the range of xi values embraces arrangements of greater compactness, hence demonstrating the inherent limitations of free-energy methods when ambiguous ordering parameters are utilized. 相似文献
997.
Dunne KS Bisaro F Odell B Paris JM Gouverneur V 《The Journal of organic chemistry》2005,70(26):10803-10809
[reaction: see text] The preparation of phosphorus-containing trienes featuring two diastereotopic vinyl moieties followed by a diastereoselective ring-closing metathesis is described. This methodology allowed for the synthesis of novel highly functionalized P-stereogenic heterocycles featuring both an exo- and an endocyclic double bond. An investigation into the factors influencing the diastereochemical outcome of the ring-closing metathesis is also presented, revealing that the geometry of the double bonds conjugated to phosphorus is important and that 1,3-stereoinduction is superior to 1,4-stereoinduction for these reactions. 相似文献
998.
A new homogous series of thermotropic mesomorphic polyesters with high inherent viscosity has been synthesized. Mesogenic elements are separated by flexible spacers CO(CH2)nCO in the backbone. A study of their mesomorphic properties is reported. 相似文献
999.
A boron-mediated syn- and anti-stereoselective aldol reaction giving rise to various beta-hydroxyenones was coupled to a Pd((II))-mediated oxidative cyclization to give 2,3,6-trisubstituted syn- and anti-dihydropyranones in good yields. The Pd((II))-mediated oxidative cyclization was expanded to alpha-hydroxyenones leading to furan-3(2H)-one derivatives, which include natural product bullatenone and a known precursor of geiparvarin. The sole product of the oxidative cyclization of alpha,beta-dihydroxyenone was a five-membered furan-3(2H)-one derivative, suggesting that the ring closure of these diols is both chemo- and regioselective. 相似文献
1000.
Massue J Bellec N Chopin S Levillain E Roisnel T Clérac R Lorcy D 《Inorganic chemistry》2005,44(24):8740-8748
The reaction of tris(alkylthio)tetrathiafulvalene thiolates with 3-chloro-2,4-pentanedione affords tetrathiafulvalene (TTF) moieties substituted by the acetylacetone function (TTFSacacH), precursors of novel redox-active ligands: the acetylacetonate ions (TTFSacac). These TTFSacacHs have been characterized by X-ray diffraction analyses, and similar trends have been observed, such as a TTF core almost planar and the acetylacetone substituent located in a plane almost perpendicular to the plane formed by the TTF core. Their chelating ability has been demonstrated by the formation of the corresponding M(TTFSacac)2(pyridine)2 complexes in the presence of M(II)(OAc)2.H2O (M = Ni2+, Zn2+). These complexes with TTFSacac moieties, Ni(TTFSacac)2(pyridine)2, 6b, and Zn(TTFSacac)2(pyridine)2, 7b, have been characterized by X-ray diffraction analyses, showing in all structures the metal(II) center chelated by two TTFacac units in the equatorial plane and the octahedral coordination geometry around the metal completed by two axial pyridine ligands. Cyclic voltammetry and UV-visible-near infrared spectroscopic measurements have evidenced a sizable interaction between the two electroactive ligands and the stabilization of a mixed-valence state in the one-electron oxidized complexes. 相似文献