全文获取类型
收费全文 | 8148篇 |
免费 | 426篇 |
国内免费 | 37篇 |
专业分类
化学 | 5753篇 |
晶体学 | 20篇 |
力学 | 204篇 |
数学 | 1403篇 |
物理学 | 1231篇 |
出版年
2023年 | 77篇 |
2022年 | 112篇 |
2021年 | 135篇 |
2020年 | 189篇 |
2019年 | 191篇 |
2018年 | 117篇 |
2017年 | 115篇 |
2016年 | 360篇 |
2015年 | 316篇 |
2014年 | 297篇 |
2013年 | 478篇 |
2012年 | 556篇 |
2011年 | 655篇 |
2010年 | 385篇 |
2009年 | 327篇 |
2008年 | 519篇 |
2007年 | 472篇 |
2006年 | 441篇 |
2005年 | 412篇 |
2004年 | 348篇 |
2003年 | 316篇 |
2002年 | 290篇 |
2001年 | 171篇 |
2000年 | 121篇 |
1999年 | 121篇 |
1998年 | 93篇 |
1997年 | 102篇 |
1996年 | 104篇 |
1995年 | 85篇 |
1994年 | 59篇 |
1993年 | 63篇 |
1992年 | 53篇 |
1991年 | 36篇 |
1990年 | 38篇 |
1989年 | 38篇 |
1988年 | 36篇 |
1987年 | 27篇 |
1986年 | 32篇 |
1985年 | 25篇 |
1984年 | 22篇 |
1983年 | 16篇 |
1982年 | 22篇 |
1981年 | 16篇 |
1980年 | 19篇 |
1979年 | 10篇 |
1978年 | 21篇 |
1977年 | 13篇 |
1975年 | 11篇 |
1974年 | 13篇 |
1970年 | 8篇 |
排序方式: 共有8611条查询结果,搜索用时 31 毫秒
121.
The linear ordering problem is an NP-hard combinatorial problem with a large number of applications. Contrary to another very popular problem from the same category, the traveling salesman problem, relatively little space in the literature has been devoted to the linear ordering problem so far. This is particularly true for the question of developing good heuristic algorithms solving this problem.In the paper we propose a new heuristic algorithm solving the linear ordering problem. In this algorithm we made use of the sorting through insertion pattern as well as of the operation of permutation reversal. The surprisingly positive effect of the reversal operation, justified in part theoretically and confirmed in computational examples, seems to be the result of a unique property of the problem, called in the paper the symmetry of the linear ordering problem. This property consists in the fact that if a given permutation is an optimal solution of the problem with the criterion function being maximized, then the reversed permutation is a solution of the problem with the same criterion function being minimized. 相似文献
122.
Volkmar Nejedl Michael Panzner Stefan Baunack Ulrich Franz Arnold Luft Klaus Wetzig 《Mikrochimica acta》1998,130(1-2):89-95
The laser induced modification of iron surfaces with atmospheric species was investigated by means of Auger electron spectroscopy (AES) and scanning electron microscopy (SEM). Different laser systems were used for irradiating iron samples in a wide range of the laser processing parameters up to small foci and ultra short pulses.A nitriding of iron connected with an oxidation of the near surface region was observed in the wavelength range between 193 nm and 10.6 m using large foci (0.1 cm2) and short pulses (10...1400ns). In case of small foci (7·10–6cm2) with ns-pulses (50 ns) an enrichment of the iron melt with nitrogen and an advanced oxidation of the surrounding area of the laser spot were detected. When using shorter pulses (200 fs, 40 ps) no indications for a nitriding were found. 相似文献
123.
124.
O-Ethyl N-1-adamantylphosphoramidothioate was synthesized and found to fragment on heating in inert solvents to form the pyrophosphate AdNHP(S)(OEt)OP(S)(OEt)OH. The proposed mechanism involves an elimination of the amine portion with release of ethyl metathiophosphate (EtOP(S)O), as was confirmed in previous work for the comparable structure with oxygen. This transient compound then phosphorylates the starting phosphoramidothioate. O-Ethyl N,N-diethylphosphoramidothioate was also synthesized, and while it gave a similar pyro compound on heating, the reaction mixture was more complex. Both phosphoramidothioates, however, served effectively as thiophosphorylating agents toward alcohols, a silanol, and the silanol groups on the surface of silica gel. Exploratory experiments showed that these phosphoramidothioates also could thiophosphorylate the OH group of a monoester of phosphoric acid, as well as that of phosphinic acids, forming anhydrides with the partial structure 相似文献
125.
The synthesis of the octasaccharide [p-(trifluoroacetamido)phenyl]ethyl 4-O-[2-O-(2-acetamido-2-deoxy-alpha-D-glucopyranosyl)-beta-D-glucopyranosyl]-6-O-[2-O-[4-O-(4-O-alpha-D-galactopyranosyl-beta-D-galactopyranosyl)-alpha-D-glucopyranosyl]-beta-D-glucopyranosyl]-3-O-beta-D-glucopyranosyl-alpha-D-glucopyranoside, representing the outer part of the lipooligosaccharide from Moraxella catarrhalis serotype A, is described, together with a hepta-, a hexa-, and a pentasaccaride, composing parts thereof with shorter oligosaccharide chains substituted in the 6-position of the central 3,4,6-branched glucose moiety. The versatility of the use of thioglycosides in oligosaccharide synthesis is shown, since throughout the synthesis thioglycosides are used as glycosyl donor precursors, either directly in dimethyl(methylthio)sulfonium triflate (DMTST)-promoted coupling reactions or after conversion to the corresponding glycosyl bromide in silver triflate-promoted couplings. The effects of different protecting groups, anomeric leaving groups, and solvents used in the various coupling reactions are often substantial, which necessitates the use of easily convertible intermediates. 相似文献
126.
127.
Kurt Günther Reinhold Carle Ilona Fleischhauer Stefan Merget 《Fresenius' Journal of Analytical Chemistry》1993,345(12):787-790
Summary A semi-preparative low-pressure liquid-chromatographic procedure using tribenzoylcellulose has been developed for the separation and isolation of the four -bisabolol stereoisomers. Stereochemical assignments were made by HPLC-polarimeter coupling and by using the authentical isomers. This method can be applied to the quality control of chamomile preparations, as it allows the detection of adulterations resulting from admixtures of synthetic -bisabolol. In addition, the isolation of all four -bisabolol stereoisomers from commercially available synthetic -bisabolol has been made possible. 相似文献
128.
Carbonnelle S Loco JV Overmeire IV Windal I Wouwe NV Leeuwen SV Goeyens L 《Talanta》2004,63(5):1255-1259
Differences between chemical activated luciferase gene expression (CALUX) bioassay and chemoanalyses results are observed.This paper shows that calculations of the TEQ values using REP values instead of WHO TEF values give different results. The REP values do affect the results obtained by the CALUX technique. These differences are more marked for the dioxin like PCB compounds (CALUX TEQ values are lower than WHO TEQ values) than for the dioxin compounds (CALUX TEQ values are higher than WHO TEQ values).The CALUX results were compared with the concentrations of the congeners’ spiked into the oil. 相似文献
129.
Goldsmith JI Hudson WR Lowry MS Anderson TH Bernhard S 《Journal of the American Chemical Society》2005,127(20):7502-7510
The catalytic process of photoinduced hydrogen generation via the reduction of water has been investigated. The use of parallel synthetic techniques has facilitated the synthesis of a 32 member library of heteroleptic iridium complexes that was screened, using high-throughput photophysical techniques, to identify six potential photosensitizers for use in catalytic photoinduced hydrogen production. A Pd/Ni thin film hydrogen selective sensor allowed for rapid quantification of hydrogen produced via illumination of aqueous systems of the photosensitizer, tris(2,2'-dipyridyl)dichlorocobalt ([Co(bpy)(3)]Cl(2)), and triethanolamine (a sacrificial reductant) with ultra-bright light emitting diodes (LEDs). The use of an 8-well parallel photoreactor expedited the investigation of the hydrogen evolution process and facilitated mechanistic studies. All six compounds investigated produced considerably more hydrogen than commonly utilized photosensitizers and had relative quantum efficiencies of hydrogen production up to 37 times greater than that of Ru(bpy)(3)(2+). 相似文献
130.
Described is an asymmetric synthesis of new Delta(3a,4)-unsaturated, fused bicyclic proline analogues from cyclic bis(allylsulfoximine)titanium complexes and N-tert-butylsulfonyl imino ethyl ester. Treatment of the enantiomerically pure five-, six-, seven-, and eight-membered cyclic bis(allylsulfoximine)titanium complexes with the imino ester gave mixtures of the corresponding (E,syn)- and (Z,syn)-configured, delta-sulfoximine substituted, cyclic gamma,delta-unsaturated alpha-amino acid esters with high regio- and diastereoselectivities in good yields. Activation of the N-methyl sulfoximine group of these amino acid derivatives through methylation with Me(3)OBF(4) afforded in nearly quantitative yields the corresponding (dimethylamino)sulfoxonium salts. A novel migratory cyclization of these salts with DBU gave via an isomerization to the corresponding allylic (dimethylamino)sulfoxonium salts and an intramolecular substitution of the (dimethylamino)sulfoxonium group the enantio- and diastereomerically pure, bicyclic, N-tert-butylsulfonyl protected proline analogues having a six- and eight-membered unsaturated carbocyclic ring. Cyclization of the alkenyl (dimethylamino)sulfoxonium salts was independent of the configuration of the double bond. N,N-Dimethylphenylsulfinamide of > or =99% ee was obtained in good yield as a further reaction product. Conversion of the sulfinamide to N,S-dimethyl-S-phenylsulfoximine of > or =99% ee, the starting material for the synthesis of the allylic sulfoximines, had been accomplished previously. Finally, cleavage of the tert-butylsulfonyl protecting group with anhydrous acid furnished the fused bicyclic proline analogue containing an unsaturated six-membered ring in high yield. 相似文献