全文获取类型
收费全文 | 704篇 |
免费 | 20篇 |
国内免费 | 3篇 |
专业分类
化学 | 495篇 |
晶体学 | 9篇 |
力学 | 8篇 |
数学 | 105篇 |
物理学 | 110篇 |
出版年
2023年 | 2篇 |
2022年 | 2篇 |
2021年 | 10篇 |
2020年 | 11篇 |
2019年 | 12篇 |
2018年 | 8篇 |
2017年 | 11篇 |
2016年 | 25篇 |
2015年 | 11篇 |
2014年 | 24篇 |
2013年 | 51篇 |
2012年 | 40篇 |
2011年 | 48篇 |
2010年 | 39篇 |
2009年 | 25篇 |
2008年 | 44篇 |
2007年 | 37篇 |
2006年 | 34篇 |
2005年 | 33篇 |
2004年 | 39篇 |
2003年 | 20篇 |
2002年 | 21篇 |
2001年 | 13篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 15篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 9篇 |
1990年 | 11篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 8篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1973年 | 2篇 |
1965年 | 3篇 |
排序方式: 共有727条查询结果,搜索用时 15 毫秒
31.
Enzymatic oligosaccharide synthesis using recombinant glycosyltransferases is able to overcome the difficulties associated with chemical methods. Nonetheless, sugar nucleotide regeneration cycles are necessary for the glycosylation. The multistep enzyme reaction can be efficiently carried out on superbeads that are prepared by immobilizing multienzyme mixtures on bead support through fused binding domains. 相似文献
32.
Beat Ernst Reinhold Oehrlein Daniel Bellu Jozef Gonda Rainer Jeschke Udo Nubbemeyer 《Helvetica chimica acta》1997,80(3):876-891
A novel type of ketene-Claisen rearrangement in which the precursor of the rearrangement is generated in situ by reaction of optically active allyl thioethers with dichloroketene is described. A characteristic feature of this rearrangement is the excellent chemoselectivity in favor of allyl thioethers vs. allyl ethers, i.e., exclusive chirality transfer of the allylic sulfur moiety is observed with 12, 13 , and 25--27 . The cyclic, optically active allyl thioethers (+)-(R)- 4 and (?)-(S)- 4 and the open-chain allyl thioethers 11--13 rearrange with in situ generated dichloroketene to the optically active thioesters (?)-(S)- 28 , (+)-(R)- 28 , and 31-33 , respectively. A chirality-transfer of > 99% in the cyclic cases (+)-(R)- 4 and (?)-(S)- 4 , and 96--98 % in the open-chain cases 11--13 is observed. Furthermore, the dichloroketene-Claisen rearrangement is characterized by a high asymmetric 1,2-induction. The chiral allylic sulfides 25--27 give the optically active thioesters 36--38 with a 1,2-induction > 99% as determined by NMR-shift experiments. 相似文献
33.
Zusammenfassung Die Dünnschichtchromatographie von Fettsäuren wurde mit der Papierchromatographie solcher Säuren hinsichtlich ihrer Trennwirkung verglichen. Ein Verfahren zur quantitativen Bestimmung auf Dünn-schichten getrennter Fettsäuren wurde ausgearbeitet.
Summary The thin layer chromatography of fatty acids was compared with the paper chromatography of such acids with respect to their separation. A method was worked out for the quantitative determination of fatty acids separated on thin layers.
Résumé On compare la chromatographie en couche mince des acides gras avec celle sur papier, du point de vue de leur pouvoir de séparation. On a mis au point un procédé de dosage quantitatif des acides gras séparés sur couches minces.相似文献
34.
The triple fluorescence of benzanilide and the dielectric medium modulation of its competitive excitation 总被引:1,自引:0,他引:1
The fluorescence of the benzanilide molecule at 298 K is inferred to consist of three independent electronic transitions associated with the single ground-state molecular species. F1 (λmax340 nm), the normal fluorescence is observed weakly and is ascribed to an n,π*,-π,π* mixed state. F′2 is ascribed to the proton-transfer imidol tautomer fluorescence (previously reported) with unresolved λmax (inferred at ≈460 nm). F″2 is ascribed to a charge-transfer state fluorescence to the ground state, and occurs as a resolved CT transition in tetrahydrofuran at λmax 520 nm. Comparison of the spectra of N-methylbenzanilide exhibiting only F1 and F″2 (CT) permitted the analysis of the benzanilide spectra. 相似文献
35.
The bipartite entanglement in pure and mixed states of a quantum spin-1 Heisenberg dimer with exchange and uniaxial single-ion anisotropies is quantified through the negativity in a presence of the external magnetic field. At zero temperature the negativity shows a marked stepwise dependence on a magnetic field with two abrupt jumps and plateaus, which can be attributed to the quantum antiferromagnetic and quantum ferrimagnetic ground states. The magnetic-field-driven phase transition between the quantum antiferromagnetic and quantum ferrimagnetic ground states manifests itself at nonzero temperatures by a local minimum of the negativity, which is followed by a peculiar field-induced rise of the negativity observable in a range of moderately strong magnetic fields. The rising temperature generally smears out abrupt jumps and plateaus of the negativity, which cannot be distinguished in the relevant dependencies above a certain temperature. It is shown that the thermal entanglement is most persistent against rising temperature at the magnetic field, for which an energy gap between a ground state and a first excited state is highest. Besides, temperature variations of the negativity of the spin-1 Heisenberg dimer with an easy-axis single-ion anisotropy may exhibit a singular point-kink, at which the negativity has discontinuity in its first derivative. The homodinuclear nickel complex [Ni(Medpt)(-ox)(HO)](ClO)·2HO provides a suitable experimental platform of the antiferromagnetic spin-1 Heisenberg dimer, which allowed us to estimate a strength of the bipartite entanglement between two exchange-coupled Ni magnetic ions on the grounds of the interaction constants reported previously from the fitting procedure of the magnetization data. It is verified that the negativity of this dinuclear compound is highly magnetic-field-orientation dependent due to presence of a relatively strong uniaxial single-ion anisotropy. 相似文献
36.
Jozef Gonda Dávid Maliňák Margaréta Kováčová Miroslava Martinková Martin Walko 《Tetrahedron: Asymmetry》2013,24(23):1514-1519
A flexible approach to the stereoselective synthesis of (5S)-5-C-methyl- and (5S)-5-C-ethyl-β-l-lyxo-hexofuranoses 15a, 22 starting from 1,2:5,6-di-O-isopropylidene-α-d-gulofuranose 3 as the source of chirality is described. The corresponding C-5 alkyl groups were introduced via a Wittig olefination followed by Pd/C-mediated hydrogenation of the conformationally restricted alkenes in a highly diastereoselective manner. 相似文献
37.
Franz Dieter Fischer Jozef Predan Reinhold Kienzler 《Archive of Applied Mechanics (Ingenieur Archiv)》2014,84(9-11):1325-1337
Formation of crack arrays plays an increasing role in several fields of applied physics. The energy-release rate of the cracks controls the development of the array. Therefore, following the concept of configurational forces, a simplified analytical expression is provided for the energy-release rate, which is based both on numerical studies and on a specially adapted beam model. Comparisons of this easy-to-use estimate of the energy-release rate with established results from the literature as well as detailed numerical results are presented. The provided estimate of the energy-release rate can easily be extended to non-equidistant cracks and an anisotropic material. 相似文献
38.
39.
Mihaela Gulea Isabelle Abrunhosa Jozef Drabowicz Guillaume Grach Matthieu Hamel Serge Masson 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1267-1272
Abstract A new method to prepare enantioenriched sulfinates was developed to obtain optically active ortho-methylsulfinyl(phenylphosphonates). It consists of a diastereoselective oxidation of sulfenates to sulfinates. Additionally, preliminary results concerning the synthesis of ortho-phophonylated benzylic thiol derivatives via a new P═S to P═C [1,4]-rearrangement and a first synthetic application of these compounds are also described. 相似文献
40.