全文获取类型
收费全文 | 909篇 |
免费 | 24篇 |
国内免费 | 4篇 |
专业分类
化学 | 652篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 155篇 |
物理学 | 113篇 |
出版年
2023年 | 5篇 |
2022年 | 24篇 |
2021年 | 25篇 |
2020年 | 13篇 |
2019年 | 21篇 |
2018年 | 16篇 |
2017年 | 17篇 |
2016年 | 20篇 |
2015年 | 30篇 |
2014年 | 39篇 |
2013年 | 53篇 |
2012年 | 61篇 |
2011年 | 67篇 |
2010年 | 37篇 |
2009年 | 41篇 |
2008年 | 63篇 |
2007年 | 50篇 |
2006年 | 53篇 |
2005年 | 41篇 |
2004年 | 46篇 |
2003年 | 32篇 |
2002年 | 26篇 |
2001年 | 6篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 11篇 |
1997年 | 13篇 |
1996年 | 9篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1974年 | 2篇 |
1874年 | 1篇 |
1871年 | 1篇 |
1870年 | 1篇 |
排序方式: 共有937条查询结果,搜索用时 0 毫秒
61.
A shear cell was constructed in two variants for simultaneous small-angle X-ray scattering and freeze fracture. Using this cell, the changes in the layer structure and the domain formation of the Synperonic A7-water system were investigated under shear. The reconstructions of both the layer and domain structures were not observed in the steady state after 1 h (following a 2 h long shear period). Destruction of the lamellar arrangement and formation of aggregates occurred during the stress. It was concluded that the tixotropic behavior originates rather from the change of the domain structure with a typical size range of microm than from the changes of the inner structure of domains with lamellar arrangement. 相似文献
62.
Pd-silica catalysts prepared by depositing Pd onto silica precursors modified by surface methyl or phenyl groups through the reduction of Pd2+ ions with surface Si-H functions exhibit high activity and selectivity in Heck coupling. 相似文献
63.
64.
65.
66.
Measurements of induced losses on primary coated single-mode fibers strained against the inner wall of loose tube cable materials are reported. Fibers have been chosen from current types such as match and depressed clad with mode field diameters (MFD) and cut-off wavelengths spanning the expected range of production tolerances. The loss dependence on MFD and cut-off is characterized, and the combination high MFD/low cut-off turns out to be the most bend sensitive parameter combination while the opposite case with low MFD/high cut-off gives the best performance. Different tube materials provide different bend loss performance depending on the microstructure of the tube and the amount and type of filling jelly. 相似文献
67.
68.
The synthesis of two riboside-containing arsenic compounds, methyl-2,3-O-isopropylidene-5-dimethyl-arsinoyl-β-d-ribofuranoside and methyl-2,3-O-isopropylidene-5-deoxy-5-dimethyl-thioarsinoyl-β-d- ribofuranoside is presented in this paper. Intermediates and final products of the synthesis were examined by gas chromatography and thin layer chromatography. The purity of the products was assessed by NMR spectroscopy. Trimethylsilylation was used to volatilise sugar compounds and thus use of the costly HPLC–MS technique was avoided. The results affirmed the presence of tautomers in case of arsenosugars. 相似文献
69.
Toxic metal complexes of macrocyclic cyclen molecule – synthesis,structure and complexing properties
M. Litecká R. Gyepes M. Vilková M. Almáši M. Walko 《Journal of Coordination Chemistry》2017,70(10):1698-1712
Toxic metal (Cd2+, Hg2+, Pb2+, and Ag+) complexes with the tetradentate macrocyclic ligand - cyclen (1,4,7,10-tetraazacyclododecane, [12]aneN4, L) were prepared and studied in the solid state by IR, X-ray diffraction, elemental and thermal analysis. Diffraction results have yielded three molecular structures, [Cd([12]ane-κ4N1,4,7,10)(NO3)2)] (1), [Hg([12]ane-κ4N1,4,7,10)(NO3-κ2O,O`)]NO3 (2), [Pb2([12]ane-κ4N1,4,7,10)2][Pb(NO3)6] (3) and one polymeric structure {[Ag2([12]ane-κ3N1,4,7)(μ2-[12]aneN10)](NO3)2?2H2O)}n (4) featuring a unique coordination mode not observed before with cyclen as a ligand. The monodentate (1) and chelate (with small bite angle 50.3(3)°, (2) coordination modes of nitrate ligands were confirmed. Stereochemically active 6s2 lone pair was suggested in 3 and DFT results confirmed no significant metal–metal covalent bond. The stability constants of the complexes with Cd2+ and Pb2+ ions were determined by potentiometric methods in aqueous solutions. Additionally, the structures of complexes in solution were observed by 1H NMR. Both methods confirm similar cyclen complexing properties toward Zn2+ biometal and Cd2+, Pb2+ toxic metals. 相似文献
70.
Attila Bende 《Theoretical chemistry accounts》2010,125(3-6):253-268
The equilibrium structures, binding energies, vibrational harmonic frequencies, and the anharmonic corrections for two different (cyclic and asymmetric) urea dimers and for the adenine–thymine DNA base pair system have been studied using the second-order Møller–Plesset perturbation theory (MP2) method and different density functional theory (DFT) exchange–correlation (XC) functionals (BLYP, B3LYP, PBE, HCTH407, KMLYP, and BH and HLYP) with the D95V, D95V**, and D95V++** basis sets. The widely used a posteriori Boys–Bernardi or counterpoise correction scheme for basis set superposition error (BSSE) has been included in the calculations to take into account the BSSE effects during geometry optimization (on structure), on binding energies and on the different levels of approximation used for calculating the vibrational frequencies. The results obtained with the ab initio MP2 method are compared with those calculated with different DFT XC functionals; and finally the suitability of these DFT XC functionals to describe intermolecular hydrogen bonds as well as harmonic frequencies and the anharmonic corrections is assessed and discussed. 相似文献