全文获取类型
收费全文 | 235篇 |
免费 | 6篇 |
国内免费 | 1篇 |
专业分类
化学 | 181篇 |
晶体学 | 2篇 |
力学 | 3篇 |
数学 | 15篇 |
物理学 | 41篇 |
出版年
2023年 | 4篇 |
2021年 | 6篇 |
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 2篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 6篇 |
2013年 | 9篇 |
2012年 | 14篇 |
2011年 | 22篇 |
2010年 | 14篇 |
2009年 | 8篇 |
2008年 | 18篇 |
2007年 | 12篇 |
2006年 | 18篇 |
2005年 | 16篇 |
2004年 | 15篇 |
2003年 | 11篇 |
2002年 | 10篇 |
2001年 | 10篇 |
2000年 | 6篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1995年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1986年 | 1篇 |
排序方式: 共有242条查询结果,搜索用时 15 毫秒
121.
122.
123.
The crystal structures of drawn copolyamides 6/6.6, 6/6.T, 6/6.1, 6/PXD.6, 6/MXD.6, and 6/MXD.I were examined by wide-angle x-ray diffraction. Copolyamide 6/6.6, which follows the inclusion model, shows only α-characteristics at all the comonomer compositions examined (0–33.3 mol%). However, the other copolyamides, which follow either the partial-inclusion or complete-exclusion model, show γ-characteristics more predominantly as the comonomer content increases. The interplanar spacing of the (200) planes, which corresponds to the hydrogen bond distance between antiparallel chains, remain constant, whereas the spacing of the (020) planes corresponding to the distance between hydrogen bonded sheets increases monotonically with increasing the comonomer content. It is also observed that both the crystal perfection index and the crystal thickness decrease as the comonomer content increases. 相似文献
124.
Gwi-Taek Jeong Don-Hee Park Baik Hwang Je-Chang Woo 《Applied biochemistry and biotechnology》2003,107(1-3):493-503
This study investigated the effects of flask-to-liquid volume ratio on the growth of Panax ginseng hairy root, transformed by Agrobacterium rhizogenes, in flask cultures and compared the characteristics of various bioreactors for scale-up. The flask-to-liquid volume ratio
was optimum at 1.5 mL of air/mL of medium in flask cultures, and hairy root growth was not affected above the optimum ratio.
In 500-mL flask culture, hairy root showed two growth phases. After the first exponential growth, specific growth rate decreased.
The growth characteristics of P. ginseng hairy root in various bioreactors were investigated. Hairy root growth was about 55-fold of inoculum after 39 d in a 5-L
bioreactor and about 38-fold of inoculum after 40 d in a 19-L bioreactor. Carbon yield was higher in a 19-L bioreactor than
in others, but it did not show any linear relationship to the growth rate of hairy roots in bioreactors. 相似文献
125.
Gherman BF Baik MH Lippard SJ Friesner RA 《Journal of the American Chemical Society》2004,126(9):2978-2990
Using broken-symmetry unrestricted Density Functional Theory, the mechanism of enzymatic dioxygen activation by the hydroxylase component of soluble methane monooxygenase (MMOH) is determined to atomic detail. After a thorough examination of mechanistic alternatives, an optimal pathway was identified. The diiron(II) state H(red) reacts with dioxygen to give a ferromagnetically coupled diiron(II,III) H(superoxo) structure, which undergoes intersystem crossing to the antiferromagnetic surface and affords H(peroxo), a symmetric diiron(III) unit with a nonplanar mu-eta(2):eta(2)-O(2)(2)(-) binding mode. Homolytic cleavage of the O-O bond yields the catalytically competent intermediate Q, which has a di (mu-oxo)diiron(IV) core. A carboxylate shift involving Glu243 is essential to the formation of the symmetric H(peroxo) and Q structures. Both thermodynamic and kinetic features agree well with experimental data, and computed spin-exchange coupling constants are in accord with spectroscopic values. Evidence is presented for pH-independent decay of H(red) and H(peroxo). Key electron-transfer steps that occur in the course of generating Q from H(red) are also detailed and interpreted. In contrast to prior theoretical studies, a requisite large model has been employed, electron spins and couplings have been treated in a quantitative manner, potential energy surfaces have been extensively explored, and quantitative total energies have been determined along the reaction pathway. 相似文献
126.
Yu JH Joo J Park HM Baik SI Kim YW Kim SC Hyeon T 《Journal of the American Chemical Society》2005,127(15):5662-5670
Quantum-sized ZnS nanocrystals with quasi-spherical and rod shapes were synthesized by the aging reaction mixtures containing diethylzinc, sulfur, and amine. Uniform-sized ZnS nanorods with the average dimension of 5 nm x 21 nm, along with a small fraction of 5 nm-sized quasi-spherical nanocrystals, were synthesized by adding diethylzinc to a solution containing sulfur and hexadecylamine at 125 degrees C, followed by aging at 300 degrees C. Subsequent secondary aging of the nanocrystals in oleylamine at 60 degrees C for 24 h produced nearly pure nanorods. Structural characterizations showed that these nanorods had a cubic zinc blende structure, whereas the fabrication of nanorods with this structure has been known to be difficult to achieve via colloidal chemical synthetic routes. High-resolution TEM images and reaction studies demonstrated that these nanorods are formed from the oriented attachment of quasi-spherical nanocrystals. Monodisperse 5 nm-sized quasi-spherical ZnS nanocrystals were separately synthesized by adding diethylzinc to sulfur dissolved in a mixture of hexadecylamine and 1-octadecene at 45 degrees C, followed by aging at 300 degrees C. When oleic acid was substituted for hexadecylamine and all other procedures were unchanged, we obtained 10 nm-sized quasi-spherical ZnS nanocrystals, but with broad particle size distribution. These two different-sized quasi-spherical ZnS nanocrystals showed different proportions of zinc blende and wurtzite crystal structures. The UV absorption spectra and photoluminescence excitation spectra of the 5 nm ZnS quasi-spherical nanocrystals and of the nanorods showed a blue-shift from the bulk band-gap, thus showing a quantum confinement effect. The photoluminescence spectra of the ZnS nanorods and quasi-spherical nanocrystals showed a well-defined excitonic emission feature and size- and shape-dependent quantum confinement effects. 相似文献
127.
Madhu Sudan Manna Seok Yeol Yoo Mohammed Sharique Hyoju Choi Bimal Pudasaini Prof. Dr. Mu-Hyun Baik Prof. Dr. Uttam K. Tambar 《Angewandte Chemie (International ed. in English)》2023,62(35):e202304848
We report a copper-catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either SN2 or SN2′ products under two sets of copper-catalyzed conditions, which enables the preparation of a broad range of products with E-alkene selectivity. Density functional theory calculations reveal the origins of the regioselectivity based on the different behaviors of homo- and heterocuprates. 相似文献
128.
Reaction of a (PNP)Ni radical with NO finishes in the time of mixing to form a 1:1 adduct with a NO stretching frequency of 1654 cm (-1). NMR data of this diamagnetic product indicate C 2 v symmetry, which is contradicted by the X-ray structure, which shows it to be nonplanar at Ni, with a geometry intermediate between planar and tetrahedral; the planar geometry is thus the transition state for fluxionality giving time-averaged C 2 v symmetry. The X-ray structure, together with DFT calculations, reveals that the "half-bent" NiNO unit and the intermediate coordination geometry result from a Ni --> NO charge transfer, which has a nonintegral value, resulting in a continuum between NO (+) (hence Ni (0)) and NO (-) (hence Ni (II)). This is related to the nonaxially symmetric character of the Ni --> NO back-donation caused by the (PNP) environment on Ni. Steric effects of ( t )Bu and even chelate constraints are ruled out as the cause of the unusual electronic and structural features. 相似文献
129.
Chemical reasoning based on ligand-field theory suggests that homoleptic cyano complexes should exhibit low-spin configurations, particularly when the coordination sphere is nearly saturated. Recently, the well-known chromium hexacyano complex anion [Cr(CN)6](4-) was shown to lose cyanide to afford [Cr(CN)5](3-) in the absence of coordinating cations. Furthermore, (NEt 4)3[Cr(CN)5] was found to be in a high-spin (S=2) ground state, which challenges the common notion that cyanide is a strong field ligand and should always enforce low-spin configurations. Using density functional theory coupled to a continuum solvation model, we examined both the instability of the hexacyanochromate(II) anion and the relative energies of the different spin states of the pentacyanochromate(II) anion. By making direct comparisons to the analogous Fe (II) complex, we found that cyanide electronically behaves as a strong-field ligand for both metals because the orbital interaction is energetically more favorable in the low-spin configuration than in the corresponding high-spin configuration. The Coulombic repulsion between the anionic cyanide ligands, however, dominates the overall energetics and ultimately gives preference to the high-spin complex, where the ligand-ligand separation is larger. Our calculations highlight that for a quantitative understanding of spin-state energetic ordering in a transition metal complex, ligand-ligand electrostatic interactions must be taken into account in addition to classical ligand-field arguments based on M-L orbital interaction energies. 相似文献
130.
We consider the totally asymmetric simple exclusion process on a ring with flat and step initial conditions. We assume that the size of the ring and the number of particles tend to infinity proportionally and evaluate the fluctuations of tagged particles and currents. The crossover from the KPZ dynamics to the equilibrium dynamics occurs when the time is proportional to the 3/2 power of the ring size. We compute the limiting distributions in this relaxation time scale. The analysis is based on an explicit formula of the finite‐time one‐point distribution obtained from the coordinate Bethe ansatz method. © 2017 Wiley Periodicals, Inc. 相似文献