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排序方式: 共有351条查询结果,搜索用时 31 毫秒
1.
Dr. Amey Nimkar Dr. Sandeepan Maity Prof. Robert A Flowers II Prof. Shmaryahu Hoz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10499-10504
The work described herein compares the effect of additives (HMPA, methanol, ethylene glycol, pinacol, N-methylethanolamine) on thermal and photochemical reactions of samarium diiodide (SmI2). In thermal reactions, additives that coordinate to SmI2 induce a significant increase in reaction rate. In photochemical reactions, the presence of an electronegative atom with a highly localized negative charge on the substrate leads to a rate deceleration. In order to benefit from the columbic interaction with the positively charged samarium cation, these substrates react preferentially by an inner sphere reduction mechanism. The addition of ligands prevents this close interaction causing rate retardation. Furthermore, studies demonstrate that excited state quenching of SmII by ethylene glycol and other additives indicate that it is unlikely to be the major cause for the observed rate retardation. This effect provides a simple diagnostic tool to distinguish between an inner and an outer sphere reduction mechanism. 相似文献
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Shinkar’ E. V. Smolyaninov I. V. Kuzmin V. V. Berberova N. T. 《Russian Journal of General Chemistry》2019,89(4):689-696
Russian Journal of General Chemistry - A novel and efficient method for the synthesis of biologically active organic di-, tri- and tetrasulfides has been proposed. Different methods of redox... 相似文献
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Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes 下载免费PDF全文
Nidal Saleh Barry Moore II Monika Srebro Nicolas Vanthuyne Loïc Toupet J. A. Gareth Williams Christian Roussel Kirandeep K. Deol Gilles Muller Jochen Autschbach Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1673-1681
Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene‐bipyridine proligand 1 a and in its “rollover” cycloplatinated derivative 2 a . Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum‐chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene‐bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge‐transfer‐type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation. 相似文献
4.
Ivan V. Smolyaninov Georgy K. Fukin Nadezhda T. Berberova Andrey I. Poddelsky 《Molecules (Basel, Switzerland)》2021,26(8)
A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh3, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catechol thioethers and Ph3SbBr2 in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 1–3 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the “catechol/o-semiquinone” redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical. 相似文献
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M. J. R. Cantow T. Y. Ting E. M. Barrall II R. S. Porter E. R. George 《Rheologica Acta》1986,25(1):69-71
The shear dependence of the bulk viscosities of two structurally different types of perfluoropolyether fluids was determined by two different techniques. The first involved direct measurement in a high shear Couette viscometer, the second utilized the time-temperature superposition principle to establish master curves from viscosity determinations at low shear rates and temperature; the results are comparable. Both fluids begin to show non-Newtonian behavior at shear rates above 10,000 s–1. 相似文献
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