全文获取类型
收费全文 | 677篇 |
免费 | 6篇 |
专业分类
化学 | 491篇 |
晶体学 | 12篇 |
力学 | 26篇 |
数学 | 39篇 |
物理学 | 115篇 |
出版年
2021年 | 7篇 |
2018年 | 7篇 |
2016年 | 7篇 |
2013年 | 29篇 |
2012年 | 25篇 |
2011年 | 25篇 |
2010年 | 13篇 |
2009年 | 13篇 |
2008年 | 25篇 |
2007年 | 33篇 |
2006年 | 20篇 |
2005年 | 19篇 |
2004年 | 18篇 |
2003年 | 18篇 |
2002年 | 28篇 |
2001年 | 11篇 |
2000年 | 16篇 |
1999年 | 12篇 |
1998年 | 8篇 |
1997年 | 7篇 |
1996年 | 9篇 |
1995年 | 9篇 |
1994年 | 12篇 |
1993年 | 15篇 |
1992年 | 22篇 |
1991年 | 13篇 |
1990年 | 9篇 |
1988年 | 14篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1974年 | 12篇 |
1973年 | 8篇 |
1972年 | 10篇 |
1971年 | 12篇 |
1970年 | 6篇 |
1969年 | 5篇 |
1960年 | 5篇 |
1958年 | 9篇 |
1954年 | 5篇 |
排序方式: 共有683条查询结果,搜索用时 546 毫秒
11.
12.
13.
14.
The decrease in D-->A bond lengths, previously reported for some Lewis acid/base complexes, in going from the gas to the solid phases is investigated by obtaining an accurate crystal structure of solid ND(3)BF(3) by powder neutron diffraction. The B-N internuclear distance is 1.554(3) A, 0.118 A shorter than the most recent gas-phase microwave value and 0.121 A shorter than the single molecule geometry optimized (1.672 A, CISD/6-311++G(d,p)) bond length. The crystal structure also shows N-D.F-B hydrogen bonds. The effects of this change in structure and of intermolecular hydrogen-bonding on nuclear magnetic shielding (i.e., chemical shifts) and the nuclear quadrupolar coupling constants (QCC) are investigated by ab initio molecular orbital and density functional theory calculations. These calculations show that the nitrogen ((15)N and (14)N) and boron ((11)B and (10)B) chemical shifts should be rather insensitive to changes in r(BN) and that the concomitant changes in molecular structure. Calculations on hydrogen-bonded clusters, based on the crystal structure, indicate that H-bonding should also have very little effect on the chemical shifts. On the other hand, the (11)B and (14)N QCCs show large changes because of both effects. An analysis of the (10)B[(19)F] line shape in solid ND(3)(10)BF(3) yields a (11)B QCC of +/-0.130 MHz. This is reasonably close an earlier value of +/-0.080 MHz and the value of +/-0.050 MHz calculated for a [NH(3)BF(3)](4) cluster. The gas-phase value is 1.20 MHz. Temperature-dependent deuterium T(1) measurements yield an activation energy for rotation of the ND(3) group in solid ND(3)BF(3) of 9.5 +/- 0.1 kJ/mol. Simulations of the temperature-dependent T(1) anisotropy gave an E(a) of 9.5 +/- 0.2 kJ/mol and a preexponential factor, A, of 3.0 +/- 0.1 x 10(12) s(-)(1). Our calculated value for a [NH(3)BF(3)](4) cluster is 16.4 kJ/mol. Both are much higher than the previous value of 3.9 kJ/mol, from solid-state proton T(1) measurements. 相似文献
15.
16.
1,3,5-Trisubstituted hexahy drotriazines react with hydrogen chloride in the presence of anhydrous solvents to form useful intermediates for the introduction of the RNHCH2- group into compounds which undergo the Mannich reaction. The effectiveness of the new aminomethyl-ating agent has been demonstrated by the preparation of secondary aminomethyl sulfide hydro-chlorides. 相似文献
17.
Hodgson DM Kirton EH Miles SM Norsikian SL Reynolds NJ Coote SJ 《Organic & biomolecular chemistry》2005,3(10):1893-1904
Organolithium-induced deprotonation of terminal epoxides in the presence of appropriate diamine ligands allows trapping with a range of electrophiles, yielding functionalised di- and tri-substituted epoxides in good yields and with control of stereochemistry at the epoxide. 相似文献
18.
Köse ME Crutchley RJ Derosa MC Ananthakrishnan N Reynolds JR Schanze KS 《Langmuir : the ACS journal of surfaces and colloids》2005,21(18):8255-8262
Polymer films consisting of a linear poly(dimethylsiloxane) end-functionalized with a luminescent Ir(III) complex (Ir-PDMS), blended with polystyrene (PS), function as optical oxygen sensors. The sensor response arises by quenching of the luminescence from the Ir(III) chromophore by oxygen that permeates into the polymer film. The morphology and luminescence oxygen sensor properties of blend films consisting of Ir-PDMS and PS have been characterized by fluorescence microscopy, atomic force microscopy, and scanning electron microscopy. The investigations demonstrate that microscale phase segregation occurs in the films. In blends that contain a relatively small amount of Ir-PDMS in PS (ca. 10 wt %), the Ir-PDMS exists as circular domains, with diameters ranging from 2 to 5 mum, surrounded by the majority PS phase. For larger weight fractions of Ir-PDMS in the blends, the film morphology becomes bicontinuous. A novel epifluorescence microscopy method is applied that allows the construction of Stern-Volmer quenching images that quantify the oxygen sensor response of the blend films with micrometer spatial resolution. These images provide a map of the oxygen permeability of the polymer blend films with a spatial resolution of ca. 1 mum. The results of this investigation show that the micrometer-sized Ir-PMDS domains display a 2-3-fold higher oxygen sensor response compared to the surrounding PS matrix. This result is consistent with the fact that PDMS is considerably more gas permeable compared to PS. The relationship of the microscale morphology of the blends to their performance as macroscale optical oxygen sensors is discussed. 相似文献
19.
Frey GL Reynolds KJ Friend RH Cohen H Feldman Y 《Journal of the American Chemical Society》2003,125(19):5998-6007
The development of low-cost, large-area electronic applications requires the deposition of active materials in simple and inexpensive techniques at room temperature, properties usually associated with polymer films. In this study, we demonstrate the integration of solution-processed inorganic films in light-emitting diodes. The layered transition metal dichalcogenide (LTMDC) films are deposited through Li intercalation and exfoliation in aqueous solution and partially oxidized in an oxygen plasma generator. The chemical composition and thickness of the LTMDC and corresponding transition metal oxide (TMO) films are investigated by X-ray photoelectron spectroscopy. The morphology and topography of the films are studied by atomic force microscopy. X-ray powder diffraction is used to determine the orientation of the LTMDC film. Finally, the LTMDC and their corresponding oxides are utilized as hole-injecting and electron-blocking materials in polymer light-emitting diodes with the general structure ITO/LTMDC/TMO/polyfluorene/Ca/Al. Efficient hole injection and electron blocking by the inorganic layers result in outstanding device performance and high efficiency. 相似文献
20.
Aboelella NW Lewis EA Reynolds AM Brennessel WW Cramer CJ Tolman WB 《Journal of the American Chemical Society》2002,124(36):10660-10661
The X-ray structure of a 1:1 Cu/O(2) adduct revealed side-on (eta(2)) O(2) coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)-(O(2)(2-)) resonance form, and provided insights into the key bonding interactions. Reaction of a 1:1 adduct supported by a slightly different beta-diketiminate ligand with Cu(I) reagents resulted in the formation of novel asymmetric bis(mu-oxo) complexes that were identified by EPR, UV-vis, and Raman spectroscopy, as well as by an X-ray structure in one instance. 相似文献