全文获取类型
收费全文 | 1335篇 |
免费 | 13篇 |
国内免费 | 13篇 |
专业分类
化学 | 860篇 |
晶体学 | 5篇 |
力学 | 19篇 |
综合类 | 1篇 |
数学 | 296篇 |
物理学 | 180篇 |
出版年
2021年 | 11篇 |
2020年 | 8篇 |
2018年 | 10篇 |
2016年 | 19篇 |
2015年 | 10篇 |
2014年 | 15篇 |
2013年 | 70篇 |
2012年 | 54篇 |
2011年 | 67篇 |
2010年 | 39篇 |
2009年 | 28篇 |
2008年 | 65篇 |
2007年 | 63篇 |
2006年 | 65篇 |
2005年 | 64篇 |
2004年 | 60篇 |
2003年 | 50篇 |
2002年 | 60篇 |
2001年 | 22篇 |
2000年 | 20篇 |
1999年 | 16篇 |
1998年 | 8篇 |
1997年 | 18篇 |
1996年 | 22篇 |
1995年 | 15篇 |
1994年 | 10篇 |
1993年 | 16篇 |
1992年 | 17篇 |
1991年 | 16篇 |
1990年 | 20篇 |
1989年 | 14篇 |
1988年 | 12篇 |
1987年 | 17篇 |
1986年 | 12篇 |
1985年 | 23篇 |
1984年 | 37篇 |
1983年 | 18篇 |
1982年 | 27篇 |
1981年 | 19篇 |
1980年 | 8篇 |
1979年 | 25篇 |
1978年 | 28篇 |
1977年 | 21篇 |
1976年 | 22篇 |
1975年 | 25篇 |
1974年 | 20篇 |
1973年 | 19篇 |
1972年 | 13篇 |
1971年 | 7篇 |
1968年 | 9篇 |
排序方式: 共有1361条查询结果,搜索用时 15 毫秒
41.
Larry Smith 《manuscripta mathematica》1978,24(2):221-228
The purpose of this note is to construct examples of non-trivial rank 2 complex bundles over CP(n) with vanishing Chern classes for all n5. 相似文献
42.
Daewon Hong Patrick J. Carroll Larry G. Sneddon 《Journal of organometallic chemistry》2003,680(1-2):61-65
The new 11-vertex nido-diphosphaborane, 7,9-Ph2-nido-7,9-P2B9H9, has been synthesized by the reaction of Me4N+[nido-B9H12−] with PhPCl2 in the presence of NaH. A single crystal X-ray diffraction determination and DFT/GIAO/NMR methods have both established that the compound has an open cage structure containing the phosphorus atoms in non-adjacent positions on the open face. 相似文献
43.
The electron paramagnetic resonance (EPR) and saturation transfer electron paramagnetic resonance (ST-EPR) spectra typical of nitroxide spin labels obeying an isotropic, brownian diffusion model are theoretically investigated. The derivative approximation discussed in the first paper of this series (I) is examined and generalized to consider large modulation amplitudes. The approximation considers both molecular and applied modulation effects with the Zeeman modulation frequency acting as a perturbation parameter. The application of the approximation to first and second harmonic simulations is discussed. The observations of I are preserved for first harmonic spectra. The approximation is able to accurately reproduce the in-phase absorption and in-phase-quadrature dispersion signals. In-phase dispersion signals are reproducible at low microwave powers while in-phase-quadrature signals may be reproduced at higher powers. The approximation is of limited utility for second harmonic simulations and is particularly unable to reproduce the in-phase-quadrature absorption signal at this harmonic. The approximation enables a marked reduction in both the core and CPU time required for simulations. Factors of 3 and 4.2 respectively were realized in the simulations of slow isotropic brownian diffusion. 相似文献
44.
Gottfried AC Wang J Wilson EE Beck LW Banaszak Holl MM Kampf JW 《Inorganic chemistry》2004,43(24):7665-7670
The combination of 2 equiv of bis[bis(trimethylsilyl)amide]germylene (5) with 2 equiv of 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) in tetrahydrofuran (THF) results in the ring-opening of 1 equiv of THF to form 2,2,8,8-tetrakis(1,1,1,3,3,3-hexamethyl-disilazan-2-yl)-5,16-diphenyl-7,9,14-trioxa-1,3,5,16,18,19-hexaaza-2,8-digerma-tricyclo[13.2.1.13,6]nonadeca-6(19),15(18)-diene-4,17-dione (6). This fast and nearly quantitative reaction builds a 15-membered ring from five different molecules. The new ring, structurally assigned by X-ray crystallography, contains a flexible methylene chain that moves rapidly on the NMR time scale. 相似文献
45.
The sensitive detection of sulfur-containing analytes is of interest in many industrial applications; selective detection is also desirable since these compounds are usually present at trace levels in difficult matrixes. The purpose of this article is to review the use of the Sievers® ozone-based sulfur chemiluminescence detector, and its coupling with gas chromatography, supercritical fluid chromatography, and high performance liquid chromatography. Detection limits, linearity, response factors, and selectivity are discussed for each of these techniques. Critical operational parameters for the SCD are also described. The use of other sulfur selective detectors for SFC and HPLC is also briefly summarized. 相似文献
46.
Munir M. Ahmad Martin R. Bryce Joan Halfpenny Larry Weiler 《Tetrahedron letters》1984,25(38):4275-4278
Bis(triphenylphosphoranylidene)ammonium iodide (PPN+I?) forms a 2:3 complex with TCNQ [(PPN)2(TCNQ)3(CH3CN)2] that provides an example of a TCNQ complex containing acetonitrile in the crystal lattice; the material is a semi-conductor with trimerised TCNQ stacks. 相似文献
47.
The new monocarbaborane dianion, arachno-4-CB(8)H(12)(2)(-) has been synthesized from the reaction of arachno-4-CB(8)H(14) with 2 equiv of NaH in polar solvents. DFT/GIAO computations at the B3LYP/6-311G//B3LYP/6-311G level, in conjunction with 1D and 2D NMR spectroscopic studies, have confirmed that the dianion results from deprotonation of both the endo-CH and one bridging hydrogen of the parent arachno-4-CB(8)H(14). While the DFT calculations indicate that a C(1) symmetric structure is lowest in energy, the experimental solution NMR data are consistent with the dianion having a C(s)() symmetric structure, thus suggesting that it is fluxional in solution. Transition state calculations located a low-energy pathway with an activation energy of only 2.7 kcal/mol that allows the migration of the bridging hydrogen between the two enantiomeric forms of the dianion. The process can occur by a single-step, simple rotation through a transition state structure containing a -BH(2) group at the B7 boron. Averaging the calculated (11)B NMR chemical shifts of the resonances for those atoms in the static enantiomeric structures that become equivalent by this fluxional process then gives excellent agreement with the solution NMR data. Transition state calculations of the fluxional behavior previously observed for the isoelectronic arachno-4-CB(8)H(13)(-) and arachno-4-SB(8)H(11)(-) monoanions have likewise revealed related low-energy (0.3 and 5.0 kcal/mol, respectively) rearrangement mechanisms involving the simultaneous rotation of three hydrogens (two bridging and one -BH(2)) through a C(s)() symmetry transition state containing three -BH(2) groups. 相似文献
48.
CD data for a variety of N-nitrosamino acids and N-nitrosopyrrolidines are presented. The effects of nitrosamino group conformation, pyrrolidine ring geometry, different perturbing substituents, and especially intramolecular H-bonding upon the n → π* CD band are discussed. Stereochemical conclusions can be made with confidence in many cases, although no sector diagram, as yet published, successfully correlates all the available chiroptical data in this series of compounds. However, a negative CD band due to the π → π* transition was observed tor all N-nitrosamines having the L-proline configuration at C-2, regardless of nitroso group conformation; it is suggested that this band be used whenever possible for stereochemical correlations. 相似文献
49.
John Raymond O'Lear Larry Gene Wright John Nathan Louris R. Graham Cooks 《Journal of mass spectrometry : JMS》1987,22(6):348-358
A new scan is described which responds to ions that are intermediates in the dissociation of a mass-selected parent ion (mp) to give a mass-selected daughter ion (md). The scan gives a simple mass v. abundance output for ions which satisfy this condition. It is implemented here on a BEQQ hybrid mass spectrometer using, in sequence, collision-induced dissociation occurring at high energy in the first reaction region, and low-energy collisional activation in the collision quadrupole. The experiment provides information on reaction sequences not available from single scans of other types. In the several cases examined, it is demonstrated that, among many conceivable fragmentation routes connecting a parent ion with a particular fragment ion, only a few are significant. Examination of reaction intermediate spectra also appears to be a fruitful new approach to mechanistic questions, as illustrated by consideration of the behavior of several isomeric octanones. These new spectra also have analytical value: they show good signal-to-noise ratios and allow ready distinction between isobaric and isomeric ions. A comparison of the reaction intermediate spectrum with a daughter spectrum obtained by the B/E linked-scanning technique reveals the contributions of artifact peaks which result from poor parent ion mass resolution in the latter. Reaction intermediate spectra combine information from the daughter spectra of mp and the parent spectra of md and, as a specified portion of this data domain, have unique characteristics. 相似文献
50.
Inmaculada Escorihuela Larry R. Falvello Milagros Tomás 《Journal of Cluster Science》2004,15(4):425-435
The reaction of the tetranuclear cyanide aquo complex [{Pt(CN)4Cu(bipy)(H2O)}2]· 2H2O with aqueous ammonia produces the new tetranuclear ammino-containing product [{Pt(CN)4Cu(bipy)(NH3)}2] (1), with terminal cyanide groups and with NH3 coordinated to the Cu atom. The distorted trigonal bipyramidal coordination about copper in 1 differs from the square-pyramidal coordination present in the starting material. The bipyridine ligand in 1 is nearly perpendicular to the tetranuclear core of the molecule, as opposed to its coplanar disposition in the aquo complex. The two platinum atoms of the tetranuclear core in 1 form Pt···Pt interactions of 3. 2390(8) Å with platinum atoms of neighboring molecules, producing an echelon-shaped supramolecular chain held together by staggered (CN)4Pt···Pt(CN)4 linkages, an aggregate structure which does not have a precedent in chemistry derived from the Pt(CN)4 building block. 相似文献