全文获取类型
收费全文 | 1921篇 |
免费 | 15篇 |
国内免费 | 10篇 |
专业分类
化学 | 1113篇 |
晶体学 | 14篇 |
力学 | 66篇 |
数学 | 436篇 |
物理学 | 317篇 |
出版年
2020年 | 16篇 |
2019年 | 16篇 |
2016年 | 19篇 |
2015年 | 16篇 |
2014年 | 24篇 |
2013年 | 102篇 |
2012年 | 44篇 |
2011年 | 58篇 |
2010年 | 44篇 |
2009年 | 54篇 |
2008年 | 61篇 |
2007年 | 57篇 |
2006年 | 83篇 |
2005年 | 71篇 |
2004年 | 56篇 |
2003年 | 65篇 |
2002年 | 44篇 |
2001年 | 42篇 |
2000年 | 46篇 |
1999年 | 30篇 |
1998年 | 43篇 |
1997年 | 38篇 |
1996年 | 49篇 |
1995年 | 26篇 |
1994年 | 34篇 |
1993年 | 26篇 |
1992年 | 30篇 |
1991年 | 29篇 |
1990年 | 20篇 |
1989年 | 24篇 |
1988年 | 22篇 |
1987年 | 23篇 |
1986年 | 16篇 |
1985年 | 38篇 |
1984年 | 35篇 |
1983年 | 33篇 |
1982年 | 30篇 |
1981年 | 17篇 |
1980年 | 46篇 |
1979年 | 19篇 |
1978年 | 36篇 |
1977年 | 41篇 |
1976年 | 27篇 |
1975年 | 20篇 |
1974年 | 39篇 |
1973年 | 34篇 |
1972年 | 21篇 |
1971年 | 21篇 |
1969年 | 29篇 |
1968年 | 15篇 |
排序方式: 共有1946条查询结果,搜索用时 31 毫秒
51.
Norman B. Colthup 《Journal of polymer science. Part A, Polymer chemistry》1982,20(11):3167-3179
Molecular orbital calculations were used to study free radical polymerization. Calculations show that the monomer is activated during the reaction and the pi bond becomes a diradical. The radical on the carbon that is about to form the new bond is called the e radical in this article. The other is the Q radical. For different monomers it is shown indirectly that changes in the energies of formation of the Q and e radicals are related to changes in the Q and e terms in the empirical Q–e scheme of Alfrey and Price. The polar effect in the Q–e scheme involves the e-radical, unpaired electron density. Specifically, the Q–e sum (ex + ey) is correlated with the e radical spin density. Also the e term is correlated with the electron density on the unsubstituted carbon of the monomer. The relationship of the Q radical to the adjacent substituent is shown by correlating ln Q values with the energy of addition of a hydrogen atom to a monomer. These relationships give theoretical meaning to the Q–e terms and allow calculation of Q and e values from molecular orbital properties for small monomers. 相似文献
52.
A force field is presented in which the zero point energies and the effects of vibrational thermal excitation are included in the heat of formation calculations. The standard deviation of the difference between the calculated and experimental heats of formation of a diverse set of 44 hydrocarbons is 0.38 , which is the same as the average experimental error for this set of compounds. This standard deviation is substantially lower than in previous similar force fields which did not include vibrational effects, and it is argued that much of this improvement is due to the inclusion of vibrational terms in the heat of formation. This force field also reproduces the experimental structures of compounds well. 相似文献
53.
John Philip Tarburton Cynthia S. Day Victor W. Day Iraj Tavaniepour Norman H. Cromwell 《Journal of heterocyclic chemistry》1986,23(2):433-441
Solid-state structures have been determined for cis- and trans-1-cyclohexyl-2-phenyl-3-(p-toluyl)aziridines using single-crystal X-ray diffraction techniques. The cis isomer crystallizes in the centrosymmetric monoclinic space group P21/c (No. 14), with a = 18.669(3)Å, b = 5.709(1)Å, c = 17.412(2)Å, β = 96.29(1)° and Z = 4; the trans isomer crystallizes in the noncentrosymmetric orthorhombic space group Pna21 (No. 33), with a = 17.089(2)Å, b = 18.729(3)Å, c = 5.749(1)Å and Z = 4. Full-matrix least-squares refinement of the structural parameters led to the following final agreement factors: R1 (unweighted, based on F) = 0.040 and R2 (weighted, based on F) = 0.054 for the 2592 independent reflections of the cis isomer having 2θMoK¯α <55° and I>3σ1, and R1 = 0.033 and R2 = 0.031 for the 1504 independent reflections of the trans isomer having 2θMoK¯α <55° and I>3σ1. The statistically significant differences that exist between the two isomers for two bond lengths and ten bond angles (p < 0.05) appear to be the direct result of the p-toluyl group orientation with respect to the cyclohexyl and phenyl substituents. In the cis isomer it is anti with respect to the N-cyclohexyl group and cis with respect to the phenyl group, whereas in the trans isomer it is syn with respect to the N-cyclohexyl and trans with respect to the phenyl group. Three-ring to carbonyl hyperconjugation is correlated with stereoelectronic interactions in the trans isomer. Bonding, determined by X-ray and nmr studies, is discussed for the three-membered aziridine ring proper; while bonding, determined by X-ray studies, is discussed for substituents of the aziridine ring. These aziridinyl ketone compounds are of importance as potential mammalian DNA alkylating anti-tumor agents in solid-state solid-state systems. To date only a trans isomer has demonstrated this biological activity in tumor-bearing rats. 相似文献
54.
The effect of destroying carbonyl and hydroperoxide groups in oxidised polypropylene on the subsequent rate of photo-oxidation has been examined using infra-red spectroscopy. The results show that carbonyl groups dominate the rate of photo-oxidation in severely oxidised polymer. In mildly oxidised polymer hydroperoxide groups control the rate, but to a much smaller extent. Destruction of the photo-active carbonyl and hydroperoxide groups in the unoxidised and oxidised polymers by prior photolysis in an inert atmosphere gave rise to some interesting and complex effects on subsequent photo-oxidation. The results indicate that although carbonyl and hydroperoxide groups may control the rates of photo-oxidation of thermally oxidised/processed polymer, their importance as primary photo-initiators is highly questionable. Oxygen-polymer charge transfer complexes appear to be the more likely photo-initiators. 相似文献
55.
David S. Soriano Kenneth F. Podraza Norman H. Cromwell 《Journal of heterocyclic chemistry》1980,17(3):623-624
L-Azetidine-2-carboxylic acid is a naturally occurring azetidine currently used in the synthesis of abnormally high molecular weight polypeptides. The synthesis of 2-carboxy-4-methylazetidine is now reported which is a novel isomeric analog of dl -proline. Reaction of α,β-dibromo carbonyl ester with three molar equivalents of benzylamine yields 1-benzyl-2-carbomethoxy-4-methyl-azetidine. Hydrolysis of the latter compound with barium hydroxide yields 1-benzyl-2-carboxyl-4-methylazetidine which, if subjected to catalytic hydrogenation., yields the title compound in practical yield. The cis configuration is tentatively assigned to the title compound on the basis of previously published arguments. 相似文献
56.
Karl Krmer Hans U. Güdel Gerd Meyer Thorsten Heuer Norman N. Edelstein Bernd Jung Lukas Keller Peter Fischer Eugeniusz Zych Janusz Drozdzynski 《无机化学与普通化学杂志》1994,620(8):1339-1345
The ternary uranium(III) halides A2UX5 (A = K, Rb; X = Cl, Br, I) have been prepared from the binary components AX and UX3 in sealed tantalum containers. According to their Guinier X-ray powder patterns, they all crystallize with the K2PrCl5/Y2HfS5 type of structure. Lattice constants for ambient temperature are reported. Single-crystal structure refinemens were undertaken for K2UI5 and Rb2UCl5. Magnetic susceptibility data were recorded with a SQUID magnetometer from liquid helium to room temperature. One-dimensional (intrachain) and three-dimensional antiferromagnetic ordering occur at low temperatures dependent upon the U3+? U3+ distance. Absorption spectra were recorded between 4 000 and 28 000 cm?1. They show f—f transitions typical for U3+ and, depending on the halide, very strong f—d transitions above 14 000 to 15 000 cm?1, respectively. 相似文献
57.
Owens TM Ludwig BJ Fosnacht DR Bartolin JM Homann N Wells NJ Orr BG Banaszak Holl MM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(26):11422-11427
Chemisorbed monolayers of octylgermane (C8H17GeH3) on gold have been formed by vapor deposition in ultrahigh vacuum. The monolayer has been characterized by X-ray photoelectron and reflection absorption infrared spectroscopies (XPS and RAIRS) and scanning tunneling microscopy (STM). XPS data indicate the monolayer can be oxidized by exposure to ozone. STM images exhibit a complex pattern which can be modeled as strain-mediated spinodal decomposition. 相似文献
58.
Evert J. Ditzel Xavier L. R. Fontaine Norman N. Greenwood John D. Kennedy Mark Thornton-Pett 《无机化学与普通化学杂志》1992,616(10):79-85
The action of SMe2 on the ten-vertex nido-ruthenaborane [6-(η6-C6Me6)RuB9Hl3] ( 1 ) provides a high-yield route to the unsubstituted isocloso-ruthenaborane [1-(η6-C6Me6)RuB9H9] (2). The benzene analogue [1-(η6-C6Me6)RuB9H9] is prepared similarly. By contrast, reaction of (1) with PhNH2 gives a variety of B-phenylamino isocloso derivatives, including orange crystals of [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB 9 H8] ( 3 ), red-orange [1-(η6-C6Me6)-2,3-(PhNH)2-isocloso-1-RuB9H7] ( 4 ) and dark-red [1-(η6-C6Me6)-5,6,7-(PhNH)3-isocloso-1-RuB9H6] ( 5 ). Detailed 1H and 11B nmr properties of these various compounds are described. The structure of ( 3 ) has been established by a single-crystal X-ray diffraction study of the solvate [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB9H8] · 1/2 CH2Cl2; the crystals were monoclinic, space group C2/c, with a = 1895.1(3), b = 1556.6(3), c = 1716.4(3) pm, β = 104.37(1)° and z = 8. 相似文献
59.
The structures of several sulfones, including dimethyl sulfone, methyl ethyl sulfone, methyl vinyl sulfone, and diphenyl sulfone, have been fit with the MM3 force field to existing experimental data from electron diffraction and microwave spectroscopy. The vibrational spectra have also been fit for six of these compounds. The torsional parameters for the aliphatic sulfones were fit to ab initio 6-31G data. Heats of formation were also fit. © 1993 John Wiley & Sons, Inc. 相似文献
60.
Capillary sodium dodecyl sulfate (SDS)-DALT electrophoresis (SDS-DALT-CE) refers to CE separation of proteins based on their size; DALT is the abbreviation for Dalton, the unit used to describe molecular weight. In this work, seven proteins from 18 to 116 kDa were denatured by SDS, labeled by 3-(2-furoyl) quinoline-2-carboxaldehyde, separated by SDS-DALT-CE in polyethylene oxide sieving matrix, and detected by laser-induced fluorescence (LIF) in a sheath flow cuvette. This method was combined with detergent differential fractionation, which is a protein fractionation method using a series of detergent-containing buffers to sequentially extract protein fractions from cells, to analyze the proteins in HT29 human colon adenocarcinoma cells. In addition, on-column labeling was demonstrated for protein analysis by SDS-DALT-CE with LIF, and applied to analysis of proteins in a single HT29 cancer cell. Most proteins had molecular masses from 10 to 120 kDa. Similar protein profiles were obtained for single cells and protein extract of a large cell population. 相似文献