全文获取类型
收费全文 | 967篇 |
免费 | 15篇 |
国内免费 | 3篇 |
专业分类
化学 | 548篇 |
晶体学 | 15篇 |
力学 | 11篇 |
数学 | 92篇 |
物理学 | 319篇 |
出版年
2021年 | 9篇 |
2019年 | 8篇 |
2017年 | 6篇 |
2016年 | 8篇 |
2015年 | 14篇 |
2014年 | 6篇 |
2013年 | 77篇 |
2012年 | 36篇 |
2011年 | 34篇 |
2010年 | 25篇 |
2009年 | 15篇 |
2008年 | 30篇 |
2007年 | 45篇 |
2006年 | 45篇 |
2005年 | 41篇 |
2004年 | 26篇 |
2003年 | 28篇 |
2002年 | 25篇 |
2001年 | 25篇 |
2000年 | 21篇 |
1999年 | 17篇 |
1998年 | 8篇 |
1997年 | 17篇 |
1996年 | 26篇 |
1995年 | 20篇 |
1994年 | 27篇 |
1993年 | 23篇 |
1992年 | 21篇 |
1991年 | 12篇 |
1990年 | 16篇 |
1989年 | 17篇 |
1988年 | 13篇 |
1987年 | 14篇 |
1986年 | 11篇 |
1985年 | 20篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 6篇 |
1981年 | 12篇 |
1980年 | 14篇 |
1979年 | 17篇 |
1978年 | 14篇 |
1977年 | 9篇 |
1976年 | 17篇 |
1975年 | 10篇 |
1974年 | 7篇 |
1973年 | 9篇 |
1972年 | 6篇 |
1970年 | 5篇 |
1968年 | 5篇 |
排序方式: 共有985条查询结果,搜索用时 31 毫秒
51.
Frabetti PL Cheung HW Cumalat JP Dallapiccola C Ginkel JF Greene SV Johns WE Nehring MS Butler JN Cihangir S Gaines I Garren L Garbincius PH Gourlay SA Harding DJ Kasper P Kreymer A Lebrun P Shukla S Bianco S Fabbri FL Sarwar S Zallo A Culbertson R Gardner RW Greene R Wiss J Alimonti G Bellini G Caccianiga B Cinquini L Di Corato M Giammarchi M Inzani P Leveraro F Malvezzi S Menasce D Meroni E Moroni L Pedrini D Perasso L Sala A Sala S Toretta D Vittone M Buchholz D Claes D Gobbi B O'Reilly B 《Physical review letters》1993,70(12):1755-1758
52.
de la Vaissiere C Luth V Abrams GS Amidei D Baden AR Barklow T Boyarski AM Boyer J Breidenbach M Burchat P Burke DL Butler F Dillon JW Dorfan JM Feldman GJ Gidal G Gladney L Gold MS Goldhaber G Golding LG Hanson G Haggerty J Herrup D Himel T Hollebeek RJ Innes WR Jaros JA Juricic I Kadyk JA Klein SR Lankford AJ Larsen RR LeClaire BW Levi ME Lockyer NS Matteuzzi C Nelson ME Ong RA Perl ML Richter B Ross MC Rowson PC Schaad T Schellman H Schmidke WB Sheldon PD Trilling GH Yelton JM Wood DR 《Physical review letters》1985,54(19):2071-2074
53.
James W. Schweitert George B. Butler 《Journal of polymer science. Part A, Polymer chemistry》1978,16(6):1359-1365
The monomer series, o-, m-, and p-(2-vinyloxyethoxy)-β-nitrostyrenes, was studied. All three monomers were selectively polymerized through the electron-donating vinyloxy group via cationic initiation. The linear polymers from the meta and para isomers containing the electron-accepting nitrovinyl group were readily crosslinked via anionic initiation. The polymer derived from the ortho isomer was not crosslinked by this mechanism, an observation in accord with results previously reported from these laboratories in which it was shown that all o-substituted-β-nitrostyrenes having ortho substituents larger than fluorine exhibited a sterically inhibited propagation step. The meta and para isomers of this series were selectively polymerized through the electron-accepting nitrovinyl group via anionic initiation. Because of the fact that the resulting polymers were soluble only in highly polar solvents, subsequent crosslinking of these polymers via cationic initiation could not be accomplished. However, these polymers showed strong tendencies to undergo crosslinking upon long exposure to air. Because of the sterically induced ortho effect referred to above, no significant polymerization occurred in the case of the ortho isomer of this series via anionic initiation. However, it was shown in this case that initiation via the anion was rapid, and that the slow step was propagation. 相似文献
54.
Internally consistent assignments of the 31P-{1H} NMR parameters of the complexes [Pt(RCCR′)(PPh3)2] are proposed, based on the premise that the magnitude of 1J(PtP) depends mainly on the nature of the moiety CR trans to P. For a given R, 2J(PP) correlates with 1J(PtP) for thebond trans to CR. The alkynes PhCCSnEt3, PhCCSnPh3, Me3SiCCCl, Me3SiCCBr, Et3SiCCI and MeCCI undergo oxidative addition reactions with [Pt(C2H4)(PPh3)2]; the intermediate alkyne complex was detected for PhCCSnEt3, Me3SiCCCl and Me3CCBr. The triyne Me(CC)3Me forms platinum(0) complexes by coordination with the central or terminal CC bond and appears also to give a platinum(II) complex by oxidative addition. 相似文献
55.
The use of the high-temperature graphite tube with atomic absorption constitutes an exceptionally sensitive analytical method. Since only very small quantities of sample are needed, this method is highly suitable for the determination of lead in whole blood, especially when blood must be drawn from children. A technique which requires little preparation of the sample has been developed for such determinations. The graphite tube system developed can be used on any of a number of atomic absorption spectrophotometers and is better suited to routine analyses than the methods of L'vov and Massmann who pioneered the use of graphite tubes. 相似文献
56.
Gao W Butler D Tomasko DL 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8083-8089
Supercritical carbon dioxide is an efficient solvent for adsorptive separations because it can potentially be used as both the carrier solvent for adsorption and the desorbent for regeneration. Recent results have demonstrated an anomalous peak or "hump" in the adsorption isotherm near the bulk critical point when the adsorption isotherm is plotted as a function of bulk density. This work presents new data for the adsorption and desorption of carbon dioxide in the near-critical region on a crystalline, well-structured adsorbent (NaY zeolite). The results indicate a strong affinity for CO(2) as well as a significant hump near the critical point. The lattice model previously developed by Aranovich and Donohue is applied to analyze the adsorption. 相似文献
57.
Butler MS 《Natural product reports》2005,22(2):162-195
Natural product and natural product-derived compounds that are being evaluated in clinical trials or in registration (current 31 December 2004) have been reviewed. Natural product derived drugs launched in the United States of America, Europe and Japan since 1998 and new natural product templates discovered since 1990 are discussed. 相似文献
58.
Bernard Gordon Jacqueline S. Butler Ian R. Harrison 《Journal of polymer science. Part A, Polymer chemistry》1987,25(8):2139-2142
Catalysts bound to polymers in the form of crosslinked beads have been demonstrated to have a number of advantages over homogeneous catalysts. However, there are several problems that exist due to the polymer support being in the form of a bead. The rate of reaction depends on the presence of solvents that adequately swell the bead in order to allow access to the catalytic sites. Differences in polarity and reactant size can inhibit diffusion into the bead. Recently a new system has been developed whereby tris(triphenyl phosphine) chlororhodium (I) (Wilkinson's catalyst) is bound to the surface of polyethylene single crystals. Polyethylene single crystals have a very high surface to volume ratio allowing for greater ease of reaction compared to a bead system. In a previous paper we showed that there is a dramatic increase in catalytic activity and that the reaction rate increased as the polarity of solvent was increased, even in ethanol where the homogeneous catalyst is not soluble and the polystyrene bead support would not swell. In this letter we are describing the activity of hydrogenation of olefins contained in both large and/or polar molecules. The results demonstrate the advantages of supported catalysts on polyethylene single crystals rather than on polymer beads. 相似文献
59.
A numerical method to simulate the dynamics of polymer solutions in confined geometries has been implemented and tested. The method combines a fluctuating lattice-Boltzmann model of the solvent [Ladd, Phys. Rev. Lett. 70, 1339 (1993)] with a point-particle model of the polymer chains. A friction term couples the monomers to the fluid [Ahlrichs and Dunweg, J. Chem. Phys. 111, 8225 (1999)], providing both the hydrodynamic interactions between the monomers and the correlated random forces. The coupled equations for particles and fluid are solved on an inertial time scale, which proves to be surprisingly simple and efficient, avoiding the costly linear algebra associated with Brownian dynamics. Complex confined geometries can be represented by a straightforward mapping of the boundary surfaces onto a regular three-dimensional grid. The hydrodynamic interactions between monomers are shown to compare well with solutions of the Stokes equations down to distances of the order of the grid spacing. Numerical results are presented for the radius of gyration, end-to-end distance, and diffusion coefficient of an isolated polymer chain, ranging from 16 to 1024 monomers in length. The simulations are in excellent agreement with renormalization group calculations for an excluded volume chain. We show that hydrodynamic interactions in large polymers can be systematically coarse-grained to substantially reduce the computational cost of the simulation. Finally, we examine the effects of confinement and flow on the polymer distribution and diffusion constant in a narrow channel. Our results support the qualitative conclusions of recent Brownian dynamics simulations of confined polymers [Jendrejack et al., J. Chem. Phys. 119, 1165 (2003) and Jendrejack et al., J. Chem. Phys. 120, 2513 (2004)]. 相似文献
60.
Highly reactive 4-substituted-1,2,4-triazoline-3,5-diones (TDs) have been studied extensively as dienophiles, but little work has been done on their role as enophiles and particularly on their use as propagating species in polymerization studies. The copolymerization between bis-4-substituted-1,2,4-triazoline-3,5-diones (bis-TDs) and styrene has been reported. The purpose of the present work was to synthesize new copolymers derived from a variety of substituted styrenes and bis-TDs and to study the mechanism and kinetics of this novel polymerization. Three bis-TDs were prepared: 3,3′-dimethyl-4,4′-bis[3,5-dioxo-1,2,4-triazoline-4-yl] biphenyl (8), t-1,4-bis[3,5-dioxo-1,2,4-triazoline-4-yl] methyl cyclohexane (9), and 4,4′-bis[3,5-dioxo-1,2,4-triazoline-4-yl] phenyl ether (10). Their structures were fully established by spectroscopic studies, elemental analyses, and indirectly, their quantitative ene reactions with 2,3-dimethyl-2-butene. Copolymerization between bis-TDs and substituted styrenes was carried out in dimethylformamide (DMF), tetrahydrofuran (THF), or dichloroethane (DCE). Polymers formed were characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and viscometry. Molecular weights of polymers range from 5000 to 16,000 in most cases. They were stable up to 250°C and higher. Polymers derived from bis-TDs and p-t-butylstyrene, α-methylstyrene, p-nitrostyrene, and p-acetoxystyrene contained only Diels-Alder-ene (DAe) repeating units, whereas those derived from styrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, and 4-vinylbiphenyl contained both DAe and double Diels-Alder (dDA) repeating units. A kinetic study of the copolymerization of 4,4′-bis-(3,5-dioxo-1,2,4-triazoline-4-yl) phenyl ether with α-methylstyrene, p-t-butylstyrene, styrene, p-chlorostyrene, and p-nitrostyrene in DCE was carried out; the copolymerization rate constants were 60.9, 49.8, 8.4, 5.5, and 0.8 (1 mol?1s), respectively. 相似文献