全文获取类型
收费全文 | 779篇 |
免费 | 29篇 |
国内免费 | 1篇 |
专业分类
化学 | 323篇 |
晶体学 | 4篇 |
力学 | 19篇 |
数学 | 55篇 |
物理学 | 307篇 |
无线电 | 101篇 |
出版年
2021年 | 10篇 |
2020年 | 5篇 |
2019年 | 8篇 |
2018年 | 4篇 |
2017年 | 10篇 |
2016年 | 23篇 |
2015年 | 17篇 |
2014年 | 10篇 |
2013年 | 28篇 |
2012年 | 36篇 |
2011年 | 49篇 |
2010年 | 27篇 |
2009年 | 27篇 |
2008年 | 34篇 |
2007年 | 47篇 |
2006年 | 25篇 |
2005年 | 28篇 |
2004年 | 38篇 |
2003年 | 27篇 |
2002年 | 41篇 |
2001年 | 12篇 |
2000年 | 19篇 |
1999年 | 12篇 |
1998年 | 10篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 15篇 |
1994年 | 14篇 |
1993年 | 7篇 |
1992年 | 19篇 |
1991年 | 11篇 |
1990年 | 14篇 |
1989年 | 16篇 |
1988年 | 9篇 |
1987年 | 13篇 |
1986年 | 5篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 8篇 |
1975年 | 11篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1969年 | 3篇 |
排序方式: 共有809条查询结果,搜索用时 78 毫秒
11.
12.
13.
Bortoletto D Goldberg M Horwitz N Mestayer MD Moneti GC Sharma V Shipsey IP Skwarnicki T Csorna SE Letson T Brock IC Ferguson T Artuso M Bebek C Berkelman K Blucher E Byrd J Cassel DG Cheu E Coffman DM Crawford G DeSalvo R DeWire JW Drell PS Ehrlich R Galik RS Gittelman B Gray SW Halling AM Hartill DL Heltsley BK Kandaswamy J Kowalewski R Kreinick DL Kubota Y Lewis JD Mistry NB Mueller J Namjoshi R Nandi S Nordberg E O'Grady C Peterson D Pisharody M Riley D Sapper M Silverman A Stone S Worden H 《Physical review letters》1989,62(21):2436-2439
14.
Alam MS Katayama N Kim IJ Li WC Lou XC Sun CR Bortoletto D Goldberg M Horwitz N Mestayer MD Moneti GC Sharma V Shipsey IP Skwarnicki T Csorna SE Letson T Brock IC Ferguson T Artuso M Bebek C Berkelman K Blucher E Byrd J Cassel DG Cheu E Coffman DM Crawford G DeSalvo R DeWire JW Drell PS Ehrlich R Galik RS Gittelman B Gray SW Halling AM Hartill DL Heltsley BK Kandaswamy J Kowalewski R Kreinick DL Kubota Y Lewis JD Mistry NB Mueller J Namjoshi R Nandi S Nordberg E O'Grady C Peterson D Pisharody M 《Physical review D: Particles and fields》1989,40(11):3790
15.
16.
The total syntheses of the ladybug alkaloids (±)-propyleine and (±)-isopropyleine are described. Evidence that the alkaloid propyleine is actually a rapidly interconverting mixture of propyleine and a previously unknown isomer isopropyleine is presented. 相似文献
17.
Okamura WH Zhu GD Hill DK Thomas RJ Ringe K Borchardt DB Norman AW Mueller LJ 《The Journal of organic chemistry》2002,67(5):1637-1650
Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar solutions as compared to that in the solid state is most easily rationalized on the basis that the 5(10)-torsion angle in 58 is decreased in micellar solutions as compared to that in the solid state. 相似文献
18.
Mueller JA Cowell A Chandler BD Sigman MS 《Journal of the American Chemical Society》2005,127(42):14817-14824
A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl(2)-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl(2) prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl(2) to form cationic Pd(-)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) beta-hydride elimination of Pd-alkoxide to form ketone product and a Pd-hydride. Utilizing the addition of (-)-sparteine HCl to control the [Cl(-)] and [H(+)] and the resulting derived rate law, the key microscopic kinetic and thermodynamic constants were extracted for each enantiomer of sec-phenethyl alcohol. These constants allow for the successful simulation of the oxidation rate in the presence of exogenous (-)-sparteine HCl. A rate law for oxidation of the racemic alcohol was derived that allows for the successful prediction of the experimentally measured k(rel) values when using the extracted constants. Besides a factor of 10 difference between the relative rates of beta-hydride elimination for the enantiomers, the main enhancement in enantiodetermination results from a concentration effect of (-)-sparteine HCl and the relative rates of reprotonation of the diastereomeric Pd-alkoxides. 相似文献
19.
Taw FL Mueller AH Bergman RG Brookhart M 《Journal of the American Chemical Society》2003,125(32):9808-9813
Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. 相似文献
20.
The mechanistic details of the palladium-catalyzed aerobic oxidative kinetic resolution of secondary alcohols have been elucidated. (-)-Sparteine was found to have a dual role as a chiral ligand and an exogenous base. Saturation kinetics were observed for the dependence on (-)-sparteine concentration. A first-order dependence on [alcohol] and [catalyst] as well as inhibition by addition of (-)-sparteine HCl were observed. These results are consistent with rate-limiting deprotonation under low (-)-sparteine concentrations and rate-limiting beta-hydride elimination using saturating (-)-sparteine concentrations. This conclusion is further supported by a kinetic isotope effect of 1.31 +/- 0.04 under saturation. The enantioselectivity events are also controlled by addition of (-)-sparteine in which high concentrations afford a more selective kinetic resolution. 相似文献