全文获取类型
收费全文 | 1035篇 |
免费 | 40篇 |
国内免费 | 9篇 |
专业分类
化学 | 740篇 |
晶体学 | 11篇 |
力学 | 10篇 |
数学 | 52篇 |
物理学 | 271篇 |
出版年
2023年 | 3篇 |
2021年 | 13篇 |
2020年 | 15篇 |
2019年 | 18篇 |
2018年 | 10篇 |
2017年 | 9篇 |
2016年 | 20篇 |
2015年 | 13篇 |
2014年 | 38篇 |
2013年 | 51篇 |
2012年 | 54篇 |
2011年 | 62篇 |
2010年 | 40篇 |
2009年 | 40篇 |
2008年 | 52篇 |
2007年 | 62篇 |
2006年 | 42篇 |
2005年 | 47篇 |
2004年 | 46篇 |
2003年 | 48篇 |
2002年 | 30篇 |
2001年 | 27篇 |
2000年 | 26篇 |
1999年 | 14篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 16篇 |
1995年 | 4篇 |
1994年 | 22篇 |
1993年 | 18篇 |
1992年 | 26篇 |
1991年 | 13篇 |
1990年 | 14篇 |
1989年 | 16篇 |
1988年 | 8篇 |
1987年 | 14篇 |
1986年 | 11篇 |
1985年 | 15篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 6篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 13篇 |
1976年 | 9篇 |
1975年 | 4篇 |
1974年 | 7篇 |
1972年 | 4篇 |
排序方式: 共有1084条查询结果,搜索用时 469 毫秒
41.
A technique for the separation of thiosulfate (S(2)O(3) (2-)), polythionates (S(x)O(6) (2-), x = 3 to 5) and the gold(I) thiosulfate complex (Au(S(2)O(3))(2) (3-)) using capillary electrophoresis with simultaneous UV detection at 195 and 214 nm is presented. The five species were separated in under 3 min with a total analysis time of 8 min, using an electrolyte containing 25 mM 2,2-bis(hydroxymethyl)-2,2',2"-nitrilotriethanol (bis-tris) adjusted to pH 6.0 with sulfuric acid and an applied voltage of -30 kV. While the gold(I) thiosulfate complex could be separated from the other analytes of interest under these conditions, the quantification of this complex was not possible due to inconsistent peak areas and peak splitting effects induced by the sulfur-oxygen species in the leach matrix. Detection limits calculated for 3s pressure injection at 50 mbar ranged between 0.5-2 microM. The method was linear over the ranges 40-8000, 10-2000, 10-2000, and 5-2000 microM for thiosulfate, trithionate, tetrathionate, and pentathionate, respectively. The technique was applied successfully to leach liquors containing 0.5 M ammonium thiosulfate, 2 M ammonia, 0.05 M copper sulfate and 20% w/v gold ore, diluted 1:100 prior to analysis. 相似文献
42.
[reaction: see text] On treatment of 5-siloxyhexa-1,2,5-trienes with a catalytic amount of W(CO)(6) under photoirradiation, formal Cope rearrangement proceeded to give 2-siloxyhex-1-en-5-ynes in good yield. The electrophilic activation of the allenyl moiety by W(CO)(5) triggers the intramolecular attack of the silyl enol ether in a 6-endo manner to produce a cyclohexenyl tungsten species. Carbon-carbon bond cleavage occurs by electron donation from the anionic W(CO)(5) into the silyloxonium moiety to afford the products with regeneration of the W(CO)(5)(L). 相似文献
43.
44.
A method for the determination of 3 alpha,7 alpha-dihydroxy-5 beta-cholestanoic acid (DHCA) and 3 alpha,7 alpha,12 alpha-trihydroxy-5 beta-cholestanoic acid (THCA) in human urine by gas chromatography (GC) in combination with negative ion chemical ionization (NICI) mass spectrometry is described. Unconjugated, glycine- and taurine-conjugated DHCA and THCA labelled with 18O and 2H were used as internal standards. 5 beta-Cholestanoic acids in urine were extracted with a Sep-Pak C18 cartridge, separated into the unconjugated, glycine- and taurine-conjugated fractions by ion-exchange chromatography on piperidinohydroxypropyl Sephadex LH-20 and, following alkaline hydrolysis of conjugated forms, derivatization into the pentafluorobenzyl ester-dimethylethylsilyl ethers. Subsequent resolution of each fraction into DHCA and THCA was attained by GC on a cross-linked 5% phenylmethylsilicone fused-silica capillary column where 5 beta-cholestanoic acids were monitored with a characteristic carboxylate anion [M-181]- in the NICI mode using isobutane as a reagent gas. The method was applied to separation and determination of 5 beta-cholestanoic acids in urine from a patient with Zellweger syndrome and from healthy volunteers. 相似文献
45.
Homoleptic cyclometalated iridium complexes with highly efficient red phosphorescence and application to organic light-emitting diode 总被引:7,自引:0,他引:7
Tsuboyama A Iwawaki H Furugori M Mukaide T Kamatani J Igawa S Moriyama T Miura S Takiguchi T Okada S Hoshino M Ueno K 《Journal of the American Chemical Society》2003,125(42):12971-12979
Phosphorescence studies of a series of facial homoleptic cyclometalated iridium(III) complexes have been carried out. The complexes studied have the general structure Ir(III)(C-N)(3), where (C-N) is a monoanionic cyclometalating ligand: 2-(5-methylthiophen-2-yl)pyridinato, 2-(thiophen-2-yl)-5-trifluoromethylpyridinato, 2,5-di(thiophen-2-yl)pyridinato, 2,5-di(5-methylthiophen-2-yl)pyridinato, 2-(benzo[b]thiophen-2-yl)pyridinato, 2-(9,9-dimethyl-9H-fluoren-2-yl)pyridinato, 1-phenylisoquinolinato, 1-(thiophen-2-yl)isoquinolinato, or 1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato. Luminescence properties of all the complexes at 298 K in toluene are as follows: quantum yields of phosphorescence Phi(p) = 0.08-0.29, emission peaks lambda(max) = 558-652 nm, and emission lifetimes tau = 0.74-4.7 micros. Bathochromic shifts of the Ir(thpy)(3) family [the complexes with 2-(thiophen-2-yl)pyridine derivatives] are observed by introducing appropriate substituents, e.g., methyl, trifluoromethyl, or thiophen-2-yl. However, Phi(p) of the red emissive complexes (lambda(max) > 600 nm) becomes small, caused by a significant decrease of the radiative rate constant, k(r). In contrast, the complexes with the 1-arylisoquinoline ligands are found to have marked red shifts of lambda(max) and very high Phi(p) (0.19-0.26). These complexes are found to possess dominantly (3)MLCT (metal-to-ligand charge transfer) excited states and have k(r) values approximately 1 order of magnitude larger than those of the Ir(thpy)(3) family. An organic light-emitting diode (OLED) device that uses Ir(1-phenylisoquinolinato)(3) as a phosphorescent dopant produces very high efficiency (external quantum efficiency eta(ex) = 10.3% and power efficiency 8.0 lm/W at 100 cd/m(2)) and pure-red emission with 1931 CIE (Commission Internationale de L'Eclairage) chromaticity coordinates (x = 0.68, y = 0.32). 相似文献
46.
A reversed-phase liquid chromatographic method for the determination of trace amounts of vanadium is described. Metal ions are converted into 2-(8-quinolylazo)-5-N,N-diethylaminophenol chelates in an off-line system. The chelates are injected onto a Zorbax CN column and separated with an aqueous acetonitrile mobile phase containing no chromogenic reagent. Unter these conditions, only vanadium(V) is spectrophotometrically detected at 540 nm among the metal ions Al(III), Ba(II), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ga(III), Hg(II), Mg(II), Mn(II), Ni(II), Pb(II), V(V) and Zn(II). Amounts of 8.0–200 pg of vanadium(V) in 100-μl injections can be determined without interference from 10-fold molar excesses of many cations. At 0.001 a.u.f.s., the detection limit (twice the peak-to-peak noise) for vanadium(V) is 8.0 pg in 100 μl of injected solution and the relative standard deviation at 120 pg of vanadium(V) in a 100-μl injection is 3.5%. The proposed method is applied to the determination of vanadium in rain water and airborne particulates. 相似文献
47.
48.
Miura K Hondo T Okajima S Nakagawa T Takahashi T Hosomi A 《The Journal of organic chemistry》2002,67(17):6082-6090
Acid-catalyzed intramolecular addition of a hydroxy group to alpha-alkylated vinylsilanes has been studied. Treatment of (Z)-5-alkyl-5-silyl-4-penten-1-ols 1 (R = alkyl) with 5 mol % TiCl(4) in CHCl(3) gave trans-2-alkyl-3-silyltetrahydropyrans 2 exclusively (trans/cis = >99/1 to 97/3). The cyclization efficiency and rate strongly depended on the geometry of the C-C double bond and the silyl group. The use of (E)-vinylsilanes resulted in lower yields with poor cis-selectivity. In the cyclization of (Z)-1 (R = Bu), the silyl group used, the reaction time, and the yield of 2 were as follows: SiMe(2)Ph, 9.5 h, 75%; SiMe(3), 7.5 h, 66%; SiMePh(2), 24 h, 58%; SiMe(2)-t-Bu, 0.75 h, 85%; SiMe(2)Bn, 1.5 h, 78%. This 1,2-silyl-migrative cyclization could be applied to stereoselective synthesis of trisubstituted tetrahydropyrans. The acid-catalyzed reaction of 1-, 2-, or 3-substituted (Z)-5-silyl-4-nonen-1-ols 8 gave r-2,t-3,c-6-, r-2,t-3,t-5-, or r-2,t-3,c-4-trisubstituted tetrahydropyrans with high diastereoselectivity, respectively. (Z)-4-Alkyl-4-silyl-3-buten-1-ols 5 as well as 1 underwent the 1,2-silyl-migrative cyclization to give 2-alkyl-3-silyltetrahydrofurans 6 with high trans-selectivity. This silicon-directed cyclization was also available for the stereoselective synthesis of tri- and tetrasubstituted tetrahydrofurans. 相似文献
49.
Lee K Kim H Miura T Kiyota K Kusama H Kim S Iwasawa N Lee PH 《Journal of the American Chemical Society》2003,125(32):9682-9688
3-tert-Butyldimethylsilyloxyalk-2-enylsulfonium salts, generated in situ from the reaction of alpha,beta-enones with dimethyl sulfide in the presence of TBSOTf, underwent a novel nucleophilic substitution with allylindiums to give silyl enol ethers of delta,epsilon-alkenyl ketones in good yields, which correspond to formal Michael addition products. In a similar manner, 1,4-propargylation of propargylindiums onto the sulfonium salts produced the corresponding silyl enol ethers of delta,epsilon-alkynyl ketones in good yields. Organoindium reagents derived from gamma-substituted propargyl bromide and indium afforded the corresponding silyl enol ethers of beta-allenyl ketones in good yields. The reaction proceeds via an addition-substitution mechanism involving the formation of allylic sulfonium salts. The presence of the intermediate sulfonium salt was confirmed by observation of the low-temperature (1)H NMR spectra. 相似文献
50.
Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time. 相似文献