全文获取类型
收费全文 | 2464篇 |
免费 | 60篇 |
国内免费 | 1篇 |
专业分类
化学 | 1790篇 |
晶体学 | 3篇 |
力学 | 20篇 |
数学 | 294篇 |
物理学 | 418篇 |
出版年
2023年 | 14篇 |
2021年 | 9篇 |
2020年 | 18篇 |
2019年 | 20篇 |
2018年 | 13篇 |
2017年 | 15篇 |
2016年 | 43篇 |
2015年 | 52篇 |
2014年 | 53篇 |
2013年 | 148篇 |
2012年 | 170篇 |
2011年 | 195篇 |
2010年 | 81篇 |
2009年 | 63篇 |
2008年 | 180篇 |
2007年 | 175篇 |
2006年 | 197篇 |
2005年 | 169篇 |
2004年 | 134篇 |
2003年 | 96篇 |
2002年 | 100篇 |
2001年 | 74篇 |
2000年 | 89篇 |
1999年 | 27篇 |
1998年 | 15篇 |
1997年 | 25篇 |
1996年 | 33篇 |
1995年 | 25篇 |
1994年 | 27篇 |
1993年 | 15篇 |
1992年 | 24篇 |
1991年 | 15篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 12篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 17篇 |
1984年 | 12篇 |
1983年 | 10篇 |
1982年 | 14篇 |
1981年 | 8篇 |
1980年 | 14篇 |
1979年 | 11篇 |
1978年 | 5篇 |
1977年 | 10篇 |
1975年 | 9篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1972年 | 6篇 |
排序方式: 共有2525条查询结果,搜索用时 15 毫秒
71.
For the first time, the existence of a strong intramolecular 1,4-interaction between the phosphorus atom and the oxygen atom in alpha-keto-stabilized ylides has been demonstrated by means of theoretical calculations. This interaction has a notable influence on the conformational preferences and rotational barriers of alpha-stabilized phosphorus ylides and bis-ylides. 相似文献
72.
Lázló Markó 《Journal of organometallic chemistry》1981,213(1):271-275
Two new mixed iron cobalt carbonyl sulphide clusters HFe2(CO)9S and Fe2Co(CO)8(NO)S have been prepared and characterized. The hydride complex undergoes acidic dissociation in polar solvents and the resulting anion was isolated as (Et4N)[Fe2Co(CO)9S]. An efficient high pressure synthesis has been found for H2Fe3(CO)9S. 相似文献
73.
Bouchoux G Defaye D McMahon T Likholyot A Mó O Yáñez M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(13):2900-2909
The various protonated forms of phenol (1), catechol (2), resorcinol (3), and hydroquinone (4) were explored by ab initio quantum chemical calculations at the MP2/6-31G(d) and B3LYP/6-31G(d) levels. Proton affinities (PA) of 1-4 were calculated by the combined G2(MP2,SVP) method, and their gas-phase basicities were estimated after calculation of the change in entropy on protonation. These theoretical data were compared with the corresponding experimental values determined in a high-pressure mass spectrometer. This comparison confirmed that phenols are essentially carbon bases and that protonation generally occurs in a position para to the hydroxyl group. Resorcinol is the most effective base (PA = 856 kJ mol-1) due to the participation of both oxygen atoms in the stabilization of the protonated form. Since protonation is accompanied by a freezing of the two internal rotations, a significant decrease in entropy is observed. The basicity of catechol (PA = 823 kJ mol-1) is due to the existence of an intramolecular hydrogen bond, which is strengthened upon protonation. The lower basicity of hydroquinone (PA = 808 kJ mol-1) is a consequence of the fact that protonation necessarily occurs in a position ortho to the hydroxyl group. When the previously published data are reconsidered and a corrected protonation entropy is used, a proton affinity value of 820 kJ mol-1 is obtained for phenol. 相似文献
74.
Summary The peroxidation of molybdenum(VI) was investigated in neutral and alkaline media. The stability constants of the peroxo complexes were determined by spectrophotometric measurement as (9.12±0.67)×10–7, (2.68±0.17) ×105, (1.26±0.06)×106 and (1.58±0.02) for the 11, 21 (yellow), 31 and 41 (red) species. The diperoxomolybdate disproportionates into the tetraperoxo derivative when treated with alkali. Formation of the tetraperoxo complex was found to be pH dependent according to a curve, with maximum at pH 10. Acidification of tetraperoxomolybdate solution results in the regeneration of hydrogen peroxide and the diperoxo complex is reformed. 相似文献
75.
A.R. László Bursics Martin Murray F. Gordon A. Stone 《Journal of organometallic chemistry》1976,111(1):31-42
Bis(cyclopentadienyl)mercury readily undergoes Diels—Alder reactions with RCCR (R = CO2Me or CF3), CF3CFCFCF3, CF3CFCF2, (CF3)2CC(CN)2, C2(CN)4 and PhO to give stable adducts characterised by1H, 19F and 13C NMR, spectroscopy. Similar reactions of CF3CCCF3 and CF3CFCFCF3 with the cyclopentadiene derivatives Me3MC5H5 and (Me3M)2C5H4 (M = Si, Sn) are also described. 相似文献
76.
Bose D Martinavarro-Domínguez A Gil-Agustí M Carda-Broch S Durgbanshi A Capella-Peiró ME Esteve-Romero J 《Biomedical chromatography : BMC》2005,19(5):343-349
A micellar liquid chromatographic (MLC) procedure was developed for the clinical monitoring of imipramine and its active metabolite, desipramine. The determination of these highly hydrophobic substances was carried out after direct injection of the serum samples using a mobile phase composed of 0.15 m SDS--6% (v/v) pentanol buffered at pH 7, pumped at 1.5 mL/min into a C(18) column (250 x 4.6 mm), and electrochemical detection at 650 mV. Using this MLC method, calibration was linear (r > 0.995) and the limits of detection (ng/mL) were 0.34 and 0.24 for imipramine and desipramine, respectively. Repeatabilities and intermediate precision were tested at three different concentrations in the calibration range and a CV (%) below 2.2 was obtained. In this MLC procedure, the serum is determined without treatment, thus allowing repeated serial injections without changes in retention factors, and reducing the time and consumables required to carry out the pretreatment process. The assay method can be applied to the routine determination of serum imipramine and its metabolite in therapeutic drug monitoring. 相似文献
77.
A method for the simultaneous spectrophotometric determination of calcium and magnesium in mineral waters with an FIA system is tested. The method is based on the reaction between the analytes and arsenazo(III) at pH 8.5. The calculations of the amounts of both analytes in the samples are carried out with the H-point standard addition method (HPSAM) for ternary mixtures, and with a partial least squares (PLS) model after a proper variable selection. The results obtained for the determination of calcium were comparable using both methods. The employment of the HPSAM brings to our attention the influence of the calcium concentration in the sample to the development of the reaction between magnesium and arsenazo(III). HPSAM also permits to estimate the concentration of magnesium in the samples. 相似文献
78.
[reaction: see text] Enantiomerically pure gamma-fluoroalkyl beta-amino sulfones are readily synthesized in three steps starting from fluorinated imidoyl chlorides and arylmethyl sulfones. A complementary two-step sequence starting from chiral fluorinated beta-amino sulfoxides has also been developed. To illustrate the application of this procedure, a new method for the synthesis of alpha-fluoroalkyl allylic amines in optically pure form involving a Julia methylenation-desulfonylation reaction is presented. 相似文献
79.
Cyclodehydration of achiral or racemic aryl-delta-oxoacids with (R)-phenylglycinol stereoselectively affords chiral non-racemic bicyclic lactams, from which the enantiodivergent synthesis of (R)- and (S)-2-phenylpiperidine, the diastereodivergent synthesis of cis- and trans-3-ethyl-2-phenylpiperidine, and the enantioselective synthesis of the piperidine alkaloid (-)-anabasine is reported. 相似文献
80.