全文获取类型
收费全文 | 1130篇 |
免费 | 93篇 |
国内免费 | 13篇 |
专业分类
化学 | 811篇 |
晶体学 | 1篇 |
力学 | 61篇 |
数学 | 156篇 |
物理学 | 207篇 |
出版年
2024年 | 2篇 |
2023年 | 5篇 |
2022年 | 27篇 |
2021年 | 54篇 |
2020年 | 75篇 |
2019年 | 62篇 |
2018年 | 72篇 |
2017年 | 64篇 |
2016年 | 86篇 |
2015年 | 83篇 |
2014年 | 85篇 |
2013年 | 112篇 |
2012年 | 97篇 |
2011年 | 110篇 |
2010年 | 58篇 |
2009年 | 50篇 |
2008年 | 50篇 |
2007年 | 29篇 |
2006年 | 25篇 |
2005年 | 22篇 |
2004年 | 19篇 |
2003年 | 12篇 |
2002年 | 13篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 5篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1986年 | 4篇 |
1984年 | 2篇 |
1983年 | 1篇 |
排序方式: 共有1236条查询结果,搜索用时 15 毫秒
1.
Goudarzy Forough Zolgharnein Javad Alizadeh Vahid 《Journal of Analytical Chemistry》2022,77(6):711-716
Journal of Analytical Chemistry - In this article, a new spectrofluorometric method was developed for the determination of methamphetamine based on a turn-on luminescence response of captopril... 相似文献
2.
A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection 下载免费PDF全文
Mir Ali Farajzadeh Mohammad Reza Afshar Mogaddam Ali Akbar Alizadeh Nabil 《Biomedical chromatography : BMC》2015,29(12):1921-1931
In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
3.
4.
5.
6.
Mohammad H. Alizadeh Toktam Kermani Reza Tayebee 《Monatshefte für Chemie / Chemical Monthly》2007,138(2):165-170
Summary. Esterifications of acetic acid with some linear, secondary, tertiary, and benzylic alcohols mediated by catalytic amounts
of Keggin, Wells–Dawson, and Preyssler type heteropolyacids were carried out under reflux at mild reaction conditions with good to excellent yields. Among the examined
catalysts, H3PW12O40 and H14NaP5W30O110 revealed better results than other heteropolyacids. This work was performed with the aim of simplifying the esterification
process by omitting any solvents and mineral acid catalysts. Easy work-up, low cost, and acidic waste reduction, which are
all important features from the environmental and economical points of view, are distinct aspects of this protocol. Heteropolyacid
catalysts could be separated after a simple work-up and reused for several times. 相似文献
7.
Summary. A highly efficient, selective, fast, and cheap protocol is developed for oxidation of aromatic amines and alcohols utilizing
34% hydrogen peroxide in water catalyzed by some W- and Mo-based heteropolyoxometalates. Findings showed that dodecatungstophosphoric
acid, H3PW12O40, was the most efficient catalyst in the examined oxidation reactions. This methodology may prove to be a valuable alternative
for eco-friendly green oxidation. Inherent simplicity, easy work up, and using regenerable catalysts were other key aspects
of this oxidation protocol. 相似文献
8.
Hindered internal rotation about the C‐N single bonds joining the thiuram disulfide was studied by 1H NMR complete line‐shaped analysis in different dimethyl sulfoxide‐chloroform (DMSO‐CDCl3) mixtures. From the temperature dependence of methyls proton spectra, activation parameters (Ea, ΔH≠, ΔS≠, and ΔG≠) were obtained. The Arrhenius plots showed a distinct isokinetic temperature at about 35 °C at which the exchange rate is more or less independent of the solvent composition. The resulting ΔH≠ against TΔS≠ plot showed a firmly good linear correlation, indicating the existence of an enthalpy‐entropy composition in an exchange process. 相似文献
9.
Bis(peroxo)vanadium(V) complexes are widely investigated as anticancer agents. They exert their antitumor and cyctotoxic effects through inhibition of tyrosine phosphatases and DNA cleavage, respectively. The latter process remains poorly understood. The mechanism of DNA cleavage by NH(4)[(phen)V(O)(eta(2)-O(2))(2)] (phen = 1,10-phenanthroline) was investigated. Kinetic studies on DNA cleavage revealed that the complex is a single-strand nicking agent with no specificity. EPR experiments using 2,2,6,6-tetramethyl-4-piperidone (TMP) and 5,5'-dimethyl-1-pyrroline-N-oxide (DMPO) as spin-traps for singlet oxygen and hydroxyl radical, respectively, implicated hydroxyl radical production upon photodecomposition of bis(peroxo)vanadium(V). This was corroborated by benzoate inhibition of DNA strand scission and stoichiometric oxidation of 2-propanol to acetone upon irradiation of bis(peroxo)vanadium(V) phenanthroline. High-resolution polyacrylamide gel analysis of the vanadium cleavage reaction and [Fe(II)EDTA](2)(-)/H(2)O(2) resulted in comigration of "ladder" pattern bands, which superimposed when both reactions were run on the same lane. These findings identify hydroxyl radical produced from the photooxidation of the peroxo ligand on vanadium as the active species in DNA cleavage. 相似文献
10.
The nitridorhenium(V) complexes ReNCl(2)(PCy3)(2) (1), ReNBr(2)(PCy3)(2) (2), ReNCl(2)(PPh3)(2) (3), and ReNBr(2)(PPh3)(2) (4) produce structured emission spectra upon excitation at low temperature. The origin, E(00), occurs at 15 775, 16 375, 15 875, and 16 300 cm(-1), respectively. The vibronic peaks are regularly spaced with an average energy separation corresponding to the Re triple bond N stretching frequency. The nitridorhenium stretching frequency ranges from 1095 to 1101 cm(-1), as determined by Raman and IR spectroscopy. The excited-state distortions are calculated by fitting the emission spectra. The excited state arises primarily from a d(xy) (ReN nonbonding) to d(yz) (ReN pi antibonding) transition. The rhenium-nitrogen bond length in the excited state is 0.08 A longer than in the ground electronic state, which is consistent with the difference in bond lengths of ReN bonds of bond order 3 and bond order 2.5 as determined from molecular structures. 相似文献