全文获取类型
收费全文 | 7458篇 |
免费 | 314篇 |
国内免费 | 111篇 |
专业分类
化学 | 5667篇 |
晶体学 | 40篇 |
力学 | 392篇 |
数学 | 730篇 |
物理学 | 1054篇 |
出版年
2024年 | 14篇 |
2023年 | 57篇 |
2022年 | 271篇 |
2021年 | 359篇 |
2020年 | 367篇 |
2019年 | 371篇 |
2018年 | 374篇 |
2017年 | 361篇 |
2016年 | 489篇 |
2015年 | 348篇 |
2014年 | 457篇 |
2013年 | 836篇 |
2012年 | 634篇 |
2011年 | 553篇 |
2010年 | 360篇 |
2009年 | 348篇 |
2008年 | 346篇 |
2007年 | 297篇 |
2006年 | 204篇 |
2005年 | 174篇 |
2004年 | 119篇 |
2003年 | 117篇 |
2002年 | 95篇 |
2001年 | 32篇 |
2000年 | 17篇 |
1999年 | 26篇 |
1998年 | 18篇 |
1997年 | 21篇 |
1996年 | 21篇 |
1995年 | 10篇 |
1994年 | 14篇 |
1993年 | 10篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 9篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 14篇 |
1986年 | 5篇 |
1985年 | 12篇 |
1984年 | 13篇 |
1982年 | 14篇 |
1981年 | 7篇 |
1980年 | 14篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1973年 | 3篇 |
1971年 | 3篇 |
排序方式: 共有7883条查询结果,搜索用时 0 毫秒
51.
Theoretical determination of chromophores in the chromogenic effects of aromatic neurotoxicants 总被引:3,自引:0,他引:3
Zhan CG Dixon DA Sabri MI Kim MS Spencer PS 《Journal of the American Chemical Society》2002,124(11):2744-2752
We report the first computational study of the chromophores responsible for the chromogenic effects of aromatic neurotoxicants containing a 1,2-diacetyl moiety in their oxidation metabolites. A series of ab initio electronic structure calculations was performed on two representative aromatic compounds, 1,2-diacetylbenzene (1,2-DAB) and 1,2-diacetyl tetramethyl tetralin (1,2-DATT), the putative active metabolites of the neurotoxic aromatic hydrocarbon compounds 1,2-diethylbenzene (1,2-DEB) and acetyl ethyl tetramethyl tetralin (AETT), and on the products of their possible reactions with proteins that result in chromogenic effects. The electronic excitation energies determined by three different computational approaches were found to be consistent with each other. The calculated results are consistent with the conclusion/prediction that the chromogenic effects of 1,2-DAB (or 1,2-DEB) and 1,2-DATT (or AETT) could result from ninhydrin-like reactions, rather than the formation of pyrrole-like compounds. Our pK(a) calculations further indicate that the chromophore, i.e., the product of the ninhydrin-like reaction showing the blue color, is deprotonated in neutral aqueous solution. The corresponding protonated structure has a different color as it absorbs in the blue region of the visible spectrum, and its chromogenic contribution would be significant in solution at low pH. 相似文献
52.
Aliphatic and aromatic 1,3‐dithiane are oxidized to the corresponding carbonyl compounds in good yields under mild conditions by N,N′‐diiodo‐N,N′‐1,2‐ethanediyl‐bis(p‐toluenesulphonamide) [NIBTS] and silver nitrate. 相似文献
53.
M. Mohammad A. Y. Khan M. S. Subhani N. Bibi Safeer Ahmad Saba Saleemi 《Research on Chemical Intermediates》2001,27(3):259-267
Rate constants for the reaction of superoxide O-
2 with various substrates were obtained through stationary electrode polarography theory and technique. In solvent acetonitrile, the substrate and the rate constants of the reaction O-
2 + AH-
k2Product, are, AH = isopropanol (k2 < 0.01 M-1 s-1); ethanol (k2 = 1.42 × 102 M-1 s-1); methanol (k2 = 1.1 × 107 M-1 s-1), H2O (k2 = 1.0 × 105 M-1 s-1). In MeCN, O-2 was found to be rather unreactive towards glucose and acetone but it reacts with fructose and sucrose catalytically. However, in DMF2, O-
2reacts with glucose and fructose with k2 order of 105 M-1 s-1. The mechanism of the reaction of O-
2 with the substrates (AH) is proposed as O-
3 + AH k2O, AHk2
k-1 k [O2H + AH]-, k-2O2H + A- with k1 = 109 M-1 s-1 and k-1 = 108 -109 s-1. With these values of k-1 and k1, k k2(obs). The reversible E1/2 for O2 + e O-
2 in various solvents: MeCN, acetone, isopropanol, methanol, H2O were obtained either directly from the reversible voltammogram or from experimental voltammograms and the rate constants obtained (as above) using stationary electrode polargraphy theory; E1/2 being -0.82 (MeCN),-0.85 (acetone),-0.72 (isopropanol);-0.66 (MeOH),-0.56 (H2O) vs SCE. 相似文献
54.
Talebi M Ghassempour A Talebpour Z Rassouli A Dolatyari L 《Journal of separation science》2004,27(13):1130-1136
A simple and rapid microwave-assisted extraction (MAE) procedure was developed and optimized for the extraction of paclitaxel (Taxol) from the needles of yew trees Taxus baccata L. grown in Iranian habitats. The samples, immersed in a methanol-water mixture, were irradiated with microwaves in a closed-vessel system. The method was evaluated using a factorial design approach based on parameters such as extraction time, temperature, methanol concentration in water (v/v), and the ratio of grams of sample to 10 mL of solvent. Statistical treatment of the results revealed that the selected parameters were all significant except the extraction time. Optimum conditions would be 1.5 g samples in 10 mL solvent (90% methanol), an extraction temperature of 95 degrees C, and an extraction time of 7 min. The extracts has been analyzed by reverse-phase high-performance liquid chromatography with UV detection (LC/UV) at 227 nm for quantification. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for confirmation. The main advantage of the proposed MAE method versus conventional solvent extraction (CSE) are the considerable reductions in time (7 min versus 16 h) and in solvent consumption (20 mL versus 150 mL). The MAE procedure yielded extracts that could be analyzed directly without any preliminary clean-up or solvent exchange steps. Both extraction methods show RSDs lower than 10% and lead to comparable recoveries of paclitaxel (87-92%). 相似文献
55.
Ahmad?ShaabaniEmail author Mohammad Bagher?Teimouri Hamid Reza?Bijanzadeh 《Monatshefte für Chemie / Chemical Monthly》2004,135(5):589-593
Summary. The environment-friendly one-pot three-component condensation reactions of 4-hydroxycoumarin or 4-hydroxy-6-methylpyrone, p-substituted benzaldehyde, and alkyl or aryl isocyanides to afford furocoumarines or furopyranones in water in good yields after about one hour at 75°C are reported. 相似文献
56.
In this paper we, present some MATLAB and GAP programs and use them to find the automorphism group of the Euclidean graph
of the C80 fullerence with connectivity and geometry of I
h
symmetry point group. It is proved that this group has order 120 and is isomorphic to I
h
≊Z2×A5, where Z2 is, a cyclic group of order 2 and A5 is the alternating group on five symbols. 相似文献
57.
Akbar Ali Mohammad Huq Mirza Aminul Nazimuddin Mohamed Rahman Hafazatur Butcher Raymond J. 《Transition Metal Chemistry》2002,27(3):268-273
New cadmium(II) complexes of empirical formulae, [Cd(dpksme)X] (dpksme = anionic form of the Schiff base; X = NCS–, Cl–, I–) and [Cd(dpksme)2] · 0.5MeOH, respectively have been prepared and characterized. The mono-ligated cadmium(II) complexes, [Cd(dpksme)X] are four-coordinate and tetrahedral but the bis-ligand complex, [Cd(dpksme)2] · 0.5MeOH is six-coordinate and octahedral. The crystal and molecular structure of [Cd(dpksme)2] · 0.5MeOH has been determined by X-ray diffraction. The complex has a distorted mer-octahedral structure in which the ligands are coordinated as uninegatively charged tridentate chelating agents via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the thiolate sulfur atoms. The distortion from regular octahedral geometry is ascribed to the restricted bite angles of the ligands. The Schiff base and its cadmium(II) complexes exhibit mild antibacterial activities against Shigella dysenteriae, Bacillus cereus, Staphylococcus aureus and Escherichia coli. They are also mildly fungitoxic against the phytopathogenic fungi, Alternaria alternata and Macrophomina phaseolina. 相似文献
58.
Ali MOGHIMI Mohammad SABER‐TEHRANI Syed WAQIF‐HUSAIN Majid MOHAMMADHOSSEINI 《中国化学》2007,25(12):1859-1865
A novel and selective method for the fast determination of trace amounts of chromium species in water samples has been developed. The procedure is based on the selective formation of chromium diethyldithiocarbamate complexes at different pH in the presence of Mn(II) as an enhancement agent of chromium signals followed by elution with organic eluents and determination by atomic flame absorption spectrometry. The maximum capacity of the employed disks was found to be (396±3) µg and (376±2) µg for Cr(III) and Cr(VI), respectively. The detection limit of the proposed method is 49 and 43 ng·L?1 for Cr(III) and Cr(VI), respectively. The proposed method was successfully applied for determination of chromium species Cr(III) and Cr(VI) in different water samples. 相似文献
59.
An analytical method using alumina modified with water-soluble polyacrylic acid polymer for the simultaneous separation and
preconcentration of trace Cu and Cd in a column system, and their determination by flame atomic absorption spectrometry was
developed. The conditions for coating Al2O3 with polyacrylic acid were optimized, then the column was packed with 50 mg of this sorbent. Cd and Cu solution was passed
through a glass column at pH 4.5, and elution was carried out with 5 mL of 0.05 M HCl at a flow rate of 1 mL min−1. A sorption capacity of 10 mg Cu and 12 mg Cd was obtained for 1 g sorbent. The detection limit was calculated as 4.5 μg L−1 for Cu and 1.54 μg L−1 for Cd in the final solution. Enrichment factors of 300 for Cd and 400 for Cu were obtained. 相似文献
60.
Mehmood A Malik A Anis I Khan PM Riaz M Makhmoor T Choudhary MI 《Natural product letters》2002,16(6):371-376
Two new oleanane triterpenes; 2alpha,3alpha,24-trihydroxyolean-12-ene-28,30-dioic acid ([structure: see text]) and 2alpha,3alpha,24,28-tetrahydroxyolean-12-ene ([structure: see text]) have been isolated from the roots of Atropa acuminata. Anti-oxidant p-hydroxyphenethyl trans-ferulate ([structure: see text]), beta-sitosterol-3-O-beta-D-glucopyranoside ([structure: see text]) and oleanolic acid ([structure: see text]) have also been reported for the first time from this species. The structures were determined by spectroscopic studies including 2D-NMR. 相似文献