全文获取类型
收费全文 | 846篇 |
免费 | 16篇 |
国内免费 | 2篇 |
专业分类
化学 | 483篇 |
晶体学 | 3篇 |
力学 | 54篇 |
数学 | 69篇 |
物理学 | 255篇 |
出版年
2022年 | 9篇 |
2021年 | 12篇 |
2020年 | 18篇 |
2019年 | 11篇 |
2018年 | 16篇 |
2017年 | 21篇 |
2016年 | 31篇 |
2015年 | 16篇 |
2014年 | 26篇 |
2013年 | 75篇 |
2012年 | 37篇 |
2011年 | 32篇 |
2010年 | 41篇 |
2009年 | 29篇 |
2008年 | 43篇 |
2007年 | 42篇 |
2006年 | 38篇 |
2005年 | 34篇 |
2004年 | 31篇 |
2003年 | 8篇 |
2002年 | 11篇 |
2001年 | 11篇 |
2000年 | 10篇 |
1999年 | 7篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 6篇 |
1995年 | 12篇 |
1994年 | 6篇 |
1993年 | 12篇 |
1992年 | 11篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 5篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1984年 | 12篇 |
1983年 | 6篇 |
1982年 | 12篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 14篇 |
1978年 | 14篇 |
1977年 | 11篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1973年 | 5篇 |
1971年 | 5篇 |
1962年 | 5篇 |
排序方式: 共有864条查询结果,搜索用时 15 毫秒
21.
Background
Use of enzymes in low water media is now widely used for synthesis and kinetic resolution of organic compounds. The frequently used enzyme form is the freeze-dried powders. It has been shown earlier that removal of water molecules from enzyme by rinsing with n-propanol gives preparation (PREP) which show higher activity in low water media. The present work evaluates PREP of the lipase (from Rhizomucor miehei) for kinetic resolution of (R,S)-β-citronellol. The acylating agent was vinyl acetate and the reaction was carried out in solvent free media. 相似文献22.
A sensitive and selective method has been developed for the micro-determination of Mn(II) by the selective extraction of the yellow Mn(II)-8-hydroxyquinolinate complex with a liquid ion-exchanger, Aliquat 336, from basic medium. The molar absorptivity of the complex is 2.2 x 10(4)1.mole(-1).cm(-1) at 420 nm and the colour system obeys Beer's law in the range 0.1-3.5 ppm Mn(II) in the final solution. The composition and stability of the complex are discussed. Potential interferents have been examined and the method is applied to analysis of standard steel and bronze samples. 相似文献
23.
A simple and sensitive method for the determination of isoproturon, a widely used herbicide is described here which is based on alkaline hydrolysis of isoproturon to its corresponding primary amine followed by diazotization and coupling with p-aminoacetophenone in alkaline medium. The absorption maxima of the coloured compound formed is measured at 525 nm. Beer's law is obeyed over the concentration range of 0.5-5.0 mug in a final solution volume of 25 ml (0.02-0.2 ppm). The molar absorptivity and Sandell's sensitivity were found to be 8.6x10(5) l mol(-1) cm(-1) and 0.0002 mug cm(-2), respectively. The method has been satisfactorily applied to the determination of isoproturon in environmental and biological samples. 相似文献
24.
Summary A study of the Cd(CN)2 +x X– [Cd(CN)2X
x
]
x–
equilibrium (where X = Cl, Br or CNS) has been carried out at 18° and 38° by measuring the solubility of cadmium cyanide in potassium chloride, bromide and thiocyanate at various concentrations, and at a high ionic strength (6 M) maintained with sodium perchlorate to minimise the effect of activity coefficients. Equilibrium constants forx = 1 and 2 have been calculated and clearly favour the situation wherex = 1. H values for the dissociation of [Cd(CN)2X]– have also been calculated. 相似文献
25.
A sensitive and reproducible method is described for the quantitative determination of metadoxine in the presence of its degradation products. The method was based on high performance liquid chromatographic separation of the drug from its degradation products on the reversed phase, kromasil column [C18 (5-micron, 25 cm × 4.6 mm, i.d.)] at ambient temperature using a mobile phase consisting of methanol and water (50: 50, v/v). Flow rate was 1.0 mL min?1 with an average operating pressure of 180 kg cm?2 and t R was found to be 2.85 ± 0.05 min. Quantitation was achieved with UV detection at 286 nm based on peak area with linear calibration curves at concentration range 10–100 μg mL?1. This method has been successively applied to pharmaceutical formulation. No chromatographic interference from the tablet excipients was found. The method was validated in terms of precision, robustness, recovery and limits of detection and quantitation. Drug was subjected to acid, alkali and neutral hydrolysis, oxidation, dry heat, wet heat treatment and photo and UV degradation. As the proposed method could effectively separate the drug from its degradation products, it can be employed as stability indicating one. Moreover, the proposed HPLC method was utilized to investigate the kinetics of the acidic, alkaline and oxidative degradation processes at different temperatures and their respective apparent pseudo first order rare constant, half-life and activation energy was calculated with the help of Arrhenius plot. In addition the pH-rate profile of degradation of metadoxine in constant ionic strength buffer solutions with in the pH range 2–11 was studied. 相似文献
26.
A spectrophotometric method for determination of a microgram quantity of cerium with N-p-tolyl-p-chlorobenzohydroxamic acid is described. The orange-red-colored complex is extracted from chloroform at pH 9 which absorbs between 460 and 465 nm. Beer's law is obeyed at this wavelength. A clean-cut separation from many commonly occurring metal ions is easily accomplished. The system obeys Beer's law within the range of 0.5–28 ppm of cerium(IV). The molar absorptivity of cerium-N-p-tolyl-p-chlorobenzohydroxamic acid complex is 4.5 × 103 liters mol?1 cm?1. 相似文献
27.
Santosh K. Upadhyay Mahesh C. Agrawal 《Monatshefte für Chemie / Chemical Monthly》1979,110(2):413-418
Osmium(VIII) catalysed oxidation of lysine by ferricyanide in excess ferrocyanide shows a complex kinetics. The order in lysine falls, from 1 to 0 while that in ferricyanide increases from 0 to 2 with large increase in lysine concentration. The rates were directly proportional to [Os(VIII)] and {Const.+[Fe(CN)
6
4
]}. A suitable mechanism is proposed and discussed.
Oxidation von lysin mittels ferricyanid in der gegenwart von osmium(VIII)
Zusammenfassung Die von Os(VIII) katalysierte Oxidation von Lysin mit Ferricyanid in überschüssigem Ferrocyanid zeigt eine komplexe Kinetik. Bei starker Steigerung der Lysinkonzentration fällt die Ordnung bezüglich Lysin von 1 auf 0, während bezüglich Ferricyanid eine Erhöhung, von 0 auf 2 festzustellen ist. Die Geschwindigkeitskonstanten waren direkt proportional zu [Os(VII)] und {Const.+[Fe(CN) 6 4 ]}. Es wird ein möglicher Mechanismus vorgeschlagen und diskutiert.相似文献
28.
Noor-ul H. Khan Santosh Agrawal Rukhsana I. Kureshy Sayed H.R. Abdi Surendra Singh Raksh V. Jasra 《Journal of organometallic chemistry》2007,692(20):4361-4366
An efficient method for the addition of trimethylsilyl cyanide (TMSCN) to various aldehydes and ketones has been described using Fe(Cp)2PF6 (2.5 mol%) as a catalyst under solvent free condition. Excellent yields of trimethylsilylether of cyanohydrin up to (94%) was achieved within 10 min. 相似文献
29.
Salicylidene-o-aminobenzothiol and its 5-chloro and 5-bromo derivatives, dibasic tridentate Schiff bases, dervied from the condensation of o-aminothiol and Salicylaldehyde, 5-chloro salicylaldehyde and 5-bromo salicylaldehyde, were used for coordination with Zr(IV), Th(IV) and UO2(VI) metal inos. The I:I (metal-ligand) stoichiometry of these complexes is shown by elemental analysis and conductometric titrations. Molecular structure of these complexes are proved by Infra-red spectroscopy and thermogravimetric analysis. Magnetic susceptibility measurements of Zr(IV), Th(IV) and UO2(VI) complexes show their diamagnetic and octahedral geometry. Results show that all the complexes have solvent molecules in coordination with metal ion. 相似文献
30.
The interactions between oppositely charged surfactant/polymer mixtures have been studied using conductivity and turbidity measurements. The dependence of aggregation phenomenon on the chain length and head group modifications of conventional cationic surfactants, i.e., hexadecyl- (HTAB), tetradecyl- (TTAB), and dodecyltrimethylammonium bromides (DTAB) and dimeric cationic surfactants, i.e., decyl- (DeDGB) and dodecyldimethylgemini bromides (DDGB), is investigated. It was observed that cationic surfactants induce cooperative binding with anionic polyelectrolytes at critical aggregation concentration (cac). The cac values are considerably lower than the critical micelle concentration (cmc) values for the same surfactant. After the complete complexation, free micelles are formed at the apparent critical micelle concentration (acmc), which is slightly higher in aqueous polyelectrolyte than in pure water. Among the conventional and dimeric cationic surfactants, DTAB and DeDGB, respectively, have been found to have least interactions with oppositely charged polyelectrolytes. 相似文献