全文获取类型
收费全文 | 399篇 |
免费 | 11篇 |
国内免费 | 3篇 |
专业分类
化学 | 261篇 |
力学 | 23篇 |
数学 | 48篇 |
物理学 | 81篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 6篇 |
2021年 | 12篇 |
2020年 | 10篇 |
2019年 | 17篇 |
2018年 | 11篇 |
2017年 | 17篇 |
2016年 | 20篇 |
2015年 | 16篇 |
2014年 | 24篇 |
2013年 | 32篇 |
2012年 | 24篇 |
2011年 | 20篇 |
2010年 | 14篇 |
2009年 | 12篇 |
2008年 | 27篇 |
2007年 | 20篇 |
2006年 | 11篇 |
2005年 | 14篇 |
2004年 | 12篇 |
2003年 | 12篇 |
2002年 | 7篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 1篇 |
1991年 | 2篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 6篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1971年 | 2篇 |
1970年 | 3篇 |
1969年 | 1篇 |
1967年 | 3篇 |
排序方式: 共有413条查询结果,搜索用时 15 毫秒
101.
Summary The kinetics of osmium(VIII)-catalysed oxidation of aminoalcohols,viz., 2-aminoethanol, 3-aminopropanol, diethanolamine and triethanolamine, by chloramine-T in alkaline medium have been investigated. The reactions follow a first-order-rate dependence with respect to oxidant. The order in [aminoalcohol] decreases from unity at higher concentrations of aminoalcohols while that in [OH–] is nearly –1. The oxidation rate is directly proportional to [osmium(VIII)] in primary amino-alcohols, while that is proportional to {k+k [osmium(VIII)]} (where k and k are rate constants) in diethanolamine and triethanolamine. The uncatalysed oxidation of diethanolamine and triethanolamine follows a first-order-rate dependence in each of the oxidant and the sustrate. Suitable mechanisms consistent with the observed kinetic results are proposed. 相似文献
102.
Summary The kinetics of the ruthenium(III) catalysed oxidation of 2-aminoethanol, 3-aminopropanol, diethanolamine and triethanolamine by chloramine-T in HClO4 medium have been studied. The reactions exhibits first order rate dependence with respect to the oxidant and to the catalyst, and are zeroth order with respect to the substrate. The rate of oxidation is proportional to k[HClO4]/{k+k'[HClO4]} where k, k and k' are constants (a mixture of elementary rate constants and equilibrium constants). A suitable mechanism consistent with the observed kinetic data is proposed. 相似文献
103.
Summary Mixed ligand complexes of chromium(III), cobalt(II), cobalt(III), copper(II) and zinc(II) involving either the phenylglyoxal-p-diethylaminoanil and/or thiourea, and ammonia have been obtained by the partial or complete replacement of the strongly coordinated ammonia of ammine complexes. All the products were characterized by elemental analysis, molar conductance, magnetic susceptibility and i.r. and electronic spectral measurements for their bonding and structures. 相似文献
104.
Functionalized ormosil-modified electrodes have been developed for electroanalytical applications. The functionalized ormosil-modified electrodes are made by encapsulating potassium ferricyanide/potassium ferrocyanide within ormosil film derived from an optimum composition of 3-aminopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and phenyltrimethoxy silane in acidic medium in absence of Nafion/crown ether (system 1), in the presence of Nafion (system 2) and in the presence of dibenzo-18-crown-6 (system 3). Another modified electrode (system 4) is also developed using the reaction product of potassium ferricyanide, 3-aminopropyltrimethoxysilane and either tetrahydrofuran (THF) or cyclohexanone followed by ormosil formation in the presence of 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and phenyltrimethoxy silane in acidic medium. The electrochemical oxidation of hydrogen peroxide and ascorbic acid conducted at the surface of these four types of functionalized electrodes shows very interesting observations on the selective sensing of ascorbic acid and peroxide. The results based on cyclic voltammetry justify the relative performances on the kinetics of hydrogen peroxide oxidation and reduction. System 3 shows relatively much better oxidation kinetics of hydrogen peroxide as compared to other three systems with relatively weak reduction kinetics whereas system 4 shows relatively faster reduction kinetics of hydrogen peroxide as compared to other three systems. Similarly system 4 shows excellent response to ascorbic acid whereas system 3 shows insensitivity to ascorbic acid under similar experimental conditions. Typical response curve for the analysis of hydrogen peroxide and ascorbic acid using system 3 and system 4 respectively are reported. The results show that system 3 is the best for probing hydrogen peroxide with lowest detection limit of 0.5 μM without any interference from ascorbic acid as commonly encountered using many conventional and chemically modified electrodes. 相似文献
105.
Faiz Ahmed Khan Jyotirmayee Dash Rashmirekha Satapathy Sarasij K. Upadhyay 《Tetrahedron letters》2004,45(15):3055-3058
Knoevenagel condensation proceeds efficiently in recyclable [bmim]PF6 and [bmim]BF4 without any catalyst, and hydrotalcites in ionic liquid serve as a safe and recyclable reaction system for both Knoevenagel as well as nitroaldol condensations. 相似文献
106.
107.
Surendra K. Gautam Dhananjai Pandey S.N. Upadhyay Shahid Anwar N.P. Lalla 《Solid State Communications》2008,146(9-10):425-427
The problem of identification of the correct crystalline structure of CdS nanoclusters below 2.5 nm in size is outlined. Structure of thiophenol capped CdS nanoclusters in the size range 1.2–4.3 nm, synthesized using cadmium acetate solution in methanol, is discussed using powder XRD and electron diffraction data. Unambiguous confirmation of the wurtzite phase in CdS nanoclusters below 2.5 nm size is reported. The observation of 102 wurtzite peak in the XRD patterns of such nanoclusters indicates low stacking fault concentration. 相似文献
108.
Kirtikumar D. Bharwad Priyanka A. Shah Pranav S. Shrivastav Vinay S. Sharma 《Biomedical chromatography : BMC》2020,34(11):e4928
A practical, sensitive, and robust UPLC–MS/MS method was developed and validated to quantify lacosamide in human plasma. A simple one-step protein precipitation was used to extract lacosamide and labeled lacosamide-13C, D3 as an internal standard (IS) from 150-μL plasma. The extracts were analyzed on an Eclipse Plus C18 column (50 × 2.1 mm, 1.8 μm) using 0.1% formic acid in water and methanol:acetonitrile (50:50, v/v) under gradient conditions. The extracts were quantified on LCMS-8040 using electrospray ionization source operated in positive ionization and multiple reaction monitoring modes. The method showed good linearity from 0.02 to 20 μg/mL, which was adequate to cover lacosamide concentration assayed in formulations with different strengths. The bioanalytical assay was fully validated as per current regulatory guidelines. The intra-batch and inter-batch precision values of lacosamide were less than 4.6%. Lacosamide was found to be stable at different storage conditions. The extraction recoveries and IS-normalized matrix factors for lacosamide ranged from 97.17 to 99.68% and from 0.973 to 1.012, respectively. The validated method was successfully applied to a pharmacokinetic study with three lacosamide formulations (50, 100, and 200 mg) in 36 healthy subjects. The assay reliability was determined by reanalysis of 81 subject samples. 相似文献
109.
Abhaysingh Bhadoriya Priyanka A. Shah Pranav S. Shrivastav Mallika Sanyal Manish S. Yadav 《Biomedical chromatography : BMC》2019,33(9)
A high‐throughput and sensitive liquid chromatography–tandem mass spectrometry (LC–MS/MS) method has been developed and validated for the determination of flunarizine in human plasma. Liquid–liquid extraction under acidic conditions was used to extract flunarizine and flunarizine‐d8 from 100 μL human plasma. The mean extraction recovery obtained for flunarizine was 98.85% without compromising the sensitivity of the method. The chromatographic separation was performed on Hypersil Gold C18 (50 × 2.1 mm, 3 μm) column using methanol–10 mm ammonium formate, pH 3.0 (90:10, v/v) as the mobile phase. A tandem mass spectrometer (API‐5500) equipped with an electrospray ionization source in the positive ion mode was used for detection of flunarizine. Multiple reaction monitoring was selected for quantitation using the transitions, m/z 405.2 → 203.2 for flunarizine and m/z 413.1 → 203.2 for flunarizine‐d8. The validated concentration range was established from 0.10 to 100 ng/mL. The accuracy (96.1–103.1%), intra‐batch and inter‐batch precision (CV ≤ 5.2%) were satisfactory and the drug was stable in human plasma under all tested conditions. The method was used to evaluate the pharmacokinetics of 5 and 10 mg flunarizine tablet formulation in 24 healthy subjects. The pharmacokinetic parameters Cmax and AUC were dose‐proportional. 相似文献
110.
Jayaraman Kannappan Aditya N. Khanvilkar Gourav M. Upadhyay Ashutosh V. Bedekar 《Tetrahedron: Asymmetry》2017,28(10):1297-1303
The design and synthesis of a few simple N-benzyl derivatives of isobornyl amine is presented. The derivatives have been assessed as chiral solvating agents for effective discrimination of the signals of some acids in NMR analysis. The single crystal X-ray analysis of the salts of (R)-mandelic acid with two of the title derivatives help to understand the supramolecular interactions and assign the induced chemical shifts in 1H NMR analysis. The title derivative is found to be suitable for quantitative determination of the enantiomeric excess of unknown enantiomeric purity as well as being efficient in resolving racemic mandelic acid. 相似文献