全文获取类型
收费全文 | 1384篇 |
免费 | 31篇 |
国内免费 | 223篇 |
专业分类
化学 | 1112篇 |
晶体学 | 2篇 |
力学 | 84篇 |
数学 | 102篇 |
物理学 | 192篇 |
无线电 | 146篇 |
出版年
2023年 | 102篇 |
2022年 | 57篇 |
2021年 | 49篇 |
2020年 | 60篇 |
2019年 | 64篇 |
2018年 | 59篇 |
2017年 | 68篇 |
2016年 | 69篇 |
2015年 | 71篇 |
2014年 | 120篇 |
2013年 | 116篇 |
2012年 | 63篇 |
2011年 | 81篇 |
2010年 | 64篇 |
2009年 | 79篇 |
2008年 | 71篇 |
2007年 | 71篇 |
2006年 | 72篇 |
2005年 | 56篇 |
2004年 | 41篇 |
2003年 | 12篇 |
2002年 | 14篇 |
2001年 | 21篇 |
2000年 | 10篇 |
1999年 | 44篇 |
1998年 | 23篇 |
1997年 | 7篇 |
1996年 | 7篇 |
1995年 | 10篇 |
1994年 | 5篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 9篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有1638条查询结果,搜索用时 797 毫秒
41.
Elena E. Ferapontova John Castillo Dmitri Hushpulian Vladimir Tishkov Tatiana Chubar Irina Gazaryan Lo Gorton 《Electrochemistry communications》2005,7(12):1291-1297
Direct electron transfer (DET) reactions of recombinant tobacco peroxidase (rTOP), namely direct electroreduction of Compound I/Compound II and heme Fe3+/2+ conversion, were studied on gold electrodes. rTOP of wild type, non-glycosylated, was produced using an Escherichia coli expression system. At pH 5.0, the redox potential for direct electrochemical transformation of the Fe3+/2+ of the peroxidase heme was −143 mV vs. AgAgCl, and 0.26 ± 0.07 pmol of the adsorbed rTOP were in DET contact with the gold electrode. The total amount of the adsorbed rTOP estimated from QCM data was 53 ± 5 pmol/cm2 or 1.67 pmol when referred to the surface area of the electrodes used for electrochemical measurements. Of 1.67 pmol of adsorbed rTOP, only 0.76 pmol were catalytically active. DET between Au and the enzyme was also studied in the reaction of the bioelectrocatalytic reduction of H2O2 by cyclic voltammetry and amperometric detection of H2O2 at +50 mV with rTOP-modified Au electrodes placed in a wall-jet flow-through electrochemical cell. Maximal bioelectrocatalytic current response of the rTOP-modified gold electrodes to H2O2 was observed at pH 5.0 and stemmed from its bioelectrocatalytic reduction based on DET between Au and the active site of rTOP. Kinetic analysis of the DET reactions gave 52% of the adsorbed rTOP molecules active in DET reactions (0.4 pmol of adsorbed catalytically active rTOP, correspondingly), which correlated well with the non-catalytic-voltammetry data. DET was characterised by a heterogeneous ET rate constant of 13.2 s−1, if one takes into account the QCM data, and 19.6 s−1, if the amount of rTOP estimated from the data on DET transformation of Fe3+/2+ couple of rTOP is considered. The sensitivity for H2O2 obtained for the rTOP-modified Au electrodes was 0.7 ± 0.1 A M−1 cm−2. These are the first ever-reported data on DET reactions of anionic plant peroxidases on bare gold electrodes. 相似文献
42.
《Tetrahedron letters》2019,60(22):1493-1497
A simple and efficient method was developed for the synthesis of 1,4-thiazin-2-one O-(tert-butyl) oximes and benzo[b][1,4]thiazin-2-one O-(tert-butyl) oximes from N-tert-butoxy acyl imidoyl bromides and 2-aminothiols in the presence of K2CO3/SiO2. Twenty five novel compounds were readily synthesized in excellent yields using this procedure. The products possessed Z-stereochemistry with regard to the CN double bond. The reaction proceeded with initial substitution of bromine in the N-tert-butoxy acyl imidoyl bromides by mercapto groups in the presence of K2CO3/SiO2, and subsequent intramolecular Schiff base formation. 相似文献
43.
44.
Sandra S. Pröckl 《Tetrahedron》2005,61(41):9855-9859
In situ generation of highly active palladium species by intermediate dissolution of Pd from solid supported catalysts has been demonstrated to be a very successful approach for the activation of aryl chlorides in Heck reactions. The new ‘heterogeneous’ Pd catalysts act as reservoir for molecular Pd species with unsaturated coordination sphere in solution. Crucial Pd leaching and re-deposition onto the support can be controlled by optimization of reaction conditions and by the properties of the catalysts. Pd is re-deposited onto the support at the end of the reaction. The catalysts, palladium supported on activated carbon, on various metal oxides or fluorides and Pd complexes in zeolites, are easy to prepare, though the preparation conditions are crucial. The catalysts convert all aryl bromides completely within minutes (TON 100,000). Aryl chlorides (even deactivated ones) are converted with high yields, within 2-6 h. The catalysts belong to the most active ones in Heck reactions at all (including best homogeneous systems) and fulfill all relevant requirements for practical applications in laboratory and industry. 相似文献
45.
Isabel W. C. E. Arends Roger A. Sheldon Martin Wallau Ulf Schuchardt 《Angewandte Chemie (International ed. in English)》1997,36(11):1144-1163
Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O2, H2O2, and RO2H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted. 相似文献
46.
Libuse Jaroskova 《Tetrahedron letters》2006,47(46):8063-8067
Reductive amination of 5-hydroxy-2-adamantanone with S-α-methylbenzylamine using 5% Rh-C as the catalyst in the presence of Al(iOPr)3 gave a 3:1 mixture of the E- and Z-5-hydroxy-adamantane-1-phenethylamines. Choice of catalyst, concentration, solvent and the presence of the hydroxyl group on the adamantane influenced the stereoselectivity of the amination reaction. The desired E-isomer could be isolated by fractional crystallization from diisopropyl ether. Debenzylation gave the elusive E-2-amino-5-hydroxyadamantane in a 45% overall yield. 相似文献
47.
Patrik Nilsson 《Journal of organometallic chemistry》2005,690(18):4197-4202
An investigation of the kinetics of the Heck reaction between 4-iodoanisole and styrene catalysed by {cis-1,3-bis[(di-tert-butylphosphino)methyl]-cyclohexane} palladium (II) iodide (1) has been performed in DMF-d7 solution. Based on mercury poisoning experiments a heterogeneous palladium catalyst formed from the pre-catalyst is proposed. Saturation behaviour with respect to the olefin concentration suggests a mechanism consisting of a pre-equilibrium association of the olefin followed by a rate determining reaction with aryl halide. The equilibrium constant for the olefin association, K1, and the rate constant for the subsequent oxidative addition step, k2, were determined to (5.7 ± 2.5) × 10−3 and 18.4 ± 2.7 M−1 s−1, respectively. 相似文献
48.
Hui Qiang Tao Chen Zhuo Wang Wenqian Li Yunzhe Guo Jie Yang Xueshun Jia Hui Yang Weibo Hu Ke Wen 《中国化学快报》2021,31(12):3225-3229
The development of heterogeneous catalysts with substrate shape, size or electronic constitution selectivity is a huge challenge in photocatalysis. Reported herein is a host-guest interaction strategy to endow photocatalysts with special selectivity. By adjusting the precursors, conjugated macrocycle polymers (CMPs) with pillar[5]arene struts (CMP-1 and CMP-2) and a corresponding non-pillar[5]arene-contained conjugated organic polymer (COP-1) were prepared and the photocatalytic activities toward sulfide derivatives were investigated. The sulfides showed similar conversions when COP-1 was used as a photocatalyst, but exhibited significant differences when it turned to the CMPs. Remarkably, the conversion yield of S-1 achieved near 18 folds over the one of S-2 when CMP-2 was used as a catalyst. Mechanism studies confirmed that the “host-guest” effect of pillar[5]arene struts in CMPs was the main cause of the difference. The present work establishes CMPs as novel heterogeneous photocatalysts with substrate selectivity, and such a method will inspire the researchers concerning preparation of heterogeneous catalysts with excellent selectivity. 相似文献
49.
Venkatanarayana Pappula Ramachandra Reddy DonthiriChandra Mohan Darapaneni Adimurthy Subbarayappa 《Tetrahedron letters》2014
Synthesis of β-bromostyrenes from styrene bromohydrins using H-β-zeolite as catalyst under moderate conditions is reported. The catalyst could be regenerated and reused up to three consecutive cycles. 相似文献
50.
M. A. Kumakhov 《辐射效应与固体损伤》2013,168(1-2):85-99
The redistribution of the channeled ion flux in the transverse plane has been examined. General formulae describing the flux peaking effect are obtained. Main factors on which the effect depends are investigated. An analysis is made of back-scattering experiments. The study has been made for the axial and planar channeling. 相似文献