全文获取类型
收费全文 | 672篇 |
免费 | 11篇 |
国内免费 | 2篇 |
专业分类
化学 | 359篇 |
力学 | 15篇 |
数学 | 207篇 |
物理学 | 104篇 |
出版年
2020年 | 6篇 |
2017年 | 7篇 |
2016年 | 13篇 |
2015年 | 13篇 |
2014年 | 10篇 |
2013年 | 26篇 |
2012年 | 37篇 |
2011年 | 21篇 |
2010年 | 23篇 |
2009年 | 20篇 |
2008年 | 18篇 |
2007年 | 21篇 |
2006年 | 17篇 |
2005年 | 24篇 |
2004年 | 23篇 |
2003年 | 16篇 |
2002年 | 8篇 |
2000年 | 11篇 |
1999年 | 9篇 |
1998年 | 13篇 |
1997年 | 7篇 |
1996年 | 11篇 |
1995年 | 11篇 |
1994年 | 15篇 |
1993年 | 12篇 |
1992年 | 18篇 |
1991年 | 11篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 15篇 |
1987年 | 14篇 |
1986年 | 10篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 9篇 |
1982年 | 13篇 |
1981年 | 12篇 |
1980年 | 7篇 |
1979年 | 21篇 |
1978年 | 7篇 |
1977年 | 9篇 |
1976年 | 7篇 |
1975年 | 10篇 |
1971年 | 5篇 |
1969年 | 7篇 |
1966年 | 5篇 |
1965年 | 8篇 |
1964年 | 4篇 |
1960年 | 6篇 |
1958年 | 4篇 |
排序方式: 共有685条查询结果,搜索用时 890 毫秒
51.
52.
Friedrich Schoder Ulrike Plaia Robert Metzner Wilfried Sperber Wolfgang Beck Wolf Peter Fehlhammer Prof. Dr. 《无机化学与普通化学杂志》2010,636(5):700-709
The reactions of [Re(CO)6]+, [FeCp(CO)2CS]+ and [FeCp(CNPh)3]+ with the metallo nitrile ylides [M–{C+=N–C–(H)CO2Et}(CO)5]– (M = Cr, W) and the chromio nitrile imine [Cr–{C+=N–N–H}(CO)5]– (generated by mono‐α‐deprotonation of the parent isocyanide complexes) to give neutral 5‐metallated 1,3‐oxazolin‐ ( 1 ), 1,3‐thiazolin‐ ( 2 ), imidazolin‐ ( 3 , 4 ), 1,3,4‐oxdiazolin‐ ( 5 ), 1,3,4‐thiadiazolin‐ ( 6 ) and 1,3,4‐triazolin‐2‐ylidene ( 8 ) chromium and tungsten complexes represent the first all‐organometallic versions of Huisgen’s 1,3‐dipolar cycloadditions. The formation of 6 and 8 is accompanied by partial decomposition to (OC)5Cr–C≡N–FeCpL2 {L = CO ( 7 ), CNPh ( 9 )}. The structures of 4a and 5 have been characterized by X‐ray diffraction. 相似文献
53.
Mark Eggink Maikel Wijtmans Ansgar Kretschmer Jeroen Kool Henk Lingeman Iwan J. P. de Esch Wilfried M. A. Niessen Hubertus Irth 《Analytical and bioanalytical chemistry》2010,397(2):665-675
Based on the template of a recently introduced derivatization reagent for aldehydes, 4-(2-(trimethylammonio)ethoxy)benzeneaminium
dibromide (4-APC), a new derivatization agent was designed with additional features for the analysis and screening of biomarkers
of lipid peroxidation. The new derivatization reagent, 4-(2-((4-bromophenethyl)dimethylammonio)ethoxy)benzenaminium dibromide
(4-APEBA) contains a bromophenethyl group to incorporate an isotopic signature to the derivatives and to add additional fragmentation
identifiers, collectively enhancing the abilities for detection and screening of unknown aldehydes. Derivatization can be
achieved under mild conditions (pH 5.7, 10 °C). By changing the secondary reagent (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
instead of sodium cyanoborohydride), 4-APEBA is also applicable to the selective derivatization of carboxylic acids. Synthesis
of the new label, exploration of the derivatization conditions, characterization of the fragmentation of the aldehyde and
carboxylic acid derivatives in MS/MS, and preliminary applications of the labeling strategy for the analysis of aldehydes
in urine and plasma are described. 相似文献
54.
Ferry Heus Martin Giera Gerdien E. de Kloe Dick van Iperen Joost Buijs Tariq T. Nahar August B. Smit Henk Lingeman Iwan J. P. de Esch Wilfried M. A. Niessen Hubertus Irth Jeroen Kool 《Analytical and bioanalytical chemistry》2010,398(7-8):3023-3032
One way to profile complex mixtures for receptor affinity is to couple liquid chromatography (LC) on-line to biochemical detection (BCD). A drawback of this hyphenated screening approach is the relatively high consumption of sample, receptor protein and (fluorescently labeled) tracer ligand. Here, we worked toward minimization of sample and reagent consumption, by coupling nano-LC on-line to a light-emitting diode (LED) based capillary confocal fluorescence detection system capable of on-line BCD with low-flow rates. In this fluorescence detection system, a capillary with an extended light path (bubble cell) was used as a detection cell in order to enhance sensitivity. The technology was applied to a fluorescent enhancement bioassay for the acetylcholine binding protein, a structural analog of the extracellular ligand-binding domain of neuronal nicotinic acetylcholine receptors. In the miniaturized setup, the sensitive and low void volume LED-induced confocal fluorescence detection system operated in flow injection analysis mode allowing the measurement of IC50 values, which were comparable with those measured by a conventional plate reader bioassay. The current setup uses 50 nL as injection volume with a carrier flow rate of 400 nL/min. Finally, coupling of the detection system to gradient reversed-phase nano-LC allowed analysis of mixtures in order to identify the bioactive compounds present by injecting 10 nL of each mixture. 相似文献
55.
Martha CT van Zeist WJ Bickelhaupt FM Irth H Niessen WM 《Journal of mass spectrometry : JMS》2010,45(11):1332-1343
Ferrocene is a popular template in material science due to its exceptional characteristics that offer the ability to optimize the selectivity and activity of catalysts by the addition of carefully selected substituents. In combinatorial catalyst development, the high susceptibility to electrophilic substitution reactions offers the opportunity for the rapid introduction of molecular diversity. Mass spectrometry (MS)-based continuous-flow systems can be applied to rapidly evaluate catalyst performance as well as to (provisionally) identify the introduced catalyst complexes. Herein, we describe the fragmentation characteristics of the [ferrocenyl bidentate + Ag](+) catalyst complexes in dedicated (high-resolution) MS(n) experiments. The investigation of the fragmentation patterns of a selected number of catalyst classes is accompanied with a density functional theory investigation of fragmentation intermediates in order to assess the viability of a selected fragmentation mechanism. 相似文献
56.
Wilfried N?rtersh?user 《Hyperfine Interactions》2011,199(1-3):131-140
An overview on laser spectroscopic work on highly charged ions (HCI) currently performed or in preparation at GSI is given. This includes laser spectroscopy on HCI in ion traps at the HITRAP facility and at the experimental storage ring (ESR). 相似文献
57.
This document describes the homogenization of a folded sandwich core. By using a numerical homogenization concept the components of the elasticity tensor of the foldcore continuum are determined. The foldcore exhibits an effective orthotropic behaviour with the particularity that it can be auxetic. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
58.
Martin Giera Jon S. B. de Vlieger Henk Lingeman Hubertus Irth Wilfried M. A. Niessen 《Rapid communications in mass spectrometry : RCM》2010,24(10):1439-1446
Structural elucidation of six regioisomers of mono‐N‐octyl derivatized neomycin is achieved using MSn (up to n = 4) on an ion trap time‐of‐flight (IT‐TOF) instrument equipped with electrospray ionization. The mixture of six derivatized neomycin analogues was generated by reductive amination in a shotgun synthetic approach. In parallel to the liquid chromatography/mass spectrometry (LC/MS) detection, the antibacterial activity of the neomycin regioisomers was tested by post‐column addition of buffer and bacterial inocula, subsequent microfractionation of the resulting mixture, incubation, and finally a chemiluminescence‐based bioactivity measurement based on the production of bacterial ATP. The MS‐based high‐resolution screening approach described can be applied in medicinal chemistry to help in designing and producing new antibiotic substances, which is particularly challenging due to the high functionality of most antibiotic substances, therefore requiring advanced (hyphenated) separation and detection techniques for compound mixtures. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
59.
60.