全文获取类型
收费全文 | 4704篇 |
免费 | 497篇 |
国内免费 | 626篇 |
专业分类
化学 | 4079篇 |
晶体学 | 13篇 |
力学 | 66篇 |
综合类 | 96篇 |
数学 | 564篇 |
物理学 | 1009篇 |
出版年
2024年 | 8篇 |
2023年 | 39篇 |
2022年 | 87篇 |
2021年 | 168篇 |
2020年 | 177篇 |
2019年 | 132篇 |
2018年 | 124篇 |
2017年 | 141篇 |
2016年 | 209篇 |
2015年 | 188篇 |
2014年 | 288篇 |
2013年 | 375篇 |
2012年 | 264篇 |
2011年 | 309篇 |
2010年 | 249篇 |
2009年 | 302篇 |
2008年 | 301篇 |
2007年 | 306篇 |
2006年 | 318篇 |
2005年 | 301篇 |
2004年 | 256篇 |
2003年 | 209篇 |
2002年 | 135篇 |
2001年 | 129篇 |
2000年 | 99篇 |
1999年 | 92篇 |
1998年 | 109篇 |
1997年 | 85篇 |
1996年 | 68篇 |
1995年 | 60篇 |
1994年 | 62篇 |
1993年 | 38篇 |
1992年 | 24篇 |
1991年 | 27篇 |
1990年 | 22篇 |
1989年 | 23篇 |
1988年 | 22篇 |
1987年 | 13篇 |
1986年 | 19篇 |
1985年 | 11篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有5827条查询结果,搜索用时 15 毫秒
131.
Hosoya K Hira N Watabe Y Tanaka N Kubo T Kaya K 《Analytical and bioanalytical chemistry》2004,380(2):343-345
Thiacalix[4]arene (5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathiacalix[4]arene) is an amphiphilic molecule comprising four p-tert-butylphenol-like groups ortho-linked by single sulfur atoms. This molecule has a high electron density area owing to the close proximity of the hydroxyl groups and sulfur atoms. We studied the applicability of this interesting compound as a selector for high-performance liquid chromatography (HPLC) thereby presumably exploiting this feature. Firstly, uniformly sized polymer particles were prepared by using a multi-step swelling and polymerization method with ethylene glycol dimethacrylate (EDMA) as a cross-linker. Methacrylic acid (MAA) was introduced onto the surface of the resulting polymer particles through a new modification method. Thiacalix[4]arene was chemically bonded through the MAA group by using 1,4-dibromobutane as a spacer to reduce steric hindrance around the MAA and the polymer particle itself. The performance of the prepared polymer-based thiacalix[4]arene-modified stationary phase was evaluated with HPLC. Specific chromatographic retention behavior was observed for catechol relative to positional isomers of xylene, cresol, and benzene-diol. Catecholamine and catechol showed specific chromatographic retention behavior. 相似文献
132.
133.
Molt O Rübeling D Schäfer G Schrader T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4225-4232
Host molecule 1 displays a high affinity in water towards catecholamines and especially related structures such as beta-blockers with extended aromatic pi-faces (up to 7x10(3) M(-1) for each single complexation step or 5x10(7) M(-2) for both steps). The amphiphilic structural design leads to an extensive self-association of host molecules through their aromatic flanks. Above a cmc (critical micelle concentration) of 3x10(-4) M, host 1 forms micelles that produce a favorable microenvironment for hydrophobic interactions with the included guest molecules. Electrostatic attraction of the ammonium alcohol by the phosphonate anions is thus combined with hydrophobic contributions between the aromatic moieties. Ionic hydrogen bonds with polar OH or NH groups of the guest enforce the non-covalent interactions, and finally lead to increased specificity. Both its affinity and its selectivity towards adrenergic receptor substrates are greatly enhanced if the receptor molecule 1 is transferred from water into a lipid monolayer. Catecholamines and beta-blockers lead to drastically different effects at concentrations approaching the micromolar regime. Especially beta-blockers with minute structural changes can be easily distinguished from each other. In both cases, extensive hydrophobic interactions with a self-associated and/or self-organized microenvironment are largely responsible for the observed high efficiency and specificity. 相似文献
134.
135.
Stoikov I. I. Gafiullina L. I. Ibragimova D. Sh. Antipin I. S. Konovalov A. I. 《Russian Chemical Bulletin》2004,53(6):1172-1180
New calix[4]arenes, di- and tetrasubstituted at the lower rim, with different functional groups were synthesized. They were studied as carriers of a series of dicarboxylic and -hydroxycarboxylic acids through a liquid impregnated membrane. The calix[4]arenes under study are capable of molecular recognition of oxalic acid in the series of structurally similar dicarboxylic and -hydroxycarboxylic acids. The regularities found make it possible to change purposefully the receptor ability of 1,3-disubstituted calix[4]arenes by variation of the nature of substituents. 相似文献
136.
137.
138.
Cobas JC Constantino-Castillo V Martín-Pastor M del Río-Portilla F 《Magnetic resonance in chemistry : MRC》2005,43(10):843-848
(1)H NMR scalar coupling constants are a rich source of information on molecular structure, but their extraction from spectra can be less than straightforward. Previous approaches to J extraction include methods proposed by Hoye, Golotvin, and the 'modified J-doubling' method. Here we describe the ACCA method, currently implemented in the NMR package MestReC, which allows a high degree of automation in the extraction of coupling patterns even in the case of complex multiplets with sublinewidth splitting. The new approach is illustrated by application to strychnine, for which it has detected previously unreported couplings. 相似文献
139.
Classification of white wine aromas with an electronic nose 总被引:3,自引:0,他引:3
This paper reports the use of a tin dioxide multisensor array based electronic nose for recognition of 29 typical aromas in white wine. Headspace technique has been used to extract aroma of the wine. Multivariate analysis, including principal component analysis (PCA) as well as probabilistic neural networks (PNNs), has been used to identify the main aroma added to the wine. The results showed that in spite of the strong influence of ethanol and other majority compounds of wine, the system could discriminate correctly the aromatic compounds added to the wine with a minimum accuracy of 97.2%. 相似文献
140.
The nanometer scale is a special place where all sciences meet and develop a particularly strong interdisciplinarity. While biology is a source of inspiration for nanoscientists, chemistry has a central role in turning inspirations and methods from biological systems to nanotechnological use. DNA is the biological molecule by which nanoscience and nanotechnology is mostly fascinated. Nature uses DNA not only as a repository of the genetic information, but also as a controller of the expression of the genes it contains. Thus, there are codes embedded in the DNA sequence that serve to control recognition processes on the atomic scale, such as the base pairing, and others that control processes taking place on the nanoscale. From the chemical point of view, DNA is the supramolecular building block with the highest informational content. Nanoscience has therefore the opportunity of using DNA molecules to increase the level of complexity and efficiency in self-assembling and self-directing processes. 相似文献