全文获取类型
收费全文 | 2536篇 |
免费 | 50篇 |
国内免费 | 6篇 |
专业分类
化学 | 1983篇 |
晶体学 | 27篇 |
力学 | 30篇 |
数学 | 78篇 |
物理学 | 474篇 |
出版年
2020年 | 17篇 |
2019年 | 18篇 |
2018年 | 15篇 |
2017年 | 21篇 |
2016年 | 33篇 |
2015年 | 39篇 |
2014年 | 48篇 |
2013年 | 121篇 |
2012年 | 98篇 |
2011年 | 109篇 |
2010年 | 76篇 |
2009年 | 67篇 |
2008年 | 121篇 |
2007年 | 154篇 |
2006年 | 149篇 |
2005年 | 165篇 |
2004年 | 133篇 |
2003年 | 126篇 |
2002年 | 101篇 |
2001年 | 57篇 |
2000年 | 58篇 |
1999年 | 41篇 |
1998年 | 22篇 |
1997年 | 37篇 |
1996年 | 37篇 |
1995年 | 23篇 |
1994年 | 34篇 |
1993年 | 20篇 |
1992年 | 34篇 |
1991年 | 28篇 |
1990年 | 30篇 |
1989年 | 20篇 |
1988年 | 35篇 |
1987年 | 26篇 |
1986年 | 25篇 |
1985年 | 39篇 |
1984年 | 50篇 |
1983年 | 22篇 |
1982年 | 42篇 |
1981年 | 38篇 |
1980年 | 46篇 |
1979年 | 29篇 |
1978年 | 23篇 |
1977年 | 23篇 |
1976年 | 20篇 |
1975年 | 18篇 |
1974年 | 17篇 |
1973年 | 13篇 |
1968年 | 13篇 |
1967年 | 12篇 |
排序方式: 共有2592条查询结果,搜索用时 93 毫秒
21.
Atsunori Matsuda Tatsuo Matoda Yoshinori Kotani Toshihiro Kogure Masahiro Tatsumisago Tsutomu Minami 《Journal of Sol-Gel Science and Technology》2003,26(1-3):517-521
Anatase nanocrystals were precipitated mainly at the surface of the silica-titania gel films with hot water treatment, whereas the addition of poly(ethylene glycol) (PEG) in the films led to the dispersion of anatase nanocrystals in the whole of the films after the treatment. Both films with and without PEG showed high photocatalytic activities for acetaldehyde, NO
x
and stearic acid in the gas-solid system, and for methylene blue and potassium iodide in the liquid-solid system. The addition of PEG improved the photocatalytic activities of the resultant films due to the smaller anatase crystallites and the porous film structure. The residual silica under-layer of the superficially anatase-precipitated films is expected to act as a protective one for an organic polymer substrate against the photocatalytic degradation. 相似文献
22.
A chiral HWE reagent reacted with an alternative carbonyl group of meso-α-diketones of bicyclo[2.2.1] system to give non-racemic (Z)- and (E)-olefins, respectively. 相似文献
23.
24.
To approach more realistic mechanisms for asymmetric aziridine synthesis from guanidinium ylides and aryl aldehydes, reactions were systematically carried out by using a variety of p-substituted benzaldehydes under modified conditions. Two kinds of reaction mechanisms controlled by the nature of the p-substituents of aryl aldehydes is proposed for the two-steps aziridine synthesis composed of a C-C bond formation by nucleophilic addition of guanidinium ylides to aryl aldehydes (step 1) and the fragmentation of intermediate adducts to aziridine products by intramolecular nucleophilic substitution (step 2). A SNi-like mechanism via cationic-like transition state is proposed for step 2 in the asymmetric synthesis using EDG-substituted benzaldehydes, whereas with EWG-substituted benzaldehydes, a SN2-like mechanism is proposed. Hammett analysis, based on the diastereomeric ratio in the aziridine products, is consistent with the proposed rate-determining steps in these two mechanisms. A second Hammett analysis, based on the enantiomeric ratio of the aziridine products, clearly reveals the difference in the susceptibilities to the electronic substituents effect between step 1 and step 2. 相似文献
25.
Fumoto M Hinou H Ohta T Ito T Yamada K Takimoto A Kondo H Shimizu H Inazu T Nakahara Y Nishimura S 《Journal of the American Chemical Society》2005,127(33):11804-11818
The chemoselective polymer blotting method allows for rapid and efficient synthesis of glycopeptides based on a "catch and release" strategy between solid-phase and water-soluble polymer supports. We have developed a heterobifunctional linker sensitive to glutamic acid specific protease (BLase). The general procedure consists of five steps, namely (i) the solid-phase synthesis of glycopeptide containing BLase sensitive linker, (ii) subsequent deprotections and the release of the glycopeptide from the resin, (iii) chemoselective blotting of the glycopeptide intermediates in the presence of water-soluble polymers with oxylamino functional groups, (iv) sugar elongations using glycosyltransferases, and (v) the release of target glycopeptides from the polymer platform by selective BLase promoted hydrolysis. The combined use of the solid-phase chemical syntheses of peptides and the enzymatic syntheses of carbohydrates on water-soluble polymers would greatly contribute to the production of complicated glycopeptide libraries, thereby enhancing applicative research. We report here a high-throughput synthetic system for the various types of MUC1 glycopeptides exhibiting a variety of sugar moieties. It is our belief that this concept will become part of the entrenched repertoire for the synthesis of biologically important glycopeptides on the basis of glycosyltransferase reactions in automated and combinatorial syntheses. 相似文献
26.
Atsunori Matsuda Tatsuo Matoda Toshihiro Kogure Kiyoharu Tadanaga Tsutomu Minami Masahiro Tatsumisago 《Journal of Sol-Gel Science and Technology》2004,31(1-3):229-233
Titania nanosheet-precipitated coatings have been prepared by treating SiO2-TiO2 gel films on glass substrates with hot water at 90°C under vibration. Longitudinal vibrations at about 6 Hz during the treatment enhanced the formation of titania nanosheet. The titania nanosheet consisted of several layers with a spacing of about 0.6 nm and was identified as hydrated titania with a lepidocrocite-type structure. The morphology of the titania nanosheet-precipitated coatings is probably achieved by lowering of the concentration of hydrolyzed titania species at the surface due to rapid water flow driven by the vibrations. The coatings were transparent in the visible range and showed high photocatalytic activity and antifogging property. 相似文献
27.
Electrothermal atomization of arsenic with a metal micro-tube atomizer has been studied. Thiourea and thionalide were found to give effective atomization of arsenic. A method involving extraction of the thionalide complex for determining traces of arsenic in water and soil is described. 相似文献
28.
Five paeonol glycosides, suffruticosides A, B, C, D, and E, and a monoterpene glucoside, galloyl-oxypaeoniflorin, were isolated from the glycosidic fraction of Chinese Moutan Cortex, the root cortex of Paeonia suffruticosa Andrews, together with paeonolide, apiopaeonoside, galloyl-paeoniflorin, oxypaeoniflorin, and paeoniflorin. The structures of five suffruticosides and galloyl-oxypaeoniflorin were elucidated on the basis of chemical and physicochemical evidence. Suffruticosides A, B, C, and D, galloyl-oxypaeoniflorin, and galloyl-paeoniflorin exhibited more potent radical scavenging effects than alpha-tocopherol. 相似文献
29.
A liquid chromatograph directly coupled with a quadrupole mass spectrometer through a vacuum nebulizing interface was applied to the analysis of various free fatty acids. Chemical ionization mass spectra of the C7? C22 free fatty acids were first examined using either methanol or benzene as the reagents. Then the practical compositional analysis of the fatty acids were performed with various biological samples such as bean oil, rape oil, palm oil and milk fat where most of the fatty acids are included as their triglycerides. 相似文献
30.
Tsutomu Kagiya Shizuo Narisawa Taizo Ichida Kenichi Fukui Hisao Yokota Masatsune Kondo 《Journal of polymer science. Part A, Polymer chemistry》1966,4(2):293-299
The copolymerization of carbon monoxide and aziridines such as ethylenimine and propylenimine was carried out by γ-ray irradiation. Aziridines and carbon monoxide were allowed to copolymerize under γ-ray irradiation from a Co60 source and gave a crystalline solid copolymer. The yield of the copolymer increased with reaction temperature. The composition of copolymers obtained did not depend on the feed ratio of monomers and was found to be almost equimolar. The copolymer of ethylenimine and carbon monoxide melted at about 322–335°C. with decomposition and has an infrared spectrum identical with that of poly-β-alanine obtained by the hydrogen-migration polymerization of acrylamide. The hydrolyzed product of the ethylenimine–carbon monoxide copolymer was confirmed to be β-alanine by paper chromatography. These results lead to the conclusion that the copolymerization of aziridines and carbon monoxide took place alternatively by γ-ray irradiation, and produced crystalline poly-β-alanines. 相似文献