全文获取类型
收费全文 | 1012篇 |
免费 | 32篇 |
国内免费 | 6篇 |
专业分类
化学 | 870篇 |
晶体学 | 16篇 |
力学 | 7篇 |
数学 | 21篇 |
物理学 | 136篇 |
出版年
2023年 | 5篇 |
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 16篇 |
2019年 | 13篇 |
2018年 | 8篇 |
2017年 | 5篇 |
2016年 | 18篇 |
2015年 | 17篇 |
2014年 | 24篇 |
2013年 | 37篇 |
2012年 | 79篇 |
2011年 | 98篇 |
2010年 | 43篇 |
2009年 | 31篇 |
2008年 | 65篇 |
2007年 | 73篇 |
2006年 | 51篇 |
2005年 | 71篇 |
2004年 | 60篇 |
2003年 | 43篇 |
2002年 | 36篇 |
2001年 | 11篇 |
2000年 | 15篇 |
1999年 | 13篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 9篇 |
1995年 | 18篇 |
1994年 | 10篇 |
1992年 | 16篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 8篇 |
1978年 | 5篇 |
1974年 | 4篇 |
1971年 | 4篇 |
1969年 | 6篇 |
1968年 | 7篇 |
1967年 | 10篇 |
1966年 | 5篇 |
排序方式: 共有1050条查询结果,搜索用时 15 毫秒
91.
Optical biosensor arrays for rapidly determining the glucose concentrations in a large number of beverage and blood samples were developed by immobilizing glucose oxidase (GOD) on oxygen sensor layer. Glucose oxidase was first encapsulated in silica based gels through sol-gel approach and then immobilized on 96-well microarrays integrated with oxygen sensing film at the bottom. The oxygen sensing film was made of an organically modified silica film (ORMOSIL) doped with tris(4,7-diphenyl-1,10-phenanthroline) ruthenium dichloride (Ru(dpp)3Cl2). The oxidation reaction of glucose by glucose oxidase could be monitored through fluorescence intensity enhancement due to the oxygen consumption in the reaction. The luminescence changing rate evaluated by the dynamic transient method (DTM) was correlated with the glucose concentration with the wide linear range from 0.1 to 5.0 mM (Y = 13.28X − 0.128, R = 0.9968) and low detection limit (0.06 mM). The effects of pH and coexisting ions were systemically studied. The results showed that the optical biosensor arrays worked under a wide range of pH value, and normal interfering species such as Na+, K+, Cl−, PO43−, and ascorbic acid did not cause apparent interference on the measurement. The activity of glucose oxidase was mostly retained even after 2-month storage, indicating their long-term stability. 相似文献
92.
Bishnu Prasad Bastakoti Sudhina Guragain Yuuichi Yokoyama Shin-ichi Yusa Kenichi Nakashima 《Colloid and polymer science》2010,288(9):991-996
Organic–inorganic nanohybrid particles are prepared in aqueous solution from poly(ethylene oxide-b-sodium 2-acrylamido-1-propanesulfonate-b-styrene) (PEO-b-PAMPS-b-PS) triblock copolymer and ferric ions. The hybrid micelles were characterized by dynamic light scattering, scanning electron
microscopy, transmission electron microscopy, and zeta-potential measurements. The hydrodynamic diameter of the hybrid micelles
ranges from 68 to 118 nm depending on the concentration of the polymer and the amount of ferric ions loaded on the polymer.
Zeta-potential measurements revealed that the micelles are assembled mainly by electrostatic interaction between the ferric
ions and the negatively charged PAMPS block in the PEO-b-PAMPS-b-PS. 相似文献
93.
Treatment of 1,6-dialkylhexa-1,5-diene-3,4-diones with bis(iodozincio)methane gave zinc alkoxides of cis-5,6-dialkylcyclohepta-3,7-diene-1,3-diol in good yields at room temperature. The reaction proceeded with high stereospecificity. Bis(iodozincio)methane converted the diketone into the cis-divinylcyclopropane-1,2-diol stereoselectively; this diol transformed into the corresponding cycloheptane derivative stereospecifically via Cope rearrangement. 相似文献
94.
Yuta Marushima Yuri Uchiumi Kenichi Ogu Akiko Hori 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(8):o406-o409
Two C2‐symmetric meso‐alkynylporphyrins, namely 5,15‐bis[(4‐butyl‐2,3,5,6‐tetrafluorophenyl)ethynyl]‐10,20‐dipropylporphyrin, C50H42F8N4, (I), and 5,15‐bis[(4‐butylphenyl)ethynyl]‐10,20‐dipropylporphyrin, C50H50N4, (II), show remarkable π–π stacking that forms columns of porphyrin centers. The tetrafluorophenylene moieties in (I) show intermolecular interactions with each other through the F atoms, forming one‐dimensional ribbons. No significant π–π interactions are observed in the plane of the phenylene and tetrafluorophenylene moieties in either (I) or (II). The molecules of both compounds lie about inversion centers. 相似文献
95.
96.
A facile preparation of 3-acyl-substituted isoxazolines, benzisoxazoles, and isoxazoles from the corresponding 3-carboxylate esters is described. The process, involving reaction of the ester derivative of 3-carboxylic acid substituted heterocycles with Grignard or alkynyl lithium reagents, leads to direct generation of the corresponding 3-acyl heterocycle. The presence of α-imino ester moieties in the heterocyclic substrates for the reactions is thought to be a key feature governing the nature of these transformations. The synthetic utility of the new methodology is demonstrated by its application in a two-step route for the preparation of novel linked bis-heterocycles. 相似文献
97.
98.
Tsuneo Suzuki Kiyoshi Tanemura Chizuko Okada The Late Kenichi Arai Akira Awaji Takahachi Shimizu Takaaki Horaguchi 《Journal of heterocyclic chemistry》2001,38(6):1409-1418
7‐Alkanoyloxy‐3,7‐dimefhyl‐7,8‐dihydro‐6H‐isochromene‐6,8‐diones 12‐15 were synthesized in 69‐16% yields from the reaction of 2,4‐dihydroxy‐3‐methyl‐6‐(2‐oxopropyl)benzaldehyde 11 with p‐toluenesulfonic acid in various carboxylic acids such as acetic acid, propionic acid, butyric acid and heptanoic acid followed by oxidation with lead tetraacetate. On the other hand, (±)‐daldinin A 5 (oleate) was not obtained using oleic acid as a medium. In the cases of heptanoic acid and oleic acid, esters 16 and 17 were produced in 23 and 9% yields, respectively. 6,8‐Dihydroxy‐3,7‐dimethyl‐2‐benzopyrylium p‐toluenesulfonate 31 is considered as the intermediate for the production of 12‐15. Overall yields of isochromenes 12‐15 were 26‐6% starting from 2‐methylresorcinol for seven steps. 相似文献
99.
Tetsuro Shimo Mikio Yasutake Teruo Shinmyozu Kenichi Somekawa 《Analytical sciences》2003,19(3):471-472
A photochemical cycloaddition reaction of methyl 2-pyrone-5-carboxylate with methacrylonitrile mainly gave a [4 + 2] cycloadduct, assigned as methyl endo-8-cyano-exo-8-methyl-3-oxo-2-oxabicyclo[2.2.2]oct-5-ene-6-carboxylate, whose structure was determined by an X-ray diffraction study. The formation of the cycloadduct was reasonably explained by considering a biradical intermediate having a less steric hindrance between the methoxycarbonyl group and the cyano group. 相似文献
100.
Yusai Ito Naoki Sugimoto Takumi Akiyama Takeshi Yamazaki Kenichi Tanamoto 《Tetrahedron letters》2009,50(28):4084-11715
Cepaic acid was isolated as a novel xanthylium yellow pigment from the dried outer scales of the yellow onion Allium cepa Linne. Its structure was elucidated on the basis of ESI-MS and 2D NMR spectroscopy as a 9-carboxy-1,3,6,8-tetrahydroxyxanthylium, which suggests that cepaic acid and other yellow pigments in the dried outer skin of onion were formed by the nucleophilic reaction of phloroglucinol derived from quercetin, a flavonol in onion scales, by autoxidation to glyoxylic acid. To our knowledge, this is the first report of such a pigment in yellow onion. 相似文献