全文获取类型
收费全文 | 531篇 |
免费 | 10篇 |
国内免费 | 2篇 |
专业分类
化学 | 377篇 |
晶体学 | 3篇 |
力学 | 13篇 |
数学 | 83篇 |
物理学 | 67篇 |
出版年
2022年 | 3篇 |
2020年 | 9篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2017年 | 8篇 |
2016年 | 6篇 |
2015年 | 10篇 |
2014年 | 12篇 |
2013年 | 21篇 |
2012年 | 29篇 |
2011年 | 33篇 |
2010年 | 15篇 |
2009年 | 14篇 |
2008年 | 29篇 |
2007年 | 33篇 |
2006年 | 38篇 |
2005年 | 29篇 |
2004年 | 33篇 |
2003年 | 15篇 |
2002年 | 26篇 |
2001年 | 4篇 |
1999年 | 5篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1992年 | 10篇 |
1991年 | 8篇 |
1990年 | 2篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 2篇 |
1982年 | 12篇 |
1981年 | 9篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 7篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1972年 | 2篇 |
1968年 | 2篇 |
1964年 | 2篇 |
排序方式: 共有543条查询结果,搜索用时 15 毫秒
1.
Oscillation is found in many biological systems, and among them the enzymatic oscillatory reaction has been well studied using an enzyme solution. We show in this study for the first time that oscillation occurs when catalase is immobilized to controlled pore glass (CPG). The oscillatory wave mode changes with the distance among the CPG, electrode, or dialysis membrane. The lower substrate concentration results in oscillation with a longer period. This tendency agrees with a previous study using an enzyme solution. Furthermore, we show that the oscillation occurs when no dialysis membrane is used. These results show the wider applicability of the system to analysis or novel device fabrication. 相似文献
2.
Yasuhiro Ikezoe Sadahiro Ishizaki Hiroharu Yui Masanori Fujinami Tsuguo Sawada 《Analytical sciences》2004,20(3):435-440
The oscillation of the interfacial tension and electrical potential at a water/nitrobenzene interface was observed with homologous anionic surfactant molecules, sodium-alkyl-sulfates. Concerning small molecules with a short hydrophobic carbon chain, the oscillation period and amplitude decreased with a decrease of the length of the alkyl chain. On the other hand, when surfactant molecules with a long hydrophobic carbon chain were used, no remarkable periodic oscillation occurred after the first oscillation. In all systems, an interfacial flow by Marangoni convection was observed when the oscillation took place. By monitoring the movement of carbon powder scattered on the liquid/liquid interface with a CCD camera, we could observe that the liquid/liquid interface expanded outward from the area on which the surfactant molecules adsorbed when the oscillation occurred. When the small molecule was used, the speed of expansion of the interface (flow speed) was small and shrinkage followed by expansion of the interface repeatedly occurred. However, when the large molecule was used, the flow speed was large and expansion occurred only one time. These results show that hydrodynamic factors and surface activities are important in chemical oscillation systems. 相似文献
3.
Yoshikazu Takada 《Annals of the Institute of Statistical Mathematics》1998,50(2):325-335
This paper gives a condition which implies the nonexistence of parametric statistical procedures with bounded risk or error performance characteristics. Many examples for which such a condition is satisfied are considered. 相似文献
4.
The engineering of many modern electronic devices demands control over a crystal down to the thickness of a single layer of atoms—and future demands will be even more challenging. Such control is achieved by the method of crystal growth known as epitaxy, and that makes this method the subject of intense study. More than that, recent advances are revolutionizing our knowledge of how surfaces grow. In fact, growing surfaces show a beautifully rich variety of phenomena, many of which are only now beginning to be uncovered. In the past few years many surface imaging techniques have been used to give us a close look at how crystals grow—while they are growing. The purpose of this article will be to illustrate some of the ways real surfaces grow and change as revealed by some of the latest in situ microscopic imaging technologies.
It is often said that crystal growth is more of an art than a science. Here we will show that it is emphatically both. 相似文献
5.
Masahiro Nakao Chikako Yamazaki Hiroshi Tominaga Takako Yamaguchi Yoshikazu Fujita 《Analytical sciences》2006,22(2):313-316
A simple and highly sensitive spectrophotometric method for the determination of anthracycline anticancer agents, such as Daunorubicin hydrochloride (DAU), was established by using aluminum(III) and Chromazurol S (CAS) in a nonionic surfactant micellar medium. In the case of determination of DAU, the apparent molar absorptivity was 1.3 x 10(5) dm3 mol(-1) cm(-1) at 615 nm. Beer's law was obeyed in the concentration range of 0.028 - 2.82 microg ml(-1) for DAU. Owing to no need for solvent extraction, this method could be applied to assays of DAU and related drugs in pharmaceutical preparations. 相似文献
6.
7.
(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5. 相似文献
8.
Otaka A Yukimasa A Watanabe J Sasaki Y Oishi S Tamamura H Fujii N 《Chemical communications (Cambridge, England)》2003,(15):1834-1835
Gamma-acetoxy-alpha,beta-enoates were easily reduced by samarium diiodide (SmI2) in THF to generate samarium dienolates which were kinetically trapped with ease at their alpha-positions by electrophiles (proton, aldehydes or ketones) to yield (E)-alkene dipeptide isosteres or gamma-amino acid derivatives in high chemical yields. 相似文献
9.
Otaka A Watanabe J Yukimasa A Sasaki Y Watanabe H Kinoshita T Oishi S Tamamura H Fujii N 《The Journal of organic chemistry》2004,69(5):1634-1645
A samarium diiodide (SmI(2))-mediated reduction of gamma,gamma-difluoro-alpha,beta-enoates (15, 29, and 34) was successfully applied to the synthesis of (Z)-fluoroalkene dipeptide isosteres (23, 30, and 35), which have served as potential dipeptide mimetics. Reduction of the gamma,gamma-difluoro-alpha,beta-enoates by SmI(2) proceeded via successive two-electron transfers to form dienolate species which upon kinetically controlled trapping with t-BuOH yielded Xaa-Gly-type fluoroalkene isosteres exemplified by 23, 30, and 35. Replacement of the t-BuOH kinetic trapping agent with aldehydes or ketones provided access to alpha-substituted fluoroalkene isosteres (43 and 45) through aldol reactions of Sm-dienolates with the carbonyl compounds. Of particular note, the use of the SmI(2)-HCHO reagent system with chiral enoate 34 provided D-Phe-psi[(Z)-CF[double bond]CH]-D/L-Ser isosteres (45), which could be converted to enantiomerically pure isosteres (49-52) that bore a variety of side chain functionalities at the alpha-position. This was achieved by a sequence of manipulations consisting of beta-lactone formation followed by chromatographic separation and ring-opening with soft nucleophiles. Included in the present work is the first utilization of a Rh-catalyzed Reformatsky reaction of chiral imines for the stereoselective preparation of alpha,alpha-difluoro-beta-amino acid derivatives (28 and 33). The appropriate choice of reagents (carbonyl compounds for kinetic trapping or ring-opening nucleophiles and imines for Reformatsky reactions) allows the presented methodology to yield various fluoroalkene isosteres possessing a wide range of side chain functionalities. 相似文献
10.
Kazuhiro Watanabe Noboru Akino Tetsuo Aoyagi Noboru Ebisawa Yukio Fujiwara Atsusi Honda Takashi Inoue Takao Itoh Mikito Kawai Minoru Kazawa Junichi Koizumi Masaaki Kuriyama Kenji Miyamoto Naoki Miyamoto Kazuhiko Mogaki Yoshihiro Ohara Tokumichi Ohga Yoshikazu Okumura Hiroshi Oohara Katsumi Ohshima Fujio Satoh Kazuhiko Shimizu Syunji Takahashi Hirotsugu Usami Katsutomi Usui Masahiro Yamamoto Takeshi Yamazaki 《Radiation Physics and Chemistry》1997,49(6):631-639
A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D− ion beam. In the preliminary experiment using one ion source, a D− ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D− beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/ID− < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H− ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator. 相似文献