全文获取类型
收费全文 | 474篇 |
免费 | 24篇 |
国内免费 | 2篇 |
专业分类
化学 | 389篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 16篇 |
物理学 | 90篇 |
出版年
2024年 | 4篇 |
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 13篇 |
2020年 | 22篇 |
2019年 | 10篇 |
2018年 | 15篇 |
2017年 | 4篇 |
2016年 | 9篇 |
2015年 | 9篇 |
2014年 | 11篇 |
2013年 | 30篇 |
2012年 | 37篇 |
2011年 | 28篇 |
2010年 | 12篇 |
2009年 | 19篇 |
2008年 | 34篇 |
2007年 | 28篇 |
2006年 | 18篇 |
2005年 | 26篇 |
2004年 | 22篇 |
2003年 | 22篇 |
2002年 | 10篇 |
2001年 | 7篇 |
2000年 | 2篇 |
1999年 | 7篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 3篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1967年 | 1篇 |
1966年 | 2篇 |
1965年 | 1篇 |
排序方式: 共有500条查询结果,搜索用时 140 毫秒
21.
Elaine Tsui Anthony J. Metrano Yuto Tsuchiya Robert R. Knowles 《Angewandte Chemie (International ed. in English)》2020,59(29):11845-11849
We report a catalytic, light‐driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible‐light irradiation in the presence of an IrIII‐based photoredox catalyst, a Brønsted base catalyst, and a hydrogen‐atom transfer (HAT) co‐catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O?H bonds through a proton‐coupled electron‐transfer mechanism. This method exhibits a broad substrate scope and high functional‐group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented. 相似文献
22.
A. Uedono T. Kawano S. Tanigawa M. Ban M. Kyoto T. Uozumi 《Journal of Polymer Science.Polymer Physics》1996,34(13):2145-2151
Relaxation processes in polyethylene (PE) and polystyrene (PS) were studied by positron annihilation technique. For PE, above the glass transition temperature, Tg, the size of free volumes and its concentration were increased by the micro-Brownian motion of molecules. For PS, local motions of molecules in backbone chains were found to start above 260 K. However, these local motions were suppressed by an interphenyl correlation. For both PE and PS, below 250–260 K, the formation probability of positronium atoms increased with decreasing temperature. This fact was assigned to the freezing in of the local motions of molecules. For PS, an onset of the local motions of molecules was observed above 100 K. These motions were expected to be associated with liberation of phenyl groups. © 1996 John Wiley & Sons, Inc. 相似文献
23.
Megumi Ban Michihisa Kyoto Akira Uedono Takao Kawano Shoichiro Tanigawa 《Journal of Polymer Science.Polymer Physics》1996,34(7):1189-1195
Free volume characteristics in three samples of monodisperse polystyrene were investigated by positron annihilation technique over a temperature range from 300 to 380 K. The number-average molecular weight of the samples ranged from 5730 to 1,524,000. The observed lifetime spectra were resolved into three components, where the longest lifetime, τ3 was associated with the pick-off annihilation of ortho-positronium (o-Ps) trapped by free volumes. The change of the temperature coefficient of τ3 was observed at around 350 K, at which the value of τ3 was a constant value of 2,3 ns for all specimens with different molecular weights. There was no discrete change of τ3 in intensity, which is corresponding to the number of free volumes. The size of free volume at glass transition was evaluated to be 0.l nm3. © 1996 John Wiley & Sons, Inc. 相似文献
24.
25.
Hiroyuki Kawano Haruhiko Shimoji Shoji Yoshikawa Katsumasa Miyatake Kazumori Hama Shuji Nakamura 《Optical Review》2008,15(2):118-124
Alignment error of an image sensor relative to the optical axis of a star sensor head and alignment errors between four heads
were calculated from pictures taken in an orbital experiment. When comparing the image sensor alignment parameters in the
orbital test and a ground test, both values matched well. By determining the relative relationship of the four heads using
four pictures taken at the same moment in orbit and uploading the parameters to the star sensor system in orbit, the estimated
attitude error was improved from 0.29 to 0.17°, though the accuracy was limited by the ±0.2° determination accuracy of the
satellite itself. We estimated the attitude determination accuracy from separation angles between boresights of the four heads,
calculated from pattern matching between downloaded pictures and a star catalogue. The estimated accuracy, in terms of potential
optical performance, was 0.60 arcmin at 3σ, which is sufficient to satisfy the specification of 1 arcmin. 相似文献
26.
Umakoshi K Yamasaki T Fukuoka A Kawano H Ichikawa M Onishi M 《Inorganic chemistry》2002,41(16):4093-4095
Treatment of pyridine-2-thiol (pytH) with H(2) (60 atm) in the presence of 5-methylpyridine-2-thiolate (5-mpyt)-bridged dinuclear Pt(III), Pt(II), or Pd(II) complexes (1 mol %) in DMF at 150 degrees C for 72 h leads to the formation of pyridine in 3-51% yield. From the (1)H NMR study of the exchange reactions and of the products under D(2) pressure, it is suggested that the catalytic reaction involves bimetallic activation of the pyt ligand followed by the liberation of pyridine and H(2)S. 相似文献
27.
Ohkita M Kawano M Suzuki T Tsuji T 《Chemical communications (Cambridge, England)》2002,(24):3054-3055
The crystallization of 2,4,6-triethynyl-1,3,5-triazine (2) leads to a pi-stacked layered structure of a C(sp)-H...N hydrogen-bonded unique hexagonal network structure, which may be regarded as a supramolecular analogue of a hitherto unknown graphyne network: in-plane intermolecular interactions are short and linear H...N contacts (2.31 and 2.34 A) and the interlayer separation is 3.23 A. 相似文献
28.
29.
A novel coordination gelator exhibits reversible chromatic and sol-gel phase-transition phenomena triggered by thermal and chemical stimuli. 相似文献
30.
Peter D. Mlynek Masaki Kawano Michael A. Kozee Lawrence F. Dahl 《Journal of Cluster Science》2001,12(1):313-338
Reactions of [Ni6(CO)12]2- (1) with CuBr2 have given rise in small yields (10%) to the first example of a close-packed copper-nickel carbonyl cluster; its formulation as [CuxNi35-x(CO)40]5- (with x=3 or 5) is based upon a low-temperature CCD X-ray crystallographic determination coupled with an elemental analysis and X-ray fluorescence measurements. This air-unstable black pentaanion (2) together with one co-crystallized bromide anion, six [NMe4]+ counterions, and one solvated acetone molecule comprise the crystallographic independent part in a monoclinic unit cell of P21/n symmetry (with Z=4). The geometrically unprecedented 35-atom hcp M(A)2M(B)3Ni30 polyhedron of pseudo-D3h symmetry consists of a central 15-atom equilateral 4M(B)3Ni12 triangle that is capped on both sides by two symmetry-related 10-atom equilateral 3M(A)Ni9 triangles. The 35-atom M(A)2M(B)3Ni30 core is encapsulated by 40 COs, whose connectivities, due to an extra CO ligand on one of the three triangular sides, reduce the pseudo D3h symmetry of the metal core to Cs. An elemental analysis via AA and X-ray fluorescence measurements resulted in Cu/Ni ratios of 3.2/31.8 and 3.7/31.3, respectively, that are consistent with the metal core being either Cu5Ni30 (i.e., M(A)=M(B)=Cu) or Cu3Ni32 (i.e., M(A)=Ni; M(B)=Cu). Several attempts to determine the actual stoichiometry of the metal core by use of electrospray FT/MS/ICR measurements were unsuccessful. The maximum metal-core diameter of 2 is ca. 0.41 nm parallel and 0.85 nm perpendicular to the principal 3-fold axis. 相似文献