全文获取类型
收费全文 | 404篇 |
免费 | 13篇 |
国内免费 | 1篇 |
专业分类
化学 | 288篇 |
晶体学 | 5篇 |
力学 | 5篇 |
数学 | 6篇 |
物理学 | 114篇 |
出版年
2022年 | 4篇 |
2020年 | 3篇 |
2019年 | 9篇 |
2018年 | 5篇 |
2016年 | 3篇 |
2015年 | 10篇 |
2014年 | 14篇 |
2013年 | 20篇 |
2012年 | 10篇 |
2011年 | 22篇 |
2010年 | 15篇 |
2009年 | 13篇 |
2008年 | 25篇 |
2007年 | 9篇 |
2006年 | 25篇 |
2005年 | 15篇 |
2004年 | 25篇 |
2003年 | 27篇 |
2002年 | 16篇 |
2001年 | 17篇 |
2000年 | 11篇 |
1999年 | 9篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 6篇 |
1990年 | 6篇 |
1989年 | 12篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 6篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1960年 | 1篇 |
1929年 | 2篇 |
排序方式: 共有418条查询结果,搜索用时 15 毫秒
61.
Redox‐Driven Symmetry Change for Terbium(III) Bis(porphyrinato) Double‐Decker Complexes by the Azimuthal Rotation of the Porphyrin Macrocycles
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Ken‐ichi Yamashita Takayo Yamanaka Naoya Sakata Prof. Dr. Takuji Ogawa 《化学:亚洲杂志》2018,13(13):1692-1698
Molecular structures for three oxidation forms (anion, radical, and cation) of terbium(III) bis(porphyrinato) double‐decker complexes have been systematically studied. We found that the redox state controls the azimuthal rotation angle (φ) between the two porphyrin macrocycles. For [TbIII(tpp)2]n (tpp: tetraphenylporphyrinato, n=?1, 0, and +1), φ decreases at each stage of the oxidation process. The decrease in φ is due to the higher steric repulsion between the phenyl rings on the porphyrin macrocycle and the β hydrogen atoms on the other porphyrin macrocycle, which results from the shorter interfacial distance between the two porphyrin macrocycles. Conversely, φ=45° for both [TbIII(oep)2]?1 and [TbIII(oep)2]0 (oep: octaethylporphyrinato), but φ=36° for [TbIII(oep)2]+1. Theoretical calculations suggest that the smaller azimuthal rotation angle of the cation form is due to the electronic interaction in the doubly oxidized ligand system. 相似文献
62.
63.
T. Tatsukawa T. Shirai T. Imaizumi T. Idehara I. Ogawa T. Kanemaki 《International Journal of Infrared and Millimeter Waves》1998,19(6):859-874
The ESR of Cr3+ in dark ruby is measured using a high frequency ESR spectrometer with a wide frequency range which uses a gyrotron as the radiation source. For this purpose, GYROTRON FU- IV A developed at Fukui University was optimized for use in an ESR apparatus operating in the millimeter-wave range.The observed fine structure constant D for ruby is found to be D –5.728 GHz and the g-values g 1.981, g 1.982. Both the values of |D| and g are smaller than those obtained at lower frequencies by other work. Higher order terms of the spin hamiltonian are discussed in order to understand the ruby ESR results in this higher frequency range. 相似文献
64.
Soga S Shirai H Kobori M Hirayama N 《Journal of chemical information and modeling》2008,48(8):1679-1685
The idea that there should be a specific site on a protein for a particular functional small molecule is widespread. It is, however, usually not so easy to understand what characteristics of the site determine the binding ability of the functional small molecule. We have focused on the concurrence rate of the 20 standard amino acids at such binding sites. In order to correlate the concurrence rate and the specific binding site, we have analyzed high-quality X-ray structures of complexes between proteins and small molecules. A novel index characterizing the binding site based on the concurrency rate has been introduced. Using this index we have identified that there is a specific concavity designated as a chemocavity where a specific group of small molecules, i.e., canonical molecular group, is highly inclined to be bound. This study has demonstrated that a chemocavity is reserved for a specific canonical molecular group, and the prevalent idea has been confirmed. 相似文献
65.
Terumichi Enomoto Mifuyu Ueno Yumi Shimada Ryuichi Shirai Kiyomi Kakiuchi 《Tetrahedron》2008,64(18):4051-4059
We report here on the construction of the ABC-ring framework of (±)-Taxol using an intramolecular aldol reaction as a key step. AB-ring compound 8 was converted to ketoaldehyde 25 as a precursor of an aldol reaction via introduction of oxygen-functionalities and a methoxycarbonyl group, which can be converted to a methyl group, in the proper positions of the B-ring. An aldol reaction of ketoaldehyde with LDA led to the formation of the desired product 27, which corresponds to the ABC-ring framework of (±)-Taxol. 相似文献
66.
Hidayah Ariffin Haruo Nishida Yoshihito Shirai Mohd Ali Hassan 《Polymer Degradation and Stability》2008,93(8):1433-1439
The thermal degradation of poly(3-hydroxybutyrate) (PHB) was investigated by kinetic analyses in detail to clarify its complex degradation behavior, resulting in a finding of mixed mechanisms comprising at least a thermal random degradation with subsequent auto-accelerated transesterification, and a kinetically favored chain reaction from crotonate chain ends. The thermal degradation behavior of PHB varied with changes in time and/or temperature. From the kinetic analysis of changes in molecular weight, it was found that a non-auto-catalytic random degradation proceeding in the initial period was followed by an auto-accelerated reaction in the middle period. From the kinetic analysis of weight loss behavior, it is proposed that there are some kinetically favored scissions occurring at the chain ends, where the degradation proceeded by a 0th-order weight loss process in the middle stage. The observed 0th-order weight loss process was assumed to be an unzipping reaction occurring at ester groups neighboring the crotonate end groups. 相似文献
67.
Masahiko Matsukata Ken-ichi Sawamura Tsutomu Shirai Mitsuko Takada Yasushi Sekine Eiichi Kikuchi 《Journal of membrane science》2008,316(1-2):18-27
Controlling the growth of zeolite crystals on a porous alumina support is essential for preparing a compact zeolite membarne. First, mordenite seed crystals applied on a nonporous -alumina disk were grown and morphological change of mordenite crystals were observed in the course of growth. Then, mordenite membranes were synthesized on a porous -alumina tube under the same conditions employed in the study using the alumina disks. We found that seed crystal growth was widely controllable by changing water content in reaction solution, which resulted in better control of the morphology of mordenite crystals for synthesizing a thin compact mordenite membrane. Separation properties for mordenite membranes were studied in water–hydrogen binary system at 473 K with 10 kPa of water partial pressure, where no capillary condensation was expected in non-zeolitic pores. Separation factor for a mordenite membrane with a few defects was poor; however, a defect-free mordenite membrane prepared under a suitable condition highly separated steam from hydrogen. 相似文献
68.
T. Shimada K. Hiruma M. Shirai M. Yazawa K. Haraguchi T. Sato M. Matsui T. Katsuyama 《Superlattices and Microstructures》1998,24(6):453-458
The self-organized, position-controlled and parallel growth of GaAs and InAs nanowhiskers is successfully demonstrated by using a metal–organic chemical vapour deposition method. The growth takes place preferentially along the 111 As direction with the aid of the catalytic effect of Au nanodroplets, and not along 111 Ga or In directions. The diameter and length of the whisker can be controlled artificially down to 10 nm and to over 1 μm, respectively. Doping and composition control of p- or n-type such as GaAs–InAs heterostructure formation are possible along the length direction of the whisker by changing the source gases. In order to control the growth position of the whisker, positioning of a Au nanodroplet is essential and realized by a lithographic method. By choosing the [111]B direction to the substrate surface and normal to the patterned side edges, and by positioning the Au nanodroplet on the side wall, the positioned planar nanowhisker growth and bridging are successfully demonstrated. The growth mechanism of the nanowhiskers is revealed by the scanning and transmission electron microscope observations. Nanometer-size Au-alloy droplets play an important role in the growth of the whiskers. The whisker growth process is governed by the vapor–liquid–solid growth mechanism. 相似文献
69.
S. Mitsudo Aripin T. Shirai T. Matsuda T. Kanemaki T. Idehara 《International Journal of Infrared and Millimeter Waves》2000,21(4):661-676
ESR device using a submillimeter wave gyrotron as a radiation source and a pulse magnet for high field up to 30 T has been constructed. Our gyrotrons (Gyrotron FU series) were developed as millimeter and submillimeter wave radiation sources and have attractive advantages for ESR spectroscopy, for example, high power and frequency tunability over broad range. The ESR device has been successfully applied to three cases of ESR measurements. In the first case, the temperature dependence of ESR was measured for a typical antiferromagnetic material MnO at the frequency of 301 GHz. In the second case, the dependence of the fine structure constant of the ruby on the magnetic field intensity was measured in the millimeter to submillimeter wave region. In these two cases, the gyrotron was operated by complete cw mode. In the final case, a pulse technique was applied to the ESR, the gyrotron was operated in pulse mode and the pulsed magnetic field was generated in the synchronized phase with the gyrotron operation. 相似文献
70.
Kanji Suyama Shizue Yamaguchi Masamitsu Shirai Masahiro Tsunooka 《Journal of polymer science. Part A, Polymer chemistry》2000,38(17):3043-3051
Copolymers bearing photoacid generating groups and/or photobase generating groups were dyed after UV irradiation with a dye bath containing both an acid dye and a basic dye. Acetophenone O‐acryloyloxime (AAPO) was used as a monomer bearing acyloxyimino (AOI) group that generates a primary amino group upon irradiation, which is followed by hydrolysis. Phenacylsulfonylstyrene (PSSt) and 1,2,3,4‐tetrahydronaphthylideneamino p‐styrenesulfonate (NISS) were chosen as monomers having β‐keto sulfone (β‐KS) and iminosulfonate (IS) groups, respectively, which yielded acid groups when irradiated. Copolymers of AAPO and methyl methacrylate (MMA) were dyed with only the acid dye, and those of PSSt or NISS were dyed with only the basic dye after irradiation. AAPO‐PSSt‐MMA films became dyeable with the acid dye when irradiated for a short time and with the basic dye with further irradiation. However, AAPO‐NISS‐MMA copolymers showed the reverse dyeing behavior. IR spectra revealed that AOI groups were photochemically decomposed prior to the β‐KS groups for AAPO‐PSSt‐MMA, and AOI and IS groups decomposed simultaneously for AAPO‐NISS‐MMA. These results suggested the possibility of adsorption of different ionic dyes on the films by a change of irradiation time; in fact, color patterns could be obtained in a single staining process using the dye bath. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3043–3051, 2000 相似文献