全文获取类型
收费全文 | 1351篇 |
免费 | 55篇 |
国内免费 | 3篇 |
专业分类
化学 | 1026篇 |
晶体学 | 7篇 |
力学 | 11篇 |
数学 | 73篇 |
物理学 | 292篇 |
出版年
2023年 | 6篇 |
2021年 | 9篇 |
2020年 | 10篇 |
2019年 | 17篇 |
2018年 | 12篇 |
2017年 | 9篇 |
2016年 | 26篇 |
2015年 | 26篇 |
2014年 | 29篇 |
2013年 | 67篇 |
2012年 | 56篇 |
2011年 | 89篇 |
2010年 | 52篇 |
2009年 | 45篇 |
2008年 | 67篇 |
2007年 | 75篇 |
2006年 | 68篇 |
2005年 | 76篇 |
2004年 | 64篇 |
2003年 | 65篇 |
2002年 | 51篇 |
2001年 | 29篇 |
2000年 | 21篇 |
1999年 | 12篇 |
1998年 | 12篇 |
1997年 | 10篇 |
1996年 | 17篇 |
1995年 | 16篇 |
1994年 | 28篇 |
1993年 | 19篇 |
1992年 | 21篇 |
1991年 | 21篇 |
1990年 | 16篇 |
1989年 | 11篇 |
1988年 | 19篇 |
1987年 | 14篇 |
1986年 | 9篇 |
1985年 | 33篇 |
1984年 | 16篇 |
1983年 | 10篇 |
1982年 | 13篇 |
1981年 | 29篇 |
1980年 | 20篇 |
1979年 | 24篇 |
1978年 | 9篇 |
1977年 | 14篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1973年 | 10篇 |
1972年 | 5篇 |
排序方式: 共有1409条查询结果,搜索用时 15 毫秒
21.
Recyclable carbon fiber‐reinforced plastics (CFRP) containing degradable acetal linkages: Synthesis,properties, and chemical recycling 下载免费PDF全文
Ayaka Yamaguchi Tamotsu Hashimoto Yoshinori Kakichi Michio Urushisaki Toshikazu Sakaguchi Kazumasa Kawabe Keiichi Kondo Hirohumi Iyo 《Journal of polymer science. Part A, Polymer chemistry》2015,53(8):1052-1059
Two epoxy resins containing degradable acetal linkages were synthesized by the reaction of cresol novolak‐type phenolic resin (CN) with vinyl ethers containing a glycidyl group [cyclohexane dimethanol vinyl glycidyl ether (CHDMVG) and 4‐vinyloxybutyl glycidyl ether (VBGE). Carbon fiber‐reinforced plastics (CFRPs) were prepared by heating laminated prepreg sheets with CN‐CHDMVG resin (derived from CN and CHDMVG) and CN‐VBGE resin (derived from CN and VBGE), in which carbon fibers are impregnated with epoxy resins containing curing agents [dicyandiamide (DICY)] and curing accelerator [3‐(3,4‐dichlorophenyl)‐1,1‐dimethylurea (DCMU)]. CN‐CHDMVG‐based CFRPs and CN‐VBGE‐based CFRPs exhibited almost the same tensile strength as the conventional bisphenol‐A‐based CFRPs. CN‐CHDMVG‐based CFRPs and CN‐VBGE‐based CFRPs underwent smooth breakdown with the treatment of hydrochloric acid in tetrahydrofuran at room temperature for 24 h to regenerate strands of carbon fibers. The surface conditions of the recovered carbon fibers had little changes during degradation and recovery processes on the basis of scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The recovered carbon fibers exhibited almost the same tensile strength as virgin carbon fibers and hence would be reused for the production of CFRPs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1052–1059 相似文献
22.
Nobutaka Yamaoka Kohei Sumida Itsuki Itani Hiroko Kubo Yusuke Ohnishi Sho Sekiguchi Dr. Toshifumi Dohi Prof. Dr. Yasuyuki Kita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):15004-15011
Metal‐free oxidative C? C coupling by using polyalkoxybenzene‐derived diaryliodonium(III) salts as both the oxidant and aryl source has been developed. These salts can induce single‐electron‐transfer (SET) oxidation to yield electron‐rich arenes and subsequently transfer the polyalkoxyphenyl group into in situ generated aromatic radical cations to produce biaryl products. The reaction is promoted by a Lewis acid that activates the iodonium salts. It has been revealed that the reactivity of the salts under acidic conditions is quite different to their known behavior under basic conditions. The reactivity preference of a series of iodonium salts in the SET oxidation and their ligand transfer abilities have been systematically investigated and the results are summarized in this report. 相似文献
23.
Koji Yamamoto Kazuki Higuchi Masahiro Ogawa Hiromitsu Sogawa Shigeki Kuwata Yoshihiro Hayashi Susumu Kawauchi Toshikazu Takata 《化学:亚洲杂志》2020,15(3):356-359
We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes. 相似文献
24.
Prof. Nobutaka Fujieda Kyohei Umakoshi Yuta Ochi Dr. Yosuke Nishikawa Prof. Sachiko Yanagisawa Prof. Minoru Kubo Prof. Genji Kurisu Prof. Shinobu Itoh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13487-13492
The dinuclear copper enzyme, tyrosinase, activates O2 to form a (μ-η2:η2-peroxido)dicopper(II) species, which hydroxylates phenols to catechols. However, the exact mechanism of phenolase reaction in the catalytic site of tyrosinase is still under debate. We herein report the near atomic resolution X-ray crystal structures of the active tyrosinases with substrate l -tyrosine. At their catalytic sites, CuA moved toward l -tyrosine (CuA1 → CuA2), whose phenol oxygen directly coordinates to CuA2, involving the movement of CuB (CuB1 → CuB2). The crystal structures and spectroscopic analyses of the dioxygen-bound tyrosinases demonstrated that the peroxide ligand rotated, spontaneously weakening its O−O bond. Thus, the copper migration induced by the substrate-binding is accompanied by rearrangement of the bound peroxide species so as to provide one of the peroxide oxygen atoms with access to the phenol substrate's ϵ carbon atom. 相似文献
25.
A laser interferometric system (LIS) based on oblique incidence and phase shifting technique has been designed for the measurement of gear tooth flank. For a spur involute gear with a module of 2.0, 60 teeth, and a 20-mm facewidth, some critical parameters of the LIS are calculated, the oblique incidence angle is 84.5°, the beam diameter is 20 mm, and the focal length of imaging lens is 100 mm, and the resolution of CCD camera is 1360 × 1024 pixels. To test the capability of the designed LIS, the numerical simulation is done for the LIS. The actual LIS is built on an optical platform and the experiment is carried out. Both interference fringe patterns from the numerical simulation and the actual experiment are good and coincident with each other, which show the designed LIS is feasible. 相似文献
26.
Farouq Ahmed Ryo NagumoRyuji Miura Suzuki AiHideyuki Tsuboi Nozomu HatakeyamaAkira Endou Hiromitsu TakabaMomoji Kubo Akira Miyamoto 《Applied Surface Science》2011,257(24):10503-10513
The notion of “active sites” is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface. 相似文献
27.
Dr. Toru Amaya Riyo Suzuki Prof. Dr. Toshikazu Hirao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):653-656
N,N′‐Diphenyl‐p‐benzoquinonediimine, a redox‐active unit of polyaniline, efficiently induced the oxidative homocoupling of various aryl‐ and vinylmagnesium reagents in suppressing the side reactions, such as 1,2‐ or 1,4‐addition reaction. 相似文献
28.
(Imido)vanadium(V) complexes have attracted much attention because of their potential applications as catalysts. Compared with oxo ligands, imido ligands can possess a substituent on the imido nitrogen so that the steric and electronic characters of the metal center are considered to be controlled by the properties of the nitrogen substituent. In such a sense, the design of the imido ligands is envisioned to be one of the key factors in the development of efficient catalysts. Furthermore, architectural control of transition metal-directed assembly to create organized nanostructures is of importance for advanced materials. This review highlights self-assembling properties of (arylimido)vanadium(V) compounds. 相似文献
29.
Terthiophene-appended gold nanoparticles were prepared by the reduction of AuCl4−(C8H17)4N+ with NaBH4 in the presence of bis[2,5-di(3-hexylthiophen-2-yl)thiophene-3-carboxyloxyhexanyl]disulfide. A hexagonal self-assembly of particles with gold core diameters (1.9±0.1 nm) was detected by high-angle annular dark-field scanning transmission electron microscopy. The electric conductivity of the iodine-doped film was 9.1×10−6 S cm−1, which was ascribable to the terthiophene-based inter-ligand π-π interactions. The Au/terthiophene hybrid spin-coated film consisted of a highly three-dimensional assembled structure of terthiophenes, as inferred from grazing-incidence small-angle X-ray scattering, indicating that such monodispersed and small-sized gold nanoparticles can serve as a template for this organization. In this study, a gold nanoparticle-templated assembly of oligothiophenes has been fabricated for proposing a method to develop tailor-made organizations of π-conjugated oligomers. 相似文献
30.
Shigeru Oae Kazuyuki Iida Toshikazu Takata 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):103-113
Abstract Reduction of sulfimides and sulfoximides with p-toluenesulfonyl nitrite, a new nitrosating agent, gave nearly quantitatively the corresponding deimination products, sulfides and sulfoxides, respectively. In the reaction of dialkyl and aryl alkyl sulfoximides with t-butyl thionitrate, N-t-butylthiosulfoximides were obtained besides the usual deimination products, although diaryl sulfoximides were readily deiminated to the corresponding sulfoxides in good yields in the same treatment. t-Butyl thionitrate was also found to deiminate diphenyl sulfimide to give diphenyl sulfide in good yield. Sulfoximides reacted sluggishly with t-butyl thionitrite, however, eventually affording a small amount of sulfoxides. 相似文献