全文获取类型
收费全文 | 536篇 |
免费 | 24篇 |
国内免费 | 6篇 |
专业分类
化学 | 448篇 |
晶体学 | 4篇 |
力学 | 2篇 |
数学 | 18篇 |
物理学 | 94篇 |
出版年
2023年 | 6篇 |
2022年 | 8篇 |
2021年 | 16篇 |
2020年 | 28篇 |
2019年 | 28篇 |
2018年 | 7篇 |
2017年 | 10篇 |
2016年 | 17篇 |
2015年 | 16篇 |
2014年 | 19篇 |
2013年 | 36篇 |
2012年 | 43篇 |
2011年 | 41篇 |
2010年 | 16篇 |
2009年 | 16篇 |
2008年 | 46篇 |
2007年 | 28篇 |
2006年 | 22篇 |
2005年 | 32篇 |
2004年 | 22篇 |
2003年 | 20篇 |
2002年 | 18篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1987年 | 1篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1975年 | 5篇 |
1972年 | 1篇 |
排序方式: 共有566条查询结果,搜索用时 15 毫秒
171.
Prof. Dr. Shū Kobayashi Toshimitsu Endo Takumi Yoshino Dr. Uwe Schneider Dr. Masaharu Ueno 《化学:亚洲杂志》2013,8(9):2033-2045
Zn(OH)2‐catalyzed allylation reactions of aldehydes with allylboronates in aqueous media have been developed. In contrast to conventional allylboration reactions of aldehydes in organic solvents, the α‐addition products were obtained exclusively. A catalytic cycle in which the allylzinc species was generated through a B‐to‐Zn exchange process is proposed and kinetic studies were performed. The key intermediate, an allylzinc species, was detected by HRMS (ESI) analysis and by online continuous MS (ESI) analysis. This analysis revealed that, in aqueous media, the allylzinc species competitively reacted with the aldehydes and water. An investigation of the reactivity and selectivity of the allylzinc species by using several typical allylboronates ( 6a , 6b , 6c , 6d ) clarified several important roles of water in this allylation reaction. The allylation reactions of aldehydes with allylboronic acid 2,2‐dimethyl‐1,3‐propanediol esters proceeded smoothly in the presence of catalytic amounts of Zn(OH)2 and achiral ligand 4d in aqueous media to afford the corresponding syn‐adducts in high yields with high diastereoselectivities. In all cases, the α‐addition products were obtained and a wide substrate scope was tolerated. Furthermore, this reaction was applied to asymmetric catalysis by using chiral ligand 9 . Based on the X‐ray structure of the Zn‐ 9 complex, several nonsymmetrical chiral ligands were also found to be effective. This reaction was further applied to catalytic asymmetric alkylallylation, chloroallylation, and alkoxyallylation processes and the synthetic utility of these reactions has been demonstrated. 相似文献
172.
Mami Fujii Takashi Nishiyama Tominari Choshi Nanase Satsuki Takaya Fujiwaki Takumi Abe Minoru Ishikura Satoshi Hibino 《Tetrahedron》2014
A novel one-pot synthesis of carbazole-1,4-quinone by consecutive Pd-catalyzed cyclocarbonylation, desilylation, and oxidation reactions is described. We propose a possible mechanism of the cyclocarbonylation reaction between 3-iodo-2-propenylindole and CO (1 atm) in the presence of a tributyl(vinyl)tin and Pd-catalyst and the resulting acylpalladium species was directly coupled with a terminal alkene to produce the carbazole-1,4-quinone. To our knowledge, this is the first example of this type of reaction. A new formal total synthesis of a carbazole-1,4-quinone alkaloid, murrayaquinone A was established using this reaction. 相似文献
173.
High pressure X-ray diffraction study of SrMnO3 perovskite 总被引:1,自引:0,他引:1
Using a diamond anvil cell device and synchrotron radiation, the in-situ high-pressure structure of SrMnO3 has been investigated. At pressure up to 28.6 GPa, no pressure-induced phase transition is observed. The lattice parameters as a function of pressure is reported, and the relationship of the axial compression coefficients is βa>βc. The isothermal bulk modulus K298=266(4) GPa is also obtained by fitting the pressure-volume data using the Murnaghan equation of state. 相似文献
174.
M. Matsushita S. NakanoH. Ohfuji I. YamadaT. Kikegawa 《Journal of magnetism and magnetic materials》2011,323(6):838-841
We have investigated the pressure variation of the volume and structure of an FCC Fe64Mn36 anti-ferromagnetic Invar alloy. The inclination of the pressure-volume (P-V) curve of the FCC structure becomes discontinuous at a pressure of 4 GPa. According to the bulk modulus at zero pressure estimated by the Birch-Murnaghan equation of state, the pressure between 4 and 10 GPa is 33 GPa larger than that at a pressure below 4 GPa. Considering previous experiments on magnetism at high pressure the Neel temperature at 4 GPa almost decreases to room temperature. These results suggest that the increase in the bulk modulus by 33 GPa can be attributed to the pressure-induced magnetic phase transition from anti-ferromagnetism to paramagnetism. Volume at zero pressure was estimated using the Birch-Murnaghan equation of state. The volume of FCC structure in the anti-ferromagnetic state was 1.17% larger than the volume in the paramagnetic state, namely, the spontaneous magnetostriction was 1.17%. Pressure-induced structural transition from FCC to HCP occurs with an increase in the pressure, especially at up to 5 GPa. The value of c/a is 1.62; this value almost corresponds to that of an ideal HCP structure. The bulk modulus of the HCP structure estimated by the Birch-Murnaghan equation of state is larger than that of the FCC structure, and the volume/atom ratio is smaller than that of the FCC structure. 相似文献
175.
Yusuke Ishigaki Takumi Hashimoto Kazuma Sugawara Shuichi Suzuki Takanori Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(16):6581-6584
Thermally switchable redox properties have been reported to be due to a change in the spin state of newly designed overcrowded ethylenes, which can adopt closed‐shell folded and open‐shell twisted forms. In this study, tetrathienylanthraquinodimethane derivatives were designed to be in thermal equilibrium between a more stable folded form and less stable but more donating twisted diradical in solution, so that the oxidation potential can be controlled by heating/cooling. This is the first example of a switching of redox properties based on a thermally equilibrated twisted diradical, which can be more readily oxidized to the twisted dication. 相似文献
176.
Dr. Lei Zhang Takumi Oishi Liuzhou Gao Shiyu Hu Linlin Yang Prof. Dr. Wei Li Shengjun Wu Prof. Dr. Rong Shang Prof. Dr. Yohsuke Yamamoto Prof. Dr. Shuhua Li Prof. Dr. Wei Wang Prof. Dr. Guxiang Zeng 《Chemphyschem》2020,21(23):2573-2578
A new efficient metal-based frustrated Lewis pair constructed by (PtBu3)2Pt and B(C6F5)3 was designed through density functional theory calculations for the catalytic dehydrogenation of ammonia borane (AB). The reaction was composed by the successive dehydrogenation of AB and H2 liberation, which occurs through the cooperative functions of the Pt(0) center and the B(C6F5)3 moiety. Two equivalents of H2 were predicted to be liberated from each AB molecule. The generation of the second H2 is the rate-determining step, with a Gibbs energy barrier and reaction energy of 27.4 and 12.8 kcal/mol, respectively. 相似文献
177.
The synthetic utility of alkyl‐onium salt compounds is widely recognized in the field of organic chemistry. Among the wide variety of onium salts, quaternary ammonium, phosphonium, and tertiary sulfonium salts have been the most useful compounds in organic syntheses. These compounds have been very useful reagents in the construction of organic building blocks. In addition, onium salts are known as reliable catalysts, which are used to promote important organic transformations by serving as phase‐transfer and ion‐pair catalysts through the activation of nucleophiles. Although phase‐transfer catalysis is a major direction for onium salt catalysis, hydrogen‐bonding catalysis of alkyl‐onium salts, which is promoted via the activation of electrophiles, has recently become a relevant topic in the field of onium salt chemistry. This Minireview introduces new possibilities and future directions for alkyl‐onium salt chemistry based on its use in hydrogen‐bonding catalysis and on its overall utility. 相似文献
178.
HAYASHI Hirokazu SATO Takumi SHIBATA Hiroki KURATA Masaki IWAI Takashi ARAI Yasuo 《中国科学:化学(英文版)》2014,(11)
Nitride fuels have several advantages including high thermal conductivity and high metal density(like metallic fuels) and high melting point and isotropic crystal structure(like oxide fuels). Since the late 1990 s, the partitioning and transmutation of minor actinides(MA) has been studied to decrease the long-term radio-toxicity of high-level waste and to mitigate the burden of final disposal. Japan Atomic Energy Agency(JAEA) has proposed a dedicated transmutation cycle using an accelerator-driven system(ADS) with nitride fuels containing MA. The nitride fuel cycle we have developed includes a pyrochemical process. Our focus is on the electrolysis of nitride fuels and their refabrication from the recovered actinides; other processes are similar to the technology for metal fuel treatment and have been studied elsewhere. Here, we summarize our activity on the development of the pyrochemical treatment of spent nitride fuels. 相似文献
179.
Dramatic Mechanistic Change in Acid‐Catalyzed Arylation of Azafulleroids Depending on their Ambident N/C Basicity: Formation of Cyclopentene Centered Pentakisadduct
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. Naohiko Ikuma Yuta Doi Koichi Fujioka Tsubasa Mikie Dr. Ken Kokubo Prof. Dr. Takumi Oshima 《化学:亚洲杂志》2014,9(11):3084-3088
Azafulleroid, amino‐bridged [5,6]‐open fullerene, has the ambident N/C basicity of the incorporated enamine moiety. Acid‐catalyzed arylation of N‐substituted azafulleroids proceeded via two types of initial N/C protonation to perform monoarylation or 1,4‐bisarylation for the N‐alkyl substituents and shuttlecock‐type pentakisarylation for the N‐phenyl substituent. The dramatic product change was explained by considering the possible mechanism as well as the DFT computational results. 相似文献
180.
The structure and equation of state of CsCl-type sodium chloride have been determined using high-pressure powder X-ray diffraction from 32 to 134 GPa. The CsCl-type phase remains stable over this entire pressure range. Pressure-volume data can be fitted with a Vinet equation of state with K30 GPa=135.1 GPa, K′30 GPa=3.9, and V30 GPa=27.70 Å3. The nearest-neighbour distance between sodium and chlorine atoms decreased as pressure increased. Significant discrepancies of nearest-neighbour distance between previous theoretical predictions and this study were observed at pressures higher than 70 GPa. 相似文献