全文获取类型
收费全文 | 675篇 |
免费 | 52篇 |
国内免费 | 3篇 |
专业分类
化学 | 606篇 |
晶体学 | 14篇 |
力学 | 5篇 |
数学 | 16篇 |
物理学 | 89篇 |
出版年
2023年 | 7篇 |
2022年 | 2篇 |
2021年 | 19篇 |
2020年 | 25篇 |
2019年 | 34篇 |
2018年 | 23篇 |
2017年 | 7篇 |
2016年 | 27篇 |
2015年 | 38篇 |
2014年 | 19篇 |
2013年 | 19篇 |
2012年 | 59篇 |
2011年 | 62篇 |
2010年 | 23篇 |
2009年 | 17篇 |
2008年 | 34篇 |
2007年 | 39篇 |
2006年 | 26篇 |
2005年 | 43篇 |
2004年 | 39篇 |
2003年 | 26篇 |
2002年 | 20篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1997年 | 5篇 |
1995年 | 2篇 |
1993年 | 6篇 |
1992年 | 5篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 15篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 10篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 7篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 6篇 |
1971年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1926年 | 1篇 |
排序方式: 共有730条查询结果,搜索用时 15 毫秒
101.
Kohei Takada Akikazu Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2018,56(22):2584-2594
The reversible addition-fragmentation chain transfer polymerization of diisopropyl fumarate (DiPF) was carried out using ethyl 2-[[(dodecylthio)thioxymethyl]thio]-2-methylpropionate (T1) and 1,1′-(1,2-ethanediyl) bis[2-[[(dodecylthio)thioxymethyl]thio]-2-methylpropionate] (T2) as the monofunctional and difunctional chain transfer agents (CTAs) to synthesize poly(diisopropyl fumarate) (PDiPF) with a rigid chain conformation. The obtained PDiPF had a well-controlled molecular weight, molecular weight distribution, and structure of the chain ends. Size exclusion chromatography and NMR measurements revealed an excellent introduction efficiency (84–98%) of the terminal trithiocarbonate group into the polymer chain end. They were available as the monofunctional and difunctional macro-CTAs to synthesize the AB and ABA block copolymers, respectively. While the well-controlled block copolymers were solely obtained by the polymerization of 2-ethylhexyl acrylate as the second monomer in the presence of PDiPF as the macro-CTA, the block copolymerization of DiPF using poly(2-ethylhexyl acrylate) as the macro-CTA failed. The trithiocarbonate group at the chain end was completely removed by the reaction with n-butylamine and it was valid for the improvement of the coloration and other optical properties of the transparent polymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2584–2594 相似文献
102.
Dongshuang Wu Kohei Kusada Tomokazu Yamamoto Takaaki Toriyama Syo Matsumura Ibrahima Gueye Okkyun Seo Jaemyung Kim Satoshi Hiroi Osami Sakata Shogo Kawaguchi Yoshiki Kubota Hiroshi Kitagawa 《Chemical science》2020,11(47):12731
We report the synthesis of high-entropy-alloy (HEA) nanoparticles (NPs) consisting of five platinum group metals (Ru, Rh, Pd, Ir and Pt) through a facile one-pot polyol process. We investigated the electronic structure of HEA NPs using hard X-ray photoelectron spectroscopy, which is the first direct observation of the electronic structure of HEA NPs. Significantly, the HEA NPs possessed a broad valence band spectrum without any obvious peaks. This implies that the HEA NPs have random atomic configurations leading to a variety of local electronic structures. We examined the hydrogen evolution reaction (HER) and observed a remarkably high HER activity on HEA NPs. At an overpotential of 25 mV, the turnover frequencies of HEA NPs were 9.5 and 7.8 times higher than those of a commercial Pt catalyst in 0.05 M H2SO4 and 1.0 M KOH electrolytes, respectively. Moreover, the HEA NPs showed almost no loss during a cycling test and were much more stable than the commercial Pt catalyst. Our findings on HEA NPs may provide a new paradigm for the design of catalysts.RuRhPdIrPt high-entropy-alloy nanoparticles with a broad and featureless valence band spectrum show high hydrogen evolution reaction activity. 相似文献
103.
Alkylation‐, Heating‐, and Doping‐Induced Emission Enhancement of a Polyaromatic Tube in the Solid State
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)
Kiyonori Kuroda Masafumi Otsuki Dr. Kohei Yazaki Dr. Yoshihisa Sei Prof. Dr. Munetaka Akita Dr. Michito Yoshizawa 《化学:亚洲杂志》2018,13(5):515-519
A polyaromatic tube with a subnanometer‐sized cavity was efficiently prepared on a gram‐scale through the stereo‐controlled cyclotrimerization of a diphenylanthracene derivative as a key step. The facile exterior alkylation of the polyaromatic framework leads to a moderately fluorescent tube (R=‐OC10H21; ΦF=20 %) in the solid state. The emission intensity of the solid‐state alkyl‐substituted tube is remarkably enhanced upon heating (up to 1.6 times, ΦF=31 %) as well as doping with fluorescent dyes (up to 4.2 times, ΦF=83 %) through efficient energy transfer. 相似文献
104.
Takashi Mino Kohei Watanabe Takumu Akiyama Yuki Mizutani Kazuki Miura Masatoshi Hashimoto Yasushi Yoshida Masami Sakamoto 《Tetrahedron》2018,74(28):3871-3878
We previously reported the synthesis of BICMAP (1a) via 6-diphenylphosphino-2,3-dihydrobenzofuran as a key intermediate. However, we did not successfully synthesize BICMAP analogues via a similar synthetic route. Herein we report the second-generation synthesis of BICMAP and its derivatives via diethylphosphonate as a key intermediate. 相似文献
105.
Goto A Endo K Ukai Y Irle S Saito S 《Chemical communications (Cambridge, England)》2008,(19):2212-2214
An aldol-type reaction of organonitriles with aldehydes was catalyzed by a RhI(OR) species under ambient conditions, and the reaction displayed a broad substrate scope with respect to both organonitrile and aldehyde components. 相似文献
106.
107.
Tsue H Matsui K Ishibashi K Takahashi H Tokita S Ono K Tamura R 《The Journal of organic chemistry》2008,73(19):7748-7755
To investigate the solid-state complexation of nitrogen-bridged calixarene analogues, azacalix[7]arene heptamethyl ether 1 has been prepared by applying a "5 + 2"-fragment coupling approach using Buchwald-Hartwig aryl amination reaction aided by our previously devised temporal N-silylation protocol. X-ray crystallographic analysis revealed that azacalix[7]arene 1 adopted a highly distorted 1,2-alternate conformation in the solid state as a result of intramolecular NH/O hydrogen bonding interactions and steric repulsion between the methoxy groups. In the crystal, molecules of 1 are mutually interacted by intermolecular NH/O and CH/pi interactions to establish one-dimensional (1D) hexane-filled nanochannel crystal architecture. Similarly to our recently reported azacalix[6]arene 2, the desolvated crystalline powder material of 1 was capable of selectively and rapidly adsorbing CO2 among the four main components of the atmosphere. The adsorption capacity of 1 for CO2 nearly doubled as compared to that of 2 because of the formation of the 1D nanochannel with almost twice the volume of the latter. 相似文献
108.
Yorita H Otomo K Hiramatsu H Toyama A Miura T Takeuchi H 《Journal of the American Chemical Society》2008,130(46):15266-15267
The cation-pi interaction, a noncovalent interaction of electrostatic nature between a cation and an electron-rich pi system, is increasingly recognized as an important force that influences the structures and functions of molecules including proteins. Unlike other metal cations, the transition metal cation Cu2+ is not regarded to take part in a cation-pi interaction because Cu2+ tends to oxidize the pi electron system, in particular that of Trp, and to introduce covalency in the metal-pi electron interaction. This paper reports the first spectral evidence for the cation-pi interaction between Cu2+ and Trp. The Cu2+ ion bound to the amino N-terminal Cu2+/Ni2+ binding motif composed of three amino acid residues interacts with the indole ring of the fourth Trp residue in a noncovalent manner. The Cu2+-Trp interaction produces a distinct negative band at 223 nm in circular dichroism (CD), which disappears upon mutation or depletion of the Trp residue or upon replacement of the Cu2+ ion by Ni2+. In UV absorption, a pair of negative/positive intensity changes is generated at 222/231 nm by the Cu2+-Trp interaction, being consistent with the previous observations on the indole ring interacting with K+ or a cationic His imidazole ring. The negative CD band around 223 nm is characteristic of the Cu2+-Trp pair and may be useful as a marker of the Cu2+-Trp cation-pi interaction. Coordination of negatively charged ligands to Cu2+ is suggested to be important for the cation to be involved in a cation-pi interaction. 相似文献
109.
Fujimoto T Endo K Tsuji H Nakamura M Nakamura E 《Journal of the American Chemical Society》2008,130(13):4492-4496
Construction of a nonracemic all-carbon quaternary stereocenter at the alpha-position of beta-ketoesters was achieved by way of an indium(III)-catalyzed diastereoselective alpha-alkenylation reaction of chiral enamines with 1-alkynes. The enamine bearing a chiral auxiliary derived from l-isoleucine was added to the alkyne to give an alpha-alkenylated product in excellent yield and with a stereoselectivity better than 90% ee. One can ascribe the high selectivity to a chelate intermediate involving the auxiliary and the metal atom and the high yield to efficient interactions between the indium(III) atom and the alkyne. The selectivity increased as the reaction temperature was raised to 120 degrees C and decreased at higher temperatures. 相似文献
110.
Tooru Kitagawa Yukihiro Abe Kohei Kiriyama 《Journal of Macromolecular Science: Physics》2016,55(8):774-792
The possibility to make a composite poly-p-phenylenebenzobisoxazole (PBO) fiber including a second component without distorting its original structures and mechanical properties was examined. Copper phthalocyanine was found to fulfill the above-mentioned condition and can be dispersed in the fiber molecularly. It was shown that part of the embedded copper phthalocyanine can be aligned one-dimensionally with periodicity along the fiber axis in the fiber. The color of the resultant fiber was dark blue, which is different from the original fiber having its yellowish golden color. According to X-ray diffraction analysis the preferential orientation of the a-axis of the PBO crystal was slightly more oriented by the addition of copper pthalocyanine than that of the pure PBO fiber, but the crystal size of PBO wasn't also affected. We thus show the possibility of adding a second material that can add additional properties to the fiber, but keeping the original high mechanical properties and oriented structures. 相似文献