全文获取类型
收费全文 | 261篇 |
免费 | 6篇 |
国内免费 | 1篇 |
专业分类
化学 | 235篇 |
数学 | 3篇 |
物理学 | 30篇 |
出版年
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 8篇 |
2019年 | 4篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 2篇 |
2015年 | 3篇 |
2014年 | 6篇 |
2013年 | 14篇 |
2012年 | 13篇 |
2011年 | 16篇 |
2010年 | 13篇 |
2009年 | 3篇 |
2008年 | 12篇 |
2007年 | 15篇 |
2006年 | 14篇 |
2005年 | 14篇 |
2004年 | 18篇 |
2003年 | 11篇 |
2002年 | 7篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 8篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1966年 | 1篇 |
1960年 | 1篇 |
1913年 | 2篇 |
排序方式: 共有268条查询结果,搜索用时 46 毫秒
101.
Masao Tomoi Eiji Ogawa Yasunori Hosokama Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1982,20(12):3421-3429
The rate of reaction of 1-halooctanes with aqueous sodium cyanide catalyzed by phosphonium salts attached to insoluble polystyrene resins by tetramethylene or heptamethylene spacers was studied as a function of catalyst particle size, degree of polymer crosslinking, percentage of ring substitution, and temperature. Rates of reaction of 1-bromooctane with 17–38% ring-substituted catalysts increased as spacer-chain length increased. Rates of reaction of 1-bromooctane decreased, whether the percentage of ring substitution increased or decreased from 17–19%. Rates of reaction of 1-chlorooctane increased with increasing spacer-chain length and decreasing percentage of ring substitution. Apparent activation energy for the reaction of 1-bromooctane with 9% ring-substituted, spacer-modified catalysts was 9–10 kcal/mol and 13 kcal/mol with 17–19% ring-substituted catalysts. The hydrophilicity of catalysts decreased with increasing spacer-chain length and decreasing percentage of ring substitution. The mechanisms of reaction were discussed in terms of intrinsic reactivity and intraparticle diffusion limitations on the reaction rates. 相似文献
102.
Kasahara T Nishi N Yamamoto M Kakiuchi T 《Langmuir : the ACS journal of surfaces and colloids》2004,20(3):875-881
The electrochemical instability has been shown to appear in the transfer of cationic surfactant ions across the 1,2-dichloroethane/water interface. Cyclic voltammograms possess all fundamental characteristics that are predicted by the theory of electrochemical instability: the presence of the instability window, that is, the potential range where the interface becomes unstable, the location of the instability window around the standard ion transfer potential of surface-active ions, and the dependence of the width of the instability window on the concentration of the surfactant ions. Electrocapillary measurements clearly demonstrate that the interface becomes unstable, while the interfacial tension is positive, being higher than 20 mN m(-1). The electrocapillary curve exhibits the discontinuities at both ends of the instability window, indicating the similarity between the electrochemical instability and the phase transitions induced by the temperature, pressure, and chemical potential. The results from voltammetry and interfacial tension measurements for cationic surfactants support the idea that the electrochemical instability, so far reported in the transfer of anionic surfactants across the liquid/liquid interface, is one of intrinsic properties of the two-phase systems where the partition of surface-active ions takes place. 相似文献
103.
Wakichi Fukuda Norio Ogata Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1971,9(6):1537-1549
Polymerization of styrene has been carried out in the presence of formaldehyde at 30°C in benzene solution by using boron trifluoride etherate as a catalyst. The rate of polymerization in the initial stage was accelerated with addition of formaldehyde, while the steady-state rate of polymerization was retarded in the presence of formaldehyde. The acceleration for the rate of polymerization was found only in a short time from the beginning. The steady-state rate of polymerization followed the equation: where [C]0 and [F]0 are initial concentrations of catalyst and formaldehyde, [M] is the monomer concentration, and k1, k2, and k3 are constants. It has been assumed that the chain-transfer reaction does not involve formaldehyde itself but rather the reaction products of formaldehyde, such as polystyrene having ethoxy or hydroxymethyl ends. The apparent chain-transfer constant for the added formaldehyde has been determined to be 1.63. 相似文献
104.
Masami Matsuda Kiyomi Funabashi 《Journal of polymer science. Part A, Polymer chemistry》1987,25(2):669-673
The decomposition ratio of cation exchange resin (sulfonated ST-DVB copolymer) after pyrolysis is only 50 wt%, while that of ST-DVB copolymer is 90 wt%. Fundamental experiments were performed to investigate the reason for the low decomposition ratio of the former. The cation resin consists of base polymer (ST-DVB copolymer) and functional sulfonic acid groups. Chemical analyses of the pyrolysis products showed that most of the functional groups decomposed at about 300°C and generated SO2 gas. However, only a small amount of the base polymer was pyrolyzed even at 600°C and the total decomposition ratio was only 50 wt%. The XPS studies on the residue showed that 35% of the functional sulfonic acid groups was converted to sulfonyl and sulfur bridges between the base polymers during pyrolysis. These bridges made the base polymers, namely ST-DVB copolymer, thermally stable. 相似文献
105.
Ie Y Chatani N Ogo T Marshall DR Fukuyama T Kakiuchi F Murai S 《The Journal of organic chemistry》2000,65(5):1475-1488
The ruthenium-catalyzed carbonylation at a C-H bond in the benzene ring of a 2-phenyloxazoline is described. The reaction of 2-phenyloxazolines with CO and ethylene in toluene in the presence of a catalytic amount of Ru(3)(CO)(12) resulted in propionylation at an ortho C-H bond in the benzene ring. The presence of the oxazoline ring on the benzene ring is essential for the carbonylation to proceed. Other heterocycles, such as oxazine, oxazole, and thiazoline rings, also served as acceptable directing groups as did the oxazoline ring. A wide functional group compatibility was observed. The site selectivity of the carbonylation was examined using meta-substituted phenyloxazolines. It was found that the carbonylation took place exclusively at the less-hindered C-H bond, irrespective of the nature of substituents, indicating that the site selectivity was determined by steric factors. The reaction was also applicable, not only to a benzene ring, but also to naphthyl and thiophenyl rings. Olefins such as propene and trimethylvinylsilane in place of ethylene could also be used in the carbonylation reaction, while other olefins, such as 1-hexene, tert-butylethylene, vinylcyclohexane, isoprene, 1,5-hexadiene, cyclohexene, 1, 5-cyclooctadiene, styrene, methyl acrylate, vinyl acetate, allyltrimethylsilane, and triethoxyvinylsilane did not afford the coupling products. An equilibrium between 2-phenyloxazolines, carbon monoxide, and olefins exists on one hand and the corresponding ketones on the other hand, and product composition is governed by the equilibrium thermodynamics of the system. The results of deuterium labeling experiments suggest that the catalysis involves a reversible C-H bond cleavage and that the rate-determining step is not the cleavage of a C-H bond. The results of kinetic study of the effects of CO pressure show that the reaction rate accelerates with decreasing CO pressure. 相似文献
106.
Masao Tomoi Makio Goto Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1987,25(1):77-86
The acetylation of linalool with acetic anhydride was carried out in the presence of polystyrene-bound aminopyridines and triethylamine. The catalytic activity of the immobilized aminopyridines increased with decreasing percentage of ring substitution and with increasing spacer-chain length. The increased activity is attributed to an increase in the amount of aminopyridine units complexed with acetic anhydride. The acetylation could be successfully conducted by use of a mixture of the immobilized aminopyridines and polymer-supported benzyldiethylamine, which effectively trapped acetic acid formed in the reaction system. 相似文献
107.
Toshiyuki Nakagaki Shoji Umemura Yasutaka Kakiuchi Tetsuo Ueda 《Photochemistry and photobiology》1996,64(5):859-862
Abstract— The Plasmodium of the myxomycete Physarum polycephalum sporulates in bright natural environments, suggesting a relationship between photobehavior and sporulation. Thus, the action spectra for two light-dependent phenomena as well as the effects of other environmental conditions have been studied. Sporulation like photo-avoidance responded to UVC (near 270 nm) and near IR (near 750 nm) in addition to the well-documented UVA (near 350 nm) and blue (near 460 nm) regions. Sporulation and photoavoidance had similar sensitivities in the shorter wavelengths, while the former was about 100 times more sensitive in near IR. The Plasmodium moved away from light in a wide spectral range. Starvation and high temperature at 31°C (25°C in standard conditions) reduced photoavoidance to UVA and to blue light, respectively. A high fluence rate of UVC suppressed the rhythmic contraction of the Plasmodium, and the action spectrum peaked at 270 nm. These results indicate that the Physarum Plasmodium may stay at brighter places not by positive phototaxis but by weakening the negative phototaxis to sunlight or by other possible taxes such as hydrotaxis. There may be at least four different photo-systems in the Plasmodium. 相似文献
108.
An experimental investigation of the influence of superconductivity on the decay rate of99m
Tc,
T, has been performed by means of a differential method. The99m
Tc samples containing99Tc as a carrier were prepared by electrodeposition on a copper plated tungsten wire. For production of metallic technetium the samples were reduced in pure hydrogen gas at 800~1000°C. X-ray analysis of the samples showed they were surely metallic with anhcp structure. The lattice constants observed area=2.741 Å andc=4.398 Å. The transition temperature was found to be 7.5±0.2K. Comparison of two sources, normal (room temperature) and superconducting (4.2 K), did not show an appreciable effect of superconductivity on the decay rate of99m
Tc exceeding the limit of uncertainty of our experiment:/
T=(1.1±2.7) × 10–4. 相似文献
109.
RhI‐Catalyzed Intramolecular Carbonylative C−H/C−I Coupling of 2‐Iodobiphenyls Using Furfural as a Carbonyl Source
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)
Takuma Furusawa Prof. Dr. Tsumoru Morimoto Dr. Yasuhiro Nishiyama Dr. Hiroki Tanimoto Prof. Dr. Kiyomi Kakiuchi 《化学:亚洲杂志》2016,11(16):2312-2315
Synthesis of fluoren‐9‐ones by a Rh‐catalyzed intramolecular C?H/C?I carbonylative coupling of 2‐iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate‐determining step is not a C?H bond cleavage but, rather, the oxidative addition of the C?I bond to a RhI center. 相似文献
110.
Arenediazonium ions are dediazoniated through reduction by decamethylferrocene in the 1,2-dichloroethane (DCE) after the electrochemical
transfer of the arenediazonium ions from the aqueous side of the interface between the DCE and the aqueous phase (W). Cyclic
voltammetry of the ion transfer clearly shows that this process is described as an E
r
C
i process, that is, the diffusion-limited transfer of the ions across the interface followed by the irreversible dediazoniation
in the DCE phase. Arene radicals formed in DCE can initiate the radical polymerization of styrene at the interface. The polystyrene
formed in the interfacial region significantly impedes the transfer of tetraethylammonium ions across the DCEIW interface.
Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 1, pp. 80–84.
The text was submitted by the authors in English. 相似文献