全文获取类型
收费全文 | 1485篇 |
免费 | 29篇 |
国内免费 | 4篇 |
专业分类
化学 | 1249篇 |
晶体学 | 16篇 |
力学 | 19篇 |
数学 | 22篇 |
物理学 | 212篇 |
出版年
2020年 | 9篇 |
2019年 | 11篇 |
2018年 | 12篇 |
2017年 | 10篇 |
2016年 | 19篇 |
2015年 | 26篇 |
2014年 | 27篇 |
2013年 | 80篇 |
2012年 | 62篇 |
2011年 | 75篇 |
2010年 | 56篇 |
2009年 | 33篇 |
2008年 | 68篇 |
2007年 | 79篇 |
2006年 | 94篇 |
2005年 | 105篇 |
2004年 | 83篇 |
2003年 | 79篇 |
2002年 | 71篇 |
2001年 | 18篇 |
2000年 | 25篇 |
1999年 | 21篇 |
1998年 | 12篇 |
1997年 | 21篇 |
1996年 | 26篇 |
1995年 | 9篇 |
1994年 | 14篇 |
1993年 | 8篇 |
1992年 | 14篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1988年 | 16篇 |
1987年 | 10篇 |
1986年 | 13篇 |
1985年 | 12篇 |
1984年 | 27篇 |
1983年 | 12篇 |
1982年 | 24篇 |
1981年 | 29篇 |
1980年 | 35篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 8篇 |
1976年 | 17篇 |
1975年 | 10篇 |
1974年 | 11篇 |
1973年 | 14篇 |
1969年 | 9篇 |
1968年 | 13篇 |
1967年 | 11篇 |
排序方式: 共有1518条查询结果,搜索用时 0 毫秒
51.
Bunsho Ohtani Makoto Nishida Sei-ichi Nishimoto Tsutomu Kagiya 《Photochemistry and photobiology》1986,44(6):725-732
Photooxygenation reaction of an unsaturated fatty acid ester, methyl linoleate (methyl 9- cis. 12- cis -octadecadienoate, ML-H), sensitized by porphyrins and several types of dyes has been studied in aqueous emulsion and acetonitrile solution under air at 40°C. The oxygen (O2 ) uptake proceeded slowly in the absence of sensitizers upon irradiation of an aqueous emulsion and an acetonitrile solution of ML-H (20 m M ) at ℷex > 290 nm (11.4 and 6.1 μmol h-1 , respectively). The rate of O2 uptake was enhanced by a catalytic amount (0.1 m M ) of porphyrins and dyes; hematoporphyrin (HP), zinc tetrakis(N-methyl-4-pyridiniumyi)porphyrin (ZnTMPyP), methylene blue (MB), rose bengal (RB), acridine orange (AO), and acriflavine (AF). In both systems, the sensitized photooxidation of ML-H by O2 proceeded equimolarly to produce isomeric mixture of C9 and C13 hydroperoxides having the trans,cis and trans,trans conjugated diene configurations, independent of the types of the sensitizers used. The yield ratio of trans,trans/ trans,cis products in the MB-sensitized photooxygenation in acetonitrile and aqueous emulsion were almost equal (0.32 and 0.35. respectively). The sensitizing activity of the sensitizers, as measured by the quantum yield of O2 uptake, increased in the order: MB (≃ 0) < ZnTMPyP < RB < HP < AF < AO in the aqueous emulsion and AO < AF < HP < RB = MB in the acetonitrile solution. The order in homogeneous acetonitrile solution was interpreted by the sensitizing ability of the dyes to produce singlet oxygen, while that in heterogeneous aqueous emulsion was correlated to the lipophilicity of dyes as well as the singlet-oxygen-producing ability. 相似文献
52.
The structures of isobutene and 2,3-dimethyl-2-butene have been studied by gas electron diffraction. For isobutene the rotational constants obtained by Laurie by microwave spectroscopy have also been taken into account. Leastsquares analyses have given the following rg bond distances and valence angles (rav for isobutene and rα for dimethylbutene): for isobutene, r(CC) = 1.342±0.003 Å, r(C-C)= 1.508±0.002Å, r(C-H, methyl) = 1.119±0.007 Å, r(C-H, methylene) = 1.095±0.020 Å, ∠(C-CC) = 122.2±0.2°, ∠(H-C-H) = 107.9±0.8°, and ∠(C-C-H) 121.3±1.5°; for dimethylbutene, r(CC)= 1.353 ±0.004 Å, r(C-C) = 1.511±0.002 Å, r(C-H) = 1.118± 0.004 Å, ∠(C-CC)= 123.9±0.5°, and ∠(H-C-H)= 107.0±1.0°, where the uncertainties represent estimated limits of experimental error. The bond distances and valence angles in these molecules and in related molecules are compared with one another. The CC and C-C bond distances increase almost regularly with the number of methyl groups, and the C-C bonds in isobutene and dimethylbutene are shorter than those in acetaldehyde and acetone by about 0.01 Å. Systematic variations in the C-CC angles suggest the steric influence of methyl groups. 相似文献
53.
Hamao Watanabe Jun Inose Tsutomu Muraoka Masayuki Saito Yoichiro Nagai 《Journal of organometallic chemistry》1983,244(4):329-341
The reaction of 1,2-dimethoxytetramethyldisilane with styrene and α-methylstyrene in the presence of NaOMe catalyst in tetrahydrofuran (THF) gave the new silacyclopentanes 1,1-dimethyl-2,4-diphenyl-1-silacyclopentane (IIIa) and 1,1,2,4-tetramethyl-2,4-diphenyl-1-silacyclopentane (IIIb), respectively. These silacyclopentanes were found to exist as cis-trans mixtures. The use of sodium metal in place of NaOMe afforded similar results. Reactions of a polysilane mixture, MeO-(SiMe2)nOMe (n ≧ 3), with the styrenes also gave similar results. In some cases, polysilacycloalkanes such as 1,2,3-trisilacyclopentanes (IV) and 1,2,3,4-tetrasilacyclohexanes (V) were obtained as by-products. A mechanism for the formation of the silacyclopentanes and polysilacycloalkanes is presented. It was found that electron impact decomposition of silacyclopentanes IIIa and IIIb, trisilacycloalkane IV and tetrasilacycloalkane V gave molecular ions corresponding to the silacyclopropane, cyclotrisilane and cyclotetrasilane systems. 相似文献
54.
A simple method has been described for the Spectrophotometric determination of cobalt(II) with 2-(3′-sulfobenzoyl)pyridine benzoylhydrazone (SBPBH). In aqueous solution, cobalt(II) reacts with SBPBH to form a yellow complex, which is not destroyed even by the addition of 3.8 M perchloric acid. The absorption maximum of the complex in 1.5 M perchloric acid medium was found to be 400 nm; the molar absorptivity was 2.17 × 104 liters mol−1 cm−1. The proposed method is fairly selective and has been applied to the determination of cobalt in standard alloy steel samples. 相似文献
55.
Hisao Yokota Masatsune Kondo Tsutomu Kagiya Kenichi Fukui 《Journal of polymer science. Part A, Polymer chemistry》1968,6(2):435-446
The kinetic behavior on the polymerization of formaldehyde with and without acidic catalyst, in liquid carbon dioxide, in the temperature range of 30 to 50°C. was investigated. In the polymerization without catalyst both the polymer yield and the degree of polymerization increased with reaction time and also with rising temperature. With acidic catalyst, such as acetic acid and dichloroacetic acid, both the polymer yield and the degree of polymerization increased more than that in the polymerization without catalyst. The overall rate of polymerization with and without acidic catalyst was expressed by the first-order rate equation with respect to monomer concentration. From the results it was concluded that the polymerizations belonged to a type of successive polymerization with rapid initiation and no termination. The rate constant and the activation energy of each elementary process of polymerization were estimated on the basis of the results. 相似文献
56.
Tsutomu Takeichi Nobuyuki Takahashi Rikio Yokota 《Journal of polymer science. Part A, Polymer chemistry》1994,32(1):167-174
Polyimide/polyimide molecular composite (MC) films comprised of a rigid polyimide derived from biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) and a flexible polyimide derived from BPDA and bis (3,3'-diaminodiphenyl) acetylene (intA) and/or oxydianiline (ODA) were prepared by blending the polyamic acid solutions in 7 : 3 weight ratio, and then imidizing the blend films. Acetylene content in the flexible polyimide backbone was controlled by the ratio of intA and ODA. Cold-drawing of the blend polyamic acid films, followed by imidization, gives high modulus polyimide/polyimide MC films. The modulus of the MC films increased almost linearly with the draw ratio, reaching 25.5 GPa for the 40% drawn film. Acetylene groups in the flexible polyimide can be thermally cured to crosslink. The onset of exotherm appeared at 340°C on DSC, reaching maximum at 398°C. After the thermal crosslinking, the MC films maintained the high modulus, though elongation became small. Taking advantage of the crosslinkable acetylene units, two MC films were laminated and processed at 400°C for 20 min under 100 kg/cm2 to give a good-quality laminate film. The interface of the two films was strongly bonded through the crosslinking of acetylene groups. Laminate films maintained the high modulus afforded by the cold-drawing. © 1994 John Wiley & Sons, Inc. 相似文献
57.
Both enantiomers of 1,1-diethoxyethyl(aminomethyl)phosphinates were prepared through chromatographic separation of a diastereomeric mixture derived from (S)-phenylethylamine and 1,1-diethoxyethyl-H-phosphinate. The individual enantiomer was transformed into α-substituted α-amino-H-phosphinate with high enantiomeric purity by a highly diastereoselective alkylation at the α-carbon on the basis of our previously developed method. 相似文献
58.
Enhancement of Solar Hydrogen Evolution from Water by Surface Modification with CdS and TiO2 on Porous CuInS2 Photocathodes Prepared by an Electrodeposition–Sulfurization Method 下载免费PDF全文
Dr. Jiao Zhao Dr. Tsutomu Minegishi Li Zhang Dr. Miao Zhong Gunawan Dr. Mamiko Nakabayashi Dr. Guijun Ma Dr. Takashi Hisatomi Dr. Masao Katayama Prof. Dr. Shigeru Ikeda Prof. Dr. Naoya Shibata Prof. Dr. Taro Yamada Prof. Dr. Kazunari Domen 《Angewandte Chemie (International ed. in English)》2014,53(44):11808-11812
Porous films of p‐type CuInS2, prepared by sulfurization of electrodeposited metals, are surface‐modified with thin layers of CdS and TiO2. This specific porous electrode evolved H2 from photoelectrochemical water reduction under simulated sunlight. Modification with thin n‐type CdS and TiO2 layers significantly increased the cathodic photocurrent and onset potential through the formation of a p–n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H2 production under the present reaction conditions. 相似文献
59.
Toshihiro Kasezawa Hideyoshi Horimai Hiroshi Tabuchi Tsutomu Shimura 《Optical Review》2016,23(6):997-1003
A new photovoltaic generation unit based on the application of holographic technologies called a Holo-Window is proposed in this work. The basic principle and the optical configuration used for the basic experimental unit are described. Suitable fabrication technology for a hologram with the broadband spectrum required to provide the appropriate sunlight capture capability is then discussed. Finally, a laboratory-prototype Holo-Window unit was developed and its performance was evaluated. 相似文献
60.