全文获取类型
收费全文 | 539篇 |
免费 | 35篇 |
国内免费 | 2篇 |
专业分类
化学 | 476篇 |
晶体学 | 6篇 |
力学 | 8篇 |
数学 | 21篇 |
物理学 | 65篇 |
出版年
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 11篇 |
2019年 | 13篇 |
2018年 | 5篇 |
2017年 | 4篇 |
2016年 | 17篇 |
2015年 | 17篇 |
2014年 | 15篇 |
2013年 | 33篇 |
2012年 | 38篇 |
2011年 | 57篇 |
2010年 | 17篇 |
2009年 | 17篇 |
2008年 | 33篇 |
2007年 | 31篇 |
2006年 | 37篇 |
2005年 | 31篇 |
2004年 | 23篇 |
2003年 | 20篇 |
2002年 | 18篇 |
2001年 | 5篇 |
2000年 | 11篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1973年 | 3篇 |
1970年 | 3篇 |
1965年 | 1篇 |
1962年 | 2篇 |
1961年 | 2篇 |
排序方式: 共有576条查询结果,搜索用时 15 毫秒
1.
Takayuki Yaegashi Shinya Yodoya Masahiko Nakamura Hiroki Takeshita Katsuhiko Takenaka Tomoo Shiomi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):999-1007
Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (Rp) equation was Rp ∝ [DEA]1.1[AIBN]0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r1 = 5.83 and r2 = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004 相似文献
2.
Teruhisa Horita Katsuhiko Yamaji Natsuko Sakai Yueping Xiong Harumi Yokokawa Tatsuya Kawada 《Ionics》2002,8(1-2):108-117
The oxygen reduction active sites were visualized around the O2/SOFC cathode/electrolyte triple phase boundaries (TPB) by the16O/18O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher18O concentration is observed on the cathode top surfaces (La0.9Sr0.1MnO3-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode.
The oxygen diffusion through the bulk of cathode occurred at the La0.9Sr0.1MnO3-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites
for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La0.9Sr0.1MnO3/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in
the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation
is less than a few μm from the TPB lines.
Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001. 相似文献
3.
Hanaoka T Hayashi H Tago T Kishida M Wakabayashi K 《Journal of colloid and interface science》2001,235(2):235-240
We investigated the in situ immobilization of ultrafine particles synthesized in a water/oil (w/o) microemulsion to silica for its possible application to supported metal catalysts. ZnS particles immobilized to silica by the ME method were consistent with those synthesized in a w/o microemulsion. Therefore, ZnS particles in a w/o microemulsion could be immobilized to silica without aggregation by this method. The relationship between the method of synthesizing Rh ultrafine particles in a w/o microemulsion and the diameter and diameter distribution of Rh particles immobilized to silica was studied. Rh-SiO(2) catalysts with a sharp diameter distribution could be prepared by immobilizing Rh-hydrazine complex particles because these complex particles would be very stable in a w/o microemulsion. The Rh particle diameters of Rh-SiO(2) catalysts prepared by changing the amount of silica produced were almost identical. Accordingly, the Rh particle diameter of Rh-SiO(2) catalysts could be controlled independently of Rh content by the ME method. Copyright 2001 Academic Press. 相似文献
4.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2007,2(3):367-376
Films of linear and branched oligomer wires of Fe(tpy)2 (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C6H4N?NC6H4? S)2 ( 1 ), two bridging ligands, 1,4‐(tpy)2C6H4 ( 3 ) and 1,3,5‐(C?C? tpy)3C6H3 ( 4 ), and metal ions were used. The quantitative complexation of the ligands and FeII ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k1 (s?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k2 (cm2 mol?1 s?1). The strong effect of the electrolyte concentration on both k1 and k2 indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k1 and k2 on the potential gave intrinsic kinetic parameters without overpotential effects: k10=110 s?1, k20=2.6×1012 cm2 mol?1 s?1 for [n Fe 3 ], and k10=100 s?1, k20=4.1×1011 cm2 mol?1 s?1 for [n Fe 4 ] (n=number of complexation cycles). 相似文献
5.
Satoshi Ito Kazuya Koizumi Katsuhiko Fukuda Naohiro Kameta Tsukasa Ikeda Toru Oba Kazuhisa Hiratani 《Tetrahedron letters》2006,47(48):8563-8566
A new series of BINOL-based macrocycles with two phenolic protons have been synthesized via oxidative coupling reaction using CuCl(OH)-TMEDA. 相似文献
6.
Ammoniacal copper quat (ACQ) compound wood preservative is comprised of copper and quaternary ammonium compounds with benzalkonium chloride (BAC) as the active ingredient. Solid-phase extraction (SPE) followed by liquid chromatography with ultraviolet detection (LC-UV) was developed for quantitative determination of BAC in treated wood. Five species of wood were used, Japanese cedar (Cryptomeria japonica), Japanese larch (Larix leptolepis), Yezo spruce (Picea jezoensis), Sakhalin fir (Abies sachalinensis), and western hemlock (Tsuga heterophylla). BAC used in the present study was composed of 66% C12, 33% C14 and less than 1% C16. BAC was added to each wood species (500 mg) then extracted with HCl-ethanol (20 ml) and quantitatively determined with LC-UV (262 nm). Wood extractives from the heartwood of each species, except western hemlock, interfered with quantitative determination of BAC, but SPE with an Oasis MCX cartridge was effective in preventing this. Using the present methods, BAC homologue peaks were clearly confirmed without interference. Recoveries from wood ranged from 92 to 101% and the limit of quantitation was approximately 240 microg/g wood for the C12 and C14 homologues. 相似文献
7.
Kenjiro Hattori Tomoko Takeuchi Mika Ogata Ayumi Takanohashi Katsuhiko Mikuni Katsuyoshi Nakanishi Hideo Imata 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):339-342
We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G2βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G2βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on
the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The
SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful
for the repeated measurement. 相似文献
8.
Michio Horiike Gu Yuan Chul-Sa Kim Chisato Hirano Katsuhiko Shibuya 《Journal of mass spectrometry : JMS》1992,27(9):944-948
Fourteen isomers of chemically unmodified hexadecenol were analysed by two types of quadrupole mass spectrometer, coupled with a gas chromatograph, for the location of the double-bond position. A series of spectra were interpreted in terms of mass spectral patterns on a fuzzy classification, in which the intensity ratios of six diagnostic pairs of the predominant ions were preferred in devising similarity indices. The accuracy of the method in the location of double-bond position was confirmed by testing with other series of spectra. 相似文献
9.
Katsuhiko?Kamio Yoshifumi?Kusumoto Masashi?Sakai Katumitu?HayakawaEmail author 《Colloid and polymer science》2003,281(7):608-613
The conformation of the sodium salt of poly(l-glutamic acid) (P(Glu)) in solutions of the cationic bipolar amphiphile 1, 20-isosanediylbis(alkylammonium chloride) (C 20(RA) 2) with different alkyl head groups as a function of amphiphile concentration was investigated using circular dichroism (CD). RA included methylammonium (MA), ethylammonium (EA), propylammonium (PA), butylammonium (BA), and pentylammonium (PeA) cationic groups. The CD spectrum of each C 20(RA) 2 had a double minima corresponding to the a-helix of P(Glu), which was replaced by CD spectra with a single minimum at wavelengths larger than 222 nm as concentration increased. These changes in the CD spectrum were ascribed to the conformational change from random coil to a-helix and to aggregates of helices. In C 20(EA) 2 solutions, a step-like change in the CD intensity was observed at 222 nm as a function of the ratio of C 20(RA) 2 to P(Glu). At the step, the CD spectrum of the complete a-helix was observed. At 10–35 °C, an a-helix was induced in P(Glu) in the order: C 20(EA) 2>C 20(MA) 2>C 20(PA) 2>C 20(BA) 2>C 20(PeA) 2. This order was ascribed to the best fit of ethylammonium to the P(Glu) side chain. 相似文献
10.
Tomooka K Komine N Fujiki D Nakai T Yanagitsuru S 《Journal of the American Chemical Society》2005,127(35):12182-12183
Remarkably stable planar chirality was found in a nine-membered diallylic cyclic ether. Enantiomerically enriched ether was prepared by a kinetic resolution of a racemic one, which is valuable as a novel type of chiral building block. 相似文献