全文获取类型
收费全文 | 348篇 |
免费 | 2篇 |
国内免费 | 3篇 |
专业分类
化学 | 256篇 |
晶体学 | 2篇 |
数学 | 41篇 |
物理学 | 54篇 |
出版年
2019年 | 5篇 |
2018年 | 2篇 |
2017年 | 1篇 |
2016年 | 2篇 |
2015年 | 8篇 |
2014年 | 6篇 |
2013年 | 19篇 |
2012年 | 12篇 |
2011年 | 20篇 |
2010年 | 9篇 |
2009年 | 8篇 |
2008年 | 32篇 |
2007年 | 19篇 |
2006年 | 29篇 |
2005年 | 16篇 |
2004年 | 19篇 |
2003年 | 19篇 |
2002年 | 21篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 7篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 4篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 2篇 |
排序方式: 共有353条查询结果,搜索用时 0 毫秒
1.
Kohji Masaki Shin-ichi Ohkawara Tomohiro Hirano Makiko Seno Tsuneyuki Sato 《Journal of polymer science. Part A, Polymer chemistry》2004,42(17):4437-4447
The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R0) of the vinyl group was expressed by R0 = k[DCPO]0.8[vinyl group]−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004 相似文献
2.
3.
Kohji Chihara Takeshi Takemura Tsuguo Yamaoka N. Yamamoto Arnold Schaffer Ralph S. Becker 《Photochemistry and photobiology》1979,29(5):1001-1008
Abstract— The absorption and emission spectra, lifetimes and quantum yields of all-trans retinol have been examined as a function of solvent and temperature. In addition, the spectroscopy of retinyl ether and 2 other polyene alcohols have been determined. Based on the results obtained, we conclude that the singlet excited state of retinol and retinyl cther is of a forbidden character and of the type loosely called 1 A- g . Retinol forms a dimer in an alkane solvent when cooling from 298 to 77 K. A general structure for the dimer is proposed. 相似文献
4.
5.
Ikedou K Yamamoto H Nagashima H Nemoto N Tashiro K 《The journal of physical chemistry. B》2005,109(21):10668-10675
We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P2(1)2(1)2(1)) and the triclinic (P) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches. 相似文献
6.
Oligonucleotides containing 2-thiouridine (s2U) in place of uridine form stable RNA duplexes with complementary RNAs. Particularly, this modified nucleoside has proved to recognize highly selectively adenosine, the genuine partner, without formation of a mismatched base pair with the guanosine counterpart. In this paper, we describe new methods for the synthesis of 2-thiouridine and various 2'-O-alkyl-2-thiouridine derivatives. Oligoribonucleotides having these modified nucleoside derivatives were synthesized, and their hybridization and structural properties were studied in detail by the 1H NMR analysis of these modified nucleosides and Tm experiments of RNA duplexes with their complementary RNA strands. 相似文献
7.
Shinsuke Nakamoto Kohji Tashiro Akikazu Matsumoto 《Journal of Polymer Science.Polymer Physics》2003,41(5):444-453
The Raman shift and crystallite modulus were measured under the application of tensile force for a giant single crystal and a series of uniaxially oriented semicrystalline samples of poly(trans‐1,4‐diethyl muconate) (polyEMU). The apparent Raman shift factor αapp or a vibrational frequency shift per 1 GPa tensile stress was higher for the semicrystalline samples with lower crystallinity or lower bulk modulus. The apparent crystallite modulus E or Young's modulus along the chain axis in the crystalline region was not constant but varied remarkably between the giant single crystal and semicrystalline samples. A systematic change in αapp and E among the polyEMU samples with different preparation history could be interpreted quantitatively on the basis of a mechanical series parallel model consisting of crystalline and amorphous phases. The origin of different E and αapp was speculated to be a stress concentration on the taut‐tie chain contained as a parallel crystalline component in the mechanical model. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 444–453, 2003 相似文献
8.
Summary The cross-linkings of the surface polymer layer on mono disperse, poly(maleic anhydride-styrene)-modified silica particles
by the reaction with diisocyanate were studied. The extent of cross-linking was estimated by the weight decrease by immersing
the particles in the buffer solution of pH 2.0, 4.0 and 9.0 at a room temperature for 24 h. The reaction of the polymer-modified
silica with 1,6-diisocyanatohexane afforded relatively stable composite particles which lost less than 5 wt% of the polymer
in aqueous solution in the pH range 2.0–9.0. The diisocyanate was a preferable cross-linker to 2,4-diisocyanatotoluene in
terms of stability in acidic or basic aqueous solution. The flexibility of the cross-linker molecule possibly plays an important
role in the cross-linking reaction. The carboxyl and amino groups were formed by treating the cross-linked composite particles
with diluted HCl solution; 5–6 and 0.5–1.1 μmol g-1, respectively. The cross-linked composite particles exhibited the characteristic property of ζ-potential, −44 to −47 mV and
−102 to −107 mV in a neutral aqueous solution and ethanol, respectively.
Received: 26 May 1997 Accepted: 4 August 1997 相似文献
9.
Yasuhiko Kawamura Kohji Akitomo Masaaki Oe Tokunaru Horie Masao Tsukayama 《Tetrahedron letters》1997,38(52):3610-8992
Upon irradiation (>340 nm) of a benzene solution of diazofluorene with di-p-tolyl- or di-p-anisyl disulfide, the corresponding 9,9′-bis(arylmercapto)bifluorenyl was afforded in moderate to good yield accompanied by formation of 9,9′-bis(arylmercapto)fluorene. The major reaction pathway is considered to be a disulfur ylide formation followed by two times of successive Stevens rearrangement or by concerted electron redistribution via [2,3]sigmatropic rearrangement. 相似文献
10.
Shigeru Sasaki Kohji Sasaki Mariko Watanabe Kazunobu Ogawa Noboru Morita Masaaki Yoshifuji 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):256-261
Abstract Synthesis, redox properties, and electronic spectra of the sterically crowded triarylphosphines conjugated with π-electron systems, especially electron acceptors such as carbonyl group, are briefly reviewed. The sterically crowded triarylphosphines conjugated with various π-electron systems were synthesized from the common synthetic intermediate, (bromoaryl)phosphine, by conventional manner. The sterically crowded triarylphosphines conjugated with the electron acceptors exhibit visible absorption and fluorescence with large Stokes shift. Large solvent effect, redshift in polar solvent, and good correlation with the difference of the oxidation potential of the phosphine moiety and the reduction potential of the acceptor moiety suggest polar excited state resulting from HOMO-LUMO transition. 相似文献