全文获取类型
收费全文 | 1094篇 |
免费 | 19篇 |
国内免费 | 7篇 |
专业分类
化学 | 829篇 |
晶体学 | 11篇 |
力学 | 40篇 |
数学 | 48篇 |
物理学 | 192篇 |
出版年
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 6篇 |
2019年 | 18篇 |
2018年 | 11篇 |
2016年 | 11篇 |
2015年 | 13篇 |
2014年 | 16篇 |
2013年 | 69篇 |
2012年 | 52篇 |
2011年 | 51篇 |
2010年 | 43篇 |
2009年 | 41篇 |
2008年 | 68篇 |
2007年 | 62篇 |
2006年 | 53篇 |
2005年 | 60篇 |
2004年 | 48篇 |
2003年 | 47篇 |
2002年 | 57篇 |
2001年 | 18篇 |
2000年 | 14篇 |
1999年 | 11篇 |
1998年 | 15篇 |
1997年 | 21篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 12篇 |
1992年 | 14篇 |
1991年 | 12篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 12篇 |
1987年 | 18篇 |
1986年 | 9篇 |
1985年 | 15篇 |
1984年 | 20篇 |
1982年 | 11篇 |
1981年 | 14篇 |
1980年 | 11篇 |
1979年 | 10篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1974年 | 8篇 |
1973年 | 10篇 |
1972年 | 11篇 |
1971年 | 7篇 |
1970年 | 6篇 |
1966年 | 7篇 |
排序方式: 共有1120条查询结果,搜索用时 0 毫秒
41.
Masahiro Irie Senzo Sasaoka Yukio Yamamoto Koichiro Hayashi 《Journal of polymer science. Part A, Polymer chemistry》1979,17(3):815-820
Photopolymerization of cyclohexene oxide in the presence of electron acceptors was studied in a bulk system (in liquid as well as in solid states). The polymerization was proved to proceed by a cationic mechanism in both states by the effect of inhibitors. In a liquid phase the light intensity dependence of the rate of polymerization and the molecular weight distribution showed a contribution of a free ionic polymerization. Any discontinuous phenomenon in the rate as well as in the molecular weight was not discerned between liquid(above ?36°C) and plastic crystal (between ?36 and ?81°C) phases. A quantum yield of monomer consumption as high as 8 × 103 was observed in the plastic crystal phase. Below ?81°C in the normal crystal phase the rate as well as the molecular weight was remarkably suppressed. 相似文献
42.
Kiyoshi Koyama Masato Nishimura 《Journal of polymer science. Part A, Polymer chemistry》1972,10(9):2601-2608
The polymerization of vinyl monomers initiated by binary initiator systems composed of a copper–amine complex type resin and organic halides has been studied. These binary systems initiated the polymerization of various vinyl monomers. A kinetic study of the polymerization of methyl methacrylate initiated by the copper–amine complex resin–CCl4 system was carried out, and it was found that the polymerization proceeds by way of a radical mechanism. This fact was also supported by the copolymerization of methyl methacrylate with styrene. The overall activation energy of the polymerization of methyl methacrylate was estimated as 8.4 kcal/mole. The activity of the initiator systems was greatly dependent upon the dissociation energy of carbon–halogen bonds in the organic halides. A possible initiation mechanism with the binary systems is proposed and discussed. 相似文献
43.
Masahiro Irie Setsuko Tomimoto Koichiro Hayashi 《Journal of polymer science. Part A, Polymer chemistry》1972,10(11):3235-3242
The dependence of the rate of polymerization on light intensity and the stereoregularity of the polymer was studied to elucidate the propagation and termination mechanisms of the photoinduced cationic polymerization of α-methylstyrene in the presence of tetracyanobenzene in methylene chloride. The rate of polymerization was proportional to the light intensity. The polymer is highly syndiotactic, and the stereoregularity is similar to that of polymers obtained by radiation-induced cationic polymerization. The initiation mechanism was also studied by electron spin resonance, by which the anion radical of tetracyanobenzene formed from a photoexcited complex between α-methylstyrene and tetracyanobenzene was observed. The cation radical of α-methylstyrene, counterpart of the anion radical, is believed to initiate the polymerization. 相似文献
44.
45.
Sterically bulky pyrazines have been successfully utilized for the preparation of discrete oligo-nuclear TBP (trigonal bipyramidal), SqP (square pyramidal), and Oh (octahedral) copper(II) complexes. We have synthesized a unique linear pentanuclear complex [{Cu(hfac)2}5(μ-2-butyl-3-methylpyrazine)4]. The two terminal copper(II) ions have a SqP structure while the three inner ions have an Oh one. The solvent molecule was incorporated in the clearance of the lattice. From another reaction under harsh conditions, we separated [{Cu(hfac)2}3(μ-2-butyl-3-methylpyrazine)2], which can be regarded as the central moiety of the pentanuclear one. We also prepared a dinuclear complex [{Cu(hfac)2}2(μ-tetramethylpyrazine)], in which the pyrazine nitrogen atoms were located at TBP equatorial positions. Single-crystal EPR measurements supported its compressed TBP structure. The exchange coupling was antiferromagnetic with JTBP–TBP/kB = −3.6 K. The linear trinuclear [{Cu(hfac)2}3(μ-2,3,5-trimethylpyrazine)2], having two TBP Cu ions with an intervening Oh Cu ion, showed very weak antiferromagnetic coupling. DFT calculations on these compounds indicated that the σ-type orbital overlap between the Cu and N atoms is essential for superexchange interactions. 相似文献
46.
A highly efficient and mild method for the synthesis of 1,5-hexadienes, nickel-catalyzed reactions of Boc-protected allyl alcohols with homoallyl alcohols, has been developed. Nickel-mediated retro-allylation allows for the use of homoallyl alcohols as allylmetal equivalents in the synthesis of 1,5-hexadienes. 相似文献
47.
[reaction: see text] This paper describes cobalt-mediated cross-coupling reactions of alkyl halides with 1-(trimethylsilyl)ethenylmagnesium bromide and 2-(trimethylsilyl)ethynylmagnesium bromide, respectively. The cobalt system allows for employing secondary as well as primary alkyl halides as the substrates. The reactions offer facile formations of alkyl-alkenyl and alkyl-alkynyl bonds. The reaction mechanism would include single-electron transfer from a cobalt complex to alkyl halide to generate the corresponding alkyl radical. The cobalt system thus enables sequential radical cyclization/alkenylation and cyclization/alkynylation reactions of 6-halo-1-hexene derivatives. 相似文献
48.
Retro-allylation of homoallyl alcohol by rhodium catalysis occurs to generate allylrhodium species. This allylrhodium reacts with aldehydes to give the corresponding secondary alcohols in situ. Isomerization of these alcohols proceeds in the same pots to furnish the corresponding saturated ketones in good yields. [reaction: see text] 相似文献
49.
[reaction: see text] Allylzirconium reagents are effective for radical allylation of alpha-halo carbonyl compounds. The key steps would be homolytic cleavage of the zirconium-carbon bond and halogen abstraction by the resulting Cp(2)ZrCl(III). Zirconocene-olefin complex can be also utilized for the allylation of alpha-halo compounds. 相似文献
50.
Koichiro Fukuda Miyuki Hisamura Nobuyuki Tera 《Journal of solid state chemistry》2007,180(6):1809-1815
A new quaternary layered carbide, Zr2[Al3.56Si0.44]C5, has been synthesized and characterized by X-ray powder diffraction, transmission electron microscopy and thermopower and electrical conductivity measurements. The crystal structure was successfully determined using direct methods, and further refined by the Rietveld method. The crystal is trigonal (space group R3m, Z=3) with lattice dimensions of a=0.331059(5), c=4.09450(5) nm and V=0.38864(1) nm3. The final reliability indices calculated from the Rietveld refinement were Rwp=6.24%, Rp=4.21% and RB=0.82%. The crystal structure is composed of electroconductive NaCl-type ZrC slabs separated by Al4C3-type [Al3.56Si0.44]C3 layers. This material had thermoelectric properties superior to those of the ternary layered carbides Zr2Al3C4 and Zr3Al3C5, with the power factor reaching 7.6×10−5W m−1 K−2. 相似文献