全文获取类型
收费全文 | 613篇 |
免费 | 14篇 |
国内免费 | 2篇 |
专业分类
化学 | 479篇 |
晶体学 | 8篇 |
力学 | 9篇 |
数学 | 17篇 |
物理学 | 116篇 |
出版年
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 10篇 |
2019年 | 9篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 8篇 |
2015年 | 12篇 |
2014年 | 11篇 |
2013年 | 32篇 |
2012年 | 18篇 |
2011年 | 31篇 |
2010年 | 23篇 |
2009年 | 25篇 |
2008年 | 24篇 |
2007年 | 32篇 |
2006年 | 27篇 |
2005年 | 32篇 |
2004年 | 30篇 |
2003年 | 23篇 |
2002年 | 26篇 |
2001年 | 16篇 |
2000年 | 18篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1995年 | 5篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 11篇 |
1991年 | 8篇 |
1989年 | 5篇 |
1987年 | 3篇 |
1986年 | 9篇 |
1985年 | 17篇 |
1984年 | 8篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 9篇 |
1979年 | 11篇 |
1977年 | 6篇 |
1976年 | 9篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1972年 | 5篇 |
1971年 | 4篇 |
1970年 | 6篇 |
1967年 | 6篇 |
1966年 | 4篇 |
排序方式: 共有629条查询结果,搜索用时 15 毫秒
21.
22.
N-Acyl-α-amino acids are synthesized by the amidocarbonylation of allylic alcohols catalyzed by homogeneous binary systems which consist of cobalt carbonyl and rhodium (or iron or palladium) complexes. 相似文献
23.
Fullerene cyclopentadienide (PhCH(2))(2)Ph(3)C(60)(-) and indenide (PhCH(2))(2)PhC(60)(-), each bearing two different organic groups, were efficiently synthesized through regioselective reactions of 1,4-(PhCH(2))(2)C(60) with an organocopper reagent (PhMgBr/CuBr.SMe(2)) or a Grignard reagent (PhMgBr) followed by deprotonation with KO(t)()Bu. 相似文献
24.
Nagao S Hirai Y Suzuki A Yamamoto Y 《Journal of the American Chemical Society》2005,127(12):4146-4147
A 19F NMR study on the acid-alkaline transition in sperm whale myoglobin reconstituted with a perfluoromethyl heme, 13,17-bis(2-carboxylatoethyl)-3,8-diethyl-2,12,18-trimethyl-7-trifluoromethylporphyrinatoiron(III), demonstrated that the thermodynamics of the transition is predominantly controlled by the stability of acidic form. 相似文献
25.
The incorporation of CdS nanoparticles, prepared in reverse micellar systems, into thiol-modified mesoporous silica, such as FM41 (functionalized MCM-41) and FM48 (functionalized MCM-48), has been investigated. The nanoparticles were immobilized in the mesopores via the incorporation of water droplets of the reverse micelles. A particle-sieving effect for FM41 having large (L-FM41, 3.8 nm) and medium (M-FM41, 3.6 nm) pore size was observed, in that the incorporation of the CdS nanoparticles was decreased with increasing particle size and with decreasing pore size of the FM41. Chemical vapor deposition treatment employed to narrow the mesopores of the CdS-FM41 enhanced the stability of CdS nanoparticles against heat treatment. The CdS-FM41 composites demonstrated photocatalytic activity for H(2) generation from 2-propanol aqueous solution, the better photocatalytic activity being obtained with the larger pore size for CdS-L-FM41. Copyright 2001 Academic Press. 相似文献
26.
1,3,5-Trihydroxyisocyanuric acid (THICA), which serves as an efficient radical-producing catalyst from hydrocarbons, was successfully prepared by two methods. The reaction of O-benzylhydroxyamine with phenyl chloroformate gave formbenzyloxycarbamic acid phenyl ester of which subsequent treatment with dimethylaminopyridine (DMAP) produced 1,3,5-tribenzyloxyisocyanurate leading to THICA by hydrogenation with H2 on Pd/C. The other method involved the direct synthesis of 1,3,5-tribenzyloxyisocyanurate from O-benzylhydroxyamine and diphenyl carbonate. The aerobic oxidation of p-methylanisole catalyzed using THICA as a key catalyst afforded p-anisic acid in almost quantitative yield (>99%). 相似文献
27.
Hirai A Matsui A Komatsu K Tanino K Miyashita M 《Chemical communications (Cambridge, England)》2002,(17):1970-1971
A highly regio- and stereoselective alpha-methylation reaction of gamma,delta-epoxy-alpha,beta-unsaturated esters was achieved by using a Me2Zn-CuCN reagent. 相似文献
28.
The chelating behavior of a new resin prepared by polycondensation of N-(o-hydroxybenzyl) iminodiacetic acid (o-HDA) with phenol and formaldehyde, is compared with that of the monomer, with p-HDA resin and p-HDA monomer, and with Chelex-100. The order of chelate stability for the o-HDA resin is Cu(II) > Ni(II) > Zn(II) > Co(II). An unusually high stability of the o-HDA and o-HDA resin iron(III) chelates in acidic solution is attributed to the participation of the o-hydroxyl group in the coordination process. 相似文献
29.
Di(triptycyl)carbene: a fairly persistent triplet dialkylcarbene 总被引:1,自引:0,他引:1
Iiba E Hirai K Tomioka H Yoshioka Y 《Journal of the American Chemical Society》2002,124(48):14308-14309
The title carbene was generated and characterized by matrix spectroscopy (ESR and UV/vis) and laser flash photolysis along with theoretical calculations, which revealed interesting effects of triptycyl groups on structure and reactivities of carbenes. 相似文献
30.
Hidefumi Hirai Makoto Komiyama 《Journal of polymer science. Part A, Polymer chemistry》1975,13(11):2419-2435
The alternating copolymerization of methyl methacrylate with styrene in the presence of stannic chloride at ?50°C in toluene was kinetically investigated both under photoirradiation and with the tri-n-butylboron-benzoyl peroxide initiator. The concentrations of the binary and ternary molecular complexes in the copolymerization solution were estimated by use of the equilibrium constants. The rates are found to be proportional to the 1.5th and 1.0th orders of the concentration of the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene, under photoirradiation and with initiator, respectively. The conversion increases proportionally with the polymerization time, while the degree of polymerization is constant irrespective of the time. The rates depend linearly upon the square root of the intensity of the incident light and upon the concentration of tri-n-butylboron, respectively. The alternating copolymerization is confirmed experimentally to precede the homopolymerization of the monomer charged in large excess both under photoirradiation and with initiator. The kinetic results indicate consistently that the alternating copolymerization proceeds through the homopolymerization of the ternary molecular complex in the steady state with a bimolecular termination. Both the conventional radical mechanism and the double complex mechanism are unsuitable for the present alternating copolymerization. 相似文献