全文获取类型
收费全文 | 182篇 |
免费 | 5篇 |
专业分类
化学 | 150篇 |
数学 | 1篇 |
物理学 | 36篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2020年 | 1篇 |
2019年 | 1篇 |
2016年 | 2篇 |
2015年 | 4篇 |
2014年 | 10篇 |
2013年 | 9篇 |
2012年 | 16篇 |
2011年 | 14篇 |
2010年 | 5篇 |
2009年 | 8篇 |
2008年 | 12篇 |
2007年 | 13篇 |
2006年 | 11篇 |
2005年 | 8篇 |
2004年 | 9篇 |
2003年 | 5篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1989年 | 2篇 |
1986年 | 1篇 |
1984年 | 4篇 |
1982年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
排序方式: 共有187条查询结果,搜索用时 46 毫秒
1.
Andreia PeixotoMariette M. Pereira M.Graça P.M.S. NevesArtur M.S. Silva José A.S. Cavaleiro 《Tetrahedron letters》2003,44(30):5593-5595
Formyl derivatives of protoporphyrin-IX dimethyl ester metal complexes were obtained via hydroformylation reactions, catalysed by rhodium-triphenylphosphine complexes. The regioselectivity of the reaction is remarkably dependent on the metal centre of the porphyrin, yielding 100% of the branched aldehyde with zinc(II) complexes and 75% with the nickel(II). The NMR characterisation of the new compounds was carried out after their derivatisation into acetals. 相似文献
2.
3.
Domingues MR Santana-Marques MG Domingues P Faustino MA Neves MG Cavaleiro JA Ferrer-Correia AJ 《Rapid communications in mass spectrometry : RCM》2000,14(21):2025-2029
New synthesised porphyrin dimers, with an amide or ester linkage between the two porphyrin units, were studied using liquid secondary ion mass spectrometry (LSIMS). The formation of reduced species was observed for all the compounds and it was found that the extent of reduction is dependent on the matrix used and on the structure of the porphyrin dimer. The main fragmentation pathways lead to monomer fragments resulting from cleavage of the amide or ester linkage between the two porphyrin units. The consistency of the fragmentations for all the dimers studied leads to the proposal of a common designation for the fragment ions. LSIMS, in addition to molecular weight determination, can provide important structural information for this type of compound. 相似文献
4.
5.
Chupakhin O. N. Rusinov G. L. Beresnev D. G. Bashirov S. Sh. Neves M. G. P. M. S. Cavaleiro J. A. S. 《Russian Chemical Bulletin》2004,53(1):160-163
In the reaction with quinazoline and 5-phenyl-1,2,4-triazin-5(2H)-one, 5,10,15,20-tetra(4-methoxyphenyl)porphyrin exhibits nucleophilic properties. In quinazoline excess, C—C coupling occurs at the C=N bond of azines and position 3 of the aryl ring to form 5,10,15,20-tetrakis(3-heteryl-4-methoxyphenyl)porphyrins. Monoheteryl-substituted porphyrin was obtained by the reaction of equimolar amounts of 5,10,15,20-tetra(4-methoxyphenyl)porphyrin and 5-phenyl-1,2,4-triazin-5(2H)-one. 相似文献
6.
7.
8.
An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
9.
Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献