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61.
The gas-phase acidities DeltaG degrees (acid) of some 20 amides/enols of amides RNHCOCHYY'/RNHC(OH)=CYY' [R = Ph, i-Pr; Y, Y' = CO(2)R', CO(2)R' ', or CN, CO(2)R', R', R' ' = Me, CH(2)CF(3), CH(CF(3))(2)], the N-Ph and N-Pr-i amides of Meldrum's acid, 1,3-cyclopentanedione, dimedone, and 1,3-indanedione, and some N-p-BrC(6)H(4) derivatives and of nine CH(2)YY' (Y, Y' = CN, CO(2)R', CO(2)R' '), including the cyclic carbon acids listed above, were determined by ICR. The acidities were calculated at the B3LYP/6-31+G//B3LYP/6-31+G level for both the enol and the amide species or for the carbon acid and the enol on the CO in the CH(2)YY' series. For 12 of the compounds, calculations were also conducted with the larger base sets 6-311+G and G-311+G. The DeltaG degrees (acid) values changed from 341.3 kcal/mol for CH(2)(CO(2)Me)(2) to 301.0 kcal/mol for PhNHC(OH)=C(CN)CH(CF(3))(2). The acidities increased for combinations of Y and Y' based on the order CO(2)Me < CO(2)CH(2)CF(3) < CN, CO(2)CH(CF(3))(2) for a single group and reflect the increased electron-withdrawal ability of Y,Y' coupled with the ability to achieve planarity of the crowded anion. The acidities of corresponding YY'-substituted systems follow the order N-Ph enols > N-Pr-i enols > CH(2)YY'. Better linear relationships between DeltaG degrees (acid) values calculated for the enols and the observed values than those for the values calculated for the amides suggest that the ionization site is the enolic O-H of most of the noncyclic trisubstituted methanes. The experimental DeltaG degrees (acid) value for Meldrum's acid matches the recently reported calculated value. The calculated structures and natural charges of all species are given, and the changes occurring in them on ionization are discussed. Correlations between the DeltaG degrees (acid) values and the pK(enol) values, which are linear for the trisubstituted methanes, excluding YY' = (CN)(2) and nonlinear for the CH(2)YY' systems, are discussed. 相似文献
62.
邻苯二亚胺纤维素水溶液的荧光行为 总被引:3,自引:0,他引:3
目前,用于制造光致发光材料的基材均为合成高分子材料,如聚氯乙烯(PVC)等热塑性材料以及不饱和聚酯等热固性材料[1].天然高分子材料发光性能的研究并不多见.而与合成高分子相比,纤维素的结构特征决定了它易参与化学反应,可用以制备各种用途的功能材料,如高... 相似文献
63.
PC/PBT共混体系的研究:Ⅰ.PC,PBT熔融共混时的酯交换反应 总被引:9,自引:0,他引:9
采用红外光谱、核磁共振等测试手段,系统地研究了PC、PBT熔融共混时的酯交换反应,发现PBT中残余的Ti催化剂会对酯交换反应起催化作用。通过加入能和Ti催化剂络合添加剂,可以控制酯交换程度,这为控制PC/PBT合金的性能提供了一个非常有效的方法。 相似文献
64.
Constituting the artificial carbon cycle,for example,through recycling CO2 and converting CH4 to value-added fuels and chemicals with solar energy,offers a sustainable future for humankind to tackle the global environmental issues and energy crisis.However,significant bottlenecks remain in such photocatalytic conversion,mainly related to the reaction activity and product selectivity.Herein,we share our efforts and systematic research progress on addressing the double bottlenecks for achieving solar-driven artificial carbon cycle,with specifically focusing on the photocatalytic CO2 and CH4 conversion.We further elucidate the common fundamentals behind various designed photocatalytic materials systems.Toward future development,we highlight the opportunities and challenges in the research field. 相似文献
65.
ThestudyofphotoionizationandphotodissociationprocessesinducedbyintensefemtosecondlaserpuIses(>lo"W/cm')withpolyatomicmoleculesbecomesofinterestbecausesomenewphenomenahavebeenobserved'-3.Sofar,mostoftheinvestigationsfocusontheexperimentalexplorationofphotoionizationprocesses'-'.Butthephotoionizationmechanismofpolyatomicmoleculesinanintensefslaserfieldisstillambiguous'.,.Incontrasttothephotoionizationprocesses,theunderstandingoffragmentationofmolecularionisevenpoorer.Corkumetal,'.,'reportedthef… 相似文献
66.
Xiong Ya Zou Xiao-Hua Wu Jian-Zhong Ji Liang-Nian Li Run-Hua Zhou Jian-Ying Yu Kai-Bei 《Transition Metal Chemistry》1999,24(3):263-267
A new polypyridyl ligand, MCP {MCP = 2-(3-chlorophenyl)imidazo[4,5-f]1,10-phenanthroline} and its ruthenium(II) complex, [Ru(bpy)2(MCP)](ClO4)2· 0.5MeCN (bpy = 2,2-bipyridine), have been synthesized and characterized. The structure of the complex was determined by single crystal X-ray diffraction techniques. The MCP ligand is essentially planar and the stacking interactions between the ligands were observed in the crystal. [Ru(bpy)2(MCP)]2+ can strongly bind to Calf thymus DNA through intercalation of MCP ligand. The Cl substitute group has no significant effect on the spectral properties and DNA-binding behaviour of the complex. 相似文献
67.
68.
69.
The integrable hierarchy constructed from a pair of KdV-type hierarchies and its associatedW algebra
For any two arbitrary positive integers n and m, using them
th KdV hierarchy and the (n+m)th KdV hierarchy as building blocks, we are able to construct another integrable hierarchy (referred to as the (n, m)th KdV hierarchy). TheW-algebra associated to the second Hamiltonian structure of the (n, m)th KdV hierarchy (calledW(n, m) algebra) is isomorphic via a Miura map to the direct sum of aW
m
-algebra, aW
n+m
-algebra and an additionalU(1) current algebra. In turn, from the latter, we can always construct a representation of aW
-algebra. 相似文献
70.
Xiong Jianfei 《数学学报(英文版)》1996,12(4):415-432
In this paper we classify (2,2)-stable unfoldings of map germs with codimensions 4 by means of the algorithm given in [4] by Wassermann. 相似文献