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以吲哚啉季铵盐为原料, 分别采用两步法和固相法合成了3种水溶性不对称吲哚方酸菁染料. 两步法为将不同N-烷基取代的2,3,3-三甲基-3H-吲哚-5-磺酸季铵盐与方酸反应, 再与另一种吲哚啉季铵盐反应制备不对称菁染料. 固相法是用对氨基苯甲酸做桥连物, 将方酸化学键连到高分子固相载体聚乙二醇上, 然后与吲哚啉季铵盐杂环母核缩合制得带有固相高分子载体的半菁, 再与另一吲哚啉季铵盐杂环母核反应切掉载体, 合成不对称菁染料. 产品用C-18反相柱进行分离提纯, 通过核磁共振氢谱和质谱对产品结构进行了表征, 测试了产品的光谱性能. 比较而言, 固相法合成不对称染料效果更好, 产率接近传统两步法的二倍, 是一种更适合的合成水溶性不对称吲哚方酸菁染料的方法. 相似文献
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方酸染料是一种重要的有机功能材料。本文用改进的溶胶-凝胶工艺,将它均匀地掺杂到无机的SiO2凝胶薄片中,制成一种新型的有机/无机凝胶杂化物。并用吸收光谱、荧光光谱等技术研究了该方酸染料在乙醇溶液中和掺杂在SiO2凝胶网络中的光物理性能。结果发现在固、液两种介质中,其光物理性能有很大差异。方酸染料在SiO2凝胶网络中,吸收光谱和荧光发射光谱的最大峰位置比在乙醇介质中有了明显蓝移,并且吸收域值随掺杂浓度增加而增大,荧光发射强度比在乙醇介质中也有了很大增强。首次对这些现象进行了解释:认为是由于方酸染料分子被包封在SiO2凝胶网络中形成分子簇集体,它的共轭π-电子和分子构型受到刚性纳米网络微孔的限域,产生了类似于无机半导体纳米粒子的量子尺寸效应。 相似文献
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合成了不对称冠醚方酸碲碳菁染料和对称冠醚方酸碲碳菁染料,并探讨了对称冠醚方酸碲碳菁的合成方法及反应条件,提出了其可能的反应机理。 相似文献
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用量子化学从头算法,在RHF/6-31G(d,p)水平上优化了八种不对称方酸染料的分子构型,并对它们的分子内电荷转移程度与暗衰值,光敏值和最大吸收波长的定量关系进行研究,发现不对称方酸染料的分子内电荷转移性质,是影响不对称方酸染料光导性和最大吸收波长的重要因素。 相似文献
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The effects of substituent type and position on the proton transfer reaction of 3-hydroxytropolone(3-OHTRN) have been investigated theoretically by using density functional theory at the level of B3LYP/ 6-31+G** method. The influence of solvent on the proton transfer reactions of substituted 3-OHTRN has been examined using the self-consistent isodensity polarized continuum model(SCI-PCM) in water. As a result, while the proton transfer reaction is kinetically the easiest by substitution on position 3 of-NH2 group in the gas phase, it is kinetically the easiest by substitution on position 5 of the same group in water. In addition, these reactions are either kinetically or thermodynamically easier in the gas phase than that in water, except the reaction of structure with-NH2 group at position 6. 相似文献
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采用密度泛函理论,在B3LYP/6-3 l1G**基组水平上,计算并考察了3-氨基-2-吡啶酮分子酮式和烯醇式结构进行结构互变的质子迁移过程中的2种可能途径:(a)分子内质子迁移,(b)水助质子迁移.计算结果表明,途经b所需要的活化能较小,氢键在降低反应活化能方面起着重要作用. 相似文献
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采用密度泛函B3LYP/6-311G**方法,对3-卤(-F、-Cl、-Br)代吡唑几何构型进行了全自由度优化,获得了它们的几何结构和电子结构。计算结果显示,N1-H型的稳定性大于N2-H型。计算并考察了3-卤代吡唑进行结构互变的质子转移过程的四种可能途径:(a)分子内质子转移;(b)水助质子转移;(c)同种二聚体双质子转移;(d)异种二聚体双质子转移。计算结果表明(以3-氟代吡唑为例),途径d所需要的活化能最小(54.89 kJ/mol),而途径a所需要的活化能最大(198.83kJ/mol),途径b和c的活化能居中间分别为(104.05 kJ/mol和69.05 kJ/mol)。研究还表明氢键在降低活化能方面起着重要的作用,卤素(-F、-Cl、-Br)对活化能的影响不大。 相似文献
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Fernández-Ramos A Martínez-Núñez E Vázquez SA Ríos MA Estévez CM Merchán M Serrano-Andrés L 《The journal of physical chemistry. A》2007,111(26):5907-5912
Multiconfigurational CASSCF and CASPT2 calculations were performed to investigate the enol --> keto tautomerization in the lowest singlet excited state of the 7-hydroxyquinoline.(NH3)3 cluster. Two different reaction mechanisms were explored. The first one corresponds to that proposed previously by Tanner et al. (Science 2003, 302, 1736) on the basis of experimental observations and CASSCF optimizations under Cs-symmetry constraints. This mechanism comprises four consecutive steps and involves nonadiabatic transitions between the valence 1pipi* state and a pisigma* Rydberg-type state, resulting in hydrogen-atom transfer. Single-point CASPT2 calculations corroborate that for Cs-symmetry pathways hydrogen-atom transfer is clearly preferred over proton transfer. The second mechanism, predicted by CASSCF optimizations without constraints, implies proton transfer along a pathway on the 1pipi* surface in which one or more ammonia molecules depart significantly from the molecular plane defined by the hydroxyquinoline ring. The results suggest that both mechanisms may be competitive with proton transfer being somewhat favorable over hydrogen-atom transfer. 相似文献
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3-羰基吡唑质子转移过程的理论研究 总被引:2,自引:1,他引:1
采用密度泛函B3LYP/6—311G^**方法,对3-羰基吡唑几何构型进行了全自由度优化,获得了它们的几何结构和电子结构.计算并考察了3-羰基吡唑的两种构象即syn和anti构象的稳定性以及3-羰基吡唑进行结构互变的质子转移过程的四种可能途径:(a)分子内质子转移;(b)水助质子转移;(C)同种二聚体双质子转移;(d)异种二聚体双质子转移.计算结果表明3-羰基吡唑的syn构象中N2-H型的稳定性大于N1-H型,进行质子转移时途径(C)所需要的活化能最小(52.78kJ/mol),途径(a)所需要的活化能最大(200.59kJ/mol);3,羰基吡唑的。anti构象中N1-H型的稳定性大于N2-H型,进行质子转移时途径(d)所需要的活化能最小(61.09kJ/mol),途径(a)所需要的活化能最大(204.15kJ/mol). 相似文献
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The proton transfer reaction of H3O+ and NH3 was studied using the crossed molecular beam technique at relative energies of 0.41, 0.81, and 1.27 eV. At all three energies, the center-of-mass flux distribution of the product ion NH4+ exhibits sharply asymmetry, and the maximum is close to the velocity and direction of the precursor ammonia beam. The reaction transforms almost all of the 1.69 eV exothermicity into internal excitation of the products at all three collision energies. At the lowest collision energy of 0.41 eV, nearly 77% of the total energy appears in NH4+ internal excitation. However, almost 100% of the incremental translational energy in the two higher-energy experiments appears in the product translational energy. Such an observation provides a classic example of the "induced repulsive energy release" mechanism that is expected to be operative on the highly skewed potential energy surfaces characteristic of the heavy+light-heavy mass combination. These results indicate that the proton transfer proceeds through a direct reaction mechanism; a Rice-Ramsperger-Kassel-Marcus theory calculation shows that the lifetime of the intermediate complex [NH3-H-H2O]+ is about 100 fs. Proton transfer occurs early on the reaction coordinate, when the incipient N-H bond is extended, and results in highly vibrationally excited NH4+ products, with excitation primarily in N-H stretching modes. 相似文献
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Teruel M de Moraes PR Xavier LA Riveros JM 《European journal of mass spectrometry (Chichester, England)》2003,9(4):279-285
Gas-phase [C, H(3), S](+) ions obtained by electron impact from (CH(3))(2)S at 14 eV undergo two distinct low-pressure ion-molecule reactions with the parent neutral: proton transfer and charge exchange. The kinetics of these reactions studied by Fourier transform ion cyclotron resonance (FT-ICR) techniques clearly suggests the [C, H(3), S](+) species to be a mixture of isomeric ions. While proton transfer is consistent with reagent ions displaying the CH(2)SH(+) connectivity, the observed charge exchange strongly argues for the presence of thiomethoxy cations, CH(3)S(+), predicted to be stable only in the triplet state. Charge exchange reactions are also observed in the reaction of these same [C, H(3), S](+) ions with benzene, toluene and phenetole. For these substrates, the CH(2)SH(+) ions can promote proton transfer and electrophilic methylene insertion in the aromatic ring with elimination of H(2)S. The results obtained for the different substrates suggest that the fraction of long-lived fraction of thiomethoxy cations obtained at 14 eV by electron ionization of dimethyl sulfide amounts to ~(22 -/+ 4)% of the [C, H(3), S](+) fragments. 相似文献
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采用密度泛函理论,在B3LYP/6-311G**基组水平上,计算并考察了4(3H)-嘧啶酮及其类似物(5-氟-4(3H)-嘧啶酮、4-巯基嘧啶和5-氟-4-巯基嘧啶)醇式结构和酮式结构进行结构互变质子迁移过程中的2种可能途径:(a)分子内质子迁移;(b)水助质子迁移.计算结果表明,途经b所需要的活化能较小.研究还表明,氢键在降低反应活化能方面起着重要的作用. 相似文献
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The molecular structures and intramolecular proton transfer reaction of 1-phenyl-3-methyl-4-(6-hydro-4-amino-5-sulfo-2,3-pyrazine)-pyrazole-5-one have been investigated with both ab initio method and the density functional theory. The solvent effects are simulated using the self-consistent reaction field (SCRF) method within the framework of the polarizable continuum model (PCM). The results show that the computed geometrical parameters at the B3LYP levels are in better agreement with experimental values than those at the RHF levels, and the choice of functional in DFT plays an important role in describing the title compound. It is found that strong hydrogen bonds (O–H···N and O···H–N) exist in the title compound, and in the proton transfer process, the O–H bond is broken while the N–H bond is formed. In addition, the order of stability of the isomers remains the same in different solvents, while the barrier height of the proton transfer reaction and dipole moments for the title compound grow with the increase of the solvent polarity. Eventually, the NBO analysis shows that the strength of the hydrogen bond reduces with the increase of the solvent polarity. 相似文献