【作者】 刘艳红；

【导师】 薛冰纯；

【作者基本信息】 山西师范大学 ， 药物分析学， 2016， 硕士

【摘要】 酰肼类衍生物是一类应用广泛的化学发光试剂,常被应用于医药、生物活性、食品、环境样品中的痕量检测等。为了进一步提高该方法的灵敏度,设计和合成邻苯二甲酰肼类衍生物已经吸引了很多的关注。本文主要从理论计算方面来研究酰肼类衍生物结构参数和电子光谱之间的性质,模拟出具有更高化学发光灵敏度的酰肼衍生物,且进一步拓宽该类化合物的应用范围。本文主要运用理论计算的方法,研究了一系列酰肼类物质的结构参数和分子电子性质。具体研究内容如下:1.本文主要通过理论计算方法对鲁米诺、5-氨基-4-巯基邻苯二甲酰肼及其衍生物在不同溶液中进行几何构型优化。主要目的是寻找一个特定的参数和化学发光性能之间的关系,为设计高的化学发光物质提供帮助。对分子键长、二面角、前线轨道能量以及化学发光强度值的分析表明,在分子轨道能隙差和化学发光强度之间存在一个线性关系。随后,我们依靠此线性关系设计了一系列的酰肼衍生物,一些分子被认为是优良的化学发光试剂。2.在密度泛函B3LYP/6-311G(d,p)的理论水平上,优化了2-(1?-芘)-[6,7-d]噻唑-6,7-二氢-5,8-酞嗪二酮与水的分子数之比为1:1~1:5的一系列水合物结构。计算结果表明,在优化后一系列的水合物分子结构中,由于存在C=O,N—H官能团,使得2-(1?-芘)-[6,7-d]噻唑-6,7-二氢-5,8-酞嗪二酮和水之间有很强的氢键相互作用。通过比较分析水合物的相对能量和结合能,确定了形成氢键后最稳定的水合物结构。然后我们对几何构型的变化、电荷分布、形成氢键后前线轨道的变化,进行了系统的研究。结果显示,几何构型的改变、电荷分布的变化,使得酰肼环羰基上的氧和氮原子的电子密度增加,氢键扮演着重要的角色。3.在实验上,已经合成的邻苯二甲酰肼以及它的衍生物被证明有着强的化学发光强度。近几年来,大量化合物的pKa值通过理论计算方法被预测,已经被证实它们的计算结果与实验值相吻合。在计算化学领域,邻苯二甲酰肼物质却很少被关注。本文中,在密度泛函B3LYP/6-311++G(d,p),B3PW91/6-311++G(d,p)和重头算HF/6-311++G(d,p)的三种理论水平上对邻苯二甲酰肼及其衍生物的pKa值进行了计算。随后,分析了结构参数、自然键轨道、化学发光强度与pKa值的关系,结果表明结构对pKa1值得影响稍大(0.25-6.99),对pKa2值的影响较小(16.66-21.11)。较高的pKa2值表明邻苯二甲酰肼类物质第二步解离需要更强的碱性环境。这些结果可被用来预测该类衍生物化学发光反应的实验条件。更多还原

【Abstract】 Phthalhydrazide derivatives are a class of sensitive chemiluminescence reagent, and they have been widely used in the antivirus, antitumor, antimalaria, insecticide, sterilization, etc. To further enhance the sensitivity and widen the application range of this method, the design and synthesis of new phthalhydrazide derivatives with high chemiluminescence quantum yield have attracted a lot of attention. In this paper, the theory calculation method was used to study phthalhydrazide derivatives properties between structure and electronic spectra, aiming to be found some molecules with good luminescence properties, and further broaden the application range of this kind of compounds.This paper mainly used the theoretical calculation methods to investigate the structure and frontier molecular orbital of the phthalhydrazide derivatives. The specific research contents are as follows:1. Phthalhydrazide compounds including luminol,7-amino-6-sulfanylphthalazine-1, 4(2 H, 3 H)-dione(ASPH) and its derivatives were investigated using quantum chemical calculation method. The main purpose was searching for the relationshipbetween a certain parameter and chemiluminescence properties,which can provide help for the design of chemiluminescence analogues with high quantum yields. By discussing the bond length,dihedral angle, frontier molecular orbital and orbital energy values, a linear correlation was observed between HOMO-LUMO energy gaps((35) Egap) and their relative chemiluminescence intensity. Based on these, a series of ASPH derivatives were simulated and some of the molecules were considered as promising excellent chemiluminescence reagent.2. Density functional theory at the B3LYP/6-311G(d, p) level was used to obtain the optimised geometries of a series of2-(1 ￠-pyrenyl)phthalazino[6, 7-d]thiazole-5, 8(6H, 7H)-dione–water complexes with stoichiometric ratios ranging from 1:1 to 1:5 both in the gas phase and in aqueous solution. All the calculations show that there are strong hydrogen bond interactions between luminol and water due to the existence of C=O and N-H groups in2-(1￠-pyrenyl)phthalazino[6, 7-d]thiazole-5, 8(6H, 7H)-dione molecule.By comparing the relative energy and binding energy, the most stable hydrogen bond complex is suggested, which involves extended hydrogen-bonding networks. Then the changes of compound geometry structure, charge distribution and frontier orbital properties induced by hydrogen bond were investigated. The results show that the hydrogen bonds increase the planarity of system. This work will be helpful for understanding the effect of hydrogen bond on hydrazide chemiluminescence reagents.3. Phthalhydrazide derivatives are a kind of strong chemiluminescence reagent. Despite its practical importance, thisfamily of compounds has been poorly characterized from a physico-chemical point of view. For instance, their pKa values have not been reported earlier in computational chemistry. In this paper,the pKavalues of some phthalhydrazide derivatives were calculated using ab initio and two density functional methods with 6-311++G(d, p)basis set and solvent effects calculated using the PCM model.Subsequently, the effect of structural modification on pKa values was analyzed. The results showed that pKa1 was influenced by structural modification as it varied between 0.25 and 6.99, and that pKa2 was relatively less variable from 16.66 to 21.11. The high values of pKa2 revealed that a strong alkaline solution was necessary for all chemiluminescent reactions of discussed phthalhydrazide derivatives. These findings are helpful to predict chemiluminescence condition of the discussed phthalhydrazide derivatives.更多还原