基于DFT和UV-Vis的金丝桃苷印迹相互作用分析

Imprinting Interaction Analysis of Hyperoside Based on DFT and UV-Vis

摘要:

为提高金丝桃苷（HYP）印迹效率，通过密度泛函理论（DFT）和紫外-可见光吸收光谱（UV-Vis）实验法对HYP、丙烯酰胺（AM）、衣康酸（IA）及其不同摩尔比例的HYP-AM和HYP-IA复合物进行理论计算和紫外光谱的测定，使用分子静电势（MEP）预测HYP、AM和IA的印迹活性位点，探讨HYP和AM（IA）分子间相互作用的印迹机理。结果表明，HYP中O11可与AM中H9（或H10）以及IA中H2（或H15）形成强氢键作用，而O12—H13、O15—H16、O25—H26、O27—H28、O41—H42、O44—H45、O47—H48、O52—H53可与AM中O7以及IA中O4（或O13）形成强氢键作用。HYP-AM和HYP-IA复合物系统的高摩尔比可以增加复合物的总相互作用能量。通过筛选不同功能单体可以增强活性位点之间的相互作用强度。HYP与AM（IA）之间发生的强氢键作用导致Ⅰ、Ⅱ、Ⅳ吸收峰发生红移，同时验证了DFT理论计算的准确性。HYP-AM和HYP-IA复合物的最优印迹比分别为〔n(HYP):n(AM)=1:8〕和〔n(HYP):n(IA)=1:7〕，且HYP-IA比HYP-AM的相互作用力更强，IA是更好的功能单体。

Abstract:

To improve the imprinting efficiency of hyperoside (HYP), the theoretical calculation and UV spectral determination of HYP, acrylamide (AM), itaconic acid (IA), and its different molar ratios of HYP-AM and HYP-IA complexes were carried out by the method of density functional theory (DFT) and the experiment of ultraviolet-visible absorption spectroscopy (UV-Vis). The imprinted active sites of HYP, AM and IA were predicted by using the molecular electrostatic potential (MEP). The imprinting mechanism of the interaction between HYP and AM (IA) molecules was discussed. The results show that O11 of HYP can form strong hydrogen bonds with H9 (or H10) of AM, and H2 (or H15) of IA. While O12—H13, O15—H16, O25—H26, O27—H28, O41—H42, O44—H45, O47—H48 and O52—H53 can form strong hydrogen bonds with O7 of AM, and O4 (or O13) of IA. The high molar ratios of HYP-AM and HYP-IA complexes can increase the total interaction energy of the complex. The strength of the interaction between the active sites can be enhanced by selecting different functional monomers. The strong hydrogen-bond interaction between HYP and AM (IA) leads to partial redshifts of the absorption peak of Ⅰ, Ⅱ and Ⅳ. Moreover, the accuracy of DFT method was verified. The optimal imprinting molar ratios of HYP-AM and HYP-IA complexes were 〔n(HYP):n(AM)=1:8〕 and〔n(HYP):n(IA)=1:7〕, respectively. HYP-IA has stronger interaction with HYP-AM, and IA is a better functional monomer.