多重量子化学理论计算解析多胺修饰壳聚糖气凝胶吸附美拉德色素分子机制

doi:10.11949/0438-1157.20240584

化工学报 ›› 2025, Vol. 76 ›› Issue (1): 107-119.DOI: 10.11949/0438-1157.20240584

多重量子化学理论计算解析多胺修饰壳聚糖气凝胶吸附美拉德色素分子机制

王佳欣¹(), 韦艳红¹, 农顺洋¹, 熊艳舒², 李楣², 李文¹()

^1.广西民族大学化学化工学院，林产化学与工程国家民委重点实验室，广西林产化学与工程重点实验室，广西林产化学与工程协同创新中心，广西南宁 530008
^2.广西大学轻工与食品工程学院，广西南宁 530004

收稿日期:2024-05-30 修回日期:2024-09-13 出版日期:2025-01-25 发布日期:2025-02-08
通讯作者: 李文
作者简介:王佳欣（2000—），女，硕士研究生，wjiaxinwang@163.com
基金资助:
国家自然科学基金青年科学基金项目(32001741);广西创新驱动发展专项资金项目（桂科AA22117014-4）;广西自然科学基金青年科学基金项目(2021GXNSFBA076002)

Molecular mechanism analysis of melanoidin adsorption by polyamine-modified chitosan aerogel based on multiple quantum chemical theory calculations

Jiaxin WANG¹(), Yanhong WEI¹, Shunyang NONG¹, Yanshu XIONG², Mei LI², Wen LI¹()

^1.Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Key Laboratory of Chemistry and Engineering of Forest Products (State Ethnic Affairs Commission), School of Chemistry and Chemical Engineering, Guangxi Minzu University, Nanning 530008, Guangxi, China
^2.School of Light Industry and Food Engineering, Guangxi University, Nanning 530004, Guangxi, China

Received:2024-05-30 Revised:2024-09-13 Online:2025-01-25 Published:2025-02-08
Contact: Wen LI

摘要/Abstract

摘要：

现有糖汁脱色剂存在食品安全隐患及吸附量低等局限性。开发一款绿色无毒且具有高吸附量的超支化聚乙烯亚胺功能化壳聚糖气凝胶（HPCA）用于糖汁脱色，并初步探究其吸附美拉德色素（MLD）性能。为将高效糖汁脱色吸附剂投入到工业化应用中，还需对吸附理论机制进行更深层次探索。通过多重量子化学理论计算，从分子角度系统揭示HPCA吸附MLD潜在机理。静电势、平均局部电离能、静电势相互作用分析结果表明，HPCA捕获MLD主要由质子化胺基与羧酸根之间电荷作用介导。在分子水平上优化出三种可视化最优捕获构型，分析结果表明强的静电相互作用使得构型Ⅰ中HPCA与MLD紧密接触成为最稳定的构型。前沿分子轨道、独立梯度模型和Hirshfeld表面分析揭示HPCA捕获MLD存在氢键和范德华力等弱相互作用，且MLD在不同捕获构型中均主要充当氢键受体。多重量子化学理论计算研究方法可为探究分子水平上吸附相互作用机制提供可行研究方向，对研究吸附微观机制具有重要意义。

关键词: 计算化学, 吸附, 凝胶, 美拉德色素, 糖汁脱色

Abstract:

Existing sugar juice decolorizers have food safety hazards and low adsorption capacity. To address these issues, we have developed a green, non-toxic, and efficient hyperbranched polyethyleneimine-functionalized chitosan aerogel (HPCA) for sugar juice decolorization and conducted preliminary investigations into its ability to adsorb melanoidin (MLD) from sugar juice. However, it is necessary to further explore the theoretical mechanisms of adsorption in order to apply efficient HPCA to industrial settings. In this study, we systematically investigated the potential mechanisms of MLD adsorption by HPCA from a molecular perspective using multiple quantum chemical theoretical calculations. Our findings on the electrostatic potential, average local ionization energy, and electrostatic potential interactions suggested that MLD capture by HPCA was primarily mediated by the charge interaction between protonated amine group on HPCA and carboxylate group on MLD. Three visualized optimal capture configurations were proposed at the molecular level, with Configuration I demonstrating the highest stability due to the strong electrostatic interactions formed from the close contact between HPCA and MLD. Frontier molecular orbitals, independent gradient model, and Hirshfeld surface analysis revealed that the MLD adsorption by HPCA involved weak interactions, such as hydrogen bond and van der Waals force. Notably, the MLD mainly acted as hydrogen bond receptor in various capture configurations. These multiple quantum chemical theory calculations provide valuable insights into the molecular-level mechanisms of adsorption and are significant for advancing the study of adsorption micro-mechanisms.

Key words: computational chemistry, adsorption, gels, melanoidin, sugar juice decolorization

中图分类号:

TS 244.2

王佳欣, 韦艳红, 农顺洋, 熊艳舒, 李楣, 李文. 多重量子化学理论计算解析多胺修饰壳聚糖气凝胶吸附美拉德色素分子机制[J]. 化工学报, 2025, 76(1): 107-119.

Jiaxin WANG, Yanhong WEI, Shunyang NONG, Yanshu XIONG, Mei LI, Wen LI. Molecular mechanism analysis of melanoidin adsorption by polyamine-modified chitosan aerogel based on multiple quantum chemical theory calculations[J]. CIESC Journal, 2025, 76(1): 107-119.

图/表 7

图1 (a)HPCA的EDS元素（C、N和O）映射图；(b)溶液pH对HPCA去除MLD的影响；(c)HPCA的SEM图像；(d)HPCA立于月季花瓣上；(e)HPCA吸附前后MLD溶液变化[7]

Fig.1 (a) EDS elemental (C, N, and O) mapping images of HPCA; (b) Influence of pH on MLD removal by HPCA; (c) SEM image of HPCA; (d) HPCA rested on the petals of Chinese rose; (e) Change of MLD aqueous solutions before and after adsorption by HPCA[7]

图2 (a) ESP彩色分子表面（白—H；蓝—N；红—O；青—C）；(b) ESP分子表面积统计分布（1 Å=0.1 nm）；(c) HPCA、PHPCA、UMLD及MLD分子表面ESP极值分析（白—H；蓝—N；红—O；黄—C）

Fig.2 (a) ESP colored molecular surface (white—H； blue—N； red—O； cyan—C); (b) ESP statistical distribution on molecular surface area（1 Å=0.1 nm）; (c) Molecular surface ESP extrema analysis of HPCA, PHPCA, UMLD, and MLD (white—H； blue—N； red—O； yellow—C)

图3 (a) ALIE彩色MLD分子表面及表面极值（白—H；蓝—N；红—O；青—C）；(b) HPCA吸附MLD结合能；HPCA吸附MLD的(c) ESP穿透构型及(d) ESP中和构型

Fig.3 (a) ALIE colored MLD molecular surface with surface extrema (white—H； blue—N； red—O； cyan—C); (b) Binding energy for MLD adsorption by HPCA; (c) ESP penetration configuration and (d) ESP neutralization configuration for HPCA adsorption of MLD

图4 (a)三种优化构型的HOMO和LUMO轨道分布及其能量值；(b) HPCA和MLD的HOMO和LUMO轨道分布及其能量值（白—H；蓝—N；红—O；青—C）

Fig.4 (a) HOMO and LUMO orbital distributions and their energy values for three optimized configurations; (b) HOMO and LUMO orbital distributions and their energy values for HPCA and MLD (white—H； blue—N； red—O； cyan—C)

图5 (a) IGM图中各种颜色的解释；(b)构型Ⅰ、(c)构型Ⅱ和 (d) 构型Ⅲ中HPCA与MLD弱相互作用散点图；(e)所有构型可视化弱相互作用区域图（白—H；蓝—N；红—O；青—C）；(f) 根据原子δg指数着色所有构型的分子结构；(g) HPCA吸附MLD所有构型的键合路径

Fig.5 (a) Interpretation of various colors in IGM map; Scatter maps of weak interaction between HPCA and MLD in (b) configuration Ⅰ, (c) configuration Ⅱ and (d) configuration Ⅲ; (e) Photographs of visualized weak-interaction regions of all configurations (white—H； blue—N； red—O； cyan—C); (f) Coloring molecule structures by atomic δg index across all configurations; (g) Bonding paths of MLD adsorption onto HPCA across all configurations

图6 构型Ⅰ、Ⅱ和Ⅲ中(a)MLD和(b)HPCA的HIS及其对应指纹图

Fig.6 HIS and corresponding fingerprint plots of (a) MLD and (b) HPCA for configurations Ⅰ, Ⅱ, and Ⅲ

图7 (a) 构型Ⅰ中MLD的(ⅰ)O···H-N、(ⅱ)H···H和(ⅲ)O-H···N的HIS及其相应指纹图；(b) 构型Ⅱ中MLD的(ⅰ)O···H-N、(ⅱ)H···H、(ⅲ)O-H···O和(ⅳ)C-H···N的HIS及其相应指纹图；(c) HIS及其相应指纹图中O原子局部接触面占总接触面之比

Fig.7 (a) HIS and the corresponding fingerprint plots of MLD for (ⅰ) O···H—N, (ⅱ) H···H, and (ⅲ) O—H···N in configuration Ⅰ; (b) HIS and the corresponding fingerprint plots of MLD for (ⅰ) O···H—N, (ⅱ) H···H, (ⅲ) O-H···O, and (ⅳ) C-H···N in configuration Ⅱ; (c) Proportion of the local contact area of O atom to the total contact area in HIS and the corresponding fingerprint plot

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多重量子化学理论计算解析多胺修饰壳聚糖气凝胶吸附美拉德色素分子机制

Molecular mechanism analysis of melanoidin adsorption by polyamine-modified chitosan aerogel based on multiple quantum chemical theory calculations

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