Article(id=1320881865532227906, tenantId=1146029695717560320, journalId=1260987677001138203, issueId=1320881182762447607, articleNumber=null, orderNo=null, doi=10.13386/j.issn1002-0306.2026050291, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1779724800000, receivedDateStr=2026-05-26, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1792852377540, onlineDateStr=2026-10-24, pubDate=1786723200000, pubDateStr=2026-08-15, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792852377540, onlineIssueDateStr=2026-10-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792852377540, creator=13701087609, updateTime=1792852377540, updator=13701087609, issue=Issue{id=1320881182762447607, tenantId=1146029695717560320, journalId=1260987677001138203, year='2026', volume='47', issue='16', pageStart='1', pageEnd='537', issueExtLink='null', onlineDate='null', pubDate='1786723200000', pubDateStr='2026-08-15', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792852214756, creator='13701087609', updateTime=1792852214756, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=185, endPage=192, ext={EN=ArticleExt(id=1320881865775497539, articleId=1320881865532227906, tenantId=1146029695717560320, journalId=1260987677001138203, language=EN, title=Interactions and Molecular Dynamics Simulation of Chitosan/Nanocellulose Hydrogels Incorporating EGCG, columnId=1261336277291548795, journalTitle=Science and Technology of Food Industry, columnName=Research and Investigation, runingTitle=null, highlight=null, articleAbstract=

The preparation of active packaging materials from chitosan (CS), cellulose nanocrystals (CN), and epigallocatechin gallate (EGCG) involved a complex multi-component system that was highly susceptible to phase separation or aggregation of active components. This necessitated the urgent development of multi-component compatibility matching models and novel interfacial regulation strategies to stabilize the system and ensure homogeneous distribution of functional constituents. This study employed a pre-constructed EGCG-loaded CS/CN nanocrystal hydrogel (EGCG hydrogel) as the model system. The morphological and structural characteristics of the layer were systematically characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). Subsequently, molecular dynamics (MD) simulations were conducted with parameterized force fields to analyze the conformational dynamics and intramolecular/intermolecular interactions within the composite hydrogel system. The results demonstrated that the CS/CN nanocrystal hydrogel serves as an effective carrier for EGCG. With EGCG incorporation, the material surface exhibited increased roughness, thicker pore walls, and a more compact overall structure compared to the pristine hydrogel. Additionally, the EGCG hydrogel retained only a broad diffraction peak at 20.0° in XRD patterns, while the characteristic sharp peaks of pure EGCG disappeared, indicating the loss of crystalline EGCG domains within the matrix. Crucially, no new covalent bond-associated peaks emerged in the FT-IR spectra, confirming that EGCG was physically entrapped via non-covalent interactions rather than chemical bonding. MD simulations further revealed that increasing EGCG loading enhanced system stability, as evidenced by reduced fluctuations in root mean square deviation (RMSD) and solvent-accessible surface area (SASA). The radius of gyration stabilized at approximately 7 nm, suggesting a consolidated molecular conformation. Moreover, the number of hydrogen bonds between CN and CS increased significantly upon EGCG addition, implying that EGCG molecules reinforce interfacial interactions within the composite network through hydrogen-bond-mediated crosslinking. This study provides a theoretical foundation for the rational design and precise fabrication of controlled-release active packaging materials.

, authors=Shouen HUANG1, Hua ZENG2, authorsList=Shouen HUANG, Hua ZENG, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Science and Technology of Food Industry. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1320881871219704153, articleId=1320881865532227906, tenantId=1146029695717560320, journalId=1260987677001138203, language=CN, title=壳聚糖与纳米纤维素水凝胶负载EGCG的互作及分子动力学模拟, columnId=1261336277849391232, journalTitle=食品工业科技, columnName=研究与探讨, runingTitle=null, highlight=null, articleAbstract=

由壳聚糖(chitosan,CS)、纳米纤维素(cellulose nanocrystals,CN)和表没食子儿茶素没食子酸酯(epigallocatechin gallate,EGCG)制备活性包装材料的过程涉及多组分的复杂体系,易引发相分离或活性成分团聚,亟需开发多组分相容性匹配模型与新型界面调控策略。本研究以前期构建负载EGCG的CS/CN水凝胶(EGCG hydrogel)为研究对象,通过扫描电镜、X射线衍射和傅里叶变换红外光谱表征其形貌及结构特征。接着通过设定力场,利用分子动力学模拟技术对水凝胶互作体系的构象、分子内和分子间作用力进行分析。结果表明,CS和CN形成的水凝胶是EGCG的优良载体,且随着EGCG的添加,其表面变得粗糙,孔壁明显增厚,整体结构更加致密。此外,EGCG hydrogel仅在20.0°处保存了较宽的衍射峰,EGCG特有的尖锐峰消失。同时,EGCG hydrogel未出现明显的新共价键特征红外光谱峰,这表明EGCG主要是通过非共价相互作用被物理包裹在内部。分子动力学模拟则发现,随着EGCG的添加量逐渐增加,水凝胶体系的均方根偏差和溶剂可及表面积更稳定,且回转半径稳定在7 nm左右。此外,体系内CN与CS间的氢键数量较未加入之前更丰富。本研究将为控释活性包装材料的理性设计与精确制备提供理论依据。

, authors=黄寿恩1, 曾桦2, authorsList=黄寿恩, 曾桦, authorCompany=null, correspAuthors=null, authorNote=

黄寿恩(1967−),男,博士,副编审,研究方向:食品装备与智能制造,E-mail:

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黄寿恩(1967−),男,博士,副编审,研究方向:食品装备与智能制造,E-mail:

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黄寿恩(1967−),男,博士,副编审,研究方向:食品装备与智能制造,E-mail:

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Food Research International, 2016, 88: 79−90., articleTitle=null, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1320881871437807962, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, xref=1, ext=[AuthorCompanyExt(id=1320881871446196571, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, companyId=1320881871437807962, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1Journal Office, Changsha University of Science and Technology, Changsha 410000, China), AuthorCompanyExt(id=1320881871450390876, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, companyId=1320881871437807962, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1长沙理工大学期刊社,湖南长沙 410000)]), AuthorCompany(id=1320881871521694045, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, xref=2, ext=[AuthorCompanyExt(id=1320881871530082654, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, companyId=1320881871521694045, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2College of Food Science and Technology, Hunan Agricultural University, Changsha 410000, China), AuthorCompanyExt(id=1320881871538471263, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, companyId=1320881871521694045, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2湖南农业大学食品科学技术学院,湖南长沙 410000)])], figs=[ArticleFig(id=1320881874562564468, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=EN, label=Fig.1, caption=Initial conformation of CS/CN hydrogels loaded with EGCG, figureFileSmall=qvhspXOfocfZXbe34G4Qug==, figureFileBig=0TxAzQpBZlHMTcTkrHBaOw==, tableContent=null), ArticleFig(id=1320881874659033461, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=CN, label=图1, caption=CS/CN水凝胶与EGCG互作的初始构象

注:(a)Hydrogel的初始构象;(b)EGCG hydrogel的初始构象。

, figureFileSmall=qvhspXOfocfZXbe34G4Qug==, figureFileBig=0TxAzQpBZlHMTcTkrHBaOw==, tableContent=null), ArticleFig(id=1320881874843582838, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=EN, label=Fig.2, caption=SEM images of Hydrogel and EGCG hydrogel, figureFileSmall=Os/aeIltsoyOSGg1hSevCQ==, figureFileBig=OgM7DqlGX8xDYZeJbY5lCg==, tableContent=null), ArticleFig(id=1320881874910691703, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=CN, label=图2, caption=Hydrogel和EGCG hydrogel的扫描电镜

注:(a)Hydrogel的微观形貌;(b)EGCG hydrogel的微观形貌。

, figureFileSmall=Os/aeIltsoyOSGg1hSevCQ==, figureFileBig=OgM7DqlGX8xDYZeJbY5lCg==, tableContent=null), ArticleFig(id=1320881874973606264, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=EN, label=Fig.3, caption=XRD patterns of Hydrogel and EGCG hydrogel, figureFileSmall=wrpaCedOz8EBYoo8k+Asrw==, figureFileBig=Fg5OPqbtnxqE4g5ZzjM28g==, tableContent=null), ArticleFig(id=1320881875044909433, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=CN, label=图3, caption=Hydrogel和EGCG hydrogel的XRD光谱, figureFileSmall=wrpaCedOz8EBYoo8k+Asrw==, figureFileBig=Fg5OPqbtnxqE4g5ZzjM28g==, tableContent=null), ArticleFig(id=1320881875107823994, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=EN, label=Fig.4, caption=FT-IR spectra of hydrogel and EGCG hydrogel, figureFileSmall=90jdi7vbsSEcE7Mk3qc3Bw==, figureFileBig=tPKg21Eet62/Wf9ZSn8V4A==, tableContent=null), ArticleFig(id=1320881875174932859, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=CN, label=图4, caption=Hydrogel和EGCG hydrogel的FT-IR光谱, figureFileSmall=90jdi7vbsSEcE7Mk3qc3Bw==, figureFileBig=tPKg21Eet62/Wf9ZSn8V4A==, tableContent=null), ArticleFig(id=1320881875250430332, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=EN, label=Fig.5, caption=Hydrogel (a) and hydrogels loaded with EGCG (b) of conformation at different times in the simulated trajectories, figureFileSmall=Uk80qJCXI7MlojsDX03iLA==, figureFileBig=xCMgUkw4AOHH5JCKQVUWVQ==, tableContent=null), ArticleFig(id=1320881875380453757, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=CN, label=图5, caption=水凝胶(a)和负载EGCG的水凝胶(b)在模拟轨迹中不同时间的构象

注:(a)Hydrogel的不同时间构象;(b)EGCG hydrogel的不同时间构象。

, figureFileSmall=Uk80qJCXI7MlojsDX03iLA==, figureFileBig=xCMgUkw4AOHH5JCKQVUWVQ==, tableContent=null), ArticleFig(id=1320881875451756926, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=EN, label=Fig.6, caption=Root mean square deviation of the hydrogel and the EGCG hydrogel, figureFileSmall=Jl7uPCJRmIhNf3Lh0P+/WA==, figureFileBig=QXPqieD3Z+/2hfStqnyriQ==, tableContent=null), ArticleFig(id=1320881875548225919, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=CN, label=图6, caption=Hydrogel和EGCG hydrogel的均方根偏差, figureFileSmall=Jl7uPCJRmIhNf3Lh0P+/WA==, figureFileBig=QXPqieD3Z+/2hfStqnyriQ==, tableContent=null), ArticleFig(id=1320881875619529088, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=EN, label=Fig.7, caption=Rg of hydrogel (a) and hydrogels loaded with EGCG (b), figureFileSmall=hb89CDctI6NA0ZHLoIEQqg==, figureFileBig=eFQc5VCCz/ju6g8aO0P0PA==, tableContent=null), ArticleFig(id=1320881875695026561, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881865532227906, language=CN, label=图7, caption=水凝胶(a)和负载EGCG的水凝胶(b)的Rg

注:(a)Hydrogel的Rg;(b)EGCG Hydrogel的Rg。

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壳聚糖与纳米纤维素水凝胶负载EGCG的互作及分子动力学模拟
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黄寿恩 1 , 曾桦 2
食品工业科技 | 研究与探讨 2026,47(16): 185-192
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食品工业科技 |研究与探讨 2026 , 47 (16) : 185 -192
壳聚糖与纳米纤维素水凝胶负载EGCG的互作及分子动力学模拟
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黄寿恩(1967−),男,博士,副编审,研究方向:食品装备与智能制造,E-mail:

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黄寿恩1 , 曾桦2
作者信息
  • 1长沙理工大学期刊社,湖南长沙 410000
  • 2湖南农业大学食品科学技术学院,湖南长沙 410000
作者简介:

黄寿恩(1967−),男,博士,副编审,研究方向:食品装备与智能制造,E-mail:

Interactions and Molecular Dynamics Simulation of Chitosan/Nanocellulose Hydrogels Incorporating EGCG
Shouen HUANG1 , Hua ZENG2
Affiliations
  • 1Journal Office, Changsha University of Science and Technology, Changsha 410000, China
  • 2College of Food Science and Technology, Hunan Agricultural University, Changsha 410000, China
出版时间: 2026-08-15 doi: 10.13386/j.issn1002-0306.2026050291
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由壳聚糖(chitosan,CS)、纳米纤维素(cellulose nanocrystals,CN)和表没食子儿茶素没食子酸酯(epigallocatechin gallate,EGCG)制备活性包装材料的过程涉及多组分的复杂体系,易引发相分离或活性成分团聚,亟需开发多组分相容性匹配模型与新型界面调控策略。本研究以前期构建负载EGCG的CS/CN水凝胶(EGCG hydrogel)为研究对象,通过扫描电镜、X射线衍射和傅里叶变换红外光谱表征其形貌及结构特征。接着通过设定力场,利用分子动力学模拟技术对水凝胶互作体系的构象、分子内和分子间作用力进行分析。结果表明,CS和CN形成的水凝胶是EGCG的优良载体,且随着EGCG的添加,其表面变得粗糙,孔壁明显增厚,整体结构更加致密。此外,EGCG hydrogel仅在20.0°处保存了较宽的衍射峰,EGCG特有的尖锐峰消失。同时,EGCG hydrogel未出现明显的新共价键特征红外光谱峰,这表明EGCG主要是通过非共价相互作用被物理包裹在内部。分子动力学模拟则发现,随着EGCG的添加量逐渐增加,水凝胶体系的均方根偏差和溶剂可及表面积更稳定,且回转半径稳定在7 nm左右。此外,体系内CN与CS间的氢键数量较未加入之前更丰富。本研究将为控释活性包装材料的理性设计与精确制备提供理论依据。

活性包装材料  /  壳聚糖  /  纳米纤维素  /  表没食子儿茶素没食子酸酯  /  分子动力学模拟

The preparation of active packaging materials from chitosan (CS), cellulose nanocrystals (CN), and epigallocatechin gallate (EGCG) involved a complex multi-component system that was highly susceptible to phase separation or aggregation of active components. This necessitated the urgent development of multi-component compatibility matching models and novel interfacial regulation strategies to stabilize the system and ensure homogeneous distribution of functional constituents. This study employed a pre-constructed EGCG-loaded CS/CN nanocrystal hydrogel (EGCG hydrogel) as the model system. The morphological and structural characteristics of the layer were systematically characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). Subsequently, molecular dynamics (MD) simulations were conducted with parameterized force fields to analyze the conformational dynamics and intramolecular/intermolecular interactions within the composite hydrogel system. The results demonstrated that the CS/CN nanocrystal hydrogel serves as an effective carrier for EGCG. With EGCG incorporation, the material surface exhibited increased roughness, thicker pore walls, and a more compact overall structure compared to the pristine hydrogel. Additionally, the EGCG hydrogel retained only a broad diffraction peak at 20.0° in XRD patterns, while the characteristic sharp peaks of pure EGCG disappeared, indicating the loss of crystalline EGCG domains within the matrix. Crucially, no new covalent bond-associated peaks emerged in the FT-IR spectra, confirming that EGCG was physically entrapped via non-covalent interactions rather than chemical bonding. MD simulations further revealed that increasing EGCG loading enhanced system stability, as evidenced by reduced fluctuations in root mean square deviation (RMSD) and solvent-accessible surface area (SASA). The radius of gyration stabilized at approximately 7 nm, suggesting a consolidated molecular conformation. Moreover, the number of hydrogen bonds between CN and CS increased significantly upon EGCG addition, implying that EGCG molecules reinforce interfacial interactions within the composite network through hydrogen-bond-mediated crosslinking. This study provides a theoretical foundation for the rational design and precise fabrication of controlled-release active packaging materials.

active packaging materials  /  chitosan  /  cellulose nanocrystals  /  epigallocatechin gallate  /  molecular dynamics simulation
黄寿恩, 曾桦. 壳聚糖与纳米纤维素水凝胶负载EGCG的互作及分子动力学模拟. 食品工业科技, 2026 , 47 (16) : 185 -192 . DOI: 10.13386/j.issn1002-0306.2026050291
Shouen HUANG, Hua ZENG. Interactions and Molecular Dynamics Simulation of Chitosan/Nanocellulose Hydrogels Incorporating EGCG[J]. Science and Technology of Food Industry, 2026 , 47 (16) : 185 -192 . DOI: 10.13386/j.issn1002-0306.2026050291
包装材料是维系食品品质、保障供应链及推动食品工业发展的关键[1−2]。然而,传统石油基塑料包装材料存在不可再生特性,且降解周期漫长,不当处置将引发“白色污染”,加剧生态环境负荷[3−4]。此外,传统材料由于缺乏功能活性成分,导致其难以适配差异化的包装需求,且残存的有害成分在长期接触过程中易向食品基质迁移,对消费者健康构成潜在风险[5−7]。因此,随着消费者对高品质食品包装材料需求的稳步增长,兼具优良阻隔性、力学强度及功能性等优势的天然多糖基聚合物被视为传统包装材料的可行替代[8−9]。其中,壳聚糖因其有序的氢键网络和延展性分子链,以及优异的安全性、透明度和柔韧性,是包装材料的良好选择[10−11]。然而,单一的壳聚糖基质在湿态稳定性上存在局限性,因此经常利用机械性能强的纳米纤维素进行物理共混改进[12]。此外,依赖CS与CN形成的生物材料缺乏抗菌、抗氧化及风味改良等功能,难以长期维持食品品质。因此,通过将植物提取物的活性成分与其复合,可进一步构建控释活性包装系统,以实现活性物质的持续、可控释放,延长货架期的同时兼具多重保鲜功能。例如,以CS为基体,负载丁香精油与CN固定的铜纳米粒抗菌纤维,可构建兼具缓冲抗震与长效保鲜功能的气凝胶活性包装,将为浆果类采后运输减损与绿色保鲜提供全新材料与技术支撑[13];通过“膨胀-渗透”法制备的可食用CN和CS双组分包装材料可显著延缓苹果的软化和氧化过程,且材料中添加的乙基对香豆酸酯较好保持了苹果的色泽和质地[14]。此外,团队前期以CS和CN为基材,对表没食子儿茶素没食子酸酯进行高效负载,构筑了一种具有重金属吸附和抗氧化功能的水凝胶[15]。总之,由CS、CN和活性成分形成的生物塑料将为可持续替代传统包装塑料提供有效方案,应用前景广阔。
基于生物材料的活性包装制备过程是一种涉及三组分的复杂体系,其不同组分间的相容性与界面相互作用难以精准调控,易引发相分离或活性成分团聚[16]。因此,常规试验表征技术无法精准阐明组分间相互作用对食品包装材料的均一性与功能稳定性的影响,亟需开发新型界面调控策略与多组分相容性匹配模型,以解析动态互作过程的微观结构演变规律和机制[5,14]。分子动力学模拟是在原子、分子水平上模拟复杂多体系过程的重要计算机模拟手段,其采用力场的方法和经典力学方程,模拟出不同组分随时间的演化过程,通过体系的微观信息,借助统计学的策略获得体系的宏观性质[17]。相较于实际实验,利用分子模拟研究多组分复杂体系具有以下优点:成本较低;可靠性高,可以有效降低实验误差;有助于更充分的理解和呈现一些通过实际实验难以获得的分子级别的结构和动力学行为[18−19]。因此,本研究拟以前期构建负载EGCG的CS/CN水凝胶(EGCG hydrogel)为研究基础[15],通过扫描电镜(scanning electron microscope,SEM)、X射线衍射(X-ray diffraction,XRD)和傅里叶变换红外光谱(fourier transform infrared spectroscopy,FT-IR)系统表征其形貌及结构特征。然后通过设定模拟力场,对水凝胶互作体系的构象、分子内和分子间作用力等进行重点分析,以期对CS/CN负载EGCG的行为进行科学的解释,并为控释活性包装材料的制备提供理论依据。
漂白木浆 山东道欣新材料有限公司;溴化钠(99.0%)、乙基[3-(二甲氨基)丙基]碳二亚胺盐酸盐(EDC,99.0%)、N-羟基琥珀酰亚胺(BR) 国药集团化学试剂有限公司;CS(BR)、2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO,98.0%)、乙醇、亚氯酸钠(80.0%)、氢氧化钠、过氧化氢(AR)、乙二胺(98.0%)、柠檬酸、戊二醛(AR) 上海阿拉丁试剂有限公司;EGCG(98.0%) 上海源叶生物科技有限公司。
LC-MSB-H型磁力搅拌器 湖南力辰仪器科技有限公司;F-009SD型超声波清洗器 深圳福洋科技集团有限公司;CY-03628型聚四氟反应釜 西安常仪仪器设备有限公司;202-0B型电热鼓风干燥箱 广东佰辉;Quanta 250 FEG型扫描电镜 美国FEI公司;D8 Advance 型X射线衍射仪 德国布鲁克AXS公司;iS10傅里叶变换红外光谱仪 美国赛默飞世尔科技公司。
依据文献[15]中的方法,首先,在500 mL烧杯中加入2.0 g绝干漂白木浆和200 g超纯水,搅拌均匀。然后,加入0.2 g的溴化钠、6.0 mL的NaClO和0.04 g的TEMPO。添加氢氧化钠缓冲液,将混合物的pH调整至10。在室温环境下持续搅拌24 h,终止氧化反应。以超纯水洗涤,直至中性。接着,将氧化产物高压均质6次,获得CN。将制备好的CN放入透析袋(14 kDa)中4 d,去除未反应的小分子物质。最后,加入超纯水,将CN悬浊液的浓度调整至1.0wt%。
依据文献[13−15]中的方法,称取2 g的CS置于98 g的2%乙酸溶液中,超声反应1 h,直至CS完全溶解。然后,向溶解液中添加5.0 g经1.2.1.1制备的CN悬浊液,并向混合体系中加入25 mL 5%的戊二醛,于室温连续搅拌2 h。接着,将混合物在60 ℃水浴里加热2 h以完成凝胶化的过程。最后,浸于超纯水中4 d以移除残留,即可得到水凝胶(Hydrogel)。
在1.2.1.2的凝胶化之前加入一定质量的EGCG来制备负载EGCG的水凝胶(EGCG hydrogel)。其中,根据吸附容量[13−15],通过质量比换算即得CS:CN:EGCG=0.26 g:1.625 g:20 mg。
将水凝胶(Hydrogel和EGCG hydrogel)在温度为−60 ℃的条件下进行48 h的冷冻干燥,制备相应的气凝胶样品,然后使用10 μm的扫描电镜观测。
利用X射线衍射仪分析CS、CN、EGCG、Hydrogel和EGCG hydrogel的晶型结构,射线源(Cu Kα,λ=0.15406 nm),管电流(40 mA)和管电压(40 kV)。
通过傅里叶变换红外光谱分析仪(FT-IR)在4000~650 cm−1范围内,以4 cm−1的分辨率探究CS、CN、EGCG、Hydrogel和EGCG hydrogel的特征官能团。
采用全原子力场对CS/CN水凝胶负载EGCG的过程进行模拟,并进行轨迹分析[20−21],包括均方根偏差(root mean square deviation,RMSD)、回转半径(radius of gyration,Rg)、径向分布函数(radial distribution function,RDF)、溶剂可及表面积(solvent accessible surface area,SASA)及氢键数变化。
为确保微观模拟可以最真实反映EGCG的最佳环境负载状态,根据团队前期关于CS/CN水凝胶负载EGCG的最适条件,通过质量比换算(CS:CN:EGCG=0.26 g:1.625 g:20 mg)及适当调整[11,15],本模拟将在15×15×15 nm的正方体盒子中分别放入了8个CS、45个CN和2个EGCG分子,对照组为在同样尺寸的盒子中放入45个CN和8个CS,详见图1。
采用Gromacs 2018.4程序,选择GAFF全原子力场[21−23],TIP3P水模型[24−26],在恒温恒压以及周期性边界条件下进行。模拟过程中,所有涉及氢原子的键均采用LINCS算法进行约束[27−29],积分步长为2 fs。静电相互作用均采用(Particle-mesh ewald)PME方法计算[30]。非键相互作用的截断值定为10 Å,并每10步更新1次。通过V-rescale温度耦合方法控制模拟温度为300 K,并采用Parrinello方法[31]控制压力为1 bar,具体的模拟细节如下:a. 使用最陡下降法对体系在真空环境中优化2500步,紧接着以共轭梯度法优化2500步,每一步的截断值都设置为10 Å,以消除原子间过近的接触,能量最小化的收敛值为100 kJ·mol−1·nm−1;b. 当整个体系完成能量优化后,设置位置限制性动力学模拟,这一过程主要是为了限制分子中的原子位置,允许溶剂分子的运动[32]。溶剂分子的驰豫时间通常为10 ps,因此设置的平衡时间是1000 ps。由于在整个过程中,需要对体系进行一个NVT和NPT平衡。因此设置模拟温度条件,将体系温度从0 K上升到300 K,在恒温恒容的条件下,给体系增加1000 kJ·mol−1·nm−1的限制力,用于平衡溶剂分子;c. 对CS/CN水凝胶负载EGCG的体系进行50 ns的分子动力学模拟,每10 ps保存一次构象[33],并呈现0、20和50 ns时的构象。其中,50 ns符合当前生物大分子体系模拟的常规时间尺度,可确保复合体系完成结构弛豫并达到热力学平衡[31−33]。
每组试验进行3次平行,结果以平均数±标准差表示。以SPSS 25软件为工具,采用最小显著性差异法进行显著性分析,P<0.05表示差异显著。利用Graphpad Prism 9.0软件绘图,并应用Gromacs 2018.4程序执行动力学模拟。
图2分别呈现Hydrogel和负载EGCG hydrogel的微观形貌。在图2(a)中,出现典型的多孔海绵状结构,孔壁相对较薄且表面较为光滑,孔径分布均匀,可能是由于CS和CN通过物理缠结或氢键作用形成的三维网络骨架[13−15]。添加适量EGCG后(图2(b)),Hydrogel孔壁明显变厚,表面变得粗糙,部分孔隙似乎被填充或缩小,整体结构显得更加致密,这可能是由于EGCG含有的酚羟基与CS的氨基/羟基及CN的羟基形成强烈的氢键网络[13−15]。
Hydrogel和负载EGCG hydrogel的晶型结构变化如图3所示。图3展示了CN具有的3个典型特征峰,分别位于22.7°、16.2°与14.9°,这3个特征峰归属于纤维素I的晶型结构[11−12,15]。CS则在20.0°处存在一个较宽的衍射峰,归属于CS的非晶型结构[13−15]。Hydrogel则呈现无定形网络结构,这可能是由于CN和CS交联后,原有的结晶结构被破坏[13−15]。EGCG具有多个尖锐且密集的特征峰[11−15],分别位于10.3°、12.1°、15.6°、21.5°、24.5°、25.9°与28.2°。形成EGCG hydrogel后,其仅在20.0°处保存较宽的衍射峰,上述的EGCG尖锐峰消失,这可能是由于形成了三维网状结构将EGCG完全包裹在水凝胶内部[13−15]。
Hydrogel和负载EGCG hydrogel的官能团结构变化如图4所示。其中,CN有位于1048 cm−1的特征峰,归属于CN的碳氧伸缩与环振动模式[11−13]。CS在1646 cm−1出现新的谱峰,归属于-CH3的碳氢伸缩振动[12−13]。相较于CN或CS,Hydrogel的O-H或N-H峰(3300~3400 cm−1)发生了变宽或蓝移,暗示CN与CS之间形成新的氢键网络,导致原有的部分有序结构被破坏[13−15]。EGCG则出现大量尖锐的峰,关键是在1691 cm−1处的特征谱峰,归属于没食子酸中碳氧伸缩振动[13−15]。此外,EGCG位于3348 cm−1处有归属于O-H伸缩振动的峰[13−14]。形成EGCG hydrogel后,其在1048、1646和1691 cm−1处的特征峰几乎不可见或极度减弱,且未出现明显的新共价键特征峰(如新的酯键或酰胺键),这表明EGCG主要是通过非共价相互作用(主要是氢键和疏水相互作用)被物理包裹或吸附在水凝胶网络内,而不是发生了剧烈的化学反应[13−15]。
图5分别表示了Hydrogel(a)和负载EGCG hydrogel(b)在模拟过程中不同时间点的构象变化。CS具有复杂的双螺旋结构并且含有大量氨基、羟基和N-乙酰胺基[34]。同样的,CN表面也附有大量的带电官能团,如磺酸基和羧基[34]。两者在交联剂的作用下,通过化学键形成了具有三维孔洞结构的水凝胶(图5(a))。随着EGCG的加入,该水凝胶原有的聚集状态发生了改变。如图5(b)所示,在最初的状态下,包括EGCG、CN和CS在内的分子都呈现着相对均匀的分布,未出现聚集的状态。随着模拟时长的增加,逐渐发生了团聚现象,最初形成多个小型聚集体,然后进一步的聚集直至最终形成稳定的水凝胶结构,并达到平衡状态。值得注意的是,与不含 EGCG 的体系(图5(a))相比,添加适量EGCG后(图5(b)),CS/CN水凝胶聚集密度明显提升。
均方根偏差(root mean square deviation,RMSD)是用来计算不同构象之间的平均原子位移。图6分别表示了Hydrogel和EGCG Hydrogel轨迹的RMSD值随模拟时间的变化。相较于Hydrogel,EGCG hydrogel中的RMSD变化更为集中,除初始10 ns 内波动较大外,后续稳定维持在8.5 nm左右。此外,在整个模拟过程中,EGCG hydrogel中的RMSD值均要小于Hydrogel。说明在没有EGCG存在的情况下,Hydrogel的结构并不稳定,更容易散开,而EGCG的存在则更有利于Hydrogel的稳定,这可能与EGCG的酚羟基结构有关[15,17]。
回转半径(radius of gyration,Rg)被用于衡量单链分子的尺寸和结构的聚合物物理学使用的量。Rg可以反映分子的整体结构的密实度,如果分子的结构很稳定,其Rg将保持一个相对稳定的值,Rg变化越大表明分子体系越膨胀[35]。图7分别反映了加入EGCG前后,水凝胶Rg的变化。由图7(a)可知,不含EGCG的体系中CN与CS的Rg存在明显差异,表明体系结构疏松、膨胀度高[17,20]。加入EGCG后,体系中的CN和CS分子的Rg值均稳定在7 nm左右。这说明,EGCG能够使原有的CN和CS体系更稳定。这一结果也验证了2.5中RMSD的计算结果。
径向分布函数(radial distribution function,RDF)是用来描述物质的密度随着与参照物距离的变化而改变的情况[36]。RDF可以很好的反应水凝胶体系中某一分子周围其他分子随距离变化的分布情况。在EGCG hydrogel中,EGCG相对CN、CS的径向分布分别对应图8中由上向下出现的第三波峰和第一波峰的曲线。由图8可知,在EGCG分子周围0.5 nm左右有较大数量的CN和CS分子聚集。由上向下出现的第四波峰和第二波峰曲线分别表示Hydrogel和EGCG hydrogel体系内CS分子周围CN分子的径向分布,两个体系中的峰值几乎都出现在0.8 nm左右,但在加入了EGCG的体系中,峰值更大,表明加入了EGCG分子的体系中整个体系组装的更好,CS分子周围同样距离范围内聚集的CN分子更多[27−29]。
混合分子体系组装形成的驱动力之一是水和疏水基团之间的不利接触,不利接触的数量可以近似于与溶剂可及表面积(solvent accessible surface area,SASA)成正比,SASA的主要计量方法是通过半径为1.4 Å的小分子探针计算整个分子的溶剂可及性表面积[37]。因此,本研究对比分析了2个水凝胶体系模拟过程中的SASA,以此来表征两个聚集体系最终形成的凝胶的紧密程度。由图9可知,Hydrogel体系中的SASA均值要大于EGCG hydrogel体系中的SASA均值。这说明EGCG的加入能够减少体系中的水和疏水基团之间的不利接触,这可能与EGCG分子占据更多空间、减少疏水基团暴露有关[20,25–26]。
在CN的表面附有大量的带电官能团,如磺酸基、羧基等,这使得纳米纤维素可以均匀稳定的分散在水中。CS分子上也分布着大量的活性氨基和羟基,能发生水解、取代和缩合等化学反应。因此,CN和CS形成水凝胶的主要驱动力就是它们分子内和分子之间氢键的相互作用[37]。本研究中分别计算了Hydrogel和EGCG hydrogel体系中的氢键数目,见图10。由图10可知,EGCG hydrogel中的氢键数目始终要大于Hydrogel的氢键数目,这说明在EGCG hydrogel分子内和分子之间存在更强的相互作用,但也不能完全排除加入的EGCG本身的结构对计算体系造成的影响。
本研究以CS和CN形成的水凝胶作为EGCG的优良载体,制备出了负载植物功能活性成分EGCG的水凝胶。微观形貌观察表明,添加适量EGCG后,Hydrogel孔壁明显变厚,表面变得粗糙,部分孔隙被填充或缩小,整体结构显得更加致密。此外,傅里叶变换红外和X射线衍射的结构表征结果证实,该水凝胶具有网状结构,且EGCG被负载进入网络结构内。这种致密化的网络结构可显著提升包装材料对氧气、水蒸气的阻隔性能,减少食品氧化变质与水分迁移,延长货架期[10−13]。采用力场方法和经典力学方程,模拟了这种涉及三组分复杂体系的微观结构演变规律和机制。匹配模型结果表明,加入EGCG分子后,水凝胶体系的RMSD更稳定。同时,体系内CN与CS间的氢键数量较未加入之前更丰富,更加证实EGCG分子有助于CN与CS分子之间更紧密的结合。此外,SASA的结果也揭示,加入EGCG分子聚集形成的体系更加紧密和稳定。径向分布分析结果则显示,不同体系中的峰值几乎都出现在0.8 nm左右,但在添加了EGCG的体系中,峰值更大,暗示EGCG将促使CS分子周围同样距离范围内聚集更丰富的CN分子。总之,EGCG将促使水凝胶体系内氢键数量的显著增加,并强化CS与CN之间的分子间相互作用,确保分子链排列更规整、聚集更紧密,并实现EGCG等功能成分的可控缓释,避免不稳定的突释、延长其有效性[14−15]。研究结果将为生鲜食品保鲜、功能性包装的CS/CN/EGCG复合水凝胶理性设计与精准制备提供明确的结构-性能关联依据。

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doi: 10.13386/j.issn1002-0306.2026050291
  • 接收时间:2026-05-26
  • 首发时间:2026-10-24
  • 出版时间:2026-08-15
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  • 收稿日期:2026-05-26
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    1长沙理工大学期刊社,湖南长沙 410000
    2湖南农业大学食品科学技术学院,湖南长沙 410000
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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