Article(id=1151437195878953595, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1151437189243089177, articleNumber=null, orderNo=null, doi=10.19812/j.cnki.jfsq11-5956/ts.20250306002, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1741190400000, receivedDateStr=2025-03-06, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1752453620165, onlineDateStr=2025-07-14, pubDate=1749916800000, pubDateStr=2025-06-15, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752453620165, onlineIssueDateStr=2025-07-14, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752453620165, creator=13701087609, updateTime=1752453620165, updator=13701087609, issue=Issue{id=1151437189243089177, tenantId=1146029695717560320, journalId=1149652044408987649, year='2025', volume='16', issue='11', pageStart='1', pageEnd='320', issueExtLink='null', onlineDate='null', pubDate='1749916800000', pubDateStr='2025-06-15', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752453618584, creator='13701087609', updateTime=1767768054466, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1215670588966883492, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1151437189243089177, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1215670588966883493, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1151437189243089177, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=215, endPage=221, ext={EN=ArticleExt(id=1151895324579737601, articleId=1151437195878953595, tenantId=1146029695717560320, journalId=1149652044408987649, language=EN, title=Research on preparation of β-cyclodextrin nanosponge and paeonol loading effects, columnId=1151895321388347923, journalTitle=Journal of Food Safety & Quality, columnName=Food Analysis and Detection, runingTitle=null, highlight=null, articleAbstract=

Objective To prepare a kind of β-cyclodextrin nanosponge and explore the paeonol loading effects. Methods The cyclodextrin nanosponge was prepared by cross-linking, the cross-linking effect were determined through infrared spectrum detection, X-ray diffraction and thermogravimetric analysis, and the morphology and pore state of nanosponge was analyzed with the scanning electron microscope; the paeonol was loaded onto the nanosponge by immersion, and the loading effect was analyzed through liquid chromatography detection. Results Through the infrared spectroscopic analysis, 6 kinds of nanosponge were produced successfully after the cross-linking reaction; the original crystalline structure of β-cyclodextrin disappeared due to the formation of new products; nanosponge had a lower thermal stability than of β-cyclodextrin; 3 kinds of nanosponge with relatively complete and uniform pore structure were produced, and their paeonol loading rates were 19.31%, 12.27% and 5.78% respectively. Conclusion The produced porous nanosponge has good paeonol loading effect, and can be used in the active packages of food or fresh products.

, authors=null, authorsList=Yan ZHANG, Li XU, Shu-Heng QIU, Xue-Ting HAN, Shuo-Qi ZHU, Hao-Rui FANG, Bao-Ying WANG, Jian-Chuang WANG, authorCompany=null, correspAuthors=Yan ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, 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=1151895347950400297, articleId=1151437195878953595, tenantId=1146029695717560320, journalId=1149652044408987649, language=CN, title=β-环糊精纳米海绵的制备及丹皮酚负载效果研究, columnId=1151895321958773274, journalTitle=食品安全质量检测学报, columnName=食品分析与检测, runingTitle=null, highlight=null, articleAbstract=

目的 制备一种β-环糊精纳米海绵, 并探究丹皮酚负载效果。方法 通过交联法制备环糊精纳米海绵, 采用红外光谱法检测、X射线衍射和热重分析, 判断交联效果, 通过扫描电子显微镜分析纳米海绵形貌和孔隙状态。采用浸泡法将丹皮酚负载于纳米海绵中, 使用液相色谱法检测分析负载效果。结果 从红外光谱法分析可知交联反应获得了6种纳米海绵, 原β-环糊精晶体结构因为生成新的产物而消失。纳米海绵热稳定性相比β-环糊精有所下降, 获得3种孔隙形貌相对完整和均匀的纳米海绵, 其对丹皮酚的负载率分别为19.31%、12.27%、5.78%。结论 合成的多孔纳米海绵负载丹皮酚效果较好, 可以应用在食品或生鲜产品的活性包装中。

, authors=null, authorsList=张岩, 徐莉, 邱书恒, 韩雪婷, 朱硕麒, 方蒿锐, 王保营, 王建闯, authorCompany=null, correspAuthors=张岩, authorNote=null, correspAuthorsNote=
* 张岩(1972—), 女, 教授, 主要研究方向为食品包装材料及活性包装。E-mail:
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Henan Agricultural Products Preservation Intelligent Packaging Engineering Technology Research Center, Zhengzhou 450046, China), AuthorCompanyExt(id=1167030858130137828, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, companyId=1167030858121749218, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2. 河南省农产品保鲜智能包装工程技术研究中心, 郑州 450046)])], figs=[ArticleFig(id=1167030860697051949, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Fig.1, caption=Fourier transform infrared spectroscopy profile of cyclodextrin nanosponge, figureFileSmall=1BgbaYTF6l1eufXloPtLQw==, figureFileBig=a7/C/0A+3pElVaTR/4CGbQ==, tableContent=null), ArticleFig(id=1167030860776743729, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=图1, caption=环糊精纳米海绵的傅里叶变换红外光谱图谱

注: (a). 不同摩尔比DPC图谱; (b). 不同摩尔比CDI图谱。

, figureFileSmall=1BgbaYTF6l1eufXloPtLQw==, figureFileBig=a7/C/0A+3pElVaTR/4CGbQ==, tableContent=null), ArticleFig(id=1167030860852241203, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Fig.2, caption=X-ray diffraction spectra of cyclodextrin nanosponges, figureFileSmall=qY5T1hBUn1Ngxc6kFdjjUQ==, figureFileBig=xZuicXQTb1B6ohxxEAP4Mg==, tableContent=null), ArticleFig(id=1167030860927738677, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=图2, caption=环糊精纳米海绵的X-射线衍射光谱图

注: (a). 不同摩尔比DPC的X-射线衍射光谱图; (b). 不同摩尔比CDI的X-射线衍射光谱图。

, figureFileSmall=qY5T1hBUn1Ngxc6kFdjjUQ==, figureFileBig=xZuicXQTb1B6ohxxEAP4Mg==, tableContent=null), ArticleFig(id=1167030861003236153, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Fig.3, caption=Thermogravimetric analysis curves of cyclodextrin nanosponges, figureFileSmall=E/4lLlUsIzHD8T/7TES3Aw==, figureFileBig=Yu/lE048Ji1kHpN7nSz/vg==, tableContent=null), ArticleFig(id=1167030861116482363, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=图3, caption=环糊精纳米海绵的热重分析曲线

注: (a). 不同摩尔比的DPC热重分析曲线; (b). 不同摩尔比CDI的热重分析曲线。

, figureFileSmall=E/4lLlUsIzHD8T/7TES3Aw==, figureFileBig=Yu/lE048Ji1kHpN7nSz/vg==, tableContent=null), ArticleFig(id=1167030861233922877, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Fig.4, caption=Scanning electron microscope image of cyclodextrin nanosponge, figureFileSmall=0yoqUiK4tFNSdJHGYxKLYw==, figureFileBig=2zf3AhjVDprpryEMyNMg/Q==, tableContent=null), ArticleFig(id=1167030861313614657, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=图4, caption=环糊精纳米海绵的扫描电子显微镜图

注: (a). β-CD与DPC摩尔比1:4; (b). β-CD与DPC摩尔比1:6; (c). β-CD与DPC摩尔比1:8; (d). β-CD与CDI摩尔比1:6; (e). β-CD与CDI摩尔比1:8; (f). β-CD与CDI摩尔比1:10。

, figureFileSmall=0yoqUiK4tFNSdJHGYxKLYw==, figureFileBig=2zf3AhjVDprpryEMyNMg/Q==, tableContent=null), ArticleFig(id=1167030861376529218, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Fig.5, caption=Structure of CDI, figureFileSmall=CbMx9hBs27sc4/wiQHeNsg==, figureFileBig=Yrgie+e3MO9fACLLn5Xi6A==, tableContent=null), ArticleFig(id=1167030861481386820, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=图5, caption=CDI的结构, figureFileSmall=CbMx9hBs27sc4/wiQHeNsg==, figureFileBig=Yrgie+e3MO9fACLLn5Xi6A==, tableContent=null), ArticleFig(id=1167030861540107077, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Fig.6, caption=Structure of DPC, figureFileSmall=P6/Qm+2neUqYxLKnPF072w==, figureFileBig=UgH/BlgVaS3/JiidBYVKdA==, tableContent=null), ArticleFig(id=1167030861607215943, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=图6, caption=DPC的结构, figureFileSmall=P6/Qm+2neUqYxLKnPF072w==, figureFileBig=UgH/BlgVaS3/JiidBYVKdA==, tableContent=null), ArticleFig(id=1167030861712073545, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Table 1, caption=

Preparation recipe of β-CD nanosponge

, figureFileSmall=null, figureFileBig=null, tableContent=
β-CD纳米海绵型号 β-CD摩尔质量/mol DPC摩尔质量/mol CDI摩尔质量/mol DMF体积/mL TEA体积/μL
1 0.005 0.02 0 30 1
2 0.005 0.03 0 30 1
3 0.005 0.04 0 30 1
4 0.005 0 0.03 30 1
5 0.005 0 0.04 30 1
6 0.005 0 0.05 30 1
), ArticleFig(id=1167030861795959627, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=表1, caption=

β-CD纳米海绵的制备配方

, figureFileSmall=null, figureFileBig=null, tableContent=
β-CD纳米海绵型号 β-CD摩尔质量/mol DPC摩尔质量/mol CDI摩尔质量/mol DMF体积/mL TEA体积/μL
1 0.005 0.02 0 30 1
2 0.005 0.03 0 30 1
3 0.005 0.04 0 30 1
4 0.005 0 0.03 30 1
5 0.005 0 0.04 30 1
6 0.005 0 0.05 30 1
), ArticleFig(id=1167030861871457101, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=EN, label=Table 2, caption=

Loading rate of cyclodextrin nanosponge with paeonol

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 离心后样品含量
/(μg/mL)
超声样品总含量
/(μg/mL)
负载率/% 标准差/% 平均负载率/%
β-CD:DPC摩尔比1:6 6.682 7.601 12.09 0.28 12.27
6.440 7.369 12.60
6.153 7.003 12.13
β-CD:CDI摩尔比1:8 5.757 7.146 19.44 0.21 19.31
5.705 7.079 19.41
5.921 7.316 19.07
β-CD:CDI摩尔比1:10 7.780 8.300 6.27 0.42 5.78
7.850 8.310 5.54
7.880 8.340 5.52
), ArticleFig(id=1167030861934371663, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1151437195878953595, language=CN, label=表2, caption=

环糊精纳米海绵载丹皮酚负载率

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 离心后样品含量
/(μg/mL)
超声样品总含量
/(μg/mL)
负载率/% 标准差/% 平均负载率/%
β-CD:DPC摩尔比1:6 6.682 7.601 12.09 0.28 12.27
6.440 7.369 12.60
6.153 7.003 12.13
β-CD:CDI摩尔比1:8 5.757 7.146 19.44 0.21 19.31
5.705 7.079 19.41
5.921 7.316 19.07
β-CD:CDI摩尔比1:10 7.780 8.300 6.27 0.42 5.78
7.850 8.310 5.54
7.880 8.340 5.52
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β-环糊精纳米海绵的制备及丹皮酚负载效果研究
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张岩 1, * , 徐莉 2 , 邱书恒 1 , 韩雪婷 1 , 朱硕麒 1 , 方蒿锐 1 , 王保营 2 , 王建闯 1
食品安全质量检测学报 | 食品分析与检测 2025,16(11): 215-221
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食品安全质量检测学报 |食品分析与检测 2025 , 16 (11) : 215 -221
β-环糊精纳米海绵的制备及丹皮酚负载效果研究
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张岩1, * , 徐莉2, 邱书恒1, 韩雪婷1, 朱硕麒1, 方蒿锐1, 王保营2, 王建闯1
作者信息
  • 1. 河南牧业经济学院包装与印刷工程学院, 郑州 450046
  • 2. 河南省农产品保鲜智能包装工程技术研究中心, 郑州 450046
通讯作者:
* 张岩(1972—), 女, 教授, 主要研究方向为食品包装材料及活性包装。E-mail:
Research on preparation of β-cyclodextrin nanosponge and paeonol loading effects
Yan ZHANG1, * , Li XU2, Shu-Heng QIU1, Xue-Ting HAN1, Shuo-Qi ZHU1, Hao-Rui FANG1, Bao-Ying WANG2, Jian-Chuang WANG1
Affiliations
  • 1. College of Packaging and Printing Engineering, Henan University of Animial Husbandry and Economy, Zhengzhou 450046, China
  • 2. Henan Agricultural Products Preservation Intelligent Packaging Engineering Technology Research Center, Zhengzhou 450046, China
出版时间: 2025-06-15 doi: 10.19812/j.cnki.jfsq11-5956/ts.20250306002
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目的 制备一种β-环糊精纳米海绵, 并探究丹皮酚负载效果。方法 通过交联法制备环糊精纳米海绵, 采用红外光谱法检测、X射线衍射和热重分析, 判断交联效果, 通过扫描电子显微镜分析纳米海绵形貌和孔隙状态。采用浸泡法将丹皮酚负载于纳米海绵中, 使用液相色谱法检测分析负载效果。结果 从红外光谱法分析可知交联反应获得了6种纳米海绵, 原β-环糊精晶体结构因为生成新的产物而消失。纳米海绵热稳定性相比β-环糊精有所下降, 获得3种孔隙形貌相对完整和均匀的纳米海绵, 其对丹皮酚的负载率分别为19.31%、12.27%、5.78%。结论 合成的多孔纳米海绵负载丹皮酚效果较好, 可以应用在食品或生鲜产品的活性包装中。

纳米海绵  /  β-环糊精  /  活性物质  /  负载  /  多孔材料

Objective To prepare a kind of β-cyclodextrin nanosponge and explore the paeonol loading effects. Methods The cyclodextrin nanosponge was prepared by cross-linking, the cross-linking effect were determined through infrared spectrum detection, X-ray diffraction and thermogravimetric analysis, and the morphology and pore state of nanosponge was analyzed with the scanning electron microscope; the paeonol was loaded onto the nanosponge by immersion, and the loading effect was analyzed through liquid chromatography detection. Results Through the infrared spectroscopic analysis, 6 kinds of nanosponge were produced successfully after the cross-linking reaction; the original crystalline structure of β-cyclodextrin disappeared due to the formation of new products; nanosponge had a lower thermal stability than of β-cyclodextrin; 3 kinds of nanosponge with relatively complete and uniform pore structure were produced, and their paeonol loading rates were 19.31%, 12.27% and 5.78% respectively. Conclusion The produced porous nanosponge has good paeonol loading effect, and can be used in the active packages of food or fresh products.

nanosponge  /  β-cyclodextrin  /  active substance  /  load  /  porous material
张岩, 徐莉, 邱书恒, 韩雪婷, 朱硕麒, 方蒿锐, 王保营, 王建闯. β-环糊精纳米海绵的制备及丹皮酚负载效果研究. 食品安全质量检测学报, 2025 , 16 (11) : 215 -221 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250306002
Yan ZHANG, Li XU, Shu-Heng QIU, Xue-Ting HAN, Shuo-Qi ZHU, Hao-Rui FANG, Bao-Ying WANG, Jian-Chuang WANG. Research on preparation of β-cyclodextrin nanosponge and paeonol loading effects[J]. Journal of Food Safety & Quality, 2025 , 16 (11) : 215 -221 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250306002
随着经济的发展和人口的增加, 环境污染和食品浪费问题日益严重。据研究显示, 我国生鲜食品因包装缺陷导致的腐败损失率高达18.7%, 其中果蔬类损耗占比超过40%[1]。传统包装材料存在的包装废弃物难降解等缺点亟待改变, 天然可降解材料又存在食品易霉、货架期短等缺点。目前, 以天然可降解材料作为包装主材料来提升绿色环保性, 引入活性物质来提升抑菌保鲜性能受到了广泛的青睐[2-5]。然而, 活性物质存在难保存、易失活等问题, 因此, 采用合适的包合物或负载材料来保障其有效性和长效性成为食品活性包装研究的热点[6-8]。在活性物质包合或负载材料的选择上, 环糊精(cyclodextrin, CD)性能优异, 脱颖而出, 备受关注[9]
CD具有独特的结构特征及物理化学性质, 已经成为构筑各种功能材料的优良结构单元[10]。纳米海绵是由β-环糊精(β-cyclodextrin, β-CD)交联而成的多孔材料, 具有高比表面积、大孔隙率等特点, 能够提高吸附效率和容量[11], 在医药、食品、环保等领域具有广阔的应用前景[12-16]。丹皮酚是从牡丹皮、芍药或徐长卿等植物中提取的天然活性物质, 具有抗氧化效果和较强的抗菌效果, 实验表明丹皮酚对草莓中灰霉病的抑制率可达72.3%[17-18], 优于传统化学防腐剂, 但因稳定性较差, 易被氧化, 水溶性差等缺陷限制了其应用领域[19]
根据近期研究证实, 基于CD的负载体系可使天然活性物质的抗菌活性持续时间延长至2.8倍[20]。因此, 本研究探索环糊精纳米海绵交联制备的方法、孔隙状态以及负载丹皮酚的情况, 旨在将天然活性物质与环糊精纳米海绵更好地结合, 更好地发挥活性物质的抗菌抗氧化作用, 为活性包装的应用提供理论基础和实验数据, 为延长食品保鲜期减少腐败浪费提供解决思路和方案。
Nicolet iS10傅里叶变换红外光谱仪(美国赛默飞世尔科技公司); K2025高效液相色谱仪(山东悟空仪器有限公司); CNW Athena C18-WP液相色谱柱(250 mm×4.6 mm, 5 μm)(上海安谱实验科技股份有限公司); APD 2000PRO X-射线衍射仪(意大利GNR分析仪器公司); STA-2500同步热分析仪(德国耐驰科学仪器商贸有限公司); ZEISS Sigma 360场发射扫描电子显微镜(德国蔡司公司)。
碳酸二苯酯(diphenyl carbonate, DPC)(纯度99%)、羰基二咪唑(N,N’-carbonyldiimidazole, CDI)(纯度≥97%)、β-CD(纯度98%)、丹皮酚(纯度99%)(上海麦克林生化科技有限公司); N,N二甲基甲酰胺(N,N-dimethylformamide, DMF)(纯度≥99.5%, 郑州派尼化学试剂厂); 三乙胺(triethylamine, TEA)(纯度≥98%, 天津市永大化学试剂有限公司)。
首先将0.005 mol β-CD与纯度≥99.5%的30 mL DMF加入圆底烧瓶中, 按照表1的配比分别加入不同种类和摩尔质量的交联剂(DPC和CDI), 将反应体系放入90 ℃水浴锅中搅拌0.5 h, 接着加入纯度大于98%的1 μL催化剂TEA, 反应2 h后静置至室温[21-23]。加水使纳米海绵析出, 并加乙醇及水反复洗涤, 去除未反应物及一些副产物[24]。最后冷冻干燥24 h得到6种粉块状纳米海绵。
将制备得到的环糊精纳米海绵进行红外光谱、热重测试和电子显微镜扫描, 根据结果选取孔隙形貌较好的3种环糊精纳米海绵进行负载实验, 分别是2号、5号和6号样品, 即β-CD与DPC摩尔比1:6、β-CD与CDI摩尔比1:8、β-CD与CDI摩尔比1:10的样品进行负载实验。具体操作步骤如下, 称取0.0114 g丹皮酚标品置于25 mL容量瓶中, 使用乙醇定容制成质量浓度为576 μg/mL的丹皮酚溶液, 稀释至50 μg/mL, 取10 mL, 将2.5 g环糊精纳米海绵浸泡其中, 静止24 h, 过滤后晾干。
(1)液相色谱法测量条件
利用高效液相色谱法测定并计算样品的载药量。液相色谱条件如下: 色谱柱: CNW Athena C18-WP液相色谱柱(250 mm×4.6 mm, 5 μm); 流动相: 乙腈-水(50:50, V:V); 检测波长: 274 nm; 柱温: 40 ℃; 流速: 1.0 mL/min; 进样体积: 10 μL[25]
(2)丹皮酚标准曲线
用流动相稀释丹皮酚标准品, 得到质量浓度为5、15、25、50、100 µg/mL的丹皮酚溶液, 使用液相色谱分别进样, 记录保留时间与峰面积。以质量浓度为横坐标(X, µg/mL), 峰面积为纵坐标(Y), 进行线性回归分析, 得回归方程为Y=45.136X-7.3574 (r2=0.996), 说明此方法下丹皮酚在5~100 µg/mL质量浓度范围内线性关系良好。
(3)丹皮酚负载率计算方法
称取已负载丹皮酚的纳米海绵样品1.5 g, 加入10 mL甲醇, 同时制备2份, 其中一瓶使用离心机离心(4000 r/min, 5 min), 将纳米海绵表面的未被负载的丹皮酚溶解到甲醇中, 取上清液使用液相色谱测定其中丹皮酚含量; 另一瓶超声10 min, 使被负载的丹皮酚脱离纳米海绵, 溶解到甲醇中, 取上清液使用液相色谱测定其中丹皮酚含量。使用公式(1)计算负载率[26]。以上实验需做3组, 用于计算平均负载率。
$\text { 负载率 } /\%=\frac{\text { 超声样品总含量 }- \text { 离心后总含量 }}{\text { 超声样品总含量 }} \times 100 \%$
本实验设置3组平行样品, 采用软件Excel 2016、Origin 2022对实验数据进行处理、作图和分析。
图1(a)图1(b)分别为DPC和CDI作为交联剂的纳米海绵的红外光谱图。如图1(a)所示, 纳米海绵在1710 cm-1的峰为碳酸酯键的羰基峰[27], 而β-CD和DPC的红外光谱图在此处无明显峰, 因此纳米海绵成功合成。红外谱图中3450、1806和1660 cm-1为-OH、C-O、C-C伸缩振动峰; 在1311 cm-1和1205 cm-1的振动峰为C-H和C=C键的弯曲振动和伸缩振动峰; 在1234 cm-1和1035 cm-1的振动峰为C-O-C的拉伸振动峰。如图1(b)所示, 纳米海绵在1760 cm-1的峰为碳酸酯键的羰基峰, β-CD和CDI的红外光谱图在此处无明显峰, 因此纳米海绵成功合成。红外谱图中3445、1825和1650 cm-1为-OH、C-O、C-C伸缩振动峰; 在1320 cm-1和1210 cm-1的振动峰为C-H和C=C键的弯曲振动和伸缩振动峰; 在1245 cm-1和 1050 cm-1的振动峰为C-O-C的拉伸振动峰。
结晶度, 形成没有晶体性的聚集体, 因此证明了DPC和β-CD交联后形成了多孔物质即纳米海绵。
图2(a)图2(b)分别为DPC和CDI作为交联剂的纳米海绵的X射线衍射图。如图2(a)所示, β-CD在10.9°、12.8°、15.2°、18.9°、22.7°和27.4°有强烈而尖锐的峰, 因此β-CD具有极强的结晶性质[28]。DPC在12.9°、13.9°、18.2°、19.1°、20.3°、23.7°、24.8°有尖锐的峰, 因此DPC也具有极强的结晶性。而DPC和β-CD交联后, 没有出现β-CD和DPC的晶体峰, 而是仅看到宽的、低强度的且无法清楚识别的峰。因此, 当DPC和β-CD交联后破坏了DPC和β-CD材料的
图2(b)所示, β-CD在10.9°、12.8°、15.2°、18.9°、22.7°和27.4°有强烈而尖锐的峰, 因此β-CD具有极强的结晶性质[28]。CDI在12.9°、13.9°、18.2°、19.1°、20.3°、23.7°、24.8°有尖锐的峰, 因此CDI也具有极强的结晶性。而CDI和β-CD交联后, 没有出现β-CD和CDI的晶体峰, 而是仅看到宽的、低强度的且无法清楚识别的峰。因此, 当CDI和β-CD交联后破坏了CDI和β-CD材料的结晶度, 形成没有晶体性的聚集体, 因此证明了CDI和β-CD交联后形成了多孔物质即纳米海绵。
图3(a)图3(b)为DPC和CDI作为交联剂的纳米海绵的热重图。如图3(a)所示, DPC作为交联剂形成的纳米海绵的热失重曲线分为3个阶段, 其中, 第一阶段失重量为0~100 ℃范围内纳米海绵表面吸附的水分子的失去, 失重量较小。第二阶段失重量为150~200 ℃范围内纳米海绵的碳化。第三阶段热失重量为300~350 ℃高分子链的断裂, 失重量较大。如图3(b)所示, CDI作为交联剂形成的纳米海绵的热失重曲线分为2个阶段, 其中, 第一阶段失重量为0~100 ℃范围内纳米海绵表面吸附的水分子的失去, 失重量较小。第二阶段失重量为100~350 ℃范围内纳米海绵的高分子链的断裂和分解, 失重量较大。对于两种不同交联剂合成的纳米海绵而言, 在200 ℃以下时, 合成的纳米海绵热稳定性略优于β-CD, 高于200 ℃后, 其热稳定性低于β-CD。
不同交联剂、不同摩尔比例的环糊精纳米海绵均呈不规则形状, 且外表面具有多孔结构, 形似海绵。如图4所示, 图4(a)~4(c)是以DPC作为交联剂与β-CD交联摩尔比例分别为1:4、1:6、1:8形成的纳米海绵, 图4(d)~4(f)是以CDI作为交联剂与β-CD交联摩尔比例分别为1:6、1:8、1:10形成的纳米海绵。在图4(a)~4(c)对比可以明显的看出, 交联摩尔比例为1:6即图4(b)形成的孔最多且密实, 因此交联效果是最好的。在图4(d)~4(f)对比可以明显地看出交联摩尔比例为1:10即图4(f)形成的孔最多且密实, 图4(e)其次。
按照1.2.3实验方法, 使用标准曲线, 根据公式(1)计算出3种纳米海绵对丹皮酚的负载率, 如表2所示。
交联剂和CD的配比是影响环糊精纳米海绵孔结构的关键因素, 因此, 不同交联剂配比的环糊精纳米海绵对丹皮酚的负载率影响极大。本研究分别以CDI和DPC作为交联剂, 与CD形成纳米海绵。其中, β-CD:CDI=1:8组的平均负载率最高, 为19.31%, 其离心后样品含量与超声样品总含量的比值表明该配比下药物与载体的结合效率较优。而β-CD:DPC=1:6组的负载率平均值为12.27%, 其3次独立测量的负载率分别为12.09%、12.60%和12.13%。这是由于CDI结构中的O无空间位阻效应(如图5所示), CDI和CD之间的交联强。因此, β-CD:CDI=1:8的负载率较高。而DPC结构中的O位于苯环中间, 有极强的刚性空间位阻效应[29](如图6所示), 影响DPC和CD的交联, 因此, β-CD:DPC=1:6的负载率较低。此外, β-CD:CDI=1:10组的平均负载率显著降低至5.78%, 这是由于CDI含量过高, 交联剂部分残留, 残留的交联剂易团聚, 使得交联剂只起到扩链的作用而达不到交联的效果, 交联反应不完全且交联程度较低, 导致CDI和CD的交联降低。因此, 纳米海绵的孔尺寸会减小[30](如图4e和4f所示), 丹皮酚的负载率降低。以上结果说明, 环糊精纳米海绵中CD和交联剂的配比对丹皮酚的负载性能具有关键影响, 这一发现为基于环糊精纳米海绵的药物递送系统设计提供了实验依据。
本研究成功制备了负载丹皮酚的β-CD纳米海绵, 并探索了不同交联剂摩尔比对纳米海绵性能的影响。通过傅里叶变换红外光谱、X-射线衍射以及热重分析等手段对制备的环糊精纳米海绵进行了表征, 结果显示所制备的纳米海绵具有预期的结构特征。
在制备过程中, 发现通过调整CD与交联剂(DPC和CDI)的摩尔比, 可以影响纳米海绵的形貌和性能。特别是当CD与DPC或CDI的摩尔比适当时, 能够制备出具有高比表面积和大孔隙率的纳米海绵, 这些特性有利于提高丹皮酚的负载量和缓释性能。
进一步, 利用高效液相色谱法, 通过对比离心和超声处理后的样品含量, 证实了纳米海绵对丹皮酚的负载效果。这些结果表明, β-CD纳米海绵作为植物源活性物质的有效载体, 具有在食品保鲜领域应用的潜力。
综上所述, 本研究为开发新型环保、高效的食品保鲜材料提供了新思路。未来, 将进一步优化纳米海绵的制备工艺, 并深入研究其在食品保鲜中的应用效果, 以期为实现食品的绿色环保贮藏和延长货架期提供科学依据。
  • 河南省重点研发与推广专项(232102111062)
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doi: 10.19812/j.cnki.jfsq11-5956/ts.20250306002
  • 接收时间:2025-03-06
  • 首发时间:2025-07-14
  • 出版时间:2025-06-15
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  • 收稿日期:2025-03-06
基金
河南省重点研发与推广专项(232102111062)
河南省科技攻关项目(232102110133)
作者信息
    1. 河南牧业经济学院包装与印刷工程学院, 郑州 450046
    2. 河南省农产品保鲜智能包装工程技术研究中心, 郑州 450046

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* 张岩(1972—), 女, 教授, 主要研究方向为食品包装材料及活性包装。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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