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Article(id=1308842119851237700, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1308841897058198067, articleNumber=null, orderNo=null, doi=10.16438/j.0513-4870.2025-0586, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1747929600000, receivedDateStr=2025-05-23, revisedDate=1751904000000, revisedDateStr=2025-07-08, acceptedDate=null, acceptedDateStr=null, onlineDate=1789981878483, onlineDateStr=2026-09-21, pubDate=1783785600000, pubDateStr=2026-07-12, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789981878483, onlineIssueDateStr=2026-09-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789981878483, creator=13701087609, updateTime=1789981878483, updator=13701087609, issue=Issue{id=1308841897058198067, tenantId=1146029695717560320, journalId=1189982191388893191, year='2026', volume='61', issue='7', pageStart='2377', pageEnd='2820', issueExtLink='null', onlineDate='null', pubDate='1783785600000', pubDateStr='2026-07-12', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1789981825365, creator='13701087609', updateTime=1789984154811, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1308851667525792021, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1308841897058198067, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1308851667525792022, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1308841897058198067, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=2694, endPage=2702, ext={EN=ArticleExt(id=1308842120035787077, articleId=1308842119851237700, tenantId=1146029695717560320, journalId=1189982191388893191, language=EN, title=Selective adsorption of protocatechuic acid by high-affinity magnetic nanoparticles based on boronate affinity strategy, columnId=1190335348761793317, journalTitle=Acta Pharmaceutica Sinica, columnName=Original Articles, runingTitle=null, highlight=null, articleAbstract=

To explore a method for the selective separation and enrichment of protocatechuic acid (PCA) from actual samples of traditional Chinese medicinal materials, in this study, based on the boron affinity and molecular imprinting strategy, a specific imprinted magnetic material with high affinity for PCA was prepared by using Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) as the substrate and amplifying the number of boronic acid ligands on the product surface with branched polyethylenimine (PEI). The prepared Fe3O4@PEI@FPBA MIPs were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and other instruments, and their adsorption performance was systematically investigated. Due to the boron affinity-directed surface imprinting mechanism, the prepared Fe3O4@PEI@FPBA MIPs showed high selectivity for PCA, with a maximum adsorption capacity of 475.33 mg·g-1 and a maximum imprinting factor (IF) of 5.24. The adsorption process conformed to the pseudo-first-order kinetic model, and the adsorption isotherm conformed to the Langmuir model. In addition, the results of the repeatability test also indicated that Fe3O4@PEI@FPBA MIPs could maintain good adsorption performance after repeated use. The recovery rate of the actual sample analysis was 96.67% to 110.17% (relative standard deviation was 1.65% to 4.52%).

, authors=Tian-biao TIAN, Yi-jie MA, Yong-sheng JI, Yan-yan MA*, authorsList=Tian-biao TIAN, Yi-jie MA, Yong-sheng JI, Yan-yan MA, authorCompany=null, correspAuthors=Yan-yan MA, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright ©2026 Acta Pharmaceutica Sinica. 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=1308842121168249168, articleId=1308842119851237700, tenantId=1146029695717560320, journalId=1189982191388893191, language=CN, title=基于硼亲和策略的高亲和力磁性纳米粒子对原儿茶酸选择性吸附研究, columnId=1190335348896011050, journalTitle=药学学报, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

为探索一种从中药材实际样品中选择性分离富集原儿茶酸(protocatechuic acid, PCA) 的方法。本课题以四氧化三铁磁性纳米粒子(Fe3O4 MNPs) 为基材, 基于硼亲和作用与分子印迹策略, 使用支链聚乙烯亚胺(polyethylenimine, PEI) 对产物表面的硼酸配基数量进行扩增, 进而制备了对PCA具有高亲和力的特异性印迹四氧化三铁磁性纳米材料(Fe3O4@PEI@FPBA MIPs)。采用电子透射显微镜、傅里叶红外光谱仪等多种仪器进行表征分析, 并系统考察了其吸附性能。由于硼亲和定向表面印迹机制, 所制备的Fe3O4@PEI@FPBA MIPs对PCA具有高度选择性, 最大吸附容量可达475.33 mg·g-1, 最大印迹因子为5.24。吸附过程符合准一级动力学模型, 吸附等温线符合Langmuir模型。此外, 重复性试验结果也表明, Fe3O4@PEI@FPBA MIPs在循环使用后仍能保持较好的吸附性能。对实际样品进行分析, 回收率为96.67%~110.17% (相对标准偏差为1.65%~4.52%)。

, authors=田天标, 马祎洁, 纪永升, 马艳艳*, authorsList=田天标, 马祎洁, 纪永升, 马艳艳, authorCompany=null, correspAuthors=马艳艳, authorNote=

作者贡献:

田天标负责设计实验、收集数据并分析、撰写及修改论文; 马祎洁负责图表制作; 马艳艳、纪永升提供学术指导及基金支持。

, correspAuthorsNote=
马艳艳, E-mail:
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Spectrochim Acta A Mol Biomol Spectrosc, 2020, 227: 117542., articleTitle=null, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1308842121394741585, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, xref=null, ext=[AuthorCompanyExt(id=1308842121403130194, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, companyId=1308842121394741585, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=College of Pharmacy, Henan University of Chinese Medicine, Zhengzhou 450046, China), AuthorCompanyExt(id=1308842121411518803, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, companyId=1308842121394741585, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=河南中医药大学药学院, 河南 郑州 450046)])], figs=[ArticleFig(id=1308842123584168306, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=EN, label=null, caption=null, figureFileSmall=C8Qs0VCT0MbTfjRqjfvXSA==, figureFileBig=UubyDK1ecs4s0d3lqArxUQ==, tableContent=null), ArticleFig(id=1308842123902935411, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=CN, label=Fig.1, caption=Schematic of Fe3O4@PEI@FPBA MIPs preparation and adsorption principles. 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A: The ultrasonic dispersion results of Fe3O4@PEI@FPBA MIPs; B: The aggregation results of Fe3O4@PEI@FPBA MIPs in the presence of an external magnetic field; C: Transmission electron microscopy (TEM) images of AMNPs; D: TEM images of Fe3O4@PEI@FPBA MNPs; E: TEM images of Fe3O4@PEI@FPBA MIPs; F: Infrared spectra of AMNPs, Fe3O4@PEI@FPBA MNPs, Fe3O4@PEI@FPBA MIPs, and Fe3O4@PEI@FPBA NIPs, figureFileSmall=CLgm4NkjVQgMFN8Zx+cRsw==, figureFileBig=cVvgbzVp486W/qtXpLMQNQ==, tableContent=null), ArticleFig(id=1308842124444000630, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=EN, label=null, caption=null, figureFileSmall=LTqTgkXriJE1BnV9NcYSQg==, figureFileBig=rEs5ZGPmYRfsUcChtXkXdw==, tableContent=null), ArticleFig(id=1308842124498526583, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=CN, label=Fig.3, caption=Determination results of boronate affinity and optimization of time. A: Investigation of the binding capacity of Fe3O4@FPBA MNPs with adenosine and deoxyadenosine; B: Effect of imprinting time on the recognition performance of Fe3O4@PEI@FPBA MIPs/Fe3O4@PEI@FPBA NIPs; C: Effect of incubation time on the recognition performance of Fe3O4@PEI@FPBA MIPs; D: Effect of incubation time on the recognition performance of Fe3O4@PEI@FPBA MIPs. n = 3, $ \overline{x} $ ± s, figureFileSmall=LTqTgkXriJE1BnV9NcYSQg==, figureFileBig=rEs5ZGPmYRfsUcChtXkXdw==, tableContent=null), ArticleFig(id=1308842124565635448, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=EN, label=null, caption=null, figureFileSmall=kFxjpzQqbdPo2RaVfatKMQ==, figureFileBig=/YEhVZvLV+hcB2PMxPU5WQ==, tableContent=null), ArticleFig(id=1308842124624355705, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=CN, label=Fig.4, caption=Static adsorption results and isothermal models. A: Isothermal adsorption curves of Fe3O4@PEI@FPBA MIPs and Fe3O4@FPBA MIPs; B: Isothermal adsorption model of Fe3O4@PEI@FPBA MIPs; C: Isothermal adsorption model of Fe3O4@FPBA MIPs. n = 3, $ \overline{x} $ ± s, figureFileSmall=kFxjpzQqbdPo2RaVfatKMQ==, figureFileBig=/YEhVZvLV+hcB2PMxPU5WQ==, tableContent=null), ArticleFig(id=1308842124699853178, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=EN, label=null, caption=null, figureFileSmall=4bwSEGCjr2kg4RZyKTdVcA==, figureFileBig=GNzznPm9oWFNyQSLZh18LA==, tableContent=null), ArticleFig(id=1308842124766962043, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=CN, label=Fig.5, caption=Performance testing of Fe3O4@PEI@FPBA MIPs. A: The structural formula of the active ingredients of traditional Chinese medicine used in this research; B: Selectivity of Fe3O4@PEI@FPBA MIPs for PCA and similar molecules; C: Competitiveness of Fe3O4@PEI@FPBA MIPs for PCA and similar molecules; D: Relationship between the number of reuse of Fe3O4@PEI@FPBA MIPs and their binding capacity. n = 3, $ \overline{x} $ ± s. *P < 0.05, ****P < 0.000 1. PCA: Protocatechuic acid; CA: Caffeic acid; CGA: Chlorogenic acid, figureFileSmall=4bwSEGCjr2kg4RZyKTdVcA==, figureFileBig=GNzznPm9oWFNyQSLZh18LA==, tableContent=null), ArticleFig(id=1308842124825682300, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
Enriched materialLangmuir equation
Qm/mg·g-1KL/L·mg-1R2
Fe3O4@PEI@FPBA MIPs475.330.040.99
Fe3O4@FPBA MIPs24.390.030.99
), ArticleFig(id=1308842124905374077, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=CN, label=Tab.1, caption=

Fitting parameters of the Langmuir isotherm adsorption model

, figureFileSmall=null, figureFileBig=null, tableContent=
Enriched materialLangmuir equation
Qm/mg·g-1KL/L·mg-1R2
Fe3O4@PEI@FPBA MIPs475.330.040.99
Fe3O4@FPBA MIPs24.390.030.99
), ArticleFig(id=1308842124972482942, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
SampleSpiked
/mg·L-1		Found
($ \overline{x} $ ± s)		Recovery rate/%RSD
/%
Alpiniae Oxyphyllae
Fructus/mg·L-1		0172.27 ± 6.59-3.82
20191.67 ± 8.6797.004.52
40212.10 ± 4.31102.172.03
60234.13 ± 6.89110.172.94
80253.47 ± 6.2996.672.48
100275.30 ± 4.56109.171.65
), ArticleFig(id=1308842125064757631, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1308842119851237700, language=CN, label=Tab.2, caption=

Spiked recovery rates and RSD of PCA in the Alpiniae Oxyphyllae Fructus samples. SD: Standard deviation; RSD: Relative standard deviation

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleSpiked
/mg·L-1		Found
($ \overline{x} $ ± s)		Recovery rate/%RSD
/%
Alpiniae Oxyphyllae
Fructus/mg·L-1		0172.27 ± 6.59-3.82
20191.67 ± 8.6797.004.52
40212.10 ± 4.31102.172.03
60234.13 ± 6.89110.172.94
80253.47 ± 6.2996.672.48
100275.30 ± 4.56109.171.65
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基于硼亲和策略的高亲和力磁性纳米粒子对原儿茶酸选择性吸附研究
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田天标 , 马祎洁 , 纪永升 , 马艳艳 *
药学学报 | 研究论文 2026,61(7): 2694-2702
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药学学报 |研究论文 2026 , 61 (7) : 2694 -2702
基于硼亲和策略的高亲和力磁性纳米粒子对原儿茶酸选择性吸附研究
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田天标, 马祎洁, 纪永升, 马艳艳*
作者信息
  • 河南中医药大学药学院, 河南 郑州 450046
通讯作者:
马艳艳, E-mail:
作者简介:

作者贡献:

田天标负责设计实验、收集数据并分析、撰写及修改论文; 马祎洁负责图表制作; 马艳艳、纪永升提供学术指导及基金支持。

Selective adsorption of protocatechuic acid by high-affinity magnetic nanoparticles based on boronate affinity strategy
Tian-biao TIAN, Yi-jie MA, Yong-sheng JI, Yan-yan MA*
Affiliations
  • College of Pharmacy, Henan University of Chinese Medicine, Zhengzhou 450046, China
出版时间: 2026-07-12 doi: 10.16438/j.0513-4870.2025-0586
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为探索一种从中药材实际样品中选择性分离富集原儿茶酸(protocatechuic acid, PCA) 的方法。本课题以四氧化三铁磁性纳米粒子(Fe3O4 MNPs) 为基材, 基于硼亲和作用与分子印迹策略, 使用支链聚乙烯亚胺(polyethylenimine, PEI) 对产物表面的硼酸配基数量进行扩增, 进而制备了对PCA具有高亲和力的特异性印迹四氧化三铁磁性纳米材料(Fe3O4@PEI@FPBA MIPs)。采用电子透射显微镜、傅里叶红外光谱仪等多种仪器进行表征分析, 并系统考察了其吸附性能。由于硼亲和定向表面印迹机制, 所制备的Fe3O4@PEI@FPBA MIPs对PCA具有高度选择性, 最大吸附容量可达475.33 mg·g-1, 最大印迹因子为5.24。吸附过程符合准一级动力学模型, 吸附等温线符合Langmuir模型。此外, 重复性试验结果也表明, Fe3O4@PEI@FPBA MIPs在循环使用后仍能保持较好的吸附性能。对实际样品进行分析, 回收率为96.67%~110.17% (相对标准偏差为1.65%~4.52%)。

硼亲和  /  磁性纳米粒子  /  分子印迹聚合物  /  原儿茶酸  /  支链聚乙烯亚胺

To explore a method for the selective separation and enrichment of protocatechuic acid (PCA) from actual samples of traditional Chinese medicinal materials, in this study, based on the boron affinity and molecular imprinting strategy, a specific imprinted magnetic material with high affinity for PCA was prepared by using Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) as the substrate and amplifying the number of boronic acid ligands on the product surface with branched polyethylenimine (PEI). The prepared Fe3O4@PEI@FPBA MIPs were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and other instruments, and their adsorption performance was systematically investigated. Due to the boron affinity-directed surface imprinting mechanism, the prepared Fe3O4@PEI@FPBA MIPs showed high selectivity for PCA, with a maximum adsorption capacity of 475.33 mg·g-1 and a maximum imprinting factor (IF) of 5.24. The adsorption process conformed to the pseudo-first-order kinetic model, and the adsorption isotherm conformed to the Langmuir model. In addition, the results of the repeatability test also indicated that Fe3O4@PEI@FPBA MIPs could maintain good adsorption performance after repeated use. The recovery rate of the actual sample analysis was 96.67% to 110.17% (relative standard deviation was 1.65% to 4.52%).

boronate affinity  /  magnetic nanoparticle  /  molecularly imprinted polymer  /  protocatechuic acid  /  branched polyethylenimine
田天标, 马祎洁, 纪永升, 马艳艳. 基于硼亲和策略的高亲和力磁性纳米粒子对原儿茶酸选择性吸附研究. 药学学报, 2026 , 61 (7) : 2694 -2702 . DOI: 10.16438/j.0513-4870.2025-0586
Tian-biao TIAN, Yi-jie MA, Yong-sheng JI, Yan-yan MA. Selective adsorption of protocatechuic acid by high-affinity magnetic nanoparticles based on boronate affinity strategy[J]. Acta Pharmaceutica Sinica, 2026 , 61 (7) : 2694 -2702 . DOI: 10.16438/j.0513-4870.2025-0586
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原儿茶酸(protocatechuic acid, PCA) 又称3, 4-二羟基苯甲酸, 是一种天然酚酸类物质, 广泛分布在日常饮食及许多香料和草药中, 如谷物、麸皮、葡萄、杏仁、八角、丹参、五加等[1-5]。近年来的科学研究显示原儿茶酸具有多种药理活性, 包括抗菌、抗炎、抗氧化、抗病毒、中枢神经保护和抗癌等[6-9]。除此之外, Zheng等[10]的研究显示, 原儿茶酸对β-淀粉样蛋白诱导的神经细胞损伤具有明显的保护作用; Jiao等[11]的研究显示原儿茶酸对肝脏炎症也有着良好的改善作用。除此之外原儿茶酸还能显著降低心肌耗氧量, 提高心肌耐氧能力, 减慢心率, 还具有明显抗乙型肝炎病毒(hepatitis B virus, HBV) 的作用[12]。目前分离富集原儿茶酸的方法主要包括柱层析法[13]、C18固相萃取法[14]、甲醇回流提取法[15]、高效液相色谱法[16]。然而这些方法存在仪器成本昂贵、样品预处理复杂、技术要求精细等阻碍其应用的缺点。因此, 开发能够快速分离富集原儿茶酸的新方法是一个尤为重要的问题。
分子印迹技术是一种新兴的分子间识别技术, 该技术通过模拟酶-底物或抗体-抗原之间的相互作用, 进而对模板分子进行特异性识别, 因此又被称为“人工锁”技术。分子印迹技术的基本原理是在基底材料结合模板分子后, 加入功能性单体和交联剂, 二者通过发生聚合反应形成印迹层, 随后洗脱模板分子, 形成了只适配模板分子的印迹空腔。通过该技术制备出的分子印迹聚合物(MIPs) 具有特异性高、稳定性强、结构可预测、应用范围广、成本低廉及可重现性好等优点[17], 近年来受到了广泛关注。尤其是Xing等[18]于2015年提出了硼亲和锚定表位可控定向印迹法之后, 基于硼亲和与定向表面印迹策略的磁性纳米粒子因其亲水性强、生物相容性好、易制备等优点逐渐成为分子印迹聚合物领域的研究热点。但早期磁性材料对目标物的特异性结合容量大小主要取决于硼酸基团的数目, 过少的硼酸基团使得早期的磁性材料在应用方面存在着一定的局限性。Li等[19]也于2017年成功合成了支链聚乙烯亚胺辅助硼酸功能化磁性纳米粒子(PEI-BA-MNPs), 采用了磁性固相萃取技术并成功应用于人唾液中微量糖蛋白的选择性富集。但该研究在制备PEI-BA-MNPs过程中所使用的2, 4-二氟-3-甲酰基苯硼酸(2, 4-difluoro-3-formylphenylboronic acid, DFFPBA) 存在对人体刺激性强、运输及储存难、处理要求高等缺点。
综上考虑, 本研究首先选用具有良好生物相容性、超顺磁性、低毒性及易制备等优点的四氧化三铁磁性纳米粒子(Fe3O4 MNPs) 为基材, 接着以富含氨基且具有柔韧性、亲水性、体积小、易于后修饰、成本低等优点的支链聚乙烯亚胺(polyethylenimine, PEI) 对产物表面的硼酸配基数量进行扩增, 最后搭配具有优良的水溶性和结合能力、安全性高、纯度高的4-甲基苯硼酸(FPBA) 作为功能单体, 基于硼亲和与定向表面印迹策略, 成功制备了对PCA具有高亲和力的特异性印迹四氧化三铁磁性纳米材料(Fe3O4@PEI@FPBA MIPs)。该磁性印迹材料具有亲和力高、抗干扰能力强等优点, 并成功应用于中药实际样品中PCA的富集分离。采用透射电子显微镜(TEM)、傅里叶红外光谱仪(FTIR) 等仪器对合成材料进行表征, 结合吸附实验[20], 探究本研究制备的Fe3O4@PEI@FPBA MIPs对PCA的吸附机制, 以期在富集分离中药材有效成分领域及中药材质量评估方面发掘更广泛的应用。
材料与方法
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材料与试剂  实验中所有试剂均为分析纯并直接用于实验。4-甲酰苯硼酸、氨水(C12702264、C13112480, 上海麦克林生化科技有限公司); 2-脱氧腺苷-水合物、硅酸四乙酯、三氯化铁(Ⅲ) 六水合物、1, 6-己二胺、无水乙酸钠、氢氧化钠、乙二醇、聚乙烯亚胺、磷酸二氢钠、磷酸氢二钠(LS90V10、B2210577、A2210179、B2422090、L2121209、F2210824、K2126439、K2211255、K2216652、C2321688, 阿拉丁试剂有限公司); 氰基硼氢化钠(R21120403, 上海韶远试剂有限公司); 腺苷(E2118059, 河北百灵威超精细材料有限公司)。
仪器与设备  磁力搅拌器(LC-MS-M1, 上海力辰邦西仪器科技有限公司); 恒温水浴锅(SN-HWS-11, 上海尚普仪器设备有限公司); 超声波清洗器(KQ-500B, 昆山市超声仪器有限公司); 鼓风干燥箱(DHG-9055A, 上海一恒科学仪器有限公司); 透射电子显微镜(JEM-1010, 日本电子株式会社); 傅里叶红外光谱仪[Great 20, 中科瑞捷(天津) 科技有限公司]; 反应釜(KH-100 mL, 西安仪贝尔仪器设备有限公司); pH仪(PHSJ-3F, 上海仪电科学仪器股份有限公司); 电动搅拌器(JJ-1, 常州普天仪器制造有限公司); 超微量紫外分光仪(FLS1000C, 上海天美科学仪器有限公司)。
氨基四氧化三铁磁性纳米粒子的制备  称取2.0 g FeCl3·6H2O、13.0 g 1, 6-己二胺和4.0 g无水乙酸钠充分分散于60 mL乙二醇中, 于198 ℃反应6 h。反应结束后冷却至室温, 最后产物分别使用去离子水和无水乙醇洗涤3次。恒温烘箱内50 ℃干燥过夜, 收集产物即得到1.4 g氨基四氧化三铁磁性纳米粒子(amino-functionalized magnetic nanoparticles, AMNPs)。
Fe3O4@PEI MNPs的制备  首先, 称取200.0 mg AMNPs超声分散于40 mL 5%戊二醛中, 室温搅拌12 h; 然后, 加入已经超声分散于40 mL甲醇中的0.5 g PEI, 再次室温搅拌12 h; 最后, 加入20 mL 20.0 mg·mL-1 NaBH3CN甲醇溶液, 继续搅拌6 h, 再次重复该操作完成制备。产物使用无水甲醇洗涤3次, 得Fe3O4@PEI MNPs (160.6 mg)。
Fe3O4@PEI@FPBA MNPs的制备  称取200.0 mg Fe3O4@PEI MNPs超声分散至30 mL甲醇中, 然后加入10.0 mg·mL-1 FPBA甲醇溶液和10.0 mg·mL-1 NaBH3CN甲醇溶液, 室温下搅拌24 h, 并使用无水甲醇洗涤3次所得沉淀, 完成Fe3O4@PEI@FPBA MNPs的制备(188.1 mg)。使用AMNPs代替Fe3O4@PEI MNPs进行合成, 其余步骤保持不变, 得到产物为Fe3O4@FPBA MNPs。
Fe3O4@PEI@FPBA MIPs的制备  硼亲和可控定向表面印迹方法主要由3个步骤组成: 模板固定、定向印迹和模板洗脱。实验流程具体如下: 首先, 进行模板固定, 称取4.0 mg PCA溶于2 mL 10 mmol·L-1磷酸盐缓冲溶液(PBS, pH为8.5), 加入40.0 mg Fe3O4@ PEI@FPBA MNPs, 在室温下振摇反应2 h, 结束后取出固定了模板的Fe3O4@PEI@FPBA MNPs, 用PBS (10 mmol·L-1, pH为8.5) 冲洗3次, 去除未结合的PCA; 然后, 进行定向印迹, 将固定了模板的Fe3O4@PEI@ FPBA MNPs分散至含有2.8 mL氨水的160 mL无水乙醇, 再加入40 mL 10 mmol·L-1 TEOS预聚液, 室温下振摇开始印迹, 聚合结束后分别用去离子水和乙醇清洗3次, 去除未反应的试剂; 最后, 进行模板洗脱, 在室温下, 将印迹后的材料转移到2 mL 100 mmol·L-1醋酸溶液中, 在室温下振荡洗脱60 min。除去模板后, 用PBS (10 mmol·L-1, pH为8.5) 和乙醇各冲洗3次, 最后于50 ℃真空干燥过夜, 即得Fe3O4@PEI@FPBA MIPs (33.8 mg)。除了没有添加PCA外, 还使用相同的方法合成了原儿茶酸非特异性印迹四氧化三铁磁性纳米材料(Fe3O4@ PEI@FPBA NIPs, 34.3 mg)。使用Fe3O4@FPBA MNPs代替Fe3O4@PEI MNPs进行合成, 其余步骤保持不变, 得到产物为Fe3O4@FPBA MIPs。本实验制备示意及吸附原理如图1所示。
硼亲和能力测定  为了考察Fe3O4@PEI@FPBA MNPs的硼亲和选择性, 本研究选用腺苷和脱氧腺苷作为测试化合物。分别将4.0 mg腺苷和脱氧腺苷溶解至2 mL 10 mmol·L-1 PBS (pH为8.5) 中, 然后将40.0 mg Fe3O4@PEI@FPBA MNPs分散于上述100 μL的两种溶液中, 震荡孵育2 h。随后磁分离弃去上清液收集沉淀, 加入10 mmol·L-1 PBS (pH为8.5) 重复清洗3次。最后, 将Fe3O4@PEI@FPBA MNPs重新分散在50 μL 100 mmol·L-1醋酸溶液中, 在室温环境下进行洗脱持续1 h并收集洗脱液。通过对洗脱液进行微量紫外检测来确定Fe3O4@PEI@FPBA MNPs对腺苷或脱氧腺苷的结合量, 检测波长为260 nm。实验平行测定3次。
印迹时间优化  本实验使用前文描述的相同方法进行定向表面印迹, 将已经进行模板固定后的Fe3O4@ PEI@FPBA MNPs分散至含有2.8 mL氨水的160 mL无水乙醇, 再加入40 mL 10 mmol·L-1 TEOS预聚液进行印迹。该实验重复5次, 印迹时间分别选取10、12.5、15、17.5、20 min。后续进行模板洗脱并收集不同印迹时间的Fe3O4@PEI@FPBA MIPs。采用同样方法制备不同印迹时间的Fe3O4@PEI@FPBA NIPs作为对照组。将上述所得不同时间的Fe3O4@PEI@FPBA MIPs和Fe3O4@PEI@FPBA NIPs分别称取2.0 mg超声分散于100 μL 10 mmol·L-1 PBS (pH为8.5) 中, 再各自加入100 μL 1.0 mg·mL-1 PCA溶液, 震荡孵育2 h后进行模板洗脱, 收集洗脱液在260 nm处进行紫外检测。
萃取和解吸时间优化  通过控制变量来考察不同萃取与解吸时间对所得结果的影响。首先, 在其余条件不变的情况下, 通过改变萃取时间为20、40、60、80、100、120 min来考察萃取时间长短对实验结果的影响; 考察解吸时间方法与考察萃取时间方法一致, 解吸时间改变为10、20、30、40、50、60 min。实验平行测定3次。
吸附实验  称取40.0 mg Fe3O4@PEI@FPBA MIPs或Fe3O4@FPBA MIPs分散于空白溶液中, 通过控制变量法, 仅改变PCA溶液的浓度, 通过室温孵育完成Fe3O4@PEI@FPBA MIPs和Fe3O4@FPBA MIPs与PCA的结合来进行静态吸附测试。后续数据采用Langmuir模型评估Fe3O4@PEI@FPBA MIPs和Fe3O4@FPBA MIPs对PCA的吸附性能:
$ \frac{{C}_{\mathrm{e}}}{{Q}_{\mathrm{e}}}=\frac{{C}_{\mathrm{e}}}{{Q}_{\mathrm{m}}}+\frac{1}{\left({K}_{L}{Q}_{\mathrm{m}}\right)} $
其中, Ce为吸附平衡时溶液中PCA的浓度(mg·L-1); Qe为PCA的平衡吸附容量(mg·g-1); Qm为PCA的饱和吸附容量(mg·g-1); KL为Langmuir的吸附常数(L·mg-1)。
选择性实验和竞争性实验  本研究主要利用硼酸基团和顺式二羟基化合物的可逆结合/释放为固定/洗脱模板的性质进行表面定向印迹, 所以针对PCA (含有顺式二羟基结构的中药活性成分), 本研究选取了含有顺式二羟基结构的中药活性成分作为干扰物质, 如绿原酸(chlorogenic acid, CGA)、芦丁(rutin)、葛根素(puerain)、咖啡酸(caffeic acid, CA)、人参皂苷(ginsenoside) 来考察Fe3O4@PEI@FPBA MIPs对PCA的选择性和竞争性。分别配置上述6种化合物的PBS溶液(1.0 mg·mL-1, 100 μL), 加入含有2.0 mg Fe3O4@PEI@FPBA MIPs的100 μL PBS溶液(10 mmol·L-1, pH为8.5) 室温震荡, 清洗后进行模板洗脱, 磁分离留上清液使用微量紫外检测, 考察Fe3O4@PEI@FPBA MIPs对结构类似物的选择性。在竞争性实验中, 作者采用相同方法配置了含有1.0 mg·mL-1 PCA和1.0 mg·mL-1干扰物质的PBS (10 mmol·L-1, pH为8.5) 溶液100 μL, 加入含有2.0 mg Fe3O4@PEI@FPBA MIPs的100 μL PBS (10 mmol·L-1, pH为8.5) 溶液室温震荡, 清洗后进行模板洗脱, 磁分离留上清液使用微量紫外检测, 进而考察在PCA与干扰物同时存在时Fe3O4@PEI@FPBA MIPs是否会受到影响。实验平行测定3次, 避免误差。
重复性实验  控制其他变量不变情况下, 使用40.0 mg Fe3O4@PEI@FPBA MIPs进行10次萃取-解吸循环并收集每次洗脱液进行紫外检测, 测试Fe3O4@PEI@FPBA MIPs的再生性能。实验平行测定3次。
实际样品分析  本研究从药店购买益智仁作为实际样品, 按照药典上的方法对实际样品进行处理, 得到供试品溶液以供后续紫外分析。在线性范围内采用加标回收法对实际样品进行多次加标回收, 通过计算其准确性进而评估其作用于实际样品中的效果。
统计学方法  为了探究本研究制备的Fe3O4@ PEI@FPBA MIP吸附选择性及竞争性, 对加入模板分子及干扰物质后的溶液进行吸光度数据收集, 通过t检验, 数据以平均值±标准差($ \overline{x} $ ± s) 表示, P < 0.05认为差异具有统计学意义。
结果
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1　制备材料性质研究
如图2A、B所示, Fe3O4@PEI@FPBA MIPs在水中可以超声分散均匀, 在外部磁铁的作用下可迅速聚集到容器壁上, 去除磁铁后, 通过超声可再次使聚集的Fe3O4@PEI@FPBA MIPs重新分散, 以上情况证明制得的Fe3O4@PEI@FPBA MIPs具有良好的磁性能和分散性。对本研究制备所得的AMNPs、Fe3O4@PEI@ FPBA MNPs、Fe3O4@PEI@FPBA MIPs的形貌和大小通过TEM进行表征, 结果如图2C~E所示, AMNPs、Fe3O4@PEI@FPBA MNPs、Fe3O4@PEI@FPBA MIPs均呈球形, 尺寸均一。因为PCA的分子长度原因, 所以最适印迹层厚度较薄, 但是依然能够在Fe3O4@PEI@ FPBA MIPs上观察到聚合硅层的存在, 而AMNPs、Fe3O4@PEI@FPBA MNPs上则不存在印迹层。对本研究制备的AMNPs、Fe3O4@PEI@FPBA MNPs、Fe3O4@ PEI@FPBA MIPs、Fe3O4@PEI@FPBA NIPs进行FTIR分析, 结果如图2F所示, Fe3O4@PEI@FPBA MNPs的1 152 cm-1苯环峰, 1 397 cm-1为硼酸基团特征峰, 标志着AMNPs已被FPBA成功修饰。在Fe3O4@PEI@FPBA MIPs和Fe3O4@PEI@FPBA NIPs的红外谱图中, 1 159、1 156 cm-1均为苯环峰, 1 069 cm-1则为Si-O的特征峰, 意味着较Fe3O4@PEI@FPBA MNPs相比, Fe3O4@PEI@ FPBA MIPs和Fe3O4@PEI@FPBA NIPs其表面发生了聚合形成了印迹层。
2　硼亲和能力测定结果及时间优化
本研究选择了腺苷和脱氧腺苷作为测试化合物对Fe3O4@PEI@FPBA MNPs的硼亲和能力进行测定, 实验结果如图3A所示, 可得出Fe3O4@PEI@FPBA MNPs对腺苷(顺式二羟基化合物) 的具有良好的选择性, 而对脱氧腺苷(非顺式二羟基化合物) 的硼亲和作用力较低, 同时也证明了Fe3O4@PEI@FPBA MNPs已经成功修饰了FPBA。为了使Fe3O4@PEI@FPBA MIPs具有更出色的识别性能, 本研究对印迹时间进行了考察, 以印迹因子(imprinting factor, IF) 作为判断依据。由图3B可知, 当时间为15 min时, Fe3O4@PEI@FPBA MIPs选择性最佳, IF值达到5.24, 说明15 min的印迹时间能够形成尺寸较为合适的印迹空腔, 以实现对PCA的选择性结合。因此, 在后续试验中将印迹时间均设为15 min。在后续实验过程中, 本研究发现不同的萃取和解吸时间也会对实验结果造成影响, 故而使用控制变量法对萃取时间和解吸时间进行了优化, 实验结果如图3C、D所示, Fe3O4@PEI@FPBA MIPs的最佳萃取时间和解吸时间分别为60和30 min。
3　静态吸附结果及等温模型分析
目标物的初始浓度也是影响吸附性能的重要因素, 在10.0~50.0 mg·L-1改变PCA的初始浓度, 分别测试了Fe3O4@PEI@FPBA MIPs和Fe3O4@FPBA MIPs的吸附容量, 得到吸附等温曲线(图4A)。结果表明, 随着PCA初始浓度的增加, 使得Fe3O4@PEI@FPBA MIPs与PCA接触频繁, 吸附容量增大, 最后当浓度增加到50.0 mg·L-1时, Fe3O4@PEI@FPBA MIPs的最大吸附量达到475.33 mg·g-1, 远高于Fe3O4@FPBA MIPs。继续增大PCA浓度, Fe3O4@PEI@FPBA MIPs及Fe3O4@FPBA MIPs的吸附容量达到最大, 基本保持不变, 随后采用Langmuir模型对10.0~50.0 mg·L-1吸附结果进行拟合, 结果如图4B、C和表1所示, 证明Fe3O4@PEI@FPBA MIPs及Fe3O4@FPBA MIPs的吸附均符合Langmuir模型。
4　吸附选择性与竞争性
本研究使用的PCA及干扰物质的结构简式如图5A所示, 干扰物质与PCA均具有顺式二羟基结构, 以确保选择性及竞争性实验中干扰物质确有干扰性。选择性测试结果如图5B所示, 加有PCA的Fe3O4@PEI@ FPBA MIPs溶液, 其洗脱液在紫外检测下平均吸光度可达1.42, 远高于其结构类似物的吸光度值(0.23~0.31), 证明本研究合成的Fe3O4@PEI@FPBA MIPs对PCA的结合能力远超其他含有顺式二羟基的结构类似物。在实验组与对照组的显著性差异分析中, 经t检验得到各组的P值分别为2.49×10-6、3.08×10-6、3.88×10-7、1.02×10-6、2.98×10-6, 均小于0.000 1, 该结果证明对照组与实验组存在显著性差异。竞争性实验结果如图5C所示, 在只加有PCA的Fe3O4@PEI@FPBA MIPs溶液, 其洗脱液在紫外检测下平均吸光度可达1.47 (与选择性实验中洗脱液吸光度误差可忽略不计), 干扰物质的加入也并未对Fe3O4@PEI@FPBA MIPs的高选择性有显著影响, 在不同的扰物存在的情况下, Fe3O4@PEI@ FPBA MIPs仍然对PCA有着优异的结合能力(吸光度值仍可达到1.42~1.53)。在实验组与对照组的显著性差异分析中, 经t检验得到各组的P值分别为0.23、0.09、0.12、0.30、0.01, 其中仅有加人参皂苷的实验组P值小于0.05, 其余对照组均未出现显著性差异, 但考虑到本实验只平行测定了3次, 无法完全避免误差的出现, 所以并不能完全否定实验结果的参考价值。选择性与竞争性实验结果表明本研究制备的Fe3O4@ PEI@FPBA MIPs不仅对PCA具有优异的选择性, 还具有良好的抗干扰能力。
5　重复性实验
本测试使用20.0 mg Fe3O4@PEI@FPBA MIPs进行10次萃取-解吸循环实验, 所得结果如图5D所示, 随着循环次数的增加, Fe3O4@PEI@FPBA MIPs对PCA吸附能力有所下降, 但重复5次后吸附量仍相当于首次吸附容量的80%, 证明本研究制备的Fe3O4@PEI@ FPBA MIPs具有较好的再生性能。而吸附能力的下降可能是由材料在洗脱过程中造成的损耗或者未洗脱的PCA占据了结合位点所致[21]。
6　回收率和精密度
由表2可知, 根据前文加标后吸附洗脱液的检测结果, 本研究建立的方法回收率为96.67%~110.17%, 相对标准偏差(relative standard deviation, RSD) 为1.65%~4.52%, 且所用溶剂对试验结果影响不大, 与标准方法对比, 结果在可行性范围之内, 说明Fe3O4@PEI@FPBA MIPs可以应用于实际样品的检测。
讨论
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有研究[22]表明, 基于传统Fe3O4分子印迹聚合物的信号积累存在一系列问题, 由于Fe3O4表面存在较少的活性位点, 简单捕获在其表面的中药活性成分可能容易被随后的溶剂洗涤, 造成损失。而经PEI处理后的Fe3O4@PEI MNPs比表面积增大, 可有效地为吸附单元提供大量的活性位点, 相比未经修饰的Fe3O4, 可以构筑更多的模板空腔, 且稳定性更好。本研究首先对Fe3O4做了PEI处理, 即通过戊二醛活化后在Fe3O4表面修饰上PEI支链, 随后通过席夫碱反应在修饰了PEI的Fe3O4上结合更多的硼酸基团, 进而制备更多特异性印迹空腔。TEM结果可以观察到Fe3O4表面的SiO2印迹层, FTIR分析也验证了这一结果, Li等[23]在量子点表面做了相似的研究。
在本研究中, 作为功能单体的FPBA发挥了主要的识别作用, PCA作为典型的顺式二醇类结构中药有效成分, 当反应体系的pH大于硼酸配基的pKa时, 硼酸配基发生水解, 通过与周围-OH分子的配位作用, 使硼原子从一个平面的sp2型变成一个四面体的sp3型, 并与顺式二羟基中的邻二羟基进行酯化, 从而形成一个稳定的五元环或者六元环。在酸性条件下, 硼酸酯的环化反应使硼原子从sp3型变为sp2型, 释放出顺式二羟基化合物, 这种开/关特性保证了硼酸作为建立具有顺式二醇结构分子的印迹通用技术最具潜力的亲和配体。Xing等[18]提出的硼亲和可控定向表面分子印迹技术将硼亲和作用与分子印迹技术有效结合, 即通过模板固定、定向印迹和模板去除3个步骤成功制备出MIP, 由于材料具有丰富的硼酸位点和印迹孔穴, 可在弱碱性条件下选择性识别PCA, 建立了具有高取向性的特异性双重识别模块。在随后的选择性和竞争性试验中, 特定的靶向作用和印迹孔穴也实现了对目标物PCA的高度选择。值得注意的是, 其中可逆共价复合物的形成也使目标物的洗脱和重新结合更加容易。但随着其重复使用, 可能会伴随着空腔内PCA未完全洗脱抑或是FPBA位点被洗脱下来, 进而导致MIP结合容量下降。目前MIP相较于其余现存方法有着明显的优势, 若对其重复使用性更高的要求, 后续可以进行印迹单体、基底材料等制备过程的优化来进一步提高稳定性。
结论
收起
本研究以Fe3O4 MNPs为基材制备了一种Fe3O4@ PEI@FPBA MIPs, 能够实现对PCA的双重选择性吸附, 最大吸附容量可达475.33 mg·g-1, IF值为5.24。吸附过程符合准一级动力学模型, 吸附等温线符合Langmuir模型。此外, 重复性试验结果表明, Fe3O4@PEI@FPBA MIPs在循环使用5次后仍能保持较好的吸附性能。对实际样品进行分析, 回收率为96.67%~110.17%, 相对标准偏差为1.65%~4.52%。

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2026年第61卷第7期
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doi: 10.16438/j.0513-4870.2025-0586
  • 接收时间：2025-05-23
  • 首发时间：2026-09-21
  • 出版时间：2026-07-12
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  • 收稿日期：2025-05-23
  • 修回日期：2025-07-08
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    河南中医药大学药学院, 河南 郑州 450046

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2种不同金属材料的力学参数
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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
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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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