Article(id=1153433742661111830, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433737141412332, articleNumber=null, orderNo=null, doi=10.19812/j.cnki.jfsq11-5956/ts.20241013002, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1728748800000, receivedDateStr=2024-10-13, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1752929634013, onlineDateStr=2025-07-19, pubDate=1745510400000, pubDateStr=2025-04-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752929634013, onlineIssueDateStr=2025-07-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752929634013, creator=13701087609, updateTime=1752929634013, updator=13701087609, issue=Issue{id=1153433737141412332, tenantId=1146029695717560320, journalId=1149652044408987649, year='2025', volume='16', issue='8', pageStart='1', pageEnd='316', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752929632696, creator=13701087609, updateTime=1757293087150, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1171735391666225233, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433737141412332, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1171735391666225234, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433737141412332, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=46, endPage=53, ext={EN=ArticleExt(id=1153433743151845400, articleId=1153433742661111830, tenantId=1146029695717560320, journalId=1149652044408987649, language=EN, title=Research progress of quantum dots in the detection of food mycotoxins, columnId=1151895321526759957, journalTitle=Journal of Food Safety & Quality, columnName=Special Topic: Detection and Prevention and Control of Biotoxins in Food, runingTitle=null, highlight=null, articleAbstract=

Food mycotoxins (aflatoxin, ochratoxin, zearalenone, deoxynivalenol, etc.) are contaminants that pose a serious threat to food safety and public health. With the increasing global demand for food and the complexity of the supply chain, rapid and sensitive detection of contaminants is essential to maintain public health and well-being. In recent years, the rapid development of nanotechnology has provided new ideas for the detection of mycotoxins in food. Among them, quantum dots, as a new type of fluorescent nanomaterials, are favored in the field of biosensing due to their excellent optical properties and high sensitivity. Taking quantum dots as a starting point, this paper briefly reviewed the basic properties, synthesis, modification and functionalization of quantum dots, focused on their application in the detection of food mycotoxins, discussed the advantages and challenges of quantum dots in food mycotoxins detection, with the aim of providing new ideas for food safety detection and on-site real-time detection, and safeguarding food safety and human health.

, correspAuthors=Ting-Ting MA, 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, authorCompany=null, fund=null, authors=null, authorsList=Ting-Ting MA, Ying TANG, Jun-Li WANG, Xiao-Nan YANG), CN=ArticleExt(id=1153433748654772295, articleId=1153433742661111830, tenantId=1146029695717560320, journalId=1149652044408987649, language=CN, title=量子点在食品真菌毒素检测中的研究进展, columnId=1151895321669366295, journalTitle=食品安全质量检测学报, columnName=本期专题:食品中生物毒素检测与防控, runingTitle=null, highlight=null, articleAbstract=

食品真菌毒素(如黄曲霉毒素、赭曲霉毒素、玉米赤霉烯酮、脱氧雪腐镰刀菌烯醇等)是严重威胁食品安全和公众健康的污染物。随着全球对食品需求的不断增加和供应链复杂化, 快速、灵敏地检测污染物对于维护公众健康至关重要。近年来, 纳米技术的快速发展为食品中真菌毒素的检测提供了新思路。其中, 量子点作为一种新型的荧光纳米材料, 以其优异的光学性质和高灵敏度, 在生物传感领域备受青睐。本文以量子点为出发点, 综述了量子点的基本特性、合成方式、修饰及功能化, 重点介绍其在食品真菌毒素检测中的应用研究, 并对量子点在真菌毒素检测中的优势与挑战进行阐述, 以期为食品安全检测和现场实时检测提供新思路, 为食品安全和人类健康保驾护航。

, correspAuthors=马婷婷, authorNote=null, correspAuthorsNote=
* 马婷婷(1997—), 女, 助理工程师, 主要研究方向为食品营养与功能评价。E-mail:
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Science of The Total Environment, 2023, 856: 159073., articleTitle=A smartphone-assisted down/up-conversion dual-mode ratiometric fluorescence sensor for visual detection of mercury ions and l-penicillamine, refAbstract=null)], funds=[Fund(id=1171733651248161770, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, awardId=2023MK119, language=CN, fundingSource=国家市场监督管理总局科技项目(2023MK119), fundOrder=null, country=null), Fund(id=1171733651319464939, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, awardId=2024QNTD15, language=CN, fundingSource=陇原青年创新创业人才项目(2024QNTD15), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1171733648559612867, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, xref=null, ext=[AuthorCompanyExt(id=1171733648568001476, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, companyId=1171733648559612867, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Gansu Province Product Quality Supervision and Inspection Research Institute, Lanzhou 730050, China), AuthorCompanyExt(id=1171733648576390085, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, companyId=1171733648559612867, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=甘肃省产品质量监督检验研究院, 兰州 730050)])], figs=[ArticleFig(id=1171733650581267428, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, language=EN, label=Fig.1, caption=Schematic diagram of QDs photoluminescence[13], figureFileSmall=GeAIEVDlb/0L5E6+tpO6JA==, figureFileBig=m4g+SqyDnhqSE5R+WEY+yw==, tableContent=null), ArticleFig(id=1171733650681930725, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, language=CN, label=图1, caption=QDs光致发电原理图[13], figureFileSmall=GeAIEVDlb/0L5E6+tpO6JA==, figureFileBig=m4g+SqyDnhqSE5R+WEY+yw==, tableContent=null), ArticleFig(id=1171733650740650982, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, language=EN, label=Table 1, caption=

Limits of common mycotoxins in food (μg/kg)[5]

, figureFileSmall=null, figureFileBig=null, tableContent=
真菌毒素 食品种类 中国 国际食品
法典委员会
欧盟 美国
AFB1 玉米、花生及其乳制品 20.0 15 2 15
DON 谷物及其制品 1000 1000 500 1000
OTA 谷物、谷类及其制品 5.0 5 3 -
ZEN 谷物及其制品 60.0 - 5 -
PAT 水果、饮料类、酒类 50.0 50 50 50
), ArticleFig(id=1171733650828731367, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, language=CN, label=表1, caption=

食品中常见真菌毒素限量标准(μg/kg)[5]

, figureFileSmall=null, figureFileBig=null, tableContent=
真菌毒素 食品种类 中国 国际食品
法典委员会
欧盟 美国
AFB1 玉米、花生及其乳制品 20.0 15 2 15
DON 谷物及其制品 1000 1000 500 1000
OTA 谷物、谷类及其制品 5.0 5 3 -
ZEN 谷物及其制品 60.0 - 5 -
PAT 水果、饮料类、酒类 50.0 50 50 50
), ArticleFig(id=1171733650887451624, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, language=EN, label=Table 2, caption=

Application of QDs in the detection of food mycotoxins

, figureFileSmall=null, figureFileBig=null, tableContent=
方法 真菌毒素 QDs 检出限 线性范围 样品类型 检测
时间
参考文献
ECL传感器 AFB1 MP QDs 3.5 fg/mL 11.5 fg/mL~20 ng/mL 玉米 [31]
AFB1 GQDs 3.75 pg/mL 0.01~100 ng/mL 花生、玉米、小麦 80 min [32]
OTA CdSe@CdS QDs 0.89 ng/mL 1~100 ng/mL 百合和大黄 2 h [33]
ZEN SnO2 QDs 0.16 pg/mL 0.0005~500 ng/mL 玉米 [34]
荧光免疫技术 AFB1 SAQDMS 0.02 μg/kg 0.05~25.00 μg/kg 小麦 8 min [38]
AFB1 QDs-SA 5 ng/kg 1~10 μg/kg 花生 30 min [39]
AFB1 CdSe/ZnS QBs 9.3 pg/mL 15~500 pg/mL 饲料 20 min [35]
ZEN 102.1 pg/mL 0.15~5 ng/mL
AFB1 QDMS 0.01 ng/mL 0.01~1 ng/mL 玉米 45 min [41]
OTA 0.2 ng/mL 0.2~200 ng/mL
ZEN 0.032 ng/mL 0.032~32 ng/mL
SERS传感器 AFB1 QD-SiO2 0.087 pg/mL 10-4 ~103 ng/mL 花生、花生油 [46]
AFB1 CdTe QDs 0.100 pg/mL 10-4~103 ng/mL 花生、大米 [47]
0.094 pg/mL 10-4~103 ng/mL 玉米
其他应用 OTA Mn-CsPbBr3 QDs@SiO2 4.1 ng/mL 5.0~250 ng/mL 小麦粉、玉米粉, 红茶、咖啡、发霉无花果 [48]
ZEN CdTe QDs 13.87 pg/mL 0.05~80 ng/mL 玉米、小麦、大豆 5 min [49]
), ArticleFig(id=1171733650979726313, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433742661111830, language=CN, label=表2, caption=

QDs在食品真菌毒素中的应用

, figureFileSmall=null, figureFileBig=null, tableContent=
方法 真菌毒素 QDs 检出限 线性范围 样品类型 检测
时间
参考文献
ECL传感器 AFB1 MP QDs 3.5 fg/mL 11.5 fg/mL~20 ng/mL 玉米 [31]
AFB1 GQDs 3.75 pg/mL 0.01~100 ng/mL 花生、玉米、小麦 80 min [32]
OTA CdSe@CdS QDs 0.89 ng/mL 1~100 ng/mL 百合和大黄 2 h [33]
ZEN SnO2 QDs 0.16 pg/mL 0.0005~500 ng/mL 玉米 [34]
荧光免疫技术 AFB1 SAQDMS 0.02 μg/kg 0.05~25.00 μg/kg 小麦 8 min [38]
AFB1 QDs-SA 5 ng/kg 1~10 μg/kg 花生 30 min [39]
AFB1 CdSe/ZnS QBs 9.3 pg/mL 15~500 pg/mL 饲料 20 min [35]
ZEN 102.1 pg/mL 0.15~5 ng/mL
AFB1 QDMS 0.01 ng/mL 0.01~1 ng/mL 玉米 45 min [41]
OTA 0.2 ng/mL 0.2~200 ng/mL
ZEN 0.032 ng/mL 0.032~32 ng/mL
SERS传感器 AFB1 QD-SiO2 0.087 pg/mL 10-4 ~103 ng/mL 花生、花生油 [46]
AFB1 CdTe QDs 0.100 pg/mL 10-4~103 ng/mL 花生、大米 [47]
0.094 pg/mL 10-4~103 ng/mL 玉米
其他应用 OTA Mn-CsPbBr3 QDs@SiO2 4.1 ng/mL 5.0~250 ng/mL 小麦粉、玉米粉, 红茶、咖啡、发霉无花果 [48]
ZEN CdTe QDs 13.87 pg/mL 0.05~80 ng/mL 玉米、小麦、大豆 5 min [49]
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量子点在食品真菌毒素检测中的研究进展
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马婷婷 * , 唐璎 , 王俊丽 , 杨晓楠
食品安全质量检测学报 | 本期专题:食品中生物毒素检测与防控 2025,16(8): 46-53
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食品安全质量检测学报 | 本期专题:食品中生物毒素检测与防控 2025, 16(8): 46-53
量子点在食品真菌毒素检测中的研究进展
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马婷婷* , 唐璎, 王俊丽, 杨晓楠
作者信息
  • 甘肃省产品质量监督检验研究院, 兰州 730050

通讯作者:

* 马婷婷(1997—), 女, 助理工程师, 主要研究方向为食品营养与功能评价。E-mail:
Research progress of quantum dots in the detection of food mycotoxins
Ting-Ting MA* , Ying TANG, Jun-Li WANG, Xiao-Nan YANG
Affiliations
  • Gansu Province Product Quality Supervision and Inspection Research Institute, Lanzhou 730050, China
出版时间: 2025-04-25 doi: 10.19812/j.cnki.jfsq11-5956/ts.20241013002
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食品真菌毒素(如黄曲霉毒素、赭曲霉毒素、玉米赤霉烯酮、脱氧雪腐镰刀菌烯醇等)是严重威胁食品安全和公众健康的污染物。随着全球对食品需求的不断增加和供应链复杂化, 快速、灵敏地检测污染物对于维护公众健康至关重要。近年来, 纳米技术的快速发展为食品中真菌毒素的检测提供了新思路。其中, 量子点作为一种新型的荧光纳米材料, 以其优异的光学性质和高灵敏度, 在生物传感领域备受青睐。本文以量子点为出发点, 综述了量子点的基本特性、合成方式、修饰及功能化, 重点介绍其在食品真菌毒素检测中的应用研究, 并对量子点在真菌毒素检测中的优势与挑战进行阐述, 以期为食品安全检测和现场实时检测提供新思路, 为食品安全和人类健康保驾护航。

食品真菌毒素  /  量子点  /  快速检测技术  /  生物传感器  /  荧光免疫分析

Food mycotoxins (aflatoxin, ochratoxin, zearalenone, deoxynivalenol, etc.) are contaminants that pose a serious threat to food safety and public health. With the increasing global demand for food and the complexity of the supply chain, rapid and sensitive detection of contaminants is essential to maintain public health and well-being. In recent years, the rapid development of nanotechnology has provided new ideas for the detection of mycotoxins in food. Among them, quantum dots, as a new type of fluorescent nanomaterials, are favored in the field of biosensing due to their excellent optical properties and high sensitivity. Taking quantum dots as a starting point, this paper briefly reviewed the basic properties, synthesis, modification and functionalization of quantum dots, focused on their application in the detection of food mycotoxins, discussed the advantages and challenges of quantum dots in food mycotoxins detection, with the aim of providing new ideas for food safety detection and on-site real-time detection, and safeguarding food safety and human health.

food mycotoxins  /  quantum dots  /  rapid detection technology  /  biosensor  /  fluorescence immunoassay
马婷婷, 唐璎, 王俊丽, 杨晓楠. 量子点在食品真菌毒素检测中的研究进展. 食品安全质量检测学报, 2025 , 16 (8) : 46 -53 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20241013002
Ting-Ting MA, Ying TANG, Jun-Li WANG, Xiao-Nan YANG. Research progress of quantum dots in the detection of food mycotoxins[J]. Journal of Food Safety & Quality, 2025 , 16 (8) : 46 -53 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20241013002
随着全球经济的快速发展和人们生活质量的不断提高, 食品安全已成为一个严重的世界性问题。真菌毒素作为由霉菌产生的次级代谢产物, 具有较强的毒性和致癌性, 其广泛存在于粮食、坚果、香料等食品中。联合国粮食及农业组织(Food and Agriculture Organization of the United Nations, FAO)估计, 全球约四分之一的粮食受到真菌毒素污染[1]。食用受真菌毒素污染的食品, 可能会引起肝炎、免疫抑制、肝细胞癌和精神障碍等疾病, 在极端情况下可导致死亡, 对人类健康构成严重威胁[2]。自1960年发现黄曲霉毒素(aflatoxin, AFT)以来, 研究人员在食品和饲料中已确认和鉴定了400多种真菌毒素, 但对经济意义和健康具有重要影响的真菌毒素主要包括AFT、赭曲霉毒素(ochratoxins, OTs)、玉米赤霉烯酮(zearalenone, ZEN)、展青霉素(patulin, PAT)、伏马毒素B1 (fumonisin B1, FB1)、脱氧雪腐镰刀菌烯醇(deoxynivalenol, DON)等[3]。国际癌症研究机构(International Agency for Research on Cancer, IARC)将真菌毒素分为5大类: 1、2A、2B、4、5。第1组被认为是有足够证据证明其可导致人类癌症的毒素, 如AFT, 其中黄曲霉毒素B1 (aflatoxin B1, AFB1)具有极强的毒性和明显的致癌作用; 2B组被定义为可能导致人类癌症的真菌毒素, 如 OTs和伏马毒素, 其中FB1的含量最高, 其占伏马毒素污染总量的70%[4]。因此, 真菌毒素对人体健康、农业生产及商业贸易造成了巨大影响, 亟需科学的检测方法。
食品安全分析是保障食品安全的必要手段, 我国对真菌毒素的污染和防控非常重视。GB 2761—2017《食品安全国家标准 食品中真菌毒素限量》中规定了各类食物中真菌毒素的限量。其中, AFTB1在各类食品中的限量是0.5~20.0 μg/kg, OTsA的限量指标为5.0~10.0 μg/kg, 展青素在各类食品中的限量为50 μg/kg, ZEN在谷物及其制品中的限量指标为60 μg/kg。各国和各组织对食品中常见真菌毒素的限量标准如表1[5]。检测真菌毒素的传统方法如高效液相色谱法(high performance liquid chromatography, HPLC)、高效液相色谱-质谱法(high performance liquid chromatography-mass spectrometry, HPLC-MS)、薄层色谱法(thin layer chromatography, TLC)、酶联免疫吸附测定法(enzyme linked immunosorbent assay, ELISA)等。 这些方法虽然结果准确, 但存在操作复杂、检测时间长、灵敏度有限等问题[6]。因此, 开发高效、快速、灵敏的方法用于检测食品中真菌毒素对于维护公众健康和福祉至关重要。
在食品安全领域, 纳米材料因其优异的物化特性而表现出巨大的应用潜力。目前, 研究人员正积极将纳米材料应用于食品安全检测领域, 并取得了令人满意的成果[7]。量子点(quantum dots, QDs)是一种尺寸在1~10 nm的半导体纳米晶体, 具有独特的光学和电子特性, 如高亮度、宽激发光谱、窄而对称的发射带、良好的光稳定性和生物相容性等, 在生物检测和成像领域得到广泛应用[8]。蒙吉•巴文迪、路易斯•布鲁斯和阿列克谢•伊基莫夫因“发现和合成QDs”而被授予2023年诺贝尔化学奖[9]。基于QDs的快检方法比传统检测技术成本低、耗时短、操作简单, 且无损伤, 为真菌毒素检测提供了新思路。本文以QDs为出发点, 综述了QDs的基本特性、合成方式、修饰及功能化, 重点介绍其在食品真菌毒素检测中的研究进展, 并对其应用前景进行了展望, 以期为食品安全检测和现场实时检测提供新思路。
QDs是一种尺寸小于10 nm的胶体半导体纳米晶体, 在三维空间维度上小于等于自身的激子玻尔半径, 由元素周期表第II-VI族(如CdSe、CdS)、III-V族(如InP)或Ⅳ-Ⅵ族(如PbS、PbSe)元素组成[10]。随着纳米材料研究领域的蓬勃发展, 碳QDs、硫QDs和Ⅰ-Ⅲ-Ⅵ三元QDs (CuInSe, AgInS2和CuInS2)等新型纳米粒子也被引入到这个大家族中, 不断丰富QDs种类[11]。根据激发方式的不同, QDs的发光通常分为光致发光、电致发光和自辐射发光[12]。如图1所示, 光致发光是当QDs被光照射时, 光子被吸收, 电子从价带跃迁到导带, 形成激发态电子-空穴对(激子)。随后, 受激发的电子又从导带跃迁到价带, 重新结合激子, 再次释放光子, 使QDs发射特征性荧光[13]。QDs的发射光谱可以通过改变其尺寸和成分来调控, 这使其在荧光标记和检测中具有独特优势[14]。QDs由于其极小的尺寸, 会产生量子限域效应, 因而表现出独特的光学性质, 如吸收光谱宽, 发射光谱大小可调, 量子产率高且不易发生漂白, 发射带窄而对称, 光稳定性高等特点[12]。这些独特的光学特性增强了亮度和稳定性, 显著提高了食品安全中污染物检测的灵敏度和准确性。此外, QDs能够在不同波长发射光, 使得其能同时识别多种危害因素, 提高检测过程的高效性和全面性, 因此非常适合应用于食品安全领域[15-16]
构建QDs生物传感体系的前提是能制备出具备高荧光量子产率的QDs。合成QDs的策略主要分“自上而下”和“自下而上”[17]
“自上而下”法主要针对尺寸较大的碳材料, 通过各种化学、物理或电化学途径将其制备成特定的纳米颗粒。这种方法能够在一定程度上维持原材料的结构和性质, 并且操作简单, 但存在QDs表面缺陷的问题, 不适用于QDs的大规模制备。常见的合成方式包括电化学氧化、激光烧蚀、电弧放电等[18]。“自下而上”法是小分子物质经过成核、生长和聚合过程来制备QDs。通过合理的选择骨架分子和配体, 严格控制化学进料比例、反应时间和温度, 以精准控制产物的尺寸。该方法具有实用性高、绿色无污染、成本效益高、方法简便等优点。研究中常见的合成路线包括溶剂热法、超声波热解和溶胶凝胶等[19]。除了上述物理、化学合成方法外, QDs还可以将细菌、真菌等作为微生物底物, 利用细胞表面的正负电荷吸附金属离子, 然后经培养后将小粒径QDs穿透到细胞外的方法来制备[20-21]
未修饰的QDs通常是疏水的, 不易溶于水, 不利于直接在生物环境中应用。为了增强QDs在检测中的特异性和生物相容性, 通常需要对其进行表面修饰和功能化[22]。确保QDs被成功应用的一个关键参数是适当的表面修饰, 即纳米材料的表面用适当的官能团进行修饰以确保其在水溶液中的稳定性, 同时能稳定无机内核, 减少解离现象的发生[23]。QDs的功能化是指用生物分子修饰QDs表面, 这些生物分子修饰的QDs可以应用于生物传感器和成像分析。功能修饰有助于QDs与生物靶点的非特异性结合, 显著提高QDs的水溶性、生物相容性以及与目标分子的特异性结合能力, 从而提高检测效果[24]。生物功能化表面修饰的方法主要包括静电吸附、共价偶联和金属-配体相互作用, 功能分子包括抗体、蛋白酶、多肽、核酸等[11]
与传统的荧光材料(如半导体QDs和荧光染料)相比, QDs具有更高的光稳定性和更窄的发射光谱, 并且亮度高, 水溶性好, 化学稳定性高, 抗光漂白能力强, 毒性低和生物相容性好等优点, 在化学、生物传感中, 特别是食品安全检测领域具有极大的应用潜力。此外, QDs易与适配体/抗体结合形成功能QDs, 而不影响其发射特性或适配体/抗体的特异性, 因此在实现高灵敏度定量检测方面具有明显优势[25]。基于QDs的食品安全快速检测方法包括: QDs免疫标记、免疫磁珠分离-QDs多重荧光免疫分析、适配体-磁珠和QDs夹心分析、基于荧光QDs的“三明治”模式抗体阵列、QDs免疫层析试纸条、QDs生物传感、QDs标记流式细胞术等[26]
生物传感器是一种对生物质敏感并能迅速将目标物浓度转化为可测量信号以供检测的装置。它是由作为识别元件的固定化生物敏感材料(酶、抗体、抗原、核酸等)、合适的传感器、高效的信号放大装置等组成的协同集成分析系统, 其广泛应用于临床诊断、食品分析、环境监测等领域[27]。随着纳米技术的蓬勃发展和完善, 生物传感器的装配策略也趋于多样化和多功能化。电化学发光(electrochemiluminescence, ECL)是通过电化学方法在电极表面产生新的物质, 然后发生高能级的电子转移反应, 产生激发态发光[28]。基于电化学发光的生物传感器以其成本低、分析速度快、线性范围宽、灵敏度高、抗干扰能力强等优点在食品污染物中受到广泛关注[29]。QDs优越的光学性能和表面功能化特性使其成为生物传感器的理想材料。将适配体和QDs偶联作为信号探针, 使得基于QDs构建的ECL传感器具有电化学信号放大和荧光信号稳定等优点的同时, 具有发光度高、响应强且稳定、背景信号几乎为零、动态范围宽等特性, 从而显著提高检测准确性和灵敏度[30]
WANG等[31]构建了一种用于AFB1追踪的新型ECL传感器。利用封闭空腔结构, 将多个MP QDs结晶并嵌入ZIF-8中形成MP QDs@ZIF-8, 在水环境中实现了稳定且强大的ECL响应。所构建的ECL传感器检出限为3.5 fg/mL, 且11.55 fg/mL~20 ng/mL线性范围内可对玉米样品中的AFB1进行定量, 得到了令人满意的回收率。该ECL传感器实现了卓越的AFB1检测性能, 具有超高灵敏度、良好的选择性和稳健的重现性。该研究为设计高性能ECL食品安全传感平台提供了新的途径。LU等[32]设计了一种基于石墨烯QDs (graphene quantum dot, GQDs)作为发光材料的ECL传感器, 用于超灵敏测定AFB1。所提出的ECL感应传感器在0.01~100 ng/mL内具有线性响应, 检出限低至3.75 pg/mL。同时, 该传感器具有良好的稳定性、选择性和重现性, 在实际样品分析中也具有良好的准确性和可靠性。这些优点为其在食品安全检测提供了广阔的发展前景。JIA等[33]构建了一种基于CdSe@CdS QDs的无标记ECL适配体传感器, 用于OTA的特异性和敏感性检测。通过对百合和大黄样品中的OTA进行快速简便的分析, 验证了该方法的实用性和可行性, 回收率分别为98.1%~105.6%和99.3%~101.5%。新开发的基于QDs的ECL传感器为食品和饲料安全评价、环境监测和临床诊断中更多真菌毒素提供了一种新的通用分析工具。
近年来, 电化学发光免疫分析法(electrochemiluminescence immunoassay, ECLIA)将ECL的敏感性与免疫技术的特异性相结合, 使得ECL不需要外部光源进行激发, 有效避免了散射光的干扰, 降低了背景噪声[27]。FENG等[34]首次合成了用二氧化锡QDs修饰的金-银合金来锚定ZEN抗体, 开发了一种基于钯修饰的氧化石墨烯(Pd-GO)的超灵敏ECLIA传感器, 用于检测ZEN。其中, Pd-GO和金-银合金都具有较大的比表面积, 能够负载大量的抗原和抗体。结果表明, 该电化学发光免疫传感器在ZEN的高灵敏度检测中具有较宽的线性范围(0.0005~500.0000 ng/mL)和较低的检出限(0.16 pg/mL)。通过对实际样品中真菌毒素的检测, 表明证实了该传感器的可行性和实用性。该研究为ZEN等小分子毒素的检测提供了一种新颖、灵敏的方法, 还阐明了开发高性能ECLIA传感器用于食品安全检测的可能性。
近年来, 各种免疫分析方法被用来检测食品中的真菌毒素, 如传统的ELISA因其简便、实用和灵敏度高而成为最广泛的商业化真菌毒素快速检测方法之一。但它仍需要数小时的抗体孵育和洗涤步骤, 而且酶标记信号的使用使其缺乏稳定性。此外, ELISA一次检测只能分析一种被分析物, 无法满足在一个样品中进行多重真菌毒素检测的迫切需要[35]。因此, 亟需探索操作步骤简化、筛查方法效率高效、快速精准的免疫分析检测方法。此外, QDs纳米吸附珠(quantum dot nanobeads, QBs)是嵌入大量QDs的聚合物纳米吸附珠, 其亮度是同类QDs的数千倍[36]。与传统的荧光染料相比, QBs具有发光强、光稳定性高、光致发光光谱窄等优异的光学特性, 大大提高了光信号的稳定性和强度, 其与单克隆抗体等结合形成的荧光探针, 能增强结构稳定性和荧光强度, 从而提高抗基质干扰能力[37]
范雅靓等[38]报道了一种简便快速的检测谷物中AFB1的荧光定量免疫层析检测方法。该方法采用QDs荧光微球作为荧光标记物, 与AFB1的单克隆抗体偶联, 构建QDs荧光微球探针, 从而制备QDs荧光免疫层析检测卡。该检测卡对小麦样本的检出限为0.02 μg/kg, 定量限为0.05 μg/kg。与高效液相色谱-串联质谱法检测结果相比其具有良好的一致性。研究结果证明该方法具有较好的重复性、特异性、稳定性, 能够在低浓度范围内迅速、准确地检测微量的AFB1。YUAN等[39]利用生物素-链霉亲和素间的高亲和力和QDs的荧光稳定性, 设计一种用于检测花生中AFB1的信号放大荧光免疫层析试纸条, 可以有效保护抗体活性, 减少探针数量并实现信号放大, 该方法为实际样品中真菌毒素的快速检测提供了新思路。
由于真菌毒素的存在具有多样性和多重性, 食品往往受到多种真菌毒素的同时污染。真菌毒素的共同污染可能导致累积作用和协同作用, 对人类的健康构成更大的威胁[40]。因此, 建立多种真菌毒素同时检测的方法具有较好的应用价值和现实意义。近年来, 不少学者开始尝试在样品基质中同时检测多种真菌毒素的研究。LI等[35]设计了一种采用双QDs纳米珠-荧光酶联免疫吸附试验(fluorescence-linked immunosorbent assay, FLISA)的方法, 用于同时检测饲料中的AFB1和ZEN。在这项研究中, 发红色和绿色荧光的CdSe/ZnS QDs微球分别与AFB1和ZEN单克隆抗体偶联, 使用QBs-mAbs为结合和检测探针, 用于开发一个FLISA平台。与传统ELISA相比, 双QBs-FLISA法对AFB1和ZEN的检测灵敏度分别提高了20倍和5倍, 且该方法和液相色谱-串联质谱法分析饲料样品的结果显示出良好的一致性(r2=0.99)。这是FLISA中首次应用双QBs同时检测两种目标真菌毒素, 这也为复杂样品基质中多重分析物的测定提供了一个通用平台。LU等[41]设计了一种利用荧光强度高、信噪比高的QDs微球免疫层析试纸条, 在0.01、0.2和0.032 ng/mL的较低检出限下, 对AFB1、OTA和ZEN进行了灵敏的检测, 并在0.01~1.00 ng/mL、0.2~200.0 ng/mL和0.032 ng/mL范围内定量测定其质量浓度, 准确度高, 选择性好。更重要的是, 这些真菌毒素的检测只需简单的人工操作和便携式手持式试纸仪即可在45 min内完成现场检测。因此, 该方法是一种有望支持多种真菌毒素现场灵敏定量检测的解决方案。荧光免疫系统实现了高通量、高效的检测, 提高了实验的自动化程度, 在食品安全、环境监测等领域得到了广泛应用。
表面增强拉曼光谱(surface enhanced Raman spectroscopy, SERS)效应是指分子被吸附在粗糙金属表面时的拉曼信号增强。当分析物分子在或接近表面的粗糙贵金属(如金、银)纳米结构, 诱导偶极子的数量增加, 导致表面增强拉曼效应的形成, 导致原本微弱的拉曼信号探测增强[42]。SERS作为一种强大的振动光谱技术, 具有单分子水平的灵敏度和高分析速度[43]。SERS作为一种检测痕量样品的快速、灵敏和非破坏性分析技术, 广泛用于分子鉴定和结构表征方面, 近年来在真菌毒素检测中也得到了广泛的应用[44]。基于SERS的真菌毒素传感系统通过结合适配体修饰的磁珠和互补DNA (cDNA)功能化的SERS探针来设计[45]
MA等[46] 将信号探针和捕获探针相结合, 开发了一种稳定、有效、选择性高的SERS和荧光双信号适配体传感器, 用于AFB1检测。QDs被包埋在SiO2纳米颗粒中, 这种方法可以有效防止QDs在与外界环境接触过程中氧化, 以保证QDs荧光信号的稳定性。然后将经DTNB和cDNA修饰的金纳米粒子(gold nanoparticles, AuNPs)与QD@SiO2连接, 提供稳定的荧光和SERS信号。该传感器的检出限低至0.087 pg/mL, 适用于花生和花生油样品的实际检测。试验结果与HPLC法相比, 回收率为92.75%~104.73%。所建立的双信号适配体传感器稳定、易于操作, 可为真菌毒素检测提供新的研究思路。同样, WEI等[47]也建立了一种SERS和荧光双信号适配体传感器, 用于AFB1的检测。将荧光信号源CdTe QDs修饰在SiO2纳米颗粒的外层, 并用AFB1适配体进一步功能化。用大米、花生和玉米等实际样品对AFB1检测得到的回收率准确度在92.75%~105.24%之间, 检出限0.094 pg/mL, 线性范围为10-4~103 ng/mL, 有效证实了所建立的SERS适配体传感器可以应用于真实样品中检测AFB1。该方法既提高了灵敏度, 又保证了检测的稳定性和可靠性, 有望在食品生产中实现快速检测。
表2总结了QDs在食品真菌毒素检测的最新进展。如今, 随着智能手机的普及, 基于智能手机的传感平台成为最具前景的便携式现场监测装置, 并在食品污染物检测中得到应用和验证[50]。目前集成在智能手机中的高质量摄像头具有同时收集和处理多个数据的强大能力[51]。因此, 许多基于智能手机的传感、成像和诊断平台应运而生[52]。SALARI等[48]搭建了一种智能手机辅助的OTA的荧光检测平台, 该方法使用嵌入在介孔SiO2包封的锰掺杂卤化铅钙钛矿QDs (Mn-CsPbBr3 QDs@SiO2), 并将其用作OTA的比例荧光探针。该传感器具有出色的选择性和低检出限(4.1 ng/mL), 而且OTA线性范围很宽, 从5.0到250.0 ng/mL不等。当OTA浓度不同时, 在紫外灯下会出现从粉红色到蓝色的多色过渡, 因此可以通过使用颜色分析应用程序来实现简单的视觉和智能手机辅助OTA检测。在红茶、咖啡、发霉无花果和面粉样品中的回收率令人满意, 证实了该检测方法的可靠性。SONG等[49]成功研发了一种智能手机辅助比率FRET光电传感器, 用于谷物中ZEN的即时检测。该技术以合体修饰的碲镉(CdTe) QDs为供体, AuNPs为受体, CdTe QDs的荧光被AuNPs基于FRET猝灭, SiQDs的荧光作为参考。在ZEN存在的情况下, 适配体修饰的CdTe QDs被吸附在ZEN上, 能量受体与供体之间的距离增加, 阻止了FRET, 从而使CdTe QDs的荧光恢复。在便携式检测设备和智能手机的辅助下, 该传感器实现了谷物中ZEN的视觉即时检测。根据R/B值与ZEN浓度的线性关系, ZEN的检出限为13.87 pg/mL, 实现了ZEN的现场定性定量检测。该方法的建立在食品安全领域具有普遍适用的潜力。
QDs由于其发射波长可调、吸收宽、荧光发射强度强、量子产率高、可忽略光漂白等独特性质, 在真菌毒素的检测中展现出巨大的应用潜力。本文综述了QDs的性能特点、合成方法、修饰及功能化及其在食品真菌毒素中的应用等方面的最新进展。从ECL传感器、荧光免疫技术、SERS传感器到智能手机辅助的检测平台, QDs都能提供高灵敏度与低检出限、快速响应和高选择性的检测结果, 在食品安全检测方面显示出巨大的应用价值和广阔的应用前景。
尽管QDs在真菌毒素检测中展现了诸多优点, 但在实际应用中仍面临一些挑战: (1)由于QDs的表面通常需要修饰以增强其生物相容性, 过多的表面修饰可能会影响QDs的光学性质和生物分子结合能力。未来的研究重点可以放在QDs表面改性上, 通过引入生物相容性强、环境友好的表面修饰剂, 解决QDs在样品中的应用问题。(2) QDs在复杂生物样本中的稳定性和干扰问题仍需进一步研究。如在复杂的食物基质中, 消除基质干扰和提高靶标选择性是迫切需要解决的问题。食品样品固有的高复杂性, 其中含有多种基质成分, 可能会干扰分析结果, 直接影响分析结果的准确性。应进一步挖掘特异性强、连接方式紧密的QDs, 选择出能够与QDs高特异性结合的物质分子, 同时保持QDs的性能, 实现超灵敏快速检测。(3)此外, QDs的合成和功能化过程较为复杂, 限制了其大规模应用的推广。
综上, 随着荧光纳米和分析技术的快速发展, QDs有望在食品真菌毒素检测中达到更灵敏、精确、高效的水平, 如结合QDs与其他纳米材料(如碳纳米管、石墨烯等), 开发多功能、高灵敏度的复合传感平台, 以实现多种真菌毒素的同步检测。此外, 未来可以结合QDs传感技术与便捷的便携式检测设备, 着眼于食品链系统的各个环节, 进行实时的在线监测, 以实现食品安全检测的智能化和自动化, 从而为食品安全领域创造更好的、更广泛的实际应用价值。
  • 国家市场监督管理总局科技项目(2023MK119)
  • 陇原青年创新创业人才项目(2024QNTD15)
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2025年第16卷第8期
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doi: 10.19812/j.cnki.jfsq11-5956/ts.20241013002
  • 接收时间:2024-10-13
  • 首发时间:2025-07-19
  • 出版时间:2025-04-25
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  • 收稿日期:2024-10-13
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国家市场监督管理总局科技项目(2023MK119)
陇原青年创新创业人才项目(2024QNTD15)
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    甘肃省产品质量监督检验研究院, 兰州 730050

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* 马婷婷(1997—), 女, 助理工程师, 主要研究方向为食品营养与功能评价。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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