Article(id=1153433698746749470, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433686872679135, articleNumber=null, orderNo=null, doi=10.19812/j.cnki.jfsq11-5956/ts.20250103006, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1735833600000, receivedDateStr=2025-01-03, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1752929623542, onlineDateStr=2025-07-19, pubDate=1744646400000, pubDateStr=2025-04-15, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752929623542, onlineIssueDateStr=2025-07-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752929623542, creator=13701087609, updateTime=1752929623542, updator=13701087609, issue=Issue{id=1153433686872679135, tenantId=1146029695717560320, journalId=1149652044408987649, year='2025', volume='16', issue='7', pageStart='1', pageEnd='322', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752929620712, creator=13701087609, updateTime=1757656380159, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1173259152974561742, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433686872679135, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1173259152978756047, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433686872679135, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=109, endPage=115, ext={EN=ArticleExt(id=1153433699430421042, articleId=1153433698746749470, tenantId=1146029695717560320, journalId=1149652044408987649, language=EN, title=Determination of nitrite content in food by chronoamperometry, columnId=1151895322692776479, journalTitle=Journal of Food Safety & Quality, columnName=Special Topic: Analysis and Monitoring of Toxic and Harmful Substances in Food, runingTitle=null, highlight=null, articleAbstract=

Objective To establish a chronoamperometry detection method for accurately determining the nitrite content in food. Methods Cobalt nanoparticles, graphene oxide, and polypyrrole were electrodeposited on the electrode surface to construct an electrochemical sensor for nitrite detecting. The detection conditions were optimized, and the linear range of chronocurrent method for nitrite detection was determined. After the specificity of the detection method was verified, the samples were tested using the optimized detection conditions. Results An electrochemical sensor for nitrite detection was prepared. The optimal potential for this method was 0.85 V, the optimal pH was 8.0, and the optimal deposition time was 300 s. The interfering substances dopamine, ascorbic acid and uric acid had little impact on the detection of nitrite, and the detection of samples found that the established method had high accuracy. Conclusion An electrochemical sensor for detecting nitrite is prepared, which has good stability and high accuracy, and is suitable for the determination of nitrite content food.

, correspAuthors=Dan-Dan LIU, Qian-Qian XIE, 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=Jun-Nan SONG, Chen-Guang WANG, Dan-Dan LIU, Qian-Qian XIE), CN=ArticleExt(id=1153433730673791679, articleId=1153433698746749470, tenantId=1146029695717560320, journalId=1149652044408987649, language=CN, title=计时电流法检测食品中亚硝酸盐的含量, columnId=1151895322898297380, journalTitle=食品安全质量检测学报, columnName=本期专题:食品中有毒有害物质分析与监测, runingTitle=null, highlight=null, articleAbstract=

目的 建立计时电流法精确测定食品中亚硝酸盐含量。方法 将钴纳米粒子、氧化石墨烯以及聚吡咯聚沉于电极表面, 构建检验亚硝酸根的电化学传感器, 对检测条件进行优化, 确定了计时电流法检测亚硝酸盐的线性范围, 对检测方法的特异性进行验证后利用优化后的检测条件对样品进行检测。结果 制备出一种检测亚硝酸盐的电化学传感器, 其最优电位确定为0.85 V, 最优pH为8.0, 最优沉积时间为300 s, 干扰物质多巴胺、抗坏血酸、尿酸对于亚硝酸盐的检测结果影响较小, 且对样品进行检测发现, 所建立的方法准确度较高。结论 制备出检验亚硝酸根的电化学传感器, 该系统稳定性好、精确度高, 适用于食品中亚硝酸盐含量的测定。

, correspAuthors=刘丹丹, 解倩倩, authorNote=null, correspAuthorsNote=
* 刘丹丹(1990—), 女, 助理工程师, 主要研究方向为食品检验检测。E-mail:
解倩倩(1989—), 女, 博士, 助理研究员, 主要研究方向为食品检验检测。E-mail:
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宋俊男(1991—), 男, 硕士, 工程师, 主要研究方向为食品检验检测。E-mail:

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Micronanoelectronic Technology, 2025, 62(2): 1-11., articleTitle=Research progress of graphene materials in the field of human perception monitoring, refAbstract=null), Reference(id=1173311095918969009, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, doi=null, pmid=null, pmcid=null, year=2024, volume=40, issue=11, pageStart=200, pageEnd=210, url=null, language=null, rfNumber=[36], rfOrder=66, authorNames=王晨宇, 李肖然, 全珂, journalName=食品与机械, refType=null, unstructuredReference=王晨宇, 李肖然, 全珂, 等. 纳米材料修饰电化学传感器检测四环素的研究进展[J]. 食品与机械, 2024, 40(11): 200-210., articleTitle=纳米材料修饰电化学传感器检测四环素的研究进展, refAbstract=null), Reference(id=1173311095973494962, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, doi=null, pmid=null, pmcid=null, year=2024, volume=40, issue=11, pageStart=200, pageEnd=210, url=null, language=null, rfNumber=[36], rfOrder=67, authorNames=WANG CY, LI XR, QUAN K, journalName=Food and machinery, refType=null, unstructuredReference=WANG CY, LI XR, QUAN K, et al. Study on the detection of tetracycline by electrochemical sensors modified with nanomaterials[J]. Food and machinery, 2024, 40(11): 200-210., articleTitle=Study on the detection of tetracycline by electrochemical sensors modified with nanomaterials, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1173311087421308984, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, xref=null, ext=[AuthorCompanyExt(id=1173311087429697593, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, companyId=1173311087421308984, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. 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注: A. 修饰氧化石墨烯与聚吡咯后的电极检测样品与空白组对比c-v曲线; B. 只修饰纳米Co粒子电极检测样品与空白组对比c-v曲线; C. 修饰氧化石墨烯、聚吡咯与纳米Co粒子的电极检测样品与空白组对比c-v曲线。a. PBS pH=8.0与0.1 mmol/L NaNO2环境下所做的c-v曲线; b. PBS pH=8.0环境下所做的c-v曲线。

, figureFileSmall=t1JKEOgIbWj4m0GNVjRwhQ==, figureFileBig=OCDE5beQlNnq6dKfP4Cg/A==, tableContent=null), ArticleFig(id=1173311089405214819, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=EN, label=Fig.4, caption=Response signal of electrode to nitrite under different potential conditions, figureFileSmall=ixBOyXjjurUEvzacvASqdg==, figureFileBig=jmrnMh+uqWQWehkaUL5/Eg==, tableContent=null), ArticleFig(id=1173311089459740772, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=CN, label=图4, caption=不同电位条件下电极对亚硝酸盐的响应信号

注: a. 电位为0.40 V条件下的i-t曲线; b. 电位为0.60 V条件下的i-t曲线; c. 电位为0.80 V条件下的i-t曲线; d. 电位为0.85 V条件下的i-t曲线; e. 电位为0.90 V条件下的i-t曲线。

, figureFileSmall=ixBOyXjjurUEvzacvASqdg==, figureFileBig=jmrnMh+uqWQWehkaUL5/Eg==, tableContent=null), ArticleFig(id=1173311089535238245, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=EN, label=Fig.5, caption=Response signals of electrode to nitrite under different pH conditions, figureFileSmall=nz0liaIMIe1ZZDc+8wWAZA==, figureFileBig=Eox3tKDzbsexLPo5qiWlyw==, tableContent=null), ArticleFig(id=1173311089593958502, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=CN, label=图5, caption=不同pH条件下电极对亚硝酸盐的响应信号

注: a. pH=5.0环境下测得的i-t曲线; b. pH=6.0环境下测得的i-t曲线; c. pH=7.0环境下测得的i-t曲线; d. pH=8.0环境下测得的i-t曲线。由于pH=9.0环境下, 曲线噪音过大, 对信号影响太大, 故不作考虑。

, figureFileSmall=nz0liaIMIe1ZZDc+8wWAZA==, figureFileBig=Eox3tKDzbsexLPo5qiWlyw==, tableContent=null), ArticleFig(id=1173311089665261671, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=EN, label=Fig.6, caption=Response signal of electrode to nitrite under different deposition time of metal nanoparticles, figureFileSmall=MCofocEUoekp6Y8zVuxGrg==, figureFileBig=myuJjZSpr9wC58DnrJoPeA==, tableContent=null), ArticleFig(id=1173311089719787624, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=CN, label=图6, caption=不同金属纳米粒子沉积时间条件下电极对亚硝酸盐的响应信号

注: a. 沉积时间200 s时测得的i-t图像; b. 沉积时间300 s时测得的i-t图像; c. 沉积时间400 s时测得的i-t图像。

, figureFileSmall=MCofocEUoekp6Y8zVuxGrg==, figureFileBig=myuJjZSpr9wC58DnrJoPeA==, tableContent=null), ArticleFig(id=1173311089782702185, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=EN, label=Fig.7, caption=Measurement results of linear range, figureFileSmall=lHzF+f7WfSAKEaQe+4g0Eg==, figureFileBig=JKOkTUkQ03qMDXGVGfUCnQ==, tableContent=null), ArticleFig(id=1173311089849811050, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=CN, label=图7, caption=线性范围测定结果

注: A. 加入等浓度NaNO2所得到的i-t曲线, 将每一次加入NaNO2所得到的信号进行累加, 对应溶液中浓度的累加, 能够得到一系列对应的点, 将数据整理后, 取出其中成线性关系的点, 作出线性关系; B. 样品浓度与电流信号对应曲线。

, figureFileSmall=lHzF+f7WfSAKEaQe+4g0Eg==, figureFileBig=JKOkTUkQ03qMDXGVGfUCnQ==, tableContent=null), ArticleFig(id=1173311089904337003, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=EN, label=Fig.8, caption=i-t curve of anti-interference experiment, figureFileSmall=JYCrZRq4E4hd+zo5rlJqRA==, figureFileBig=/PyE/P2XdrppODGM7bj3oQ==, tableContent=null), ArticleFig(id=1173311089963057260, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=CN, label=图8, caption=抗干扰实验的i-t曲线, figureFileSmall=JYCrZRq4E4hd+zo5rlJqRA==, figureFileBig=/PyE/P2XdrppODGM7bj3oQ==, tableContent=null), ArticleFig(id=1173311090017583213, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=EN, label=Table 1, caption=

Test results of sample (mg/kg)

, figureFileSmall=null, figureFileBig=null, tableContent=
样本 离子色谱法 计时电流法
泡菜 11.87±0.04 11.36±0.12
牛奶 0 0
鸡蛋 1.06±0.03 0.98±0.04
), ArticleFig(id=1173311090176966766, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1153433698746749470, language=CN, label=表1, caption=

样品检测结果(mg/kg)

, figureFileSmall=null, figureFileBig=null, tableContent=
样本 离子色谱法 计时电流法
泡菜 11.87±0.04 11.36±0.12
牛奶 0 0
鸡蛋 1.06±0.03 0.98±0.04
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计时电流法检测食品中亚硝酸盐的含量
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宋俊男 1 , 王晨光 2 , 刘丹丹 1, * , 解倩倩 1, *
食品安全质量检测学报 | 本期专题:食品中有毒有害物质分析与监测 2025,16(7): 109-115
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食品安全质量检测学报 | 本期专题:食品中有毒有害物质分析与监测 2025, 16(7): 109-115
计时电流法检测食品中亚硝酸盐的含量
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宋俊男1 , 王晨光2, 刘丹丹1, * , 解倩倩1, *
作者信息
  • 1.斯坦德科创医药科技(青岛)有限公司, 青岛 266000
  • 2.天津海关工业产品安全技术中心, 天津 300041
  • 宋俊男(1991—), 男, 硕士, 工程师, 主要研究方向为食品检验检测。E-mail:

通讯作者:

* 刘丹丹(1990—), 女, 助理工程师, 主要研究方向为食品检验检测。E-mail:
解倩倩(1989—), 女, 博士, 助理研究员, 主要研究方向为食品检验检测。E-mail:
Determination of nitrite content in food by chronoamperometry
Jun-Nan SONG1 , Chen-Guang WANG2, Dan-Dan LIU1, * , Qian-Qian XIE1, *
Affiliations
  • 1. Standard Sci-tech Innovation (Qingdao) Pharmaceutical Technology Co., Ltd., Qingdao 266000, China
  • 2. Tianjin Customs Industrial Product Safety Technology Center, Tianjin 300041, China
出版时间: 2025-04-15 doi: 10.19812/j.cnki.jfsq11-5956/ts.20250103006
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目的 建立计时电流法精确测定食品中亚硝酸盐含量。方法 将钴纳米粒子、氧化石墨烯以及聚吡咯聚沉于电极表面, 构建检验亚硝酸根的电化学传感器, 对检测条件进行优化, 确定了计时电流法检测亚硝酸盐的线性范围, 对检测方法的特异性进行验证后利用优化后的检测条件对样品进行检测。结果 制备出一种检测亚硝酸盐的电化学传感器, 其最优电位确定为0.85 V, 最优pH为8.0, 最优沉积时间为300 s, 干扰物质多巴胺、抗坏血酸、尿酸对于亚硝酸盐的检测结果影响较小, 且对样品进行检测发现, 所建立的方法准确度较高。结论 制备出检验亚硝酸根的电化学传感器, 该系统稳定性好、精确度高, 适用于食品中亚硝酸盐含量的测定。

钴纳米粒子  /  氧化石墨烯  /  亚硝酸盐  /  电化学  /  计时电流法

Objective To establish a chronoamperometry detection method for accurately determining the nitrite content in food. Methods Cobalt nanoparticles, graphene oxide, and polypyrrole were electrodeposited on the electrode surface to construct an electrochemical sensor for nitrite detecting. The detection conditions were optimized, and the linear range of chronocurrent method for nitrite detection was determined. After the specificity of the detection method was verified, the samples were tested using the optimized detection conditions. Results An electrochemical sensor for nitrite detection was prepared. The optimal potential for this method was 0.85 V, the optimal pH was 8.0, and the optimal deposition time was 300 s. The interfering substances dopamine, ascorbic acid and uric acid had little impact on the detection of nitrite, and the detection of samples found that the established method had high accuracy. Conclusion An electrochemical sensor for detecting nitrite is prepared, which has good stability and high accuracy, and is suitable for the determination of nitrite content food.

cobalt nanoparticles  /  grapheme oxide  /  nitrite  /  electrochemistry  /  chronoamperometry
宋俊男, 王晨光, 刘丹丹, 解倩倩. 计时电流法检测食品中亚硝酸盐的含量. 食品安全质量检测学报, 2025 , 16 (7) : 109 -115 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250103006
Jun-Nan SONG, Chen-Guang WANG, Dan-Dan LIU, Qian-Qian XIE. Determination of nitrite content in food by chronoamperometry[J]. Journal of Food Safety & Quality, 2025 , 16 (7) : 109 -115 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250103006
亚硝酸盐主要是指NaNO2, 即亚硝酸根与金属钠离子所形成的化合物; 在日常接触的粮食、蔬菜、肉类和鱼类, 特别是腌制食品中广泛分布, 其中, 在天然食物中少量存在, 但若因运输或储存不当, 微生物的作用会加速硝酸盐向亚硝酸盐的转化, 从而提高了亚硝酸盐的含量; 在加工食品中, 亚硝酸盐场被作为一种常用的食品添加剂使用, 能够延长食品保质期, 特别是在一些低温/长期储存的加工食品中, 亚硝酸盐的使用更为普遍[1-4], 其可有效抑制肉毒芽孢杆菌的繁殖, 进而可以防止肉类在空气中逐步被氧化成为灰褐色的变性蛋白[5-6]。亚硝酸盐对人体有致癌的作用[7-8], 世界卫生科学委员会规定, 当人体摄入的亚硝酸盐含量为0~0.1 mg时, 对人体不会构成伤害。如果过量的亚硝酸盐进入人体, 血液中的低铁血红蛋白将被氧化成为高铁血红蛋白, 携氧能力丧失, 导致器官组织缺氧, 从而使人体中毒[4,7-8]
亚硝酸盐常用的检测方法主要有分光光度法[9]、化学发光法[10-12]、色谱法[10,12-17]等, 然而这类方法在检测过程中存在一定的弊端, 如分光光度法, 检测结果容易受到被测物中其他物质的干扰, 产生较大误差[18-19]。化学修饰电极是利用纳米材料修饰化学电极, 在电极表面修饰上所需的纳米材料, 从而使电极具有所需的检测特性功能, 建立化学传感器[20-22]。通过电流的变化, 对应反应物的浓度变化, 从而得到检测结果, 因其检测灵敏度高, 成为研究的热点[23-28]。近年来随着纳米材料的快速发展, 新纳米材料石墨烯由于具有更大的比表面积, 更有利于化学反应的进行[29-34]。因此本研究结合钴纳米颗粒与石墨烯的优点, 首先将玻碳电极进行氧化预处理, 然后聚沉氧化石墨烯与吡咯纳米层, 最后在此基础上, 用恒电位法聚沉纳米钴颗粒, 制备出检测亚硝酸盐的电化学传感器, 本研究旨在开发一种电化学传感器, 实现对亚硝酸盐含量的精确、快速测定, 以期为食品开发、生产及质量控制等领域提供技术支持, 促进食品行业的健康发展。
实验用泡菜、牛奶、鸡蛋均为市售。
NaH2PO4·2H2O(分析纯, 天津市登科化学试剂有限公司); Na2HPO4·12H2O、无水乙醇(分析纯)、盐酸多巴胺、氧化石墨烯、吡咯、磷酸盐缓冲溶液(phosphate buffered saline, PBS)(上海阿拉丁生化科技股份有限公司); NaNO2、KCl(分析纯)、CoCl2·6H2O(纯度99%)(天津博迪化工有限公司); 抗坏血酸(国药集团化学试剂); 尿酸(纯度99%, Acros Organics USA公司); K3[Fe(CN6)]、K4[Fe(CN6)](分析纯, 天津市广成化学试剂有限公司)。
AR224CN型电子天平(精密度0.0001 g, 上海奥豪斯仪器有限公司); CHI630C型电化学工作站(上海辰华仪器有限公司); KQ2200DE型数控超声波清洗器(昆山市超声仪器有限公司); PHSJ-3F型实验室PH计(上海仪电科学仪器股份有限公司); ICS6000型离子色谱仪(美国赛默飞世尔科技有限公司)。
首先玻碳电极在粒径为1.00、0.30、0.05 mm的Al2O3粉泥浆中进行打磨抛光, 打磨完成后, 将玻碳电极(尤其是表面)浸入二次水中, 放入超声波清洗器中清洗5 min, 将浸泡玻碳电极的二次水换成无水乙醇继续超声清洗, 5 min后再换回二次水, 超声清洗5 min。
以甘汞电极为参比电极, 铂丝电极为辅助电极, 玻碳电极为工作电极, 构成三电极系统。利用循环伏安法与恒电位法对工作电极表面进行氧化预处理, 预处理后会形成大量羟基等活性基团, 有利于下一步纳米材料的聚沉过程。具体操作为, 将3支电极浸入10 mL pH=7.2的PBS中, 在-0.2~1.4 V范围内做出5圈c-v曲线。将处理后的电极用二次水从侧面冲洗(注意不要直接冲洗电极表面), 用吸水纸将水拭干。然后将三电极系统浸入10 mL pH=5.7的PBS中, 处理300 s。利用循环伏安法, 在0.3~1.3 V范围内, 做15圈c-v曲线, 直至得到稳定重叠的曲线。电极经过氧化预处理后, 电极表面由光亮的镜面变成淡蓝色的表面。
准确称取0.01 g氧化石墨烯于称量瓶中, 加入5 mL二次水, 利用超声波清洗器使氧化石墨烯完全溶解, 溶液逐渐变为棕黄色, 然后准确移取35 µL吡咯, 利用超声波清洗器使吡咯完全溶解于溶液中。将氧化预处理后的电极与参比电极、辅助电极共同浸入配制好的氧化石墨烯与吡咯的混合液溶液中, 利用循环伏安法进行聚沉, 通过循环伏安图判定电极聚沉成功(图1)。
配制0.01 mol/L的CoCl2溶液, 移取10 mL, 将三电极系统浸入溶液, 通过条件优化, 找到最优还原电位-1.0 V, 利用恒电位法将Co离子还原为纳米Co粒子, 使Co粒子沉积到电极表面, 通过i-t曲线判定Co粒子聚沉成功(图2)。
分别对检测电位、溶液pH、沉积时间进行优化, 确定最佳检测条件, 在最佳检测条件下绘制电流与浓度的线性关系曲线, 得到线性方程; 对检测方法的特异性进行验证后利用优化后的检测条件对样品进行检测, 对所建立检测方法在实际应用中的可行性进行验证。
本研究中伏安特曲线由电化学工作站系统软件(CHI630C)生成, 用illustrator软件(23.0)对结果图进行注释。
利用循环伏安法, 依次对聚沉了氧化石墨烯+吡咯、Co纳米粒子、石墨烯+吡咯+Co纳米粒子电极的响应信号进行测定, 结果发现, 修饰了氧化石墨烯、吡咯和Co纳米粒子的电极对亚硝酸盐的响应最明显(图3)。
检测亚硝酸盐的过程中, 不同的电位选择将直接影响响应信号大小, 为了对最佳电位进行优化, 将三电极系统浸入10 mL pH=8.0的PBS溶液中, 利用恒电位法对亚硝酸盐进行检测, 每次加入亚硝酸盐溶液含量均为20 mL, 浓度为0.1 mol/L。通过改变每组样品的工作电位, 比较形成电流信号的大小, 结果发现, 当电位为0.85 V时, 电极对亚硝酸盐响应信号最明显(图4), 因此, 最优电位确定为0.85 V。
电极在检测过程中, 亚硝酸盐检测信号受PBS的pH影响, 基于此, 在确定最优电位的情况下, 通过比较不同pH环境下, 电极对亚硝酸盐的检测信号的大小, 从而确定最优pH的大小。分别准备pH=5.0、6.0、7.0、8.0、9.0的PBS, 在三电极系统中, 利用恒电位法对亚硝酸盐进行检测, 每次加入亚硝酸盐溶液含量均为20 mL, 浓度为0.1 mol/L。结果发现, 在PBS pH为8.0时, 电极对亚硝酸盐响应信号最明显(图5), 因此, 最优pH为8.0。
在聚沉Co纳米粒子过程中, 采用不同的沉积时间直接决定电极表面所含的纳米金属离子的数量与密度, 过多或者过少的纳米金属离子都会对电极对亚硝酸盐的响应信号产生影响。所以, 通过制作不同沉积时间的电极传感器, 对比测定相同条件下的亚硝酸盐样品所产生的信号大小, 能够找到最优沉积时间。分别制备沉积时间为200、300、400 s的玻碳电极, 利用恒电位法, 在pH=8.0的PBS中, 设定检测点位为0.85 V, 对NaNO2进行检测, 每次加入的NaNO2含量均为20 mL, 浓度为0.1 mol/L。通过对比可以确定, 当沉积时间为300 s时, 电极对亚硝酸盐的响应信号最大(图6), 因此沉积300 s为最优沉积时间。
确定最优条件后, 在最优条件下, 通过加入等浓度、等量的NaNO2, 得到一系列响应信号, 利用信号的累积与浓度累积的对照, 得到对应的电流与浓度的线性关系, 结果如图7所示, 求得线性方程为i=2.67273+31.68886c, r2=0.99893。
由于检测的样品中可能含有的一些化合物会对传感器产生响应信号, 对潜在干扰物质多巴胺、抗坏血酸、尿酸产生的响应信号与亚硝酸盐的响应信号进行对比, 其中, 加入的NaNO2与干扰物的浓度比例为20:1, 结果发现, 干扰物质产生的相应信号可忽略不计(图8), 证明该系统在干扰物质共存的情况下具有较高的特异性和稳定性, 可用于对实际样品的检测。
为了验证计时电流法法在实际应用的可行性, 对不同样品中硝酸盐含量进行测定。首先参考GB 5009.33—2016《食品安全国家标准 食品中亚硝酸盐与硝酸盐的测定》对不同样品进行处理, 分别使用离子色谱法及本研究建立的计时电流法对亚硝酸盐含量进行测定, 表1中的结果表明, 所建立的方法准确度较高, 具有实际应用的潜力。
食品中亚硝酸盐的快速准确检测对保障食品安全具有重要意义。计时电流法因其响应速度快、成本低且灵敏度高, 在检测过程中具有广泛的发展前景。纳米材料修饰电极具有独特的微结构与化学性质, 在电化学传感领域应用广泛[24]。本研究建立了计时电流法检测食品中亚硝酸盐的含量的检测方法, 结合钴纳米颗粒与石墨烯的优点, 选择电化学沉积法来进行纳米材料的修饰, 制备出检验亚硝酸根电化学传感器, 该系统具有稳定性好、精确度高等优点。建立的亚硝酸盐含量的测定方法, 该方法最优电位确定为0.85 V, 最优pH为8.0, 最优沉积时间为300 s; 对电极每一步的实验都进行了电极阻抗的测定实验, 证实对于电极的每一步处理都使阻抗减小, 更有利于实验测定。电极材料氧化或腐蚀一直是影响电化学传感器可靠性及准确性的因素, 本研究中在电极材料的选择上, 采用了石墨烯作为电极材料, 其具有独特的单层电子结构和六边形微结构, 比表面积大、吸附能力强, 相比传统材料具有不可比拟的优势[35-36], 然后计时电流法的长期稳定性仍是研究的重点, 在实际应用特别是大规模应用过程仍需定期校准, 确保其检测精确度和稳定性。
多巴胺、抗坏血酸、尿酸为果蔬、蛋奶、肉质品等食物中常见成分, 本研究为排除不同干扰物质对亚硝酸盐测定的干扰, 对上述干扰物质所产生的响应信号与亚硝酸盐的响应信号进行了对比, 结果发现多巴胺、抗坏血酸、尿酸对于亚硝酸盐的检测都没有造成明显的干扰, 说明该系统在干扰物质共存的情况下具有较高的特异性和稳定性。基于此, 本研究进一步选取不同种类食品样品—泡菜、牛奶及鸡蛋, 首先参考GB 5009.33采用离子色谱法对其中亚硝酸盐含量进行测定, 之后利用本研究建立的计时电流法同样对亚硝酸盐含量进行测定, 结果发现, 两种检测方法测得的亚硝酸盐含量基本一致, 所建立的检测方法在不同种类食品中具有潜在的实际应用价值。
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2025年第16卷第7期
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doi: 10.19812/j.cnki.jfsq11-5956/ts.20250103006
  • 接收时间:2025-01-03
  • 首发时间:2025-07-19
  • 出版时间:2025-04-15
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  • 收稿日期:2025-01-03
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    1.斯坦德科创医药科技(青岛)有限公司, 青岛 266000
    2.天津海关工业产品安全技术中心, 天津 300041

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* 刘丹丹(1990—), 女, 助理工程师, 主要研究方向为食品检验检测。E-mail:
解倩倩(1989—), 女, 博士, 助理研究员, 主要研究方向为食品检验检测。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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