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Article(id=1217529311062573713, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217529305693864468, articleNumber=null, orderNo=null, doi=10.19812/j.cnki.jfsq11-5956/ts.20250223001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1740240000000, receivedDateStr=2025-02-23, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1768211208358, onlineDateStr=2026-01-12, pubDate=1752508800000, pubDateStr=2025-07-15, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1768211208358, onlineIssueDateStr=2026-01-12, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1768211208358, creator=13701087609, updateTime=1768211208358, updator=13701087609, issue=Issue{id=1217529305693864468, tenantId=1146029695717560320, journalId=1149652044408987649, year='2025', volume='16', issue='13', pageStart='1', pageEnd='320', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1768211207077, creator=13701087609, updateTime=1768212057891, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1217532874337730593, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217529305693864468, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1217532874337730594, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217529305693864468, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=267, endPage=275, ext={EN=ArticleExt(id=1217529311435866794, articleId=1217529311062573713, tenantId=1146029695717560320, journalId=1149652044408987649, language=EN, title=Rapid determination of total flavonoids in Tartary buckwheat by cerium dioxide/multi-walled carbon nanotubes/acetylene black nano-electrochemical sensor method, columnId=1151923894560060071, journalTitle=Journal of Food Safety & Quality, columnName=Food Nutrition and Functional Foods, runingTitle=null, highlight=null, articleAbstract=

Objective To establish a method for the rapid determination of total flavonoids in tartary buckwheat by cerium dioxide/multi-walled carbon nanotubes/acetylene black (CeO2/MWCNTs/AB) nano-electrochemical sensor. Methods The modified material and these nanoelectrochemical sensors were characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The electrochemical behavior of rutin on the electrode surface was systematically investigated via CV. Critical parameters were optimized, including electrolyte type, pH, modifier ratio, coating volume, accumulation time and scan rate. Results One pair of well- defined redox peaks were observed at the potential of 0.54 V and 0.57 V, which indicated that the electrochemical oxidation and reduction reaction of flavonoid was reversible. The experimental conditions were optimized, the results as follows: B-R solution with pH 2.0 as the electrolyte solution, VCeO2/MWCNTs:Vacetylene black as 1:3, amounts of modified material, 12 μL, enrichment time as 9 min. At these conditions, the oxidation peak current of flavonoid linearly increased with its concentration, Ip=0.793C+3.508 (r2=0.998), and the limit of detection was 6.5×10-8 mol/L. The developed method was used to determinate total flavonoids content of tartary buckwheat, the recoveries were in the range of 99.46%-102.15%, the results were superior to ultraviolet-visible spectrophotometry. Conclusion The method is feasible for the rapid and accurate determination of total flavonoids in food with the advantages such as simple pretreatment time saving and convenience, low detection cost, high sensitivity and good accuracy.

, correspAuthors=Shu-Guo LI, 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=Zhao-Hui YUAN, Meng-Meng GUO, Jia WANG, Shu-Guo LI), CN=ArticleExt(id=1217529314925527893, articleId=1217529311062573713, tenantId=1146029695717560320, journalId=1149652044408987649, language=CN, title=二氧化铈/多壁碳纳米管/乙炔黑纳米电化学传感器法快速测定苦荞总黄酮, columnId=1151923894698472105, journalTitle=食品安全质量检测学报, columnName=食品营养及功能性食品, runingTitle=null, highlight=null, articleAbstract=目的 建立基于二氧化铈/多壁碳纳米管/乙炔黑(cerium dioxide/multi-walled carbon nanotubes/acetylene black, CeO2/MWCNTs/AB)纳米电化学传感器法快速测定苦荞麦总黄酮的分析方法。方法 采用扫描电镜、循环伏安法、阻抗技术对修饰材料及其传感器进行表征, 通过循环伏安法探究芦丁在电极表面上的电化学行为, 并对电解液的选择、pH、修饰液的比例、滴涂量、富集时间以及扫描速度等条件进行优化, 进行苦荞麦黄酮的测定。结果 循环伏安图表明在0.54 V与0.57 V电位处出现对称的氧化峰和还原峰, 证实黄酮类化合物的电化学氧化还原反应具有可逆性。对实验条件进行了优化, 结果如下: pH为2.0的B-R溶液作为电解质溶液, CeO2/MWCNTs与乙炔黑的比例1:3 (V:V), 复合修饰材料修饰量12 μL, 富集时间9 min。苦荞麦黄酮氧化峰电流与其浓度之间呈良好的线性关系, 线性方程为Ip=0.793C+3.508 (r2=0.998), 最低检出限可达到6.5×10-8 mol/L。该方法用于苦荞麦中总黄酮的检测, 其加标回收率为99.46%~102.15%。结论 该方法的检测结果优于紫外-可见光分光光度法, 同时具有样品预处理简单、快捷方便、检测成本低、灵敏度高、准确性好等优势, 可用于食品中总黄酮快速准确的分析。, correspAuthors=李书国, authorNote=null, correspAuthorsNote=
*李书国(1969—), 男, 博士, 教授, 主要研究方向为食品科学与安全。E-mail:
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#袁朝辉和郭蒙蒙为共同第一作者

袁朝辉(1975—), 男, 硕士, 主要研究方向为食品安全快速检测能力提升研究。E-mail:

郭蒙蒙(1999—), 女, 硕士, 主要研究方向为粮食功能性资源高效利用。E-mail:

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袁朝辉(1975—), 男, 硕士, 主要研究方向为食品安全快速检测能力提升研究。E-mail:

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袁朝辉(1975—), 男, 硕士, 主要研究方向为食品安全快速检测能力提升研究。E-mail:

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郭蒙蒙(1999—), 女, 硕士, 主要研究方向为粮食功能性资源高效利用。E-mail:

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unstructuredReference=柴多, 王美婷, 姜雨萌, 等. 苦荞麦不同部位代谢轮廓及活性成分分布[J]. 食品科学, 2021, 42(2): 212-217., articleTitle=苦荞麦不同部位代谢轮廓及活性成分分布, refAbstract=null), Reference(id=1217901259189830267, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, doi=null, pmid=null, pmcid=null, year=2021, volume=42, issue=2, pageStart=212, pageEnd=217, url=null, language=null, rfNumber=[1], rfOrder=1, authorNames=CHAI D, WANG MT, JIANG YM, journalName=Food Science, refType=null, unstructuredReference=CHAI D, WANG MT, JIANG YM, et al. 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Journal of Food Safety & Quality, 2023, 14(14): 227-235, articleTitle=High sensitivity composite fluorescent nanosensor based on gold nanoclusters/graphene oxide for detecting heavy metal mercury ions in aquatic products, refAbstract=null)], funds=[Fund(id=1217901258728456792, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, awardId=21327111D, language=CN, fundingSource=河北省重点研发计划项目(21327111D), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1217901250511814675, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, xref=1, ext=[AuthorCompanyExt(id=1217901250524397588, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, companyId=1217901250511814675, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 Professional Technical Ability Promotion Center of Hebei Province Market Supervision & Administration Bureau, Shijiazhuang 050021, China), AuthorCompanyExt(id=1217901250528591893, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, companyId=1217901250511814675, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 河北省市场监督管理局专业技术能力提升中心, 石家庄 050021)]), AuthorCompany(id=1217901250671198240, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, xref=2, ext=[AuthorCompanyExt(id=1217901250679586849, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, companyId=1217901250671198240, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 College of Food & Biology, Hebei University of Science & Technology, Shijiazhuang 050018, China), AuthorCompanyExt(id=1217901250683781154, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, companyId=1217901250671198240, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 河北科技大学食品与生物学院, 石家庄 050018)])], figs=[ArticleFig(id=1217901254882279781, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Fig.1, caption=Preparation process of electrochemical sensor, figureFileSmall=svM2zyRSScwtqDozbyu6/A==, figureFileBig=jQA4xDo/NLFDzVNDadwhJQ==, tableContent=null), ArticleFig(id=1217901255012303215, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=图1, caption=电化学传感器制备流程, figureFileSmall=svM2zyRSScwtqDozbyu6/A==, figureFileBig=jQA4xDo/NLFDzVNDadwhJQ==, tableContent=null), ArticleFig(id=1217901255209435525, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Fig.2, caption=Scanning electron microscopy images of different modified materials, figureFileSmall=cBCRH5utCfP/lziw41pD8w==, figureFileBig=NHo8Uz/5i951YHT/ZkK2fw==, tableContent=null), ArticleFig(id=1217901255352041872, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=图2, caption=不同修饰材料的扫描电镜图

注: A. CeO2纳米颗粒材料; B. CeO2/MWCNTs/乙炔黑纳米复合材料。

, figureFileSmall=cBCRH5utCfP/lziw41pD8w==, figureFileBig=NHo8Uz/5i951YHT/ZkK2fw==, tableContent=null), ArticleFig(id=1217901255469482398, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Fig.3, caption=Electrochemical impedance spectroscopy of different modified electrodes, figureFileSmall=XUbj/mrX6Gg8LMxoZYsT/Q==, figureFileBig=BQ5q3+lgQ+5QrUF84GzLKQ==, tableContent=null), ArticleFig(id=1217901255616283056, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=图3, caption=不同修饰电极的交流阻抗图, figureFileSmall=XUbj/mrX6Gg8LMxoZYsT/Q==, figureFileBig=BQ5q3+lgQ+5QrUF84GzLKQ==, tableContent=null), ArticleFig(id=1217901255784055238, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Fig.4, caption=CV diagrams of rutin on GCE, figureFileSmall=3PhaHdtbml4pAqCdNyq2AA==, figureFileBig=dHP0dnST7AdHB5eNClSwmg==, tableContent=null), ArticleFig(id=1217901255876329939, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=图4, caption=芦丁在GCE上的CV图

注: a. 空白电解质溶液; b. 裸GCE; c. MWCNTs 修饰电极; d. CeO2/MWCNTs修饰电极; e. CeO2/MWCNTs/乙炔黑修饰电极。

, figureFileSmall=3PhaHdtbml4pAqCdNyq2AA==, figureFileBig=dHP0dnST7AdHB5eNClSwmg==, tableContent=null), ArticleFig(id=1217901255972798945, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Fig.5, caption=Effects of rutin CV response at different scanning speeds, figureFileSmall=R3S08UAvX1nMmmrHv0Vfiw==, figureFileBig=SFKYCPLRChhNQ/FxrufpmA==, tableContent=null), ArticleFig(id=1217901256111210987, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=图5, caption=不同扫描速度下的芦丁CV响应的影响

注: a~f: 扫描速度为0.2~1.0 V/s。

, figureFileSmall=R3S08UAvX1nMmmrHv0Vfiw==, figureFileBig=SFKYCPLRChhNQ/FxrufpmA==, tableContent=null), ArticleFig(id=1217901256232845815, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Fig.6, caption=Effects of different factors on the peak current of rutin, figureFileSmall=2j5n1yeBJgYU0ZCevfc/vA==, figureFileBig=OfxC1vWuYvMYirBll66zRg==, tableContent=null), ArticleFig(id=1217901256396423681, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=图6, caption=不同因素对芦丁的峰电流的影响, figureFileSmall=2j5n1yeBJgYU0ZCevfc/vA==, figureFileBig=OfxC1vWuYvMYirBll66zRg==, tableContent=null), ArticleFig(id=1217901256585167376, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Table 1, caption=

Determination of the recovery rate of rutin spiked by electrochemical method

, figureFileSmall=null, figureFileBig=null, tableContent=
加标值/(mg/g) 实际检测值/(mg/g) RSDs/% (n=3) 回收率/%
本方法 紫外分光光度法 本方法 紫外分光光度法 本方法 紫外分光光度法
0 25.1 24.76 - - - -
1.00 25.96 25.12 3.52 3.34 99.46 97.51
5.00 30.75 30.59 1.97 2.96 102.15 102.79
10.00 35.36 33.43 2.83 3.88 100.74 96.17
), ArticleFig(id=1217901256794882594, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=表1, caption=

电化学方法测定芦丁的加标回收率

, figureFileSmall=null, figureFileBig=null, tableContent=
加标值/(mg/g) 实际检测值/(mg/g) RSDs/% (n=3) 回收率/%
本方法 紫外分光光度法 本方法 紫外分光光度法 本方法 紫外分光光度法
0 25.1 24.76 - - - -
1.00 25.96 25.12 3.52 3.34 99.46 97.51
5.00 30.75 30.59 1.97 2.96 102.15 102.79
10.00 35.36 33.43 2.83 3.88 100.74 96.17
), ArticleFig(id=1217901256929100330, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Table 2, caption=

Results of determination of rutin by different modified electrodes in electrochemical methods

, figureFileSmall=null, figureFileBig=null, tableContent=
修饰电极 测定方法 应用 检测范围/(mol/L) 检出限/(mol/L)
PLA-GO/GCE(聚L-精氨酸-氧化石墨烯复合修饰电极) 快速CV法 - 3×10-7~2×10-5 1.0×10-7
鞣酸功能化石墨烯修饰电极 CV法 芦丁药片 1×10-9~1×10-5 6×10-9
对氨基苯磺酸/石墨烯/Nafion修饰电极 差分脉冲伏安法 复方芦丁片 2.5×10-7~1×10-5 2.25×10-8
CeO2/MWCNTs/乙炔黑修饰电极 CV法 苦荞麦 5.0×10-6~8.0×10-5 6.5×10-8
), ArticleFig(id=1217901257033957940, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=表2, caption=

电化学方法中不同修饰电极测定芦丁结果

, figureFileSmall=null, figureFileBig=null, tableContent=
修饰电极 测定方法 应用 检测范围/(mol/L) 检出限/(mol/L)
PLA-GO/GCE(聚L-精氨酸-氧化石墨烯复合修饰电极) 快速CV法 - 3×10-7~2×10-5 1.0×10-7
鞣酸功能化石墨烯修饰电极 CV法 芦丁药片 1×10-9~1×10-5 6×10-9
对氨基苯磺酸/石墨烯/Nafion修饰电极 差分脉冲伏安法 复方芦丁片 2.5×10-7~1×10-5 2.25×10-8
CeO2/MWCNTs/乙炔黑修饰电极 CV法 苦荞麦 5.0×10-6~8.0×10-5 6.5×10-8
), ArticleFig(id=1217901258376135225, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=EN, label=Table 3, caption=

Advantages and disadvantages of different detection methods for rutin

, figureFileSmall=null, figureFileBig=null, tableContent=
检测方法 优势 弊端
紫外分光光度法 分析快速、成本低、作简单 复杂基质中其他组分的干扰会影响检测的准确性, 只能检测分子中特定基团的信息, 而无法获得所有化合物的信息
荧光光谱法 灵敏度高、选择性好、作简单、检测速度快 天然荧光黄酮的数量有限、荧光猝灭效应和散射光干涉问题
高效液相色谱法 检出限低、灵敏度高、分析效率高、分析范围广 检测成本高、检测时间长、作复杂、溶剂消耗量高
液相色谱-质谱法 高效的分离性能和高灵敏度 检测成本高, 设备昂贵
电化学法 简单、选择性高、检测速度快和成本效益 选择合适的修饰材料
), ArticleFig(id=1217901258485187137, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217529311062573713, language=CN, label=表3, caption=

芦丁不同检测方法的利弊

, figureFileSmall=null, figureFileBig=null, tableContent=
检测方法 优势 弊端
紫外分光光度法 分析快速、成本低、作简单 复杂基质中其他组分的干扰会影响检测的准确性, 只能检测分子中特定基团的信息, 而无法获得所有化合物的信息
荧光光谱法 灵敏度高、选择性好、作简单、检测速度快 天然荧光黄酮的数量有限、荧光猝灭效应和散射光干涉问题
高效液相色谱法 检出限低、灵敏度高、分析效率高、分析范围广 检测成本高、检测时间长、作复杂、溶剂消耗量高
液相色谱-质谱法 高效的分离性能和高灵敏度 检测成本高, 设备昂贵
电化学法 简单、选择性高、检测速度快和成本效益 选择合适的修饰材料
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二氧化铈/多壁碳纳米管/乙炔黑纳米电化学传感器法快速测定苦荞总黄酮
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袁朝辉 1, # , 郭蒙蒙 2, # , 王佳 2 , 李书国 2, *
食品安全质量检测学报 | 食品营养及功能性食品 2025,16(13): 267-275
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食品安全质量检测学报 | 食品营养及功能性食品 2025, 16(13): 267-275
二氧化铈/多壁碳纳米管/乙炔黑纳米电化学传感器法快速测定苦荞总黄酮
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袁朝辉1, # , 郭蒙蒙2, # , 王佳2, 李书国2, *
作者信息
  • 1 河北省市场监督管理局专业技术能力提升中心, 石家庄 050021
  • 2 河北科技大学食品与生物学院, 石家庄 050018

    • 袁朝辉(1975—), 男, 硕士, 主要研究方向为食品安全快速检测能力提升研究。E-mail:

    郭蒙蒙(1999—), 女, 硕士, 主要研究方向为粮食功能性资源高效利用。E-mail:

通讯作者:

*李书国(1969—), 男, 博士, 教授, 主要研究方向为食品科学与安全。E-mail:
Rapid determination of total flavonoids in Tartary buckwheat by cerium dioxide/multi-walled carbon nanotubes/acetylene black nano-electrochemical sensor method
Zhao-Hui YUAN1, # , Meng-Meng GUO2, # , Jia WANG2, Shu-Guo LI2, *
Affiliations
  • 1 Professional Technical Ability Promotion Center of Hebei Province Market Supervision & Administration Bureau, Shijiazhuang 050021, China
  • 2 College of Food & Biology, Hebei University of Science & Technology, Shijiazhuang 050018, China
出版时间: 2025-07-15 doi: 10.19812/j.cnki.jfsq11-5956/ts.20250223001
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摘要
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目的 建立基于二氧化铈/多壁碳纳米管/乙炔黑(cerium dioxide/multi-walled carbon nanotubes/acetylene black, CeO2/MWCNTs/AB)纳米电化学传感器法快速测定苦荞麦总黄酮的分析方法。方法 采用扫描电镜、循环伏安法、阻抗技术对修饰材料及其传感器进行表征, 通过循环伏安法探究芦丁在电极表面上的电化学行为, 并对电解液的选择、pH、修饰液的比例、滴涂量、富集时间以及扫描速度等条件进行优化, 进行苦荞麦黄酮的测定。结果 循环伏安图表明在0.54 V与0.57 V电位处出现对称的氧化峰和还原峰, 证实黄酮类化合物的电化学氧化还原反应具有可逆性。对实验条件进行了优化, 结果如下: pH为2.0的B-R溶液作为电解质溶液, CeO2/MWCNTs与乙炔黑的比例1:3 (V:V), 复合修饰材料修饰量12 μL, 富集时间9 min。苦荞麦黄酮氧化峰电流与其浓度之间呈良好的线性关系, 线性方程为Ip=0.793C+3.508 (r2=0.998), 最低检出限可达到6.5×10-8 mol/L。该方法用于苦荞麦中总黄酮的检测, 其加标回收率为99.46%~102.15%。结论 该方法的检测结果优于紫外-可见光分光光度法, 同时具有样品预处理简单、快捷方便、检测成本低、灵敏度高、准确性好等优势, 可用于食品中总黄酮快速准确的分析。
苦荞麦  /  总黄酮  /  纳米材料  /  电化学传感器

Objective To establish a method for the rapid determination of total flavonoids in tartary buckwheat by cerium dioxide/multi-walled carbon nanotubes/acetylene black (CeO2/MWCNTs/AB) nano-electrochemical sensor. Methods The modified material and these nanoelectrochemical sensors were characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The electrochemical behavior of rutin on the electrode surface was systematically investigated via CV. Critical parameters were optimized, including electrolyte type, pH, modifier ratio, coating volume, accumulation time and scan rate. Results One pair of well- defined redox peaks were observed at the potential of 0.54 V and 0.57 V, which indicated that the electrochemical oxidation and reduction reaction of flavonoid was reversible. The experimental conditions were optimized, the results as follows: B-R solution with pH 2.0 as the electrolyte solution, VCeO2/MWCNTs:Vacetylene black as 1:3, amounts of modified material, 12 μL, enrichment time as 9 min. At these conditions, the oxidation peak current of flavonoid linearly increased with its concentration, Ip=0.793C+3.508 (r2=0.998), and the limit of detection was 6.5×10-8 mol/L. The developed method was used to determinate total flavonoids content of tartary buckwheat, the recoveries were in the range of 99.46%-102.15%, the results were superior to ultraviolet-visible spectrophotometry. Conclusion The method is feasible for the rapid and accurate determination of total flavonoids in food with the advantages such as simple pretreatment time saving and convenience, low detection cost, high sensitivity and good accuracy.

Tartary buckwheat  /  total flavonoids  /  nanometer material  /  electrochemical sensor
袁朝辉, 郭蒙蒙, 王佳, 李书国. 二氧化铈/多壁碳纳米管/乙炔黑纳米电化学传感器法快速测定苦荞总黄酮. 食品安全质量检测学报, 2025 , 16 (13) : 267 -275 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250223001
Zhao-Hui YUAN, Meng-Meng GUO, Jia WANG, Shu-Guo LI. Rapid determination of total flavonoids in Tartary buckwheat by cerium dioxide/multi-walled carbon nanotubes/acetylene black nano-electrochemical sensor method[J]. Journal of Food Safety & Quality, 2025 , 16 (13) : 267 -275 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250223001
正文
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0 引言
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荞麦是我国主要的全营养杂粮资源, 在河北、山西、陕西、四川、陕西、内蒙古等地种植广泛。苦麦荞作为一种营养价值较高的杂粮食品, 相关的基础研究和加工设备研究较少[1], 主要集中在对麸皮、壳、种子等部位的组分鉴定, 活性物质提取, 以及功能性研究等方面[2]。苦荞作为一种营养丰富的功能性谷物, 其生物活性成分主要包括蛋白质、功能性多糖、多酚类物质以及黄酮类化合物等, 其中苦荞麦表现出显著的类黄酮生物活性, 能够积累多种具有重要生理功能的次生代谢产物[3]。苦荞中所含有的黄酮类化合物具有多种生物活性, 包括但不限于自由基清除能力、血糖、血脂调节功能、血压调控作用以及潜在的抗肿瘤效应[4-7], 鉴于黄酮类物质这些重要生理功能, 准确测定苦荞中黄酮含量对于科学评估其营养价值和功能活性具有重要的意义。
黄酮类化合物检测方法有多种, 其中分光光度法操作简便, 但灵敏度有限; 高效液相色谱法[8-9]准确可靠, 但样品预处理烦琐、检测时间长、成本较高、需要专业化的人员; 质谱法能精确分析分子结构, 但设备昂贵且操作烦琐; 电化学分析法则具有检测速度快、灵敏度高、可实现现场检测、在线检测等优势, 在医疗诊断[10]、药物分析[11]、食品分析[12]、环境检测[13]等方面应用越来广泛, 尤其是纳米材料的创新发展[14], 对生物传感器、电化学传感器信号放大、提高检测精度和灵敏度创造了条件。碳基纳米材料因其独特的物理化学性质, 如高比表面积、优良导电性能和突出的吸附能力, 在多个领域展现出广泛的应用前景[15-16]。乙炔黑作为一种特殊的碳黑材料, 因其卓越的导电性和较大的比表面积, 能有效增强电极表面的电子传导能力, 进而提升电化学检测的灵敏度[17]。二氧化铈(cerium dioxide, CeO2)作为一种关键的稀土金属氧化物, 因其独特的三价铈和四价铈混合价态及价态间的相互转换能力, 赋予了CeO2多种模拟酶的特性及出色的催化性能[18-19]。
近年来, 电化学方法因其高灵敏度、快速响应、低成本及易于微型化等优势, 在黄酮类化合物检测领域得到广泛应用。尽管电化学检测技术已取得显著进展。但仍存在抗干扰能力不足、长期稳定性有限、实际样品检测有待验证、复合材料协同作用研究不足等问题。鉴于此, 本文以多壁碳纳米管(multi-walled carbon nanotubes, MWCNTs)、CeO2及乙炔黑杂化纳米材料为复合修饰材料, 固定化到玻碳电极(glassy carbon electrode, GCE)表面, 制备了CeO2/ MWCNTs/乙炔黑/GCE纳米电化学传感器, 旨在建立一种高灵敏、稳定性好的总黄酮电化学检测方法。该传感器通过协同作用CeO2的纳米酶催化特性、MWCNTs的高导电性以及乙炔黑的较大比表面积, 能够增强电流响应信号, 并有效促进生物分子的电子转移效率。本文以苦荞麦黄酮为实际样品进行检测分析, 为快速高效地分析食物中的总黄酮水平及筛选高黄酮含量食物资源提供一种新的方法。
1 材料与方法
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1.1 材料与试剂
苦荞(产地四川大凉山)。
磷酸氢二钠、磷酸二氢钠、N,N-二甲基甲酰胺、无水乙醇、氯化钠、氢氧化钠、磷酸、硼酸、醋酸、醋酸钠、无水高氯酸锂、CeO2(分析纯, 天津永大化学试剂有限公司); 硫酸、硝酸(分析纯, 烟台市双双化学试剂有限公司); 氧化铝粉[CHI(上海)仪器公司]; 乙炔黑、羧基化MWCNTs(北京德科岛金科技有限公司); 芦丁(纯度≥95.0%, 北京索莱宝科技有限公司); 纤维素酶(酶活度10000 U/g, 上海凛恩科技发展有限公司); 实验用水均为去离子水。
1.2 仪器与设备
LK98BⅡ电化学工作站(天津市兰力科公司); 三电极系统[Ф3mm玻碳电极(glass carbon electrode, GCE)、CHI115铂丝电极、CHI111Ag/AgCl电极](上海CH Instruments公司); KQ3200DE超声清洗仪(昆山超声仪器有限公司); FA2204电子分析天平(精度0.0001 g, 上海菁海仪器有限公司); ST3100 pH计[Ohaus(常州)仪器有限公司]; GZX-9070MBE干燥箱(上海博讯医疗生物仪器股份有限公司); UV-5500PC紫外分光光度计(上海元析仪器有限公司); 85-2恒温磁力搅拌器(上海梅颖浦仪器仪表制造有限公司); TGL-10B离心机(上海安亭科学仪器厂); Quattro S环境扫描电子显微镜(捷克赛默飞世尔科技有限公司)。
1.3 方法
1.3.1 电极预处理
GCE使用前需经以下处理: 先以0.05 μm氧化铝粉在麂皮布上抛光至镜面, 再依次在硝酸:H2O=1:1 (V:V)溶液、无水乙醇、去离子水中超声清洗1 min, 确保表面无吸附物, 置于0.5 mol/L硫酸溶液中, 以50 mV/s扫速在-1.0~1.0 V电位区间循环伏安(cyclic voltammetry, CV)扫描至稳定以备用。
1.3.2 CeO2/MWCNTs/乙炔黑纳米电化学传感器的制备
称取0.10 g羧基化MWCNTs, 溶解于10 mL N,N-二甲基甲酰胺溶液。经过30 min的超声处理, 获得质量浓度为10 mg/mL黑色均一的MWCNTs修饰液[20]。
制备CeO2/MWCNTs复合修饰材料: 将2.0 mg的纳米CeO2粉末加入到0.5 mL上述MWCNTs修饰液中, 继续超声处理30 min, 最终形成稳定的黑色悬浮液, 立即密封避光储存于4 ℃环境[21]。采用微量移液枪准确移取10 μL的CeO2/MWCNTs分散液, 均匀滴涂在预处理的GCE表面, 在红外灯下干燥, 制得CeO2/MWCNTs/GCE传感器。
制备CeO2-MWCNTs/乙炔黑复合修饰材料: 将5 mL的CeO2/MWCNTs悬浊液和5 mL的乙炔黑悬浊液混合均匀, 经过20 min的超声处理后, 得到CeO2/MWCNTs/乙炔黑混合修饰液。准确移取5 μL CeO2-MWCNTs混合液和5 μL乙炔黑悬浊液滴涂在GCE表面, 并在红外灯下干燥, 如图1所示, 制得CeO2-MWCNTs/乙炔黑/GCE纳米电化学传感器[22-23]。
1.3.3 电解质及标准溶液的配制
准确配制0.04 mol/L磷酸、硼酸、醋酸和0.2 mol/L氢氧化钠溶液, 在100 mL磷酸、硼酸、醋酸3种酸的混合液中加入适当体积的氢氧化钠配制pH为2的电解质溶液, 将芦丁标准品溶于乙醇配制2.35×10-5 mol/L标准溶液, 低温避光保存备用。
1.3.4 电化学测试方法
本研究采用CeO2/MWCNTs/乙炔黑/GCE作为工作电极, 以芦丁(芸香叶苷)作为标准品, 通过CV法探究芦丁在电极表面上的电化学行为。并设定起始电位0.0 V至1.0 V的电位范围内, 以0.05 V/s的扫描速度进行CV扫描, 循环次数为1圈, 记录相应的伏安响应曲线。为优化检测性能, 采用CV法对电解液的选择、pH、修饰液的比例、滴涂量、富集时间以及扫描速度等关键因素的影响, 以提高方法的准确性和重现性。在最佳实验条件下, 进一步研究了芦丁氧化峰电流值与浓度之间的线性关系, 并建立标准曲线。基于该标准曲线, 结合电化学分析方法, 最终实现苦荞麦中芦丁的准确定量测定。
1.3.5 苦荞麦样品的处理
准确称取2.0 g苦荞麦粉, 添加0.15 mL 10 U/mL纤维素酶进行酶解, 加入15 mL乙醇溶液进行超声, 在酶解温度50 ℃条件下酶解30 min, 并在超声功率100 W、温度50 ℃的条件下超声60 min提取苦荞麦黄酮样品, 取上清液, 避光保存。
1.3.6 标准曲线
为建立芦丁定量分析的标准曲线, 配制浓度梯度为5、10、20、40、80 μmol/L的芦丁标准溶液。在优化后的CV测试条件下, 分别测定各浓度下的电化学响应电流值, 每组浓度平行测定3次, 取平均值作为最终测定值。以芦丁浓度(C, μmol/L)作为横坐标, 氧化峰电流(Ip, μA)为纵坐标, 进行线性回归方程分析, 得到标准曲线。随后将待测样品的CV数据代入该方程, 计算出苦荞麦样品中总黄酮含量。
1.3.7 加标回收率测定
在已知黄酮含量的苦荞麦样品中添加一定含量的芦丁标准品, 并根据公式(1)计算回收率:
加标回收率/%=$\frac{{{A}_{1}}-{{A}_{2}}}{{{A}_{0}}}$×100%
式中: A1为苦荞麦样品的芦丁加标实测值, mg/g; A2为苦荞麦样品的芦丁测定值, mg/g; A0为芦丁标准品的加入值, mg/g。
1.4 数据处理
本研究所有数据均为3次平行取其平均值, 运用SPSS 17软件进行数据统计分析, 采用Origin Pro 9.0软件绘图。
2 结果与分析
收起
2.1 修饰材料的结构表征
利用扫描电镜表征了CeO2纳米颗粒和CeO2/MWCNTs/乙炔黑纳米复合材料的结构, 结果如图2所示, CeO2纳米颗粒呈典型球形结构, 粒径分布均匀, 可充分分散于MWCNTs/乙炔黑复合基体中, 由于其纳米级的粒度, 通常具有一些特殊的物理和化学性质, 如高比表面积、良好的催化活性等。MWCNTs呈现同轴石墨层的中空管状形貌, 其层间距约为0.34 nm, 内外半径分别为3~7 nm及15~20 nm, 这些特点使得MWCNTs具有独特的结构和性能。乙炔黑颗粒具有类石墨层同心圆结构, 平均粒径约为30~45 nm, 与MWCNTs共同形成三维导电网络。CeO2纳米颗粒可嵌入MWCNTs管腔及乙炔黑堆积孔隙中, 形成致密分级结构。复合材料之间的协同效应显著提升电化学性能, 纳米CeO2的高比表面积与催化活性位点; MWCNTs/乙炔黑的三维导电框架加速电子传输; 三者结合后的这种多尺度孔隙结构, 增强物质扩散共同实现电子转移速率加快、电化学信号放大效应。
2.2 纳米电化学传感器的电化学表征
电化学阻抗谱(electrochemical impedance spectroscopy, EIS)是一种重要的分析方法, 它可依据阻抗的变化探究不同传感器的导电特性。在EIS图像中, 图形半圆直径越大, 传感器电阻越高。为了探究GCE等不同电极的性能, 采用电化学阻抗谱法, 并记录它们的阻抗图谱。如图3所示, 通过对比分析得出电阻大小的明确排列顺序为: GCE>MWCNTs/GCE>CeO2/MWCNTs/GCE>CeO2/MW-CNTs/乙炔黑/GCE。
由图3可知, 采用MWCNTs对裸电极进行修饰后, 电阻显著降低。这一现象归因于MWCNTs材料比表面积较大, 可结合位点较多, 有利于电子的传递, CeO2/MWCNTs修饰电极阻抗进一步降低, 这得益于CeO2具有多种模拟酶的性质及优良的催化性能[24], 能够一定程度地促进电极之间电子传递, 减小阻力; 在电极上滴涂CeO2/MWCNTs/乙炔黑后, 电极阻抗更进一步降低, 增加了导电性, 形成独特的有利于电子传递的结构, 从而加快了电子移动速率。由此可得, CeO2/MWCNTs/乙炔黑/GCE纳米电化学传感器具备良好的电子传递性能。
2.3 芦丁在不同修饰电极上的电化学行为
图4中的CV图表征了芦丁在GCE及各修饰电极上的电化学行为。结果显示, 在空白电解质溶液中(曲线a), 用GCE作为工作电极扫描时, CV图无任何峰出现; 图4裸GCE(曲线b)表明, 在含有芦丁的电解质溶液时, 出现了不太明显的还原峰和氧化峰; 曲线c、d、e不同电极表明, 所有修饰电极的芦丁氧化峰电流均显著高于裸GCE, 在0.54 V处呈现明显的还原峰, 并在0.57 V处出现氧化峰, 表明芦丁在电极表面发生了可逆的氧化还原反应。此电化学活性可归因于芦丁分子B环邻苯二酚羟基的氧化还原特性[24]。在CeO2/MWCNTs/乙炔黑修饰电极上(曲线e)的氧化峰电流最大, 是裸电极的15倍, 这是源于复合材料的协同作用, 其中, CeO2纳米颗粒通过其氧化酶活性及氧空位介导的催化作用加速电子转移过程; MWCNTs则以其较大的比表面积和π-π共轭效应, 显著提升芦丁分子在电极表面的富集密度[25]; 而乙炔黑通过三维导电网络优化电荷传输路径, 其电导率较常规碳材料显著提升。上述协同效应使得CeO2/MWCNTs/乙炔黑复合修饰材料有效地促进电极表面的电子传递效率, 提高了传感器检测的灵敏度。
2.4 扫描速度对芦丁电化学行为的影响
利用CV法深入研究了不同扫描速度(ν)对CeO2/MWCNTs/乙炔黑修饰电极中芦丁氧化行为的影响。如图5所示, 随着扫描速度的逐渐提升, 芦丁的氧化峰电势(Ep)呈规律正向偏移, 同时氧化峰电流值(Ip)显著增强。特别地, 在0.2~1.0 V/s范围内, 氧化峰电流(Ip)和扫描速度(ν)呈现良好的相关性, 其回归方程为Ip=77.764ν+2.0888 (r2=0.9974), 表明电极表面反应受扩散-吸附混合控制。进一步研究表明, 芦丁的氧化峰电位(Ep)与扫描速度(ν)同样呈现出线性关系, 其回归方程为Ep=0.0203ν+0.635 (r2=0.993), 证实了芦丁在修饰电极表面的氧化过程主要受到吸附作用的主导。
2.5 实验条件的优化
2.5.1 电解液对芦丁氧化峰电流的影响
根据黄酮类物质的性质选择合适的电解质溶液, 考察不同电解质溶液对芦丁氧化峰电流的影响。如图6A所示, 将一定浓度的芦丁溶液加入不同电解质溶液中, 使用CV法扫描, 比较其电化学行为, 记录氧化峰电流值, 电解质溶液为B-R缓冲溶液时峰电流达到最高值, 该电解质溶液具有良好的导电性能, 因此, 本研究选择B-R缓冲溶液为电解质溶液。
2.5.2 pH对芦丁氧化峰电流的影响
如图6B所示, 缓冲溶液pH对芦丁在CeO2/MWCNTs/乙炔黑修饰电极上的电化学响应具有显著影响。当pH为2.0时, 氧化峰电流达到最大值。随着pH升高, 氧化还原峰电流值呈梯度下降, 同时芦丁的氧化峰电位持续负移, 此现象表明质子可能直接参与电极表面的氧化反应过程[26]; 峰电位(Ep)与pH具有较好的线性关系, 线性回归方程为Ep=13.105-17.738x (pH) (r2=0.9933)。这表明缓冲溶液的pH是影响芦丁电化学行为的一个关键参数, 适宜的H+浓度可有效优化电子界面质子传递效率, 从而提升检测灵敏度。鉴于B-R缓冲溶液的pH范围为1.95左右, 本研究选择pH为2.0的作为最优电解质条件, 该参数选择可最大限度维持芦丁分子的电化学活性构象。
2.5.3 复合材料滴涂比例对芦丁氧化峰电流的影响
在CeO2/MWCNTs/乙炔黑修饰量为10 μL的固定条件下, 进一步研究了CeO2/MWCNTs修饰材料与乙炔黑的不同混合体积比对氧化还原峰值电流的影响。如图6C所示, 当CeO2/MWCNTs与乙炔黑的体积比达到1:3时, 电极产生的氧化峰电流达到最大值。当CeO2/MWCNTs修饰材料比例过多时, 氧化峰电流值呈下降趋势。这是由于过量CeO2/MWCNTs导致的修饰层增厚现象, 过厚的复合膜不仅阻碍电子传输, 还会减少活性位点的有效暴露面积, 从而降低电极对芦丁分子的电化学响应灵敏度。因此, 适度增加乙炔黑的修饰量, 可有效平衡导电网络构建与活性物质分散度之间的协同效应, 为进一步优化电极性能提供了重要参考。
2.5.4 复合材料修饰量对芦丁氧化峰电流的影响
在固定CeO2/MWCNTs和乙炔黑混合比例为1:3的条件下, 通过不同体积的CeO2/MWCNTs/乙炔黑分散液的滴涂体积, 探究复合材料修饰量对芦丁氧化峰电流的影响。如图6D所示, 在修饰量12 μL之前, 芦丁氧化峰电流值随修饰量的增大呈显著正相关, 当修饰量为12 μL时达到峰值电流, 此现象可归因于修饰层厚度与活性位点密度的协同效应; 随着复合材料修饰量增加(3→15 μL), 电极表面有效活性面积呈梯度扩展, 显著提升了电子传递效率和氧化还原反应。然而, 当修饰量超过12 μL后, 过厚的修饰层可能引发传质阻力增大, 导致电流响应趋于饱和。基于电流响应极值与实验重现性综合考量, 最终确定12 μL为CeO2/MWCNTs/乙炔黑分散液的最佳修饰量。
2.5.5 富集时间对芦丁氧化峰电流的影响
富集时间对芦丁在CeO2/MWCNTs/乙炔黑修饰电极表面富集的关键参数。基于上文优化的最佳检测参数组合, 进一步探究不同富集时间(3~15 min)对芦丁氧化峰电流的影响。如图6E所示, 当富集时间从3 min延长到9 min时, 氧化峰电流值随吸附时间增加呈现上升趋势, 并在9 min时达到峰值。此现象表明了修饰电极对芦丁的吸附容量与富集时间呈正相关。当富集时间超过9 min后, 氧化峰电流增长缓慢趋于平缓, 表明电极表面活性位点已达到吸附平衡状态。基于检测灵敏度与操作成本间的平衡考量, 最终确定9 min作为最佳富集时间。
2.6 芦丁浓度与其氧化峰电流的关系
在最优实验条件下, 采用CV法分别测定了芦丁在0、5、10、20、40、80 μmol/L浓度下的氧化峰电流, 并据此绘制了标准曲线。氧化峰电流(Ip)随着芦丁浓度(C)的增加而增大, 在5~80 μmol/L的浓度范围内, 芦丁的浓度与氧化峰电流线性关系良好, 其方程为Ip (μA)=0.793C (μmol/L)+ 3.508 (r2=0.998), 显示出极强的相关性。此外, 在信噪比(S/N)为3的条件下得出该方法的最低检出限为6.5×10-8 mol/L。
2.7 抗干扰性和稳定性、重复性
在芦丁标准溶液浓度固定为2.31×10-5 mol/L的条件下, 系统分析了Na+、K+、麦芽糖、抗坏血酸及生育酚等潜在干扰物质对CeO2/MWCNTs/乙炔黑修饰电极中芦丁氧化峰电流的影响。实验表明, 在10倍浓度的共存离子(Na⁺、K⁺)及化合物(麦芽糖)的影响下, 氧化峰电流基本不变; 而抗坏血酸和生育酚引起的电流响应波动影响较小, 其相对标准偏差(relative standard deviation, RSD)仅为2.7%, 证实该传感器具备优异的抗干扰性能。
针对传感器的长期稳定性, 将电极于4 ℃条件下分别保存1周和3周后进行重复测试。结果表明, 其氧化峰电流保留率分别为初始值的99.2%和97.6%, 电流下降幅度符合电化学传感器稳定性标准。进一步通过连续测定固定浓度(2.31×10-5 mol/L)芦丁标准溶液发现, 氧化还原峰电流的RSDs值始终低于3.2% (n=5), 上述数据充分验证了CeO2/MWCNTs/乙炔黑传感器在食品总黄酮分析中的可靠性[27-28]。
2.8 苦荞麦总黄酮加标回收率的验证
基于1.3.5节样品前处理方法, 分别采用电化学传感器法和紫外分光光度法测定苦荞麦提取液中总黄酮含量, 并进行加标回收实验。如表1所示, 在添加有1.00、5.00、10.00 mg/g 3个梯度的芦丁标准品后, 本方法加标回收率范围为99.46%~102.15%, 平均值100.81%, 紫外分光光度法的加标回收范围为96.17%~102.79%, 其平均值为99.47%。两种方法的对比结果表明, 电化学分析法在精密度和准确度方面展现出较优的分析性能。
2.9 不同检测方法的对比
不同的修饰电极因表面修饰的材料的组成和理化性质存在显著差异, 会对氧化峰电流产生不同的影响。在电化学方法中, 通过比较多种修饰电极对不同样品中芦丁的检测性能[29-31], 如表2所示, 在实际应用中, 需要根据具体的检测需求和目标物质选择合适的修饰电极, 以优化电化学检测的性能和效果[32-35]。
如表3所示, 传统上, 食品和生物基质中芦丁的检测和定量是使用复杂的分析方法实现的, 例如高效液相色谱法、分光光度法和基于荧光的技术。这些方法具有出色的灵敏度和精密度, 但它们也有固有的局限性, 例如昂贵的仪器、技术专长、时间要求、运营成本和有限的便携性等。电化学传感已成为克服这些限制的可行替代方案, 可提供高灵敏度、快速响应时间和经济高效的仪器检测方法。
3 结论
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以苦荞麦总黄酮为研究对象, 构建了一种基于CeO2/MWCNTs/乙炔黑/GCE电化学传感器, 并建立了食品中黄酮类化合物的快速检测方法。通过分析芦丁在修饰电极上的电化学行为, 发现其在在0.54 V和0.57 V处呈现明显的还原峰和氧化峰, 且氧化还原反应过程是可逆的, 表明该传感器具有良好的电子传递性能。
该传感器的创新是通过协同作用CeO2的纳米酶催化特性、MWCNTs的高导电性以及乙炔黑的超大比表面积, 显著增强了电流响应信号(较GCE电极提升约3.2倍), 并有效促进了生物分子的电子转移效率。在最佳条件下, 以pH为2.0的B-R溶液作为电解质溶液, CeO2/MWCNTs与乙炔黑的比例1:3 (V:V), 复合修饰材料修饰量12 μL, 富集时间9 min。苦荞麦芦丁氧化峰电流与其浓度之间呈良好的线性关系, 线性方程为Ip=0.793C+3.508 (r2=0.998), 在信噪比(S/N)为3的条件下最低检出限可达到6.5×10-8 mol/L。
实际应用于苦荞麦样品分析时, 加标回收率维持在99.46%~102.15%之间, 与紫外分光光度法的测定结果较为一致。该方法兼具快速响应、高灵敏度及良好稳定性等特点, 为食品和药品中黄酮类化合物的检测提供了一定参考。
基金
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  • 河北省重点研发计划项目(21327111D)
文献
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2025年第16卷第13期
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doi: 10.19812/j.cnki.jfsq11-5956/ts.20250223001
  • 接收时间：2025-02-23
  • 首发时间：2026-01-12
  • 出版时间：2025-07-15
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  • 收稿日期：2025-02-23
基金
河北省重点研发计划项目(21327111D)
作者信息
    1 河北省市场监督管理局专业技术能力提升中心, 石家庄 050021
    2 河北科技大学食品与生物学院, 石家庄 050018

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*李书国(1969—), 男, 博士, 教授, 主要研究方向为食品科学与安全。E-mail:
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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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