Nimisha Jadon, Ahmet Cetinkaya, Sena Piskin, Lokman Uzun, Esen Bellur Atici, Sibel A. Ozkan
{"title":"推进绿色化学对n -亚硝基二乙胺(NDEA)的敏感和选择性检测:纳米材料嵌入电聚合分子印迹聚合物传感器的作用","authors":"Nimisha Jadon, Ahmet Cetinkaya, Sena Piskin, Lokman Uzun, Esen Bellur Atici, Sibel A. Ozkan","doi":"10.1007/s00604-025-07513-2","DOIUrl":null,"url":null,"abstract":"<p><i>N</i>-Nitrosodiethylamine (NDEA), a potent carcinogen with an acceptable intake (AI) of 26.5 ng/day, poses a significant health risk, necessitating accurate detection and quantification. Here, we introduce the first-ever molecularly imprinted polymer (MIP)–based electrochemical sensor, NDEA/ZnONPs@APTES/CHT/3-TBA@MIP/GCE, for the selective and sensitive detection of NDEA. The sensor was fabricated by depositing green-synthesized 3-aminopropyl triethoxysilane (APTES)-functionalized ZnO nanoparticles (ZnONPs) onto a glassy carbon electrode (GCE), followed by electropolymerization (EP) with chitosan (CHT) and 3-thienyl boronic acid (3-TBA) to form a molecularly imprinted polymeric film. The APTES-ZnONPs were characterized using IR and Raman spectroscopies, XRD, zeta-size, and -potential analyses, while the polymeric films, synthesized with and without NDEA, were analyzed via SEM. Electrochemical characterization was performed using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV) by using 5.0 mM [Fe(CN)<sub>6</sub>]<sup>3−/4−</sup> solution as a redox probe for quantitative detection of NDEA. The developed sensor exhibited high selectivity and sensitivity for NDEA over a concentration range of 0.1–1.0 pM, achieving detection and quantification Limits of 5.92 fM and 19.80 fM in standard solutions and 12.60 fM and 42.00 fM in commercial serum samples, respectively. It maintained high recovery percentages even in biological interferents, potential impurities such as N-nitrosodimethylamine (NDMA), and drug substances like sartans, demonstrating exceptional selectivity. Furthermore, a Green Analytical Chemistry (GAC) assessment classified the sensor as an environmentally superior alternative to traditional methods, achieving a 99% greener score. This pioneering green MIP-based sensor presents a promising platform for environmental monitoring, portable and miniaturized sensing, and rapid on-site NDEA detection, addressing the urgent need for sensitive, selective, and eco-friendly analytical tools.</p>","PeriodicalId":705,"journal":{"name":"Microchimica Acta","volume":"192 10","pages":""},"PeriodicalIF":5.3000,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Advancing green chemistry for the sensitive and selective detection of N-nitrosodiethylamine (NDEA) monitoring: the role of nanomaterial-embedded electropolymerized molecularly imprinted polymer-based sensors\",\"authors\":\"Nimisha Jadon, Ahmet Cetinkaya, Sena Piskin, Lokman Uzun, Esen Bellur Atici, Sibel A. 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Electrochemical characterization was performed using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV) by using 5.0 mM [Fe(CN)<sub>6</sub>]<sup>3−/4−</sup> solution as a redox probe for quantitative detection of NDEA. The developed sensor exhibited high selectivity and sensitivity for NDEA over a concentration range of 0.1–1.0 pM, achieving detection and quantification Limits of 5.92 fM and 19.80 fM in standard solutions and 12.60 fM and 42.00 fM in commercial serum samples, respectively. It maintained high recovery percentages even in biological interferents, potential impurities such as N-nitrosodimethylamine (NDMA), and drug substances like sartans, demonstrating exceptional selectivity. Furthermore, a Green Analytical Chemistry (GAC) assessment classified the sensor as an environmentally superior alternative to traditional methods, achieving a 99% greener score. 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引用次数: 0
摘要
n -亚硝基二乙胺(NDEA)是一种强致癌物,可接受摄入量(AI)为26.5纳克/天,对健康构成重大风险,需要准确检测和定量。在这里,我们介绍了第一个基于分子印迹聚合物(MIP)的电化学传感器NDEA/ZnONPs@APTES/CHT/3-TBA@MIP/GCE,用于选择性和灵敏度检测NDEA。该传感器是将绿色合成的3-氨基丙基三乙氧基硅烷(APTES)功能化ZnO纳米粒子(ZnONPs)沉积在玻璃碳电极(GCE)上,然后与壳聚糖(CHT)和3-噻吩硼酸(3-TBA)电聚合(EP)形成分子印迹聚合物膜。采用红外光谱、拉曼光谱、XRD、zeta-size和电位分析对APTES-ZnONPs进行了表征,并通过SEM分析了添加和不添加NDEA合成的聚合物膜。采用循环伏安法(CV)和电化学阻抗法(EIS)进行电化学表征,并采用差分脉冲伏安法(DPV),以5.0 mM [Fe(CN)6]3−/4−溶液作为氧化还原探针定量检测NDEA。该传感器在0.1 ~ 1.0 pM的浓度范围内对NDEA具有较高的选择性和灵敏度,在标准溶液中检测限为5.92 fM和19.80 fM,在商业血清样品中检测限为12.60 fM和42.00 fM。即使在生物干扰物、n -亚硝基二甲胺(NDMA)等潜在杂质和沙坦等原料药中,也能保持较高的回收率,表现出优异的选择性。此外,绿色分析化学(GAC)评估将该传感器列为传统方法的环保替代品,绿色得分达到99%。这种开创性的基于mip的绿色传感器为环境监测,便携式和小型化传感以及快速现场NDEA检测提供了一个有前途的平台,解决了对敏感,选择性和环保分析工具的迫切需求。
Advancing green chemistry for the sensitive and selective detection of N-nitrosodiethylamine (NDEA) monitoring: the role of nanomaterial-embedded electropolymerized molecularly imprinted polymer-based sensors
N-Nitrosodiethylamine (NDEA), a potent carcinogen with an acceptable intake (AI) of 26.5 ng/day, poses a significant health risk, necessitating accurate detection and quantification. Here, we introduce the first-ever molecularly imprinted polymer (MIP)–based electrochemical sensor, NDEA/ZnONPs@APTES/CHT/3-TBA@MIP/GCE, for the selective and sensitive detection of NDEA. The sensor was fabricated by depositing green-synthesized 3-aminopropyl triethoxysilane (APTES)-functionalized ZnO nanoparticles (ZnONPs) onto a glassy carbon electrode (GCE), followed by electropolymerization (EP) with chitosan (CHT) and 3-thienyl boronic acid (3-TBA) to form a molecularly imprinted polymeric film. The APTES-ZnONPs were characterized using IR and Raman spectroscopies, XRD, zeta-size, and -potential analyses, while the polymeric films, synthesized with and without NDEA, were analyzed via SEM. Electrochemical characterization was performed using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV) by using 5.0 mM [Fe(CN)6]3−/4− solution as a redox probe for quantitative detection of NDEA. The developed sensor exhibited high selectivity and sensitivity for NDEA over a concentration range of 0.1–1.0 pM, achieving detection and quantification Limits of 5.92 fM and 19.80 fM in standard solutions and 12.60 fM and 42.00 fM in commercial serum samples, respectively. It maintained high recovery percentages even in biological interferents, potential impurities such as N-nitrosodimethylamine (NDMA), and drug substances like sartans, demonstrating exceptional selectivity. Furthermore, a Green Analytical Chemistry (GAC) assessment classified the sensor as an environmentally superior alternative to traditional methods, achieving a 99% greener score. This pioneering green MIP-based sensor presents a promising platform for environmental monitoring, portable and miniaturized sensing, and rapid on-site NDEA detection, addressing the urgent need for sensitive, selective, and eco-friendly analytical tools.
期刊介绍:
As a peer-reviewed journal for analytical sciences and technologies on the micro- and nanoscale, Microchimica Acta has established itself as a premier forum for truly novel approaches in chemical and biochemical analysis. Coverage includes methods and devices that provide expedient solutions to the most contemporary demands in this area. Examples are point-of-care technologies, wearable (bio)sensors, in-vivo-monitoring, micro/nanomotors and materials based on synthetic biology as well as biomedical imaging and targeting.