REQUIMTE/LAQV, Instituto Superior de Engenharia do Porto, Instituto Politécnico do Porto, Rua Dr. António Bernardino de Almeida 431, 4249-015 Porto, Portugal; Centro de Química, Universidade do Minho, Campus de Gualtar, 4710-057 Braga, Portugal; Departamento de Química Analítica y Alimentaria, Faculdade de Química, Campus Universitario de Vigo As Lagoas Marcosende, Universidade de Vigo, 36310 Vigo, Spain.
REQUIMTE/LAQV, Instituto Superior de Engenharia do Porto, Instituto Politécnico do Porto, Rua Dr. António Bernardino de Almeida 431, 4249-015 Porto, Portugal.
Talanta. 2025 Jan 1;282:127002. doi: 10.1016/j.talanta.2024.127002. Epub 2024 Oct 9.
Tetrodotoxin (TTX) is a marine biotoxin whose biosynthesis is associated with the pufferfish. Its distribution is primarily focused in Asian and tropical marine areas. Currently, this group of toxins is classified as emerging in Europe, and its presence could be related to climate change. This incidence has prompted the European Union, with the European Food Safety Authority, to establish control and monitoring mechanisms for TTX in marine products in Europe. In this context, the development of analytical tools capable of ensuring the safety of food products, especially seafood and fish, is a crucial task. This study describes the development of a molecularly imprinted polymer (MIP) based electrochemical sensor for the analysis of TTX. The MIP was synthesized through the electropolymerization of a functional monomer, ortho-phenylenediamine in the presence of a dummy template, voglibose. The MIP sensor was constructed on a screen-printed gold electrode and characterized by cyclic voltammetry. Differential pulse voltammetry, using a redox probe ([Fe(CN)]), was used in the analysis protocol. The developed sensor exhibited a linear response between 5.0 μg mL and 25.0 μg mL, with a limit of detection of 1.14 μg mL. Its high imprinting efficiency conferred outstanding selectivity towards TTX. The sensor's applicability was confirmed through recovery assays on spiked mussel samples, achieving recoveries of 81.0 %, 110.2 %, and 102.5 % for external standard addition at 30.0, 44.0, and 60.0 μg kg, respectively, with relative standard deviations below 15 %. These results are comparable to those obtained using Hydrophilic Interaction Liquid Chromatography coupled with Tandem Mass Spectrometry, a validated method carried out by the European Reference Laboratory for Marine Biotoxins. Thus, the MIP sensor represents a portable, simple, and fast tool with essential analytical functionalities for the sampling phase and pre-selection of laboratory samples for analysis.
河豚毒素 (TTX) 是一种海洋生物毒素,其生物合成与河豚鱼有关。它的分布主要集中在亚洲和热带海洋地区。目前,这组毒素在欧洲被归类为新兴毒素,其存在可能与气候变化有关。这一事件促使欧盟与欧洲食品安全局一起,在欧洲建立了对海产品中 TTX 的控制和监测机制。在这种情况下,开发能够确保食品产品(特别是海鲜和鱼类)安全的分析工具是一项至关重要的任务。本研究描述了一种基于分子印迹聚合物 (MIP) 的电化学传感器的开发,用于 TTX 的分析。MIP 通过在 dummy 模板 voglibose 的存在下,功能单体邻苯二胺的电聚合合成。MIP 传感器构建在丝网印刷金电极上,并通过循环伏安法进行了表征。差分脉冲伏安法使用氧化还原探针 ([Fe(CN)] ) 用于分析方案。所开发的传感器在 5.0 μg mL 和 25.0 μg mL 之间表现出线性响应,检测限为 1.14 μg mL。其高印迹效率赋予了 TTX 出色的选择性。通过对加标贻贝样品的回收实验验证了传感器的适用性,在 30.0、44.0 和 60.0 μg kg 下进行外部标准添加时,回收率分别为 81.0%、110.2%和 102.5%,相对标准偏差低于 15%。这些结果与使用亲水相互作用液相色谱串联质谱法(一种由欧洲海洋生物毒素参考实验室进行验证的方法)获得的结果相当。因此,MIP 传感器是一种便携式、简单、快速的工具,具有采样阶段和实验室样品预筛选的基本分析功能。