Silver nanoparticle-functionalized 3D flower-like copper (II)-porphyrin framework nanocomposites as signal enhancers for fabricating a sensitive glutathione electrochemical sensor

• Published in: Sensors and actuators. B, Chemical Vol. 342; p. 130047
• Main Authors: Liu, Tingting, Zhou, Mao, Pu, Yuxin, Liu, Liqun, Li, Feifei, Li, Mengsi, Zhang, Mingxiao
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01.09.2021; Elsevier Science Ltd
• Subjects: Catalytic oxidation; Chemical sensors; Copper; Copper (II)-porphyrin framework; Electrical resistivity; Electrochemical analysis; Glassy carbon; Glutathione; Metal-organic frameworks; Nanocomposites; Nanoflowers; Nanoparticles; Oxidation; Porphyrins; Sensors; Silver chloride; Silver nanoparticles; Square wave voltammetry; Square waves; Three dimensional flow; Square wave voltammetry; Nanoflowers; Silver nanoparticles; Copper (II)-porphyrin framework; Glutathione
• ISSN: 0925-4005; 1873-3077
• DOI: 10.1016/j.snb.2021.130047

•Cu-TCPP MOF with 3D nano flower-like morphology was synthesized and applied as the modifier of glassy carbon electrode.•Ag/Cu-TCPP/GCE exhibits high electrocatalytic activity for glutathione oxidation.•Glutathione is detected by the formation of a copper (II)-glutathione complex at low overpotential on Ag/Cu-TCPP/GCE.•The proposed sensor has wide linear dynamic range, high sensitivity, low limit of detection and excellent anti-interference capability. In this paper, sliver nanoparticle (Ag NP)-functionalized 3D copper (II)-porphyrin framework (MOF) nanoflowers were applied as modifiers of glassy carbon electrodes (GCEs) for catalytic oxidation and quantitative detection of glutathione (GSH). Specifically, Ag NPs could not only increase the electrical conductivity of Cu-TCPP (TCPP = tetrakis(4‐carboxyphenyl)porphyrin) MOF but also adsorb GSH. Meanwhile, the unique 3D flower-like structure of Cu-TCPP MOF provides a large number of attachment sites for Ag NP incorporation. With the assistance of the electrocatalytic ability of copper ions released from Cu-TCPP nanoflowers, the fabricated electrochemical sensor could realize sensitive determination of GSH without the addition of copper ions in the analytes. Under the optimum experimental conditions, the electrochemical behaviour of GSH was investigated through cyclic and square wave voltammetry, and a characteristic oxidation peak of the Cu(II)-GSH complex emerged ca. + 0.30 V vs. Ag/AgCl. The Ag/Cu-TCPP/GCE electrochemical sensor exhibited a wide linear dynamic range from 1.0 × 10–6 M to 1.0 × 10–4 M with a low detection limit of 6.6 × 10–8 M and presented excellent reproducibility, stability and anti-interference performance. More importantly, the constructed sensor was further expanded to quantify GSH in human serum samples with recoveries between 96.5–104.6%, providing an effective method for the trace of GSH in early disease diagnosis.