Multicomponent Layer-By-Layer Films of Chitosan/Phthalocyanine/AuNPs As Biosensing Platforms

Abstract

The search of new biosensing platforms is crucial to improve the performance of electrochemical biosensors. In this work, Layer by Layer films containing combinations of materials with different functionalities were used to design electrochemical biosensor platforms for phenols detection [1-3]. Catechol and hydroquinone biosensors were obtained by depositing tyrosinase (Tyr) or laccase (Lac) on the surface of LbL films formed by alternating layers of chitosan (CHI), a cationic species which acted as enzyme linker, and layers of two anionic electrocatalytic materials (sulfonated copper phthalocyanine, CuPcS and citrate capped gold nanoparticles, AuNPs). Films with different sequences [(CHI)-(AuNPs)]2, [(CHI)-(CuPc)]2, [(CHI)-(CuPc)-(CHI)-(AuNPs)]2 [(CHI)-(AuNPs)-(CHI)-(CuPc)]2, and [(CHI)-(AuNPs/CuPc)]2 (with CuPcS and AuNP mixed in the same layer) were characterized by UV–visible, FTIR spectroscopy and AFM.It was demonstrated that the resulting films provided an efficient immobilization surface for phenol oxidases. At the same time, the LbL platform improved the electron transfer between the enzymes and the electrode surface. Although all the biosensors obtained exhibited excellent performances, the sequence of the anionic and cationic layers strongly influenced the electron transfer process. The best results were obtained when CuPcS was present in the last layer which caused a 2-fold increase in the intensity over the response of the biosensor without the LbL platform. The [CHI-AuNP-CHI-CuPcS]2-Tyr bioelectrode showed an LOD of 8.7∙10-4 mM (S/N=3) for catechol and of 7.77∙10-4 mM (S/N=3) for hydroquinone. The LbL platform was not so efficient for laccase and the [CHI-AuNP-CHI-CuPcS]-Lac biosensor showed a LOD of 1.84∙10-2 mM (S/N=3) for catechol and of 1.27∙10-3 mM (S/N=3) for hydroquinone.