Synthesis of peripheral thiol functionalized (NiII) phthalocyanine and its attachment on Au electrode for electrochemical determination of L-DOPA

Abstract

This paper presents the synthesis, characterization, and electrocatalytic behavior of peripheral thiol-functionalized nickel(II) phthalocyanine (4β-NiIITTPc). The complex was synthesized and characterized using MALDI-TOF mass spectra, UV–visible, and FT-IR spectroscopies. Upon self-assembly on the Au surface from dimethylformamide solution, 4β-NiIITTPc forms via the formation of an Au-S bond. The attachment onto the Au surface was verified through Raman spectroscopy and cyclic voltammetry, with characteristic bands at 2572 and 250 cm−1 corresponding to -SH and Au-S stretching vibrations, respectively. Notably, the -SH stretching indicates that not all four -SH groups of 4β-NiIITTPc are involved in chemisorption. The resulting self-assembled film on the Au electrode exhibits well-defined oxidation peaks at +0.34 V and +0.56 V, corresponding to NiIII/NiII and NiIIPc−1/NiIIPc−2, respectively. The surface coverage was estimated from the charge associated with NiII/NiIII oxidation, yielding 1.01 × 10−10 mol cm−2. Finally, the electrocatalytic activity of the self-assembled monolayer (SAM) of 4β-NiIITTPc on Au electrodes was assessed by studying the oxidation of 3,4-dihydroxy-1-phenylalanine (L-dopa) as a probe. The SAM-modified electrode not only shifts the oxidation potential of L-dopa to a less positive potential but also enhances the oxidation current and mitigates electrode surface fouling compared to the bare Au electrode.

Keywords

• Thiol functionalized phthalocyanine
• Self-assembled monolayer
• Raman spectroscopy
• 3,4-dihydroxy-1-phenylalanine
• Electrocatalyst