Ketjen black/ferrocene dual-doped MOFs and aptamer-coupling gold nanoparticles used as a novel ratiometric electrochemical aptasensor for vanillin detection

Highlights: • A novel ratiometric electrochemical aptasensor of vanillin was developed. . • The aptasensor was fabricated by using aptamer-AuNPs/Fc-KB/ZIF-8@GCE sensing platform. • The aptasensor enabled efficient detection of vanillin in real samples with high detection recoveries. -- Abstract: In this work, a facile ratiometric electrochemical aptasensor was developed towards sensitive and selective detection of vanillin, based on Ketjen black/ferrocene dual-doped zeolite-like MOFs (Fc-KB/ZIF-8) and electrodeposited gold nanoparticles (AuNPs) coupling with DNA aptamer. Fc-KB/ZIF-8 composites were prepared via one-pot solvothermal reaction and drop-coated on glassy carbon electrode (GCE) surface to form Fc-KB/ZIF-8@GCE. AuNPs were in-situ electro-deposited on the modified GCE. 5′-SH terminated aptamer of vanillin was combined with AuNPs via Au-S coupling to form aptamer-AuNPs/Fc-KB/ZIF-8@GCE as a new sensing platform. Under optimal conditions, electrochemical (square wave voltammetry) curves of this sensing platform were measured in electrolyte solutions containing vanillin. With increase of vanillin concentration (C_van), vanillin had an increased peak current intensity (I_van, as response signal). Fc doped into ZIF-8 had slight changes in its peak current intensity (I_Fc, as reference signal). There is a well plotting linear relationship between I_van/I_Fc and the logarithm of C_van ranging from 10 nM to 0.2 mM, with a low limit of detection of 3 nM. The aptamer-AuNPs/Fc-KB/ZIF-8@GCE was applied as a ratiometric electrochemical aptasensor of vanillin. This aptasensor had sensitive and selective electrochemical signal responses on vanillin, over potential interferents. This aptasensor enabled vanillin detection in real food samples, showing high detection performance. Experimental results testified that this aptasensor had high reliability and practicability for vanillin determination in real samples.