Integration of vertically-ordered mesoporous silica-nanochannel film with electro-activated glassy carbon electrode for improved electroanalysis in complex samples

Abstract

Vertically-ordered mesoporous silica-nanochannel films (VMSF) with highly ordered nanochannels, uniform and adjustable pore size, ultra-thin thickness, and high porosity, have attracted considerable attention in analysis, molecular separation, catalysis, and nanomaterial synthesis. However, their widespread applications in practical electrochemical sensing are largely limited by the poor adhesion to common electrode materials, especially the lack of highly active substrate electrode to equip mechanically stable VMSF. Herein, we report a facile strategy to fabricate VMSF on widely used sensing electrodes without the use of any chemical adhesive for developing superior VMSF based electrochemical sensors. We demonstrate that simple electrochemical polarization (anodic polarization and subsequent cathodic reduction) to activate glassy carbon electrode (GCE) can generate a suitable surface environment allowing direct growth of stable VMSF on such pre-activated GCE (p-GCE) via electrochemically assisted self-assembly (EASA). Compared to traditional VMSF electrodes with ITO or organosilane grafted GCE as substrate, the developed VMSF/p-GCE exhibits much higher electrochemical response to four redox biomarkers (norepinephrine, dopamine, tryptophan, and uric acid). In-depth insights on mechanisms of the high electrochemical activity and incorporation stability of VMSF/p-GCE are made. We further demonstrate the VMSF/p-GCE can be employed to detect dopamine in real serum samples with exceptional sensitivity, low detection potential, as well as superior anti-interference and anti-fouling performance. In addition, high selectivity is realized as the common co-existing interference substances (ascorbic acid-AA and uric acid-UA) do not interfere with the detection.

Keywords: Biomarkers; Electrochemical pretreatment; Electrochemical sensors; Glassy carbon electrodes; Vertically-ordered mesoporous silica-nanochannel film.