Novel plant flavonoid electrochemical sensor based on in-situ and controllable double-layered membranes modified electrode

Abstract

Identification and quantification of plant flavonoids are critical to pharmacokinetic study and pharmaceutical quality control due to their distinct pharmacological functions. Here we report on a novel plant flavonoid electrochemical sensor for sensitive and selective detection of dihydromyricetin (DMY) based on double- layered membranes consisting of gold nanoparticles (Au) anchored on reduced graphene oxide (rGO) and molecularly imprinted polymers (MIPs) modified glassy carbon electrode (GCE). Both rGO-Au and MIPs membranes were directly formed on GCE via in-situ electrochemical reduction and polymerization processes step by step. The compositions, morphologies, and electrochemical properties of membranes were investigated with X-ray powder diffractometry (XRD), Fourier transform infrared spectrum (FTIR), Field emission scanning electron microscopy (FESEM) combined with various electrochemical methods. The fabricated electrochemical sensor labeled as GCE│rGO-Au/MIPs exhibited excellent performance in determining of DMY under optimal experimental conditions. A wide linear detection range (LDR) ranges from 2.0×10 −8 to 1.0×10 −4 M together with a low limit of detection (LOD) of 1.2×10 −8 M ( S/N = 3) were achieved. Moreover, the electrochemical sensor was employed to determine DMY in real samples with satisfactory results.

Preparation and Application of Molecularly Imprinted Polymers for Flavonoids: Review and Perspective

“…In 1995, Piletsky et al first achieved sensing herbicides using a MIP-based sensor [ 94 ]. Recently, sensing flavonoids using MIP-based sensors has also been reported [ 96 , 97 , 98 , 99 , 100 , 101 , 102 , 103 , 104 ].…”

“…The LOD for the sensing method was 0.24 × 10 −9 mol/L. Recently, besides MIPs, other function materials (e.g., MoS 2 [ 57 ], carboxylated multiwalled carbon nanotubes [ 98 ] and reduced graphene oxide(rGO) [ 99 , 100 ]) were also modified on the GCE to increase the detection sensitivity. For example, using this modification method, an electrochemical sensor based on Fe 3 O 4 @MIP/rGO/GCE [ 99 ] and MoS 2 -MIPs/GCE [ 57 ] was developed for sensing luteolin.…”

“…As anticipated, the LOD was from 0.0400 × 10 −6 mol/L [ 57 ] down to 1.00 × 10 −12 mol/L [ 99 ]. Furthermore, to detect dihydromyricetin from Ampelopsis grossedentata, Hu et al [ 100 ] developed an electrochemical sensor with modified MIPs and rGO on the GCE and the LOD was 1.2 × 10 −8 mol/L. In addition to GCE-based electrodes, other electrodes can also be combined with MIPs for the detection of flavonoids.…”

Application of Molecularly Imprinted Polymers in Plant Natural Products: Current Progress and Future Perspectives

“…The sensor was successfully applied to the sensitive and selective detection of dihydromyricetin. [169] In another study, electrochemical sensors based on rGO and hybrid MIPs prepared with o-phenylenediamine (functional monomer) and puerarin (template) were also reported. The rGO/MIP sensor has good selectivity and high sensitivity for the detection of puerarin through double proton and double electron process recognition and electrooxidation of puerarin.…”

Rapid Voltammetric Screening Method for the Assessment of Bioflavonoid Content Using the Disposable Bare Pencil Graphite Electrode

“…The first electrochemical investigations of flavonoids were based on their reduction at mercury electrodes, but the presence of the hydroxyl groups in their structure enables also their electrooxidation. This was investigated since the 1980s, starting with the glassy carbon electrode (GCE) [16] and employing many other electrodes either bare [5,[17][18][19], electroactivated [20,21] or modified with different carbon based materials like carbon nanotubes [22][23][24] or graphene derivatives [25][26][27][28], nanomaterials [26,[28][29][30], polymeric films [27,28,31], etc. Unfortunately, most of the electrodes encounter problems due to the electroactive surface fouling during the electrochemical investigations, especially when these are based on the oxidation of phenolic compounds, which can generate phenoxy radicals able to polymerize and produce a film covering the electrode surface.…”