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An electrochemical method was developed for ultrasensitive and selective detection of dopamine in human serum using mesoporous silica thin film modified gold microelectrodes. Vertically aligned mesoporous silica thin films were deposited onto Au microelectrodes by electrochemically assisted self-assembly (EASA). The mesochannels have uniform pore sizes of 2.1 nm in diameter and a negatively charged wall surface. Cyclic voltammetry reveals effective charge permselectivity through the negatively charged mesoporous channels. By using differential pulse voltammetry, the mesoporous silica thin film modified Au microelectrode can be employed for the ultrasensitive detection of dopamine with a detection limit as low as 0.084 μM. In addition, thanks to the electrostatic and steric effects of the silica mesochannels, excellent anti-interference and anti-fouling properties of the electrochemical sensors are demonstrated. [ABSTRACT FROM AUTHOR]

Direct, rapid, and sensitive detection of drugs in complex biological samples is essential for drug abuse control and health risk assessment. In this work, an electrochemical sensor was fabricated based on equipment of vertically-ordered mesoporous silica film (VMSF) on an electrochemically pre-treated three-dimensional graphene electrode (p-3DG), which can achieve direct and sensitive determination of methylthiopyridazine (TR) in urine. Three-dimensional graphene (3DG) with a continuous and interpenetrating graphene network was used as the supporting electrode and simple electrochemical polarization was employed to pre-treat 3DG to improve surface hydrophilicity and electrocatalytic performance. VMSF was easily grown using an electrochemical assisted self-assembly method within 10 s and was stably bound to the p-3DG surface. The nanochannel array on the as-prepared VMSF/p-3DG sensor enriched positively charged TR, leading to significantly improved electrochemical signal. Combined with the high electric activity of p-3DG and the enrichment of nanochannels, VMSF/p-3DG realized sensitive determination of TR ranging from 50 nM to 10 μM with a low detection limit (DL, 30 nM). Owing to the anti-fouling and anti-interference performance of VMSF, the common electroactive molecules including ascorbic acid (AA) and uric acid (UA) did not interfere with the detection. In addition, the detection of TR in buffer and urine exhibited similar sensitivity. Accurate detection of TR in urine was realized. [ABSTRACT FROM AUTHOR]

Herein we report a simple and rapid approach to fabricate a vertically-ordered mesoporous silica–electrochemically reduced graphene oxide nanocomposite film (VMSF/ErGO) on an indium tin oxide (ITO) electrode surface by the electrochemically-assisted self-assembly (EASA) method, which is capable of greatly promoting the electroanalytical performance of rutin compared to the previously reported VMSF modified ITO electrode and, meanwhile, displaying excellent anti-fouling and anti-interference ability in pharmaceutical formulations and human serum. Due to the excellent electrocatalytic activity of ErGO and the synergistic enrichment effects from the π–π interaction of ErGO and the hydrogen bond effect from the VMSF, the present VMSF/ErGO/ITO sensor is able to detect rutin with a wide linear range, a high sensitivity and a low limit of detection. Moreover, the VMSF/ErGO/ITO electrode could retain the high sensing performance with high transmittance upon tailoring the concentration of the modified graphene oxide (GO), which provides a simple approach for modifying transparent ITO electrodes and could be potentially used for optoelectronic devices. [ABSTRACT FROM AUTHOR]

Developing ordered mesoporous silica-based membranes with highly sensitive detection performance is of great significance for direct electrochemical detection in biological fluids against surface biofouling. Herein, we describe a facile one-step approach for the integration of a vertically-ordered mesoporous silica-nanochannel film (VMSF) with electrochemically reduced graphene oxide (ErGO) by an electrochemically assisted self-assembly (EASA) method. Electrochemical reduction of GO and growth of the VMSF simultaneously occur in a simple one-step process, forming a VMSF/ErGO layer on the glassy carbon electrode (GCE). Arising from the oxygen-containing groups, hydrophobic π-conjugated structure, and the two-dimensional planar structure of ErGO, the VMSF could be stably grown on the GCE surface and it further acted as a protective layer to prevent the internal ErGO electroactive layer from falling off the electrode surface over prolonged use. In comparison with a bare GCE, the present VMSF/ErGO/GCE sensor exhibits an excellent response to doxorubicin with a wide linear range (1 nM−20 μM), a high sensitivity (7.815 μA μM−1) and a low limit of detection (0.77 nM), due to the cooperative signal amplification originating from the electrocatalytic activity and π–π interaction of ErGO and electrostatic preconcentration effect of the VMSF. Furthermore, considering the outstanding anti-fouling and anti-interference ability of the VMSF, direct determination and long-term monitoring of doxorubicin in human whole blood was successfully achieved by the sensor. [ABSTRACT FROM AUTHOR]

Three-dimensional graphene (3DG) with macroporous structure has great potential in the field of electroanalysis owing to a large active area, excellent electron mobility and good mass transfer. However, simple and low-cost preparation of 3DG electrodes with high electrocatalytic ability is still a challenge. Here, a fast and convenient electrochemical polarization method is established to pretreat free-standing 3DG (p-3DG) to offer high electrocatalytic ability. 3DG with monolithic and macroporous structure prepared by chemical vapor deposition (CVD) is applied as the starting electrode. Electrochemical polarization is performed using electrochemical oxidation (anodization) at high potential (+6 V) followed with electrochemical reduction (cathodization) at low potential (−1 V), leading to exposure of edge of graphene and introduction of oxygen-containing groups. The as-prepared p-3DG displays increased hydrophilicity and improved electrocatalytic ability. As a proof of concept, p-3DG was used to selective electrochemical detection of two isomers of benzenediol, hydroquinone (p-BD) and catechol (o-BD). In comparison with initial 3DG, p-3DG exhibits increased reversibility of redox reaction, improved peak current and good potential resolution with high potential separation between p-BD and o-BD. Individual or selective determination of p-BD or o-BD in single substance solution or binary mixed solution is realized. Real analysis of pond water is also achieved. [ABSTRACT FROM AUTHOR]