A vertically-ordered silica-nanochannel film on graphene was prepared by a one-step electrodeposition method for antifouling detection in human whole blood.

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Convenient and sensitive detection of active analytes in complex matrix is crucial in biological, medical, and environmental analysis. Silica nanochannel array film (SNF) equipped electrochemical sensors have shown excellent anti-fouling performance in direct analysis of complex samples. In this work, we demonstrated an electrochemical sensor with anti-fouling performance for highly sensitive detection of acetaminophen (APAP) based on SNF supported by ß-cyclodextrin-graphene (CDG) nanocomposite modified Au film electrode (AuF). Because of their rich surface hydroxyls and 2D lamellar structure, CDG on AuF can serve as the nanoadhesive for compact binding SNF, which can be grown by electrochemical assisted self-assembly method in a few seconds. Attributable to the electrocatalytic property of graphene and the synergistic enrichment from both CD and SNF nanochannels towards analyte, the SNF/CDG/AuF sensor demonstrates sensitive detection of acetaminophen ranged from 0.2 to 50 μM with an ultralow limit-of-detection of 14 nM. Taking advantage of the anti-fouling ability of SNF, the sensor is able to realize accurate and convenient analysis of APAP in commercially available paracetamol tablets.

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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.

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.

Vertically ordered mesoporous silica film (VMSF) with uniform mesoporous channels perpendicular to electrode substrate has a wide range of applications in direct electroanalysis of complex samples. However, the detection of nucleic acid bases is difficult to realize at the commonly used VMSF-modified indium tin oxide (VMSF/ITO) electrode due to the high overpotentials of underlying ITO for many small organic molecules. In this work, we demonstrated an electrochemical method for the sensitive detection of guanine (G) by integration of VMSF/ITO and tris(2,2′-bipyridine) ruthenium (II) [Ru(bpy)32+] redox mediator. Ru(bpy)32+ electrostatically accumulated by VMSF is able to act as an electron shuttle between G and underlying ITO surface, showing electrocatalytic oxidation of G and enabling the quantitative determination of G with a limit of detection (LOD) of 0.058 μM and a limit of quantitation (LOQ) of 0.2 μM. Electrochemical detection performance for G could be regulated by changing the pH of the supporting electrolyte and the content of Ru(bpy)32+, achieving a wide dynamic linear range from 0.2 to 10 μM (R2 = 0.999), 2 to 100 μM (R2 = 0.999), and 10 to 500 μM (R2 = 0.998). Furthermore, owing to the good anti-fouling and anti-interference ability of VMSF, this simply sensing strategy can be applied to the direct and rapid detection of G in beer samples, and the detection of ganciclovir (G analog) content in ganciclovir eye drops.

Herein we report a simple and rapid approach to fabricate vertically-ordered mesoporous silica-electrochemically reduced graphene oxide nanocomposite film (VMSF/ErGO) on the Indium tin oxide (ITO) electrode surface by electrochemically-assisted self-assembly...