Sensitive detection of noradrenaline in human whole blood based on Au nanoparticles embedded vertically-ordered silica nanochannels modified pre-activated glassy carbon electrodes.

Sensitive determination of noradrenaline (NE), the pain-related neurotransmitters and hormone, in complex whole blood is of great significance. In this work, an electrochemical sensor was simply constructed on the pre-activated glassy carbon electrode (p-GCE) modified with vertically-ordered silica nanochannels thin film bearing amine groups (NH2-VMSF) and in-situ deposited Au nanoparticles (AuNPs). The simple and green electrochemical polarization was employed to pre-activate GCE to realize the stable binding of NH2-VMSF on the surface of electrode without the use of any adhesive layer. NH2-VMSF was conveniently and rapidly grown on p-GCE by electrochemically assisted self-assembly (EASA). With amine group as the anchor sites, AuNPs were in-situ electrochemically deposited on the nanochannels to improve the electrochemical signals of NE. Owing to signal amplification from gold nanoparticles, the fabricated AuNPs@NH2-VMSF/p-GCE sensor can achieve electrochemical detection of NE ranged from 50 nM to 2 µM and from 2 µM to 50 µM with a low limit of detection (LOD) of 10 nM. The constructed sensor exhibited high selectivity and can be easily regenerated and reused. Owing to the anti-fouling ability of nanochannel array, direct electroanalysis of NE in human whole blood was also realized.

Highly Sensitive Electrochemical Detection of Paraquat in Environmental Water Samples Using a Vertically Ordered Mesoporous Silica Film and a Nanocarbon Composite.

Herein, we demonstrate a sensitive and rapid electrochemical method for the detection of paraquat (PQ) using a glassy carbon electrode (GCE) modified with vertically ordered mesoporous silica films (VMSF) and a nanocarbon composite. The three-dimensional graphene-carbon nanotube (3DG-CNT) nanocarbon composite has a 3D network structure, a large electroactive area and oxygen-containing groups, promoting electron transfer between PQ and the underlying electrode and providing a suitable microenvironment for the stable growth of VMSF. This VMSF/3DG-CNT nanocomposite film could be prepared on the GCE's surface by a two-step electrochemical method with good controllability and convenience. Owing to the synergistic effect of the electrocatalytic ability of 3DG-CNT and the electrostatically enriched capacity of VMSF, the proposed VMSF/3DG-CNT/GCE has superior analytical sensitivity compared with the bare GCE. Furthermore, VMSF has excellent anti-fouling ability that makes the fabricated sensor exhibit satisfactory performance for direct analysis of PQ in environmental water samples.

Nanochannel array modified three-dimensional graphene electrode for sensitive electrochemical detection of 2,4,6-trichlorophenol and prochloraz.

Convenient, and sensitive detection of pesticides and their metabolites in environmental or food samples is critical for assessing potential environmental and health risks. Here, a three-dimensional (3D) electrochemical sensing platform is proposed based on the integration of nanochannel array on pre-activated 3D graphene (p-3DG) electrodes with no need of additional adhesive layers, which enables sensitive detection of prochloraz and 2,4,6-trichlorophenol (TCP) in environmental and food samples. Through two-step electrochemical polarization, organic phase anodic oxidation, and aqueous phase cathodic reduction, p-3DG electrodes with high active area and excellent electrocatalytic performance were obtained. Vertically-ordered mesoporous silica-nanochannel film (VMSF) can be rapidly grown on the surface of p-3DG by an electrochemical-assisted self-assembly (EASA) method. Taking advantage of the high electrocatalytic activity of p-3DG and the ability of nanochannels to enrich TCP through hydrogen bonding, the VMSF/p-3DG sensor can sensitively detect TCP in the range of 10 nM to 0.1 µM and 0.1-15 µM with a low limit of detection (LOD) of 2.4 nM. Compared with p-3DG and VMSF-modified 2D electrodes, the fabricated sensor has a wide detection linear range and low LOD. The coexistence of model interferents such as protein, surfactant, and humic acid did not affect the electrochemical response of TCP, confirming the high anti-fouling ability of the VMSF/p-3DG sensor. In addition, prochloraz in vegetable and fruit samples was indirectly determined because TCP was the metabolite of prochloraz.

Sensitive electrochemical detection of p-nitrophenol by pre-activated glassy carbon electrode integrated with silica nanochannel array film.

Convenient, rapid and sensitive detection of p-nitrophenol (p-NP), one of the priority environmental pollutants, in environmental samples is of great significance. Electrochemical sensor with simple fabrication process, high sensitivity and selectivity, good antifouling, and regeneration performance is highly desirable. Herein, an electrochemical sensing platform is demonstrated based on the integration of vertically-ordered mesoporous silica-nanochannel film (VMSF) on electrochemical pre-activated glassy carbon electrode (p-GCE), which is able to realize ultrasensitive detection of p-NP in environmental samples. Electrochemical pre-activation of GCE is achieved through a simple and green electrochemical polarization process including anodic oxidation at high voltage and the following cathodic reduction at low voltage. The p-GCE possesses enhanced active area and introduced active sites, and enables stable binding of VMSF. VMSF is easily grown on p-GCE through the electrochemically assisted self-assembly (EASA) method within 10 s. Owing to the hydrogen bonding between silanol groups and p-NP, VMSF nanochannels display strong enrichment effect for the detection of p-NP. The developed VMSF/p-GCE sensor can achieve sensitive detection of p-NP ranging from 10 nM to 1 µM and from 1 to 30 µM with a limit of detection (LOD) of 9.4 nM. Considering the antifouling ability of VMSF, detection of p-NP in pond water is achieved.

Silica Nanochannel Array Film Supported by ß-Cyclodextrin-Functionalized Graphene Modified Gold Film Electrode for Sensitive and Direct Electroanalysis of Acetaminophen.

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.