Portable wireless electrochemical sensing of breviscapine using core-shell ZIFs-derived Co nanoparticles embedded in N-doped carbon nanotube polyhedra-modified electrode.

A core-shell ZIF-67@ZIF-8-derived Co nanoparticles embedded in N-doped carbon nanotube polyhedra (Co/C-NCNP) hybrid nanostructure was prepared by a pyrolysis method. The synthesized Co/C-NCNP was modified on the screen-printed carbon electrode and used for the portable wireless sensitive determination of breviscapine (BVC) by differential pulse voltammetry. The Co/C-NCNP had a large surface area and excellent catalytic activity with increasing Co sites to combine with BVC for selective determination, which led to the improvement of the sensitivity of the electrochemical sensor. Under optimized conditions, the constructed sensor had linear ranges from 0.15 to 20.0 µmol/L and 20.0 to 100.0 µmol/L with the limit of detection of 0.014 µmol/L (3S0/S). The sensor was successfully applied to BVC tablet sample analysis with satisfactory results. This work provided the potential applications of zeolitic imidazolate framework-derived nanomaterials in the fabrication of electrochemical sensors for the sensitive detection of drug samples.

A Portable Electrochemical Dopamine Detector Using a Fish Scale-Derived Graphitized Carbon-Modified Screen-Printed Carbon Electrode.

In this paper, a highly conductive alkali-activated graphitized carbon (a-GC) was prepared using tilapia fish scales as precursors through enzymolysis, activation and pyrolytic carbonization methods. The prepared a-GC was modified on the surface of a screen-printed carbon electrode to construct a flexible portable electrochemical sensing platform, which was applied to the differential pulse voltametric detection of dopamine (DA) using a U-disk electrochemical workstation combined with a smart phone and Bluetooth. The prepared a-GC possesses good electrical conductivity, a large specific surface area and abundant active sites, which are beneficial for the electrooxidation of DA molecules and result in excellent sensitivity and high selectivity for DA analysis. Under the optimal conditions, the oxidation peak current of DA increased gradually, with its concentrations in the range from 1.0 µmol/L to 1000.0 µmol/L, with the detection limit as low as 0.25 µmol/L (3S/N). The proposed sensor was further applied to the determination of DA in human sweat samples, with satisfactory results, which provided an opportunity for developing noninvasive early diagnosis and nursing equipment.

Portable Wireless Intelligent Electrochemical Sensor for the Ultrasensitive Detection of Rutin Using Functionalized Black Phosphorene Nanocomposite.

To build a portable and sensitive method for monitoring the concentration of the flavonoid rutin, a new electrochemical sensing procedure was established. By using nitrogen-doped carbonized polymer dots (N-CPDs) anchoring few-layer black phosphorene (N-CPDs@FLBP) 0D-2D heterostructure and gold nanoparticles (AuNPs) as the modifiers, a carbon ionic liquid electrode and a screen-printed electrode (SPE) were used as the substrate electrodes to construct a conventional electrochemical sensor and a portable wireless intelligent electrochemical sensor, respectively. The electrochemical behavior of rutin on the fabricated electrochemical sensors was explored in detail, with the analytical performances investigated. Due to the electroactive groups of rutin, and the specific π-π stacking and cation-π interaction between the nanocomposite with rutin, the electrochemical responses of rutin were greatly enhanced on the AuNPs/N-CPDs@FLBP-modified electrodes. Under the optimal conditions, ultra-sensitive detection of rutin could be realized on AuNPs/N-CPDs@FLBP/SPE with the detection range of 1.0 nmol L-1 to 220.0 µmol L-1 and the detection limit of 0.33 nmol L-1 (S/N = 3). Finally, two kinds of sensors were applied to test the real samples with satisfactory results.

Graphene oxide with in-situ grown Prussian Blue as an electrochemical probe for microRNA-122.

An electrochemical biosensor for microRNA was constructed on the basis of direct growth of electroactive Prussian Blue (PB) on graphene oxide (GO). A mercapto-modified probe DNA that is complementary to the hepatocellular carcinoma biomarker microRNA-122 was firstly anchored on a gold electrode (AuE). Then, GO (with its large surface and multiple active sites) was adsorbed on probe DNA through π-interaction. Subsequently, the PB nanoparticles were directly grown on GO via alternative dipping the electrode in solutions of FeCl3 and hexacyanoferrate(III). Upon incubation of the resulting electrode with a solution of microRNA-122, the probe DNA on the electrode interacts with microRNA-122 to form a rigid duplex. This results in the release of electroactive PB/GO from the sensing interface and a decrease in current, typically measured at 0.18 V (vs. Ag/AgCl (3 M KCl)). The sensor covers the 10 fM to 10 nM microRNA-122 concentration range and has a 1.5 fM detection limit. The method was successfully applied to the determination of microRNA-122 in real biological samples. Graphical abstract Graphene oxide with in-situ grown Prussian Blue is applied as an electrochemical probe for the analysis of microRNA-122.

Preparation of electrochemical horseradish peroxidase biosensor with black phosphorene-zinc oxide nanocomposite and their applications.

In this work, a novel and sensitive electrochemical biosensor was constructed based on a black phosphorene (BP) and nanosized zinc oxide (ZnO@BP) nanocomposite as a modifier, which was used for the immobilization of horseradish peroxidase (HRP) on a carbon ionic liquid electrode (CILE). The ZnO@BP nanocomposite was synthesized by a simple in situ hydrothermal method with stripped black phosphorus nanoplates and ZnO. The ZnO@BP and HRP-modified electrode was developed by a casting method. ZnO@BP with highly conductivity, large surface area and good biocompatibility could maintain the bioactivity of HRP and accelerate the electron transfer rate. Cyclic voltammetry was used to study the direct electrochemistry of HRP on the Nafion/HRP/ZnO@BP/CILE with the appearance of a pair of distinct redox peaks. The constructed electrochemical HRP biosensor exhibited excellent electrocatalytic effects on the reduction of trichloroacetic acid and sodium nitrite. Real samples were detected with satisfactory results, which demonstrated the potential applications of this electrochemical HRP biosensor.

Synthesis of sp-hybridized nitrogen doped ultrathin graphdiyne and application to the electrochemical detection for 6,7-dihydroxycoumarin.

As a new type of carbon nanomaterial, graphdiyne (GDY) has unique sp hybridized carbon atom, which makes it possible to develop new nitrogen-doped configurations. In this paper, sp-hybridized nitrogen atom doped ultrathin graphdiyne (NUGDY) was prepared based on graphdiyne oxide and melamine by carbonization at high temperature. NUGDY not only preserves the typical folded and wrinkled two-dimensional morphology of GDY, but also presents a three-dimensional porous network structure, which provides sufficient interface and capacity for the loading of target analyte. Meanwhile, N doping increases the GDY defects with more active sites and higher conductivity. Then, NUGDY was modified on the surface of carbon ionic liquid electrode and the modified electrode was applied to 6,7-dihydroxycoumarin (6,7-DHC) analysis. Cyclic voltammetry, electrochemical impedance spectroscopy and chronocoulometry results show that NUGDY has good promotive effect to the electrode performances. Differential pulse voltammetric experiments show that this electrochemical sensor has a low detection limit as 2.3 nM (3S0/S) for 6,7-DHC with high sensitivity. In addition, the modified electrode has the characteristics of excellent anti-interference ability and stability, and been successfully used in the real samples determination, which provides a promising method for the sensitive detection of drug molecules.