Qingxiang Wang

A sensitive and reliable dopamine biosensor was developed based on the Au@carbon dots-chitosan composite film

A novel composite film of Au@carbon dots (Au@CDs)-chitosan (CS) modified glassy carbon electrode (Au@CDs-CS/GCE) was prepared in a simple manner and applied in the sensitive and reliable determination of dopamine (DA). The CDs had carboxyl groups with negative charge, which not only gave it have good stability but also enabled interaction with amine functional groups in DA through electrostatic interaction to multiply recognize DA with high specificity, and the Au nanoparticle could make the surface of the electrode more conductive. Compared with the bare GCE, CS/GCE, and CDs-CS/GCE electrodes, the Au@CDs-CS/GCE had higher catalytic activity toward the oxidation of DA. Furthermore, Au@CDs-CS/GCE exhibited good ability to suppress the background current from large excess ascorbic acid (AA) and uric acid (UA). Under the optimal conditions, selective detection of DA in a linear concentration range of 0.01-100.0 μM was obtained with the limit of 0.001 μM (3S/N). At the same time, the Au@CDs-CS/GCE was also applied to the detection of DA content in DAs injection with satisfactory results, and the biosensor could keep its activity for at least 2 weeks.

Highly Dispersible and Stable Copper Terephthalate Metal–Organic Framework–Graphene Oxide Nanocomposite for an Electrochemical Sensing Application

A highly dispersible and stable nanocomposite of Cu(tpa)-GO (Cu(tpa) = copper terephthalate metal-organic framework, GO = graphene oxide) was prepared through a simple ultrasonication method. The morphology and structure of the obtained composite were characterized via scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis, Fourier-transform infrared (FT-IR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). On the basis of the characterization results, the binding mechanism of the Cu(tpa) and GO was speculated to be the cooperative interaction of π-π stacking, hydrogen bonding, and Cu-O coordination. The electrochemical sensing property of Cu(tpa)-GO composite was investigated through casting the composite on a glassy carbon electrode (GCE), followed by an electro-reduction treatment to transfer the GO in the composite to the highly conductive reduced form (electrochemically reduced graphene, EGR). The results demonstrated that the electrochemical signals and peak profiles of the two drugs of acetaminophen (ACOP) and dopamine (DA) were significantly improved by the modified material, owing to the synergistic effect from high conductivity of EGR and unique electron mediating action of Cu(tpa). Under the optimum conditions, the oxidation peak currents of ACOP and DA were linearly correlated to their concentrations in the ranges of 1-100 and 1-50 μM, respectively. The detection limits for ACOP and DA were estimated to be as low as 0.36 and 0.21 μM, respectively.

Electrocatalytical oxidation and sensitive determination of acetaminophen on glassy carbon electrode modified with graphene–chitosan composite

The electrochemical behaviors of acetaminophen (ACOP) on a graphene-chitosan (GR-CS) nanocomposite modified glassy carbon electrode (GCE) were investigated by cyclic voltammetry (CV), chronocoulometry (CC) and differential pulse voltammetry (DPV). Electrochemical characterization showed that the GR-CS nanocomposite had excellent electrocatalytic activity and surface area effect. As compared with bare GCE, the redox signal of ACOP on GR-CS/GCE was greatly enhanced. The values of electron transfer rate constant (ks), diffusion coefficient (D) and the surface adsorption amount (Γ(*)) of ACOP on GR-CS/GCE were determined to be 0.25s(-1), 3.61×10(-5) cm(2) s(-1) and 1.09×10(-9) mol cm(-2), respectively. Additionally, a 2e(-)/2H(+) electrochemical reaction mechanism of ACOP was deduced based on the acidity experiment. Under the optimized conditions, the ACOP could be quantified in the range from 1.0×10(-6) to 1.0×10(-4) M with a low detection limit of 3.0×10(-7) M based on 3S/N. The interference and recovery experiments further showed that the proposed method is acceptable for the determination of ACOP in real pharmaceutical preparations.

An electrochemical sensor for gallic acid based on Fe₂O₃/electro-reduced graphene oxide composite: Estimation for the antioxidant capacity index of wines.

A highly sensitive electrochemical sensor for gallic acid (GA), an important polyphenolic compound, was fabricated using the hybrid material of chitosan (CS), fishbone-shaped Fe2O3 (fFe2O3), and electrochemically reduced graphene oxide (ERGO) as the sensing matrix. The electrochemical characterization experiments showed that the CS-fFe2O3-ERGO modified glassy carbon electrode (CS-fFe2O3-ERGO/GCE) had large surface area, excellent electronic conductivity and high stability. The GA presented a superior electrochemical response on CS-fFe2O3-ERGO/GCE in comparison with the single-component modified electrode. The electrochemical mechanism and optimal test conditions of GA on the electrode surface were carefully investigated. Under the optimal conditions, the oxidation peak currents in differential pulse voltammetry (DPV) experiments exhibited a good linear relationship with the logarithmic values of GA concentration over the range from 1.0×10(-6)M to 1.0×10(-4)M. Based on signal-to-noise (S/N) characteristic of 3, the detection limit was estimated to be 1.5×10(-7)M. The proposed sensor has also been applied for estimating the antioxidant capacity index of real samples of red and white wines.

Metal Bioavailability and Risk Assessment from Edible Brown Alga Laminaria japonica, Using Biomimetic Digestion and Absorption System and Determination by ICP-MS

A new biomimetic digestion and absorption system, including in vitro bionic digestion and biomimetic membrane extraction, was used for the first time for the pretreatment of edible Laminaria japonica . After bionic digestion, 11 species of trace metals (V, Cr, Mn, Fe, Ni, Cu, Zn, Se, As, Cd, and Pb) in the resulting chyme were transformed into their final coordinated complexes and then absorbed by the biomembrane. Similar to the biomembrane between gastrointestinal tract and blood vessels, monolayer liposome was used for the first time as a biomembrane model. Affinity-monolayer liposome metals (AMLMs) were separated, determined by ICP-MS, and then used for the metal bioavailability assessment as the bioassimilated part. The action of gastrointestinal acidity and components (including digestive enzymes) was assessed on the basis of the concentration of AMLMs; the safe dosage and tolerable upper intake level of L. japonica for adults were proposed as 33.3 and 230.8 g/day, respectively.

Imidazoline derivative templated synthesis of broccoli-like Bi2S3 and its electrocatalysis towards the direct electrochemistry of hemoglobin

A broccoli-like bismuth sulfide (bBi2S3) was synthesized via a solvothermal method using a self-made imidazoline derivative of 2-undecyl-1-dithioureido-ethyl-imidazoline as the soft template. The morphology and chemical constitution of the product were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). Electrochemical characterization experiments show that the bBi2S3 has the higher specific surface area and standard heterogeneous electron transfer rate constant than the rod-like Bi2S3 (rBi2S3). Hemoglobin (Hb) was then chosen as a protein model to investigate the electrocatalytic property of the synthesized bBi2S3. The results show that Hb entrapped in the composite film of chitosan and bBi2S3 displays an excellent direct electrochemistry, and retains its biocatalytic activity toward the electro-reduction of hydrogen peroxide. The current response in the amperometry shows a linear response to H2O2 concentrations in the range from 0.4 to 4.8µM with high sensitivity (444µAmM(-1)) and low detection limit (0.096µM). The Michaelis-Menten constant (KM(app)) of the fabricated bioelectrode for H2O2 was determined as low as 1µM. These results demonstrate that the synthesized bBi2S3 offers a new path for the immobilization of redox-active protein and the construction of the third-generation biosensors.

Application of graphene–pyrenebutyric acid nanocomposite as probe oligonucleotide immobilization platform in a DNA biosensor

A stable and uniform organic-inorganic nanocomposite that consists of graphene (GR) and pyrenebutyric acid (PBA) was obtained by ultrasonication, which was characterized by scanning electron microscopy (SEM) and UV-vis absorption spectra. The dispersion was dropped onto a gold electrode surface to obtain GR-PBA modified electrode (GR-PBA/Au). Electrochemical behaviors of the modified electrode were characterized by cyclic voltammetry and electrochemical impedance spectroscopy using [Fe(CN)6](3-/4-) as the electroactive probe. A novel DNA biosensor was constructed based on the covalent coupling of amino modified oligonucleotides with the carboxylic group on PBA. By using methylene blue (MB) as a redox-active hybridization indicator, the biosensor was applied to electrochemically detect the complementary sequence, and the results suggested that the peak currents of MB showed a good linear relationship with the logarithm values of target DNA concentrations in the range from 1.0×10(-15) to 5.0×10(-12) M with a detection limit of 3.8×10(-16) M. The selectivity experiment also showed that the biosensor can well distinguish the target DNA from the non-complementary sequences.

Label-free electrochemical lead (II) aptasensor using thionine as the signaling molecule and graphene as signal-enhancing platform

A label-free and highly sensitive electrochemical aptasensor for Pb(2+) was constructed using thionine (TH) as the signaling molecule and graphene (GR) as the signal-enhancing platform. The electrochemical sensing interface was fabricated by stepwise assembly of GR and TH on the lead (II) specific aptamer (LSA) modified electrode. Upon interaction with Pb(2+), the aptamer probe on the sensor underwent conformational switch from a single-stranded DNA form to the G-quadruplex structure, causing the GR with assembled TH released from the electrode surface into solution. As a result, the electrochemical signal of TH on the aptasensor was substantially reduced. Under the optimal experimental conditions, the attenuation of peak currents presented a good linear relationship with the logarithm of Pb(2+) concentrations over the range from 1.6×10(-13) to 1.6×10(-10)M. The detection limit was estimated to be 3.2×10(-14)M. The aptasensor also exhibited good regenerability, excellent selectivity, and acceptable reproducibility, indicating promising application in environment monitoring of lead.

An ultrasensitive DNA biosensor based on covalent immobilization of probe DNA on fern leaf-like α-Fe2O3 and chitosan Hybrid film using terephthalaldehyde as arm-linker

In this work, a novel electrochemical DNA biosensor has been developed based on the hybrid film of fern leaf-like α-Fe2O3 microparticles and chitosan (CS). The fern leaf-like α-Fe2O3 microparticles were synthesized via a facile template-free hydrothermal method, and their morphologies were characterized by X-ray diffraction, energy dispersive spectrometry, scanning electron microscope, and transmission electron microscope. Electrochemical characterization assays revealed that the hybrid film modified electrode had remarkable synergistic effects of the large accessible surface area and high electrical conductivity of semiconductive Fe2O3, and the good film stability of CS. Based on the rich amino groups on CS, the CS-Fe2O3 hybrid film was employed as a functional matrix for probe DNA immobilization using terephthalaldehyde (TPA) as a bifunctional arm-linker. The hybridization capacity of the developed biosensor was evaluated with electrochemical impedance spectroscopy (EIS) using [Fe(CN)6](3-/4-) as the indicating probe. A wide dynamic detection range from 1.0 × 10(-14) to 1.0 × 10(-10)M with ultralow detection limit of 5.6 × 10(-15)M was achieved for the target DNA. The hybridization selectivity experiments further revealed that the biosensor could discriminate fully complementary sequences from one-base mismatched, three-base mismatched, and non-complementary sequences. Moreover, the biosensor showed the advantage of good regeneration ability and reproducibility.

Hydroxyapatite/chemically reduced graphene oxide composite: Environment-friendly synthesis and high-performance electrochemical sensing for hydrazine

It is unexpectedly found that, the in-situ growth of hydroxyapatite (HAP) on graphene oxide (GO) under a moderate temperature (85°C) can effectively trigger the reduction of GO, which needs neither extra reducing agents nor high-temperature thermal treatment. The transmission electron microscope (TEM) experiment demonstrates that the rod-like HAP particles are well attached on the surface of reduced GO (rGO) to form the composite. Electrochemical sensing assays show that the synthesized HAP-rGO nanocomposite presents excellent electrocatalytic capacity for the oxidation of a toxic chemical of hydrazine. When the HAP-rGO modified electrode was utilized as an electrochemical sensor for hydrazine detection, outstanding performances in the indexes of low fabrication cost, short response time (~2s), wide linear range, low detection limit (0.43μM), and good selectivity were achieved. The developed sensor also shows satisfactory results for the detection of hydrazine in real industrial wastewater sample were achieved.