Zhuobin Yuan

Electrochemical determination of dopamine using a poly(2-picolinic acid) modified glassy carbon electrode.

A poly(2-picolinic acid) chemically modified electrode (CME) for the determination of dopamine (DA) by cyclic voltammetry is described. Compared with a bare glassy carbon electrode, the CME exhibits a 200 mV shift of the oxidation potential of DA in the cathodic direction and a marked enhancement of the current response. In pH 7.0 buffer solution, a linear calibration graph is obtained over the range from 2.5 x 10(-7) to 1.0 x 10(-5) mol dm-3 with a correlation coefficient of 0.998. The detection limit is 3.0 x 10(-8) mol dm-3. The modified electrode eliminated efficiently the interference from ascorbic acid (AA) when present in a 150-fold concentration ratio. It also showed excellent stability and reproducibility.

The comparison of different gold nanoparticles/graphene nanosheets hybrid nanocomposites in electrochemical performance and the construction of a sensitive uric acid electrochemical sensor with novel hybrid nanocomposites.

In this paper, water soluble poly(diallyldimethylammonium chloride)-graphene nanosheets (PDDA-GNs) were synthesized and characterized by UV-visible absorption spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). On the basis of PDDA-GNs, three different types of gold nanoparticles/graphene nanosheets (AuNPs/GNs) hybrid nanocomposites were obtained by one-pot synthesis, in situ reduction and adsorption methods, respectively. These nanocomposites were used as electrode materials for electrochemical determination of uric acid (UA). The results indicated adsorption to be the best method to synthesize hybrid nanocomposites from the electrochemical point of view. Given the fact positively charged PDDA-AuNPs could interact with negatively charged UA molecules, we then synthesized PDDA-protected gold nanoparticles/graphene nanosheets (PDDA-AuNPs/GNs) hybrid nanocomposites by adsorption method, for the first time. As were expected, PDDA-AuNPs/GNs gave better performance for UA than AuNPs/GNs obtained by adsorption, and the anodic peak current of UA obtained by cyclic voltammetry (CV) increased 102.1-fold in comparison to bare GCE under optimizing conditions. Differential pulse voltammetry (DPV) was used to quantitatively determine UA. The linear range of UA was from 0.5μM to 20μM and the detection limit was 0.1μM (S/N=3) with a high sensitivity of 103.08μAμM(-1)cm(-2). The assay results of urine sample provided satisfying recoveries by standard addition method. In addition, the anodic peaks of adrenaline (AD) and UA were well resolved at PDDA-AuNPs/GNs modified electrode, while they were too overlapped to separate at bare electrode, as a result of that UA was successfully detected in the presence of AD. In conclusion, rapid synthesis of PDDA-AuNPs/GNs were realized and applied as an advanced hybrid electrode material for UA determination.

Direct electrochemistry and electrocatalysis of hemoglobin immobilized in a magnetic nanoparticles-chitosan film

Magnetic nanoparticles (Fe(3)O(4)) were synthesized by a chemical coprecipitation method. X-ray diffraction (XRD) and transmission electron microscope (TEM) were used to confirm the crystallite structure and the particles radius. The Fe(3)O(4) nanoparticles and chitosan (CS) were mixed to form a matrix in which haemoglobin (Hb) can be immobilized for the fabrication of H(2)O(2) biosensor. The Fe(3)O(4)-CS-Hb film exhibited a pair of well-defined and quasi-reversible cyclic voltammetric peaks due to the redox of Hb-heme Fe (III)/Fe (II) in a pH 7.0 phosphate buffer. The formal potential of Hb-heme Fe(III)/Fe(II) couple varied linearly with the increase of pH in the range of 4.0-10.0 with a slope of 46.5 mV pH(-1), indicating that electron transfer was accompanied with single proton transportation in the electrochemical reaction. The surface coverage of Hb immobilized on Fe(3)O(4)-CS film glassy carbon electrode was about 1.13 x 10(-10)mol cm(-2). The heterogeneous electron transfer rate constant (k(s)) was 1.04 s(-1), indicating great facilitation of the electron transfer between Hb and magnetic nanoparticles-chitosan modified electrode. The modified electrode showed excellent electrocatalytic activity toward oxygen and hydrogen peroxide reduction. The apparent Michaelis-Menten constant K(M)(app) for H(2)O(2) was estimated to be 38.1 micromol L(-1).

Colorimetric sensing of clenbuterol using gold nanoparticles in the presence of melamine.

A highly sensitive method for the detection of trace amount of clenbuterol based on gold nanoparticles (AuNPs) in the presence of melamine was described in this paper. Hydrogen-bonding interaction between clenbuterol and melamine resulted in the aggregation of AuNPs and a consequent color change of AuNPs from wine red to blue. The concentration of clenbuterol could be determined with naked eye or a UV-vis spectrometer. Results showed that the absorption ratio (A(670)/A(520)) was liner with the logarithm of clenbuterol concentration in the range of 2.8×10(-10) to 2.8×10(-7)M and 2.8×10(-7) to 1.4×10(-6)M with linear coefficients of 0.996 and 0.993, respectively. The detection limit was 2.8×10(-11)M (S/N=3), which was much lower than most existing methods. The coexisting substances including dl-epinephrine, phenylalamine, tryptohan, alamine, uric acid, glycine, glycerol, glucose, MgCl(2), CaCl(2) and NaCl did not affect the determination of clenbuterol. The proposed method could be successfully applied to the determination of clenbuterol in human urine.

Colorimetric detection of melamine during the formation of gold nanoparticles

A sensitive and simple colorimetric method for determination of melamine was reported based on the seedless production of gold nanoparticles (Au-NPs). Au-NPs were synthesized by using pyrocatechol-3,5-disodiumsulfonate (PD) as reducer without adding nanoparticles seeds and stabilizing agent. PD can form intramolecular hydrogen-bonding in solution by adjacent sulfurnate and α-phenolic hydroxyl group, resulting in its weak reducing capacity and thus the synthesis of Au-NPs was slow. While in the presence of melamine, PD reacted with melamine through hydrogen-bonding. Therefore, the intramolecular hydrogen-bonding of PD was interrupted by melamine, and the α-phenolic hydroxyl group was free to reduce Au(3+), hence, the synthesis of Au-NPs was accelerated. Especially, the presence of melamine led to a shift in the surface plasmon bond and a color change of Au-NPs from green to yellow. Results showed that the absorbance ratio (A(436)/A(600)) was linear with the logarithm of melamine concentration in the range of 4.8×10(-9) to 1.6×10(-6) M with a correlation coefficient of 0.9949. The detection limit (3σ) obtained by UV-vis spectrum was 6.4×10(-10) M (i.e., 0.08 ppb). The proposed method was applied successfully to the determination of melamine in pretreated liquid milk products, and the recoveries were from 93% to 107%.

A simple one-pot synthesis of graphene nanosheet/SnO2 nanoparticle hybrid nanocomposites and their application for selective and sensitive electrochemical detection of dopamine

A novel one-pot synthesis of graphene nanosheet/SnO2 nanoparticle hybrid nanocomposites (GN/SnO2) was realized by using graphene oxide nanosheets (GONs) functionalized with sodium dodecyl sulfonate and SnCl2 as the starting materials. The morphology and structure of the synthesized SDS-GN/SnO2 nanocomposites were characterized by Raman spectroscopy, transmission electron microscopy (TEM) and X-ray diffraction analysis. It was found that SnO2 nanoparticles were homogeneously distributed on the graphene nanosheets. The electrochemical behavior of dopamine (DA) at the SDS-GN/SnO2 nanoparticle modified electrode was studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The results showed that the modified electrode exhibited excellent electrocatalytic activity towards the electrochemical oxidation of DA. The separation of the oxidation peak potentials for ascorbic acid (AA)-DA, uric acid (UA)-DA and UA-AA obtained by DPV is about 132 mV, 128 mV and 260 mV, respectively, which allows selective and sensitive detection of DA in the presence of AA and UA. The anodic peak currents were linear with the concentration of DA in the range from 1.0 × 10-7 to 1.0 × 10-5 M with a coefficient of 0.9980. The detection limit was 80 nM (S/N = 3). The proposed method could be applied for the determination of DA in real human urine samples.

Determination of dopamine in the presence of ascorbic acid using poly(3,5-dihydroxy benzoic acid) film modified electrode

A polymerized film of 3,5-dihydroxy benzoic acid (DBA) was prepared on the surface of a glassy carbon electrode (GCE) in neutral solution by cyclic voltammetry (CV). The poly(DBA) film-coated GCE exhibited excellent electrocatalytic activity toward the oxidation of dopamine (DA). A linear range of 1.0 x 10(-7) to 1.0 x 10(-4)M and a detection limit of 6.0 x 10(-8)M were observed in pH 7.4 phosphate buffer solutions. Moreover, the interference of ascorbic acid (AA) was effectively eliminated. This work provides a simple and easy approach to selective detection of DA in the presence of AA.

Sensitive electrochemical immunosensor for α-fetoprotein based on graphene/SnO2/Au nanocomposite.

A label-free electrochemical immunosensor for sensitive detection of α-fetoprotein (AFP) was developed based on graphene/SnO2/Au nanocomposite. The graphene/SnO2/Au nanocomposite modified glassy carbon electrode was used to immobilize α-fetoprotein antibody (anti-AFP) and to construct the immunosensor. Results demonstrated that the peak currents of [Ru(NH3)6](3+) decreased due to the interaction between antibody and antigen on the modified electrode. Thus, a label-free immunosensor for the detection of AFP was realized by monitoring the peak current change of [Ru(NH3)6](3+). The factors influencing the performance of the immunosensor were investigated in details. Under optimal conditions, the peak currents obtained by DPV decreased linearly with the increasing AFP concentrations in the range from 0.02 to 50 ng mL(-1) with a linear coefficient of 0.9959. This electrochemical immunoassay has a low detection limit of 0.01 ng mL(-1) (S/N=3) and was successfully applied to the determination of AFP in serum samples.

Highly sensitive and selective colorimetric sensing of antibiotics in milk

Antibiotics residues in foods are very harmful to human beings. Determination of antibiotics residues relies largely on the availability of adequate analytical techniques. Currently, there is an urgent need for on site and real time detection of antibiotics in food. In this work, a novel one step synthesis of gold nanoparticles (AuNPs) was proposed using pyrocatechol violet (PCV) as a reducer agent. Highly sensitive and selective colorimetric detection of four antibiotics kanamycin mono sulfate (KA), neomycin sulfate (NE), streptomycin sulfate (ST) and bleomycin sulfate (BL) was realized during the formation of AuNPs. PCV has -OH groups and these antibiotics have -OH, -NH2, -NH- groups, so there may be some special hydrogen-bonding interactions between PCV and these antibiotics. Therefore, the presence of KA, NE, ST and BL would influence the synthesis of AuNPs, then the color and state of AuNPs would change, which could be observed with the naked eye or a UV-vis spectrophotometer. Results showed that A670 was linear with the logarithm of KA concentration in the range from 1.0×10(-8) to 5.0×10(-7)M and 5.0×10(-7) to 5.5×10(-5)M. The detection limit of KA was 1.0×10(-9)M (S/N=3). The coexisting substances including 1.0×10(-5)M phenylalanine, alanine, glycerol, glucose, Mg(2+), Ca(2+), Na(+), K(+), CO3(2-), SO4(2-), NO3(-), Cl(-) and Br(-) did not affect the determination of 1.0×10(-7)M antibiotics. In particular, the proposed method could be applied successfully to the detection of antibiotics in the pretreated liquid milk products.

Separation and determination of rutin and quercetin in the flowers ofSophora japonica L. by capillary electrophoresis with electrochemical detection

Capillary electrophoresis with amperometric detection has been evaluated for the simultaneous determination of rutin and quercetin. The cyclic voltammogram, hydrodynamic voltammogram, and the effects of pH, concentration of buffer and sodium dodecyl sulfate (SDS), and amount of organic modifier on the separation and the detection were studied. The optimized conditions were: detection potential 1.2V, separation at 12 kV, 5 s at 15 kV for sample injection, running electrolyte 20 mmol L−1 borate buffer, pH 8.8, containing 40 mmol L−1 SDS and 10% acetonitrile. The detection limit of the method was low, 0.001 and 0.0005 mg mL−1, for rutin and quercetin, respectively; the linear ranges were wide −0.005–0.5 and 0.005–0.4 mg mL−1, respectively. The variations in peak current and migration time for eight consecutive injections of a standard solution containing 0.1 mg mL−1 of each compound were 4.78 and 3.63%, and 6.50 and 2.59% for rutin and quercetin, respectively. The levels of the two compounds in traditional Chinese herbal drugs were easily determined.