A molecularly imprinted polypyrrole electrochemiluminescence sensor based on a novel zinc-based metal-organic framework and chitosan for determination of enrofloxacin.

Nowadays, bacterial resistance caused by the abuse of antibiotics has become a worldwide problem. In this work, a quinolone antibiotic, enrofloxacin (ENR), was rapidly monitored by combining a selective molecular imprinting polymer (MIP) with the electrochemiluminescence (ECL) method. Zn-PTC, a novel zinc-based metal-organic framework (MOF) that has a large specific surface area and ultra-high luminous efficiency, was used as the ECL luminophore. Chitosan (CHIT) was used to contact the specific surface area of molecularly imprinted polymer films and further improved the detection sensitivity. Subsequently, the molecularly imprinted polypyrrole was electropolymerized on the surface of the Zn-PTC and CHIT modified glassy carbon electrode (GCE). The specific sites that could target recombining ENR were shaped on the surface of MIP after extracting the ENR templates. The specific concentrations of ENR could be detected according to the difference in ECL intensity (ΔECL) between the eluting and rebinding of ENR. After optimization, a good linear response of ΔECL and a logarithm of specific ENR concentrations could be obtained in the range of 1.0 × 10-12-1.0 × 10-4 mol L-1, with a detection limit of 9.3 × 10-13 mol L-1 (S/N = 3). Notably, this study provided a rapid, convenient, and cheap method for the detection of ENR in actual samples.

A novel core-shell composite of PCN-222@MIPIL for ultrasensitive electrochemical sensing 4-nonylphenol.

A novel core-shell composite of PCN-222 and molecularly imprinted poly (ionic liquid) (PCN-222@MIPIL) with high conductivity and selectivity was prepared for electrochemical sensing 4-nonylphenol (4-NP). The electrical conductivities of some MOFs including PCN-222, ZIF-8, NH2-UIO-66, ZIF-67, and HKUST-1 were explored. The results indicated that PCN-222 had the highest conductivity and was then used as a novel imprinted support. PCN-222@MIPIL with core-shell and porous structure was synthesized using PCN-222 as support and 4-NP as template. The average pore volume of PCN-222@MIPIL was 0.085 m3 g-1. In addition, the average pore width of PCN-222@MIPIL was from 1.1 to 2.7 nm. The electrochemical response for PCN-222@MIPIL sensor for 4-NP was 2.54, 2.14, and 4.24 times that of non-molecularly imprinted poly (ionic liquid) (PCN-222@NIPIL), PCN-222, and MIPIL sensors, respectively, which result from superior conductivity and imprinted recognition sites of PCN-222@MIPIL. The current response of PCN-222@MIPIL sensor to 4-NP concentration from 1 × 10-4 to 10 µM presented an excellent linear relationship. The detection limit of 4-NP was 0.03 nM. The synergistic effect between the PCN-222 supporter with high conductivity, specific surface area and shell layer of surface MIPIL results in the outstanding performance of PCN-222@MIPIL. PCN-222@MIPIL sensor was adopted for detecting 4-NP in real samples and presented to be a reliable approach for determining 4-NP.

A novel molecularly imprinting polypyrrole electrochemiluminescence sensor based on MIL-101-g-C3N4 for supersensitive determination of ciprofloxacin.

Ciprofloxacin (CIP), a quinolone antibiotic, was rapidly and sensitively detected by integrating the molecularly imprinted polymer (MIP) with an ultra-sensitive electrochemiluminescence (ECL) method. g-C3N4, a typical polymer semiconductor, exhibited outstanding ECL efficiency and excellent ECL stability after combining with an iron-based metal-organic framework (MIL-101). Subsequently, the molecularly imprinted polypyrrole was electropolymerized on the composites of MIL-101-g-C3N4 modified glassy carbon electrode (GCE). The specific sites that could target rebinding the CIP molecules were formed on the surface of MIP after extracting the CIP templates. The determination of specific concentrations of CIP could be realized according to the difference in ECL intensity (△ECL) between the eluting and rebinding of the CIP. Under optimal conditions, a good linear response of △ECL and the logarithm of CIP concentrations was obtained in the range 1.0 × 10-9 ~ 1.0 × 10-5 mol/L, with a detection limit of 4.5 × 10-10 mol/L (S/N = 3) (the working potential was -1.8 ~ 0 V). The RSD of all points in the calibration plot was less than 5.0% and the real samples recovery was between 98.0 and 104%. This paper displays satisfactory selectivity and sensitivity, providing a rapid, convenient, and cheap method for the determination of CIP in real samples.

A novel three-dimensional molecularly imprinted polypyrrole electrochemical sensor based on MOF derived porous carbon and nitrogen doped graphene for ultrasensitive determination of dopamine.

Herein, a novel molecular imprinting polypyrrole electrochemical sensor was fabricated based on a zirconia and carbon core-shell structure (ZrO2@C) and a nitrogen-doped graphene (NPG) modified glassy carbon electrode (GCE) for ultrasensitive recognition of dopamine (DA). The NPG was prepared by a sacrificial-template-assisted pyrolysis method and ZrO2@C was synthesized via annealing treatment of a zirconium-based metal-organic framework (UiO-66). A convenient electropolymerization method was used to prepare the pyrrole (Py) conductive molecularly imprinted polymer (MIP) in the presence of DA. The elution process of DA was performed by a simple overoxidation process under alkaline conditions. Differential pulse voltammetry (DPV) was used to assess the electrochemical performance of the sensors. The MIP-based electrochemical sensor with specific binding sites could be used for selective recognition of DA. Under the optimal conditions, the linear range of such a sensor was 5.0 × 10-9-1.0 × 10-4 mol L-1 and the detection limit was 3.3 × 10-10 mol L-1 (S/N = 3). This sensor exhibited suitable selectivity, stability, and reproducibility, which suggested that it could be a promising candidate for rapid diagnostic methods in dopamine investigations.

Hepcidin expression levels involve efficacy of pegylated interferon-α treatment in hepatitis B-infected liver.

BACKGROUND: Hepcidin is the master iron regulator hormone produced by the liver. The association of serum hepcidin with pegylated interferon therapy in patients with chronic hepatitis C infection has been studied. However, the role of serum hepcidin level in predicting the effect of pegylated interferon treatment in patients with chronic hepatitis B (CHB) infection is yet to be elucidated. Our study aims to investigate the correlation between hepcidin expression levels and the curative effect of interferon-alpha therapy in patients with CHB. METHODS: A total of 47 patients with CHB who accepted pegylated interferon-α (PEG-IFN- α) treatment were recruited. The serum level of hepcidin was estimated by ELISA. The alternation in the gene expression level of hepcidin was detected by RT-PCR, and immunofluorescence cell staining was performed to detect hepcidin peptide. The induction of antiviral proteins was analyzed by Western blotting. The predictive value of early on-treatment variation in serum hepcidin during treatment progress was assessed by receiver operating characteristic analysis. RESULTS: High levels of early on-treatment serum hepcidin were observed in patients who achieved a decline in HBsAg > 1 log10 IU/mL or HBV DNA > 1 log10 IU/mL. In vitro, an elevation of the hepcidin expression in HepG2.2.15 cells induced by PEG-IFN-α treatment was noted. Furthermore, combined treatment with hepcidin and PEG-IFN-α increased the levels of antiviral proteins. The predictive cut-off value of hepcidin for HBsAg decline > 1 log10 IU/mL was 239 pg/mL, and the sensitivity and specificity were 72.73% and 70.97%, respectively. The predictive cut-off value of hepcidin for the decline in HBV DNA > 1 log10 IU/mL was 190.4 pg/mL, and the sensitivity and specificity were 72.73% and 61.11%, respectively. Early-on treatment changes in the hepcidin level signified the predictive value of the PEG-IFN-α curative effect. CONCLUSIONS: A higher early-on treatment hepcidin level indicates a higher possibility of HBsAg and HBV DNA decline in patients with CHB during PEG-IFN-α treatment. A high early-on treatment serum hepcidin level is significant in predicting the PEG-IFN-α therapeutic effect in patients with CHB.

Evaluation of Surface Structure of Escherichia coli Using Polypyrrole Matrix.

We propose a method to evaluate the surface structure of Escherichia coli focusing on the doping state of bacterial cells into polypyrrole (PPy) matrix. We found that the orientation of doping states of E. coli O rough was different from those of other serotypes of E. coli cells, which had O-antigen on their outer membrane. The results indicated that more than seventy percent of E. coli cells having O-antigen was horizontally doped into PPy matrix based on the chemical structure and the placement of O-antigen. On the other hand, the percentage for horizontal doping state of E. coli O rough cells was only approximately fifty percent. Moreover, the cells of each E. coli serotypes were specifically bound to their own shape-complementary cavities on the microspheres, but the binding affinity of E. coli O rough was a bit lower than that of other serotypes.

Determination of Brilliant Blue FCF by a Novel Solid-state ECL Quenching Sensor of Ru(bpy)32+-poly(sulfosalicylic acid)/GCE.

A novel solid-state electrochemiluminescence (ECL) quenching sensor was constructed for determination of brilliant blue FCF (BB FCF). Under a simple electropolymerization step, poly(sulfosalicylic acid) (PSSA) film attached luminophore Ru(bpy)32+ was successfully formed on the surface of a glass carbon electrode [Ru(bpy)32+-PSSA/GCE], which exhibited excellent ECL behavior. A high quenching effect on the ECL signal of the Ru(bpy)32+-PSSA/GCE was obtained with the presence of low concentration of BB FCF. Moreover, the quenched ECL intensity showed a linear relation within the BB FCF concentration range of 0.5 - 7 and 7 - 10 µmol/L, with a detection limit of 57 nmol/L (S/N = 3). Besides, Ru(bpy)32+-PSSA/GCE exhibited good reproducibility and was successfully applied in the practical detection of BB FCF in peppermint candy samples.

Selective determination of tryptophan by using a carbon paste electrode modified with an overoxidized polypyrrole film.

We report on the selective determination of tryptophan, using a carbon paste electrode coated with an overoxidized polypyrrole film. Out of 21 protein amino acids, only tryptophan and tyrosine exhibited an oxidative voltammetric response with this electrode. Tryptophan, which was preferentially concentrated to the electrode under an open circuit condition, was determined by the stripping voltammetric technique with a linear response range of 10-100 microM. For the determination of 10 microM tryptophan, interference from a 15-fold excess of tyrosine gave an positive error of 6%, while the other amino acids did not exhibit any detectable interference.

[Preparation of molecularly imprinted polypyrrole/Fe3O4 composite material and its application in recognition of tryptophan enantiomers].

Ferrosoferric oxide (Fe(3)O(4)) magnetic material was first synthesized, and then the in-situ chemical polymerization of pyrrole was carried out on the surface of Fe(3)O(4) by using pyrole and L-tryptophan (L-Trp) as the functional monomer and templates, respectively. As a result, molecularly imprinted polypyrrole/Fe(3)O(4) composite material was obtained. This composite material was separated from the solution because of its magnetic property. Polypyrrole in the composite was overoxidized in 1 mol/L NaOH solution by applying a potential of 1.0 V, and thus L-Trp templates were de-deoped from the composite. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and electrochemical methods were employed to characterize the composite. The solution containing L- or D-Trp was pumped through a porous ceramic tube packed with the composite, separately. High performance liquid chromatography (HPLC) was adopted for the detection of L- or D-Trp in the eluate, and the results indicated that the enrichment ability of the composite for L-Trp was almost 2 times that of D-Trp. Therefore, the electro-magnetic composite material has potential applications as chromatographic stationary phase for chiral recognition.