Search

Dual-mode electrochemical aptasensor based on nitrogen-doped graphene (NG) doped with the conducting polymer polypyrrole (PPy) nanocomposite is proposed for the determination of acetamiprid. NG/PPy was electrodeposited onto the glassy carbon electrode (GCE) using cyclic voltammetry technique. NG/PPy/GCE showed outstanding electrocatalytic activity for the oxidation of nitrite due to "active region" induced by the charge redistribution of carbon atoms. The ultrasensitive dual-mode biosensor for acetamiprid could be easily developed by coupling acetamiprid aptamers with the NG/PPy hybrid. The specific binding between acetamiprid and the aptamers resulted in the increase of differential pulse voltammetry (DPV) signal change and the decrease of chronoamperometry (CA) signal, and the concentration of acetamiprid could be measured. The working potentials of DPV and CA were - 0.2 ~ 0.4 V and - 0.4 ~ 0.4 V (vs. SCE), respectively. The dual-mode acetamiprid biosensor showed a wide linear range from 10

Biosensors have tremendous revolutionary potential for the precise location and rapid detection of biomarkers for human disease. However, the minimization of nonspecific protein adsorption interactions and surface contamination is critical for their application in complex media. We report herein, the antifouling interface was constructed by electrochemical copolymerization of poly (3,4-ethylenedloxythlophene) (PEDOT) and glycyrrhiza polysaccharide (GPS). Hydrophilic PEDOT/GPS can reduce the interference and nonspecific adsorption of biological protein macromolecules, which has been verified by electrochemical and fluorescent characterization. Gold nanoparticles (AuNPs) were subsequently modified onto PEDOT/GPS surface to attach biomacromolecules containing thiol groups. MicroRNA, the promising biomarker of a large numbers of genetic diseases, was used as the testing model. Due to the robust antifouling capability of PEDOT/GPS as well as high biocompatibility of GPS/AuNPs, the fabricated biosensor based on PEDOT/GPS/AuNPs demonstrated excellent sensing performance, such as a wide detection range (0.01 nM–10 nM), a low detection limit (300 fM) and high reproducibility, showing great potential of medical applications.

Ultrasensitive and low-fouling microRNA electrochemical biosensors were successfully constructed by introducing thiol-terminated antifouling molecules (peptide sequence, polyethylene glycol, or mercapto alcohol) onto the surface of polyaniline-modified electrodes. For the three kinds of antifouling materials investigated, the newly designed and synthesized peptide exhibited superior antifouling ability to others, and it could effectively reduce the nonspecific adsorption of proteins and even prevent the fouling effect of serum. Compared with microRNA biosensors without antifouling capability, or those modified with polyethylene glycol or mercapto alcohol, the biosensor modified with the designed zwitterionic peptide showed the highest specificity for single-base mismatch, three-base mismatch, and completely complementary microRNAs. Most interestingly, the experimental results indicated that the introduction of antifouling molecules to the sensing interfaces did not significantly change the sensitivity of the biosensor. The strategy of constructing antifouling biosensors based on newly synthesized zwitterionic peptides and conducting polymers can be promisingly extended to the development of other electrochemical sensors and biosensors without encountering biofouling. Graphical abstract Ultrasensitive and low-fouling microRNA electrochemical biosensors were constructed by introducing thiol-terminated antifouling molecules (peptide sequence, polyethylene glycol, or mercapto alcohol) onto the surface of polyaniline-modified electrodes. The biosensor modified with the designed zwitterionic peptide showed the highest specificity amongst four kinds of biosensors.

A rapid, sensitive and low-fouling sensor for application to detect clinical biomarkers directly in biological media is highly desirable. Herein, we report a versatile strategy to prepare polyaniline (PANI) based conducting polymer hydrogel through the assembly of PANI and phytic acid (PA) by dynamic boronate bond. PANI/PA, a conductive hydrogel with high specific area and multiple pore structures have demonstrated excellent antifouling ability and electrochemical property. The electrochemical biosensors for microRNA can be developed by the immobilization of DNA probes onto PANI/PA interface (microRNA24 is used as a model case), and redox currents of PANI were utilized as the sensing signals to assay DNA/RNA hybridization reaction. Owing to the typical characteristics of PANI/PA hydrogel, the biosensor has shown excellent sensing performances with wide linear range (1.0 fM-1.0 pM), low sensing limit (0.34 fM) and efficient ability to detect microRNA mismatches. Given the facile processability, excellent stability and good antifouling property of the PANI/PA hydrogel, the proposed hydrogel-based biosensor may find broad applications in clinical diagnostics and biomedical devices.

The conducting polymer polypyrrole nanocones wrapped by metal cobalt (Co/PPy) are a promising platform for the detection of sodium nitrite, which can be obtained by an electrochemical deposition technique under a mild condition. Co/PPy nanocone arrays combined the high conductivity and large specific surface area of PPy nanocones with the redox properties of metal cobalt, and their 3D structure can provide more active sites for nitrite detection. Owing to the microstructure and excellent electrical properties of the nanocomposite, Co/PPy nanocone arrays were convenient to construct a high-performance nitrite sensor. The microscopic morphology and composition of Co/PPy nanocone arrays were characterized by SEM, FT-IR, XPS, and XRD, and their electrochemical performances were also investigated. The experimental results showed that Co/PPy nanocones exhibited excellent performance for nitrite determination. The sensors were used for the determination of nitrite in pickled Chinese cabbage and water samples, and the results were consistent with those of spectrophotometry. Hence, the synthesized Co/PPy nanocone arrays have a broad application prospect in food safety, environmental protection, and industrial manufacturing.

A dual-sensing platform is proposed based on multi-walled carbon nanotubes/Prussian blue-functionalized polypyrrole nanowire array (PPY/MWCNTs/PB). Highly aligned PPY nanowire arrays were electrochemically prepared on the surface of glassy carbon electrodes, which were doped with MWCNTs/PB nanocomposites. The nanomaterial combines the characteristics of the PPY nanowires (high conductivity and large specific surface area) and MWCNTs/PB (excellent catalytic performance and intrinsic redox activity). Owing to the nanowire microstructure and outstanding electrical properties, the PPY/MWCNTs/PB nanowire arrays show excellent electrocatalysis of the reduction of hydrogen peroxide and facilitate the construction of a high-performance biosensing platform for microRNA (miRNA). A linear relationship between analytical signal and concentration of hydrogen peroxide and miRNA was obtained in the range 5 to 503 µM (1.4-5.1 mM) and 0.1 pM to 1 nM, and detection limits of 1.7 μM and 33.4 fM, respectively. This new supersensitive sensing platform has broad application prospects of biomolecule and other analyte determination in drug, biomedical, plant protection, and environmental analysis. Prussian blue/multi-walled carbon nanotubes functionalized polypyrrole nanowire arrays (PPY/MWCNTs/PB) were prepared by a facile one-step electrochemical method. PPY/MWCNTs/PB nanowire arrays show excellent electrocatalysis of the reduction of H

A nanocomposite consisting of phytic acid (PA) that was doped with poly(3,4-ethylenedioxy-thiophene) (PEDOT) and modified with copper nanoparticles (CuNPs) was placed on a glassy carbon electrode and then applied in an enzymeless glucose sensor. The undulating PEDOT/PA composite has good conductivity and a large surface area, which was suitable as substrate for the uniform growth of CuNPs. The modified electrode typically operated at a potential near 0.55 V (vs. Ag/AgCl) demonstrated remarkable catalytic activity towards direct oxidation of glucose in NaOH solution (the major limitation of this sensor). Figures of merit include (a) a wide analytical range (5 to 403 μM); (b) high sensitivity (79.27 μA·μM−1·cm−2), (c) a low detection limit (0.28 μM at a signal to noise ratio of 3), and (d) fast response (< 4 s).

Honeycomb-like cobalt nanostructures modified graphene oxide doped polypyrrole (CoNSs/RGO/PPy) nanocomposites were successfully prepared via a simple two-step electrochemical synthesis route. Firstly graphene oxide (GO) doped PPy nanocomposite was electrodeposited onto a pretreated glassy carbon electrode (GCE) to obtain GO/PPy nanocomposite; secondly honeycomb-like cobalt nanostructures were electrochemical reduced onto GO/PPy nanocomposite surface in a cobalt chloride solution at − 1.0 V. During the second reduction process, GO/PPy was reduced to a more conductive RGO/PPy nanocomposite simultaneously. The electrode modified with CoNSs/RGO/PPy nanocomposites exhibited outstanding electrocatalytic performance for enzymeless glucose sensing in alkaline media. Under optimum experimental conditions, the nonenzymatic glucose sensor displayed linear ranges from 0.5 μM to 2.667 mM, a high sensitivity of 297.73 μA mM − 1 cm − 2 , a very low detection limit of 29 nM (at S/N = 3) and a superfast response time of 1 s. The developed glucose sensor displayed favorable selectivity against common interferents, excellent stability and high reproducibility, and it has great potential to successfully detect glucose concentration in real biological samples.

A glassy carbon electrode (GCE) was modified with graphene oxide-doped polypyrrole (PPy), and flower-like cobalt nanostructures were then deposited on GCE by electrochemical reduction. The modified electrode shows improved catalytic behavior towards nitrite oxidation as the result of the nanoporous structure and the synergistic effect between cobalt nanostructures and GO/PPy. It is found that the amperometric oxidation current at 0.80 V (vs SCE) is about 2.5 times larger than that of a GCE modified with carbon nanotubes. Under optimum conditions, the modified electrode displays a linear range that extends over the 1.0 μM to 3.2 mM and 6.8 – 12 mM concentration ranges, a lower detection limit of 15 nM (at an S/N ratio of 3), and a response time of 1 s. The modified electrode is adequately selective, highly stable and highly reproducible. The method was successfully applied to the determination of nitrite in pickled radish.

A reagentless and label-free voltammetric modified electrode was developed for the carcinoembryonic antigen (CEA), an important biomarker for colorectal adenocarcinoma. It is based on the use of a reticular hybrid composite consisting of polyaniline (PANI) nanowires grown on the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) that was doped with an ionic liquid (IL). The composite features excellent electrical conductivity and a porous structure, a high specific surface and inherent redox activity. It was placed on a glassy carbon electrode (GCE) and antibody against CEA was immobilized on its surface. The redox current of PANI, measured typically at 0.16 V (vs. Ag/AgCl) serves as the analytical information. This electrode displays linear range that extends from 0.001 to 10 ng mL−1, with a detection limit as low as 0.7 pg mL−1. It also possesses excellent temporal stability and selectivity.

Vertically aligned conducting polymer nanowire arrays had great potential applications in supercapacitor electrode material and exhibited enhanced electrocatalytic behavior towards the reduction of nitrite. In this paper, a facial template-free approach to synthesize large arrays of vertically aligned polyaniline (PANI) nanowires on electrochemically pretreated glassy carbon electrodes was reported by using a galvanostatic current method. The as-prepared large arrays of PANI nanowires had very narrow diameters and were oriented perpendicular to the substrate, which was a benefit to the ion diffusion when being used as the supercapacitor electrode. The highest specific capacitance of PANI nanowire arrays was measured and kept high at a large charge-discharge current density. Furthermore, it also can detect nitrite with ultrahigh sensitivity of 62.99 µA mM−1 cm−2 and a remarkable fast response time of less 1 s. The results indicated that the vertically aligned PANI nanowires could dramatically enhance the electrochemical performance.

A non-fouling electrochemical immunosensor is described for determination of the tumor biomarker carcinoembryonic antigen (CEA). It is based on the use of composite wires made by chemical grafting of hyaluronic acid onto polyaniline nanowires. The modified nanowires possess excellent antifouling property both in single protein solutions and in dilute serum samples. The current of immunoelectrode exhibits a linear response in the 0.01 pg mL−1 to 10,000 pg mL−1 CEA concentration range and 0.0075 pg mL−1 detection limit. This work demonstrates that coating an electrode with hyaluronic acid can largely reduce unspecific adsorption of proteins on the electrode surface.

By using the linear sweep voltammetric technique, a phenanthroline (Phen) and zinc(II) (Phen-Zn(II)) complex was used as the electrochemical probe for the determination of double-stranded (ds) DNA. In pH 9.0 Britton- -Robinson (B-R) buffer solution, Phen can interact with Zn(II) to form a stable electroactive [Phen-Zn(II)] complex, which had a sensitive second order derivative polarographic reductive peak at -1.300 V (vs. SCE). After the addition of dsDNA into a solution of Phen-Zn(II) complex, the reduction peak current decreased with a negative shift of the reduction peak potential and without the appearance of new peaks. The results showed that a new supramolecular complex was formed via interaction of the Phen-Zn(II) complex with dsDNA. The conditions of interaction and the electrochemical detection were carefully investigated. Under the optimum conditions, the decrease in the reduction peak current was directly proportional to the dsDNA concentration in the range of 0.4-18.0 mg L-1 with the linear regression equation: ?Ip?/nA = 349.48 + + 84.647(c/mg L-1) (n = 13, ? = 0.991) and a determination limit of 0.20 mg L-1 (3?). The relative standard deviation (RSD) for 10 parallel determinations of 10.0 mg L-1 dsDNA was found to be 2.03 %. The method was successfully applied to the detection of synthetic samples with satisfactory results.

A new electrochemical method was proposed for the determination of trace amounts of proteins based on the cupferron (Cup) and cadmium(II) complex [Cup-Cd(II)] as the voltammetric probe. In the selected pH 6.5 Britton–Robinson (B–R) buffer solution, Cup can interact with Cd(II) to form a stable complex of [Cup-Cd(II)], which had a sensitive linear sweep voltammetric reductive peak at −0.654 V (vs. SCE). The addition of human serum albumin (HSA) into [Cup-Cd(II)] complex solution could greatly decrease the reductive peak current without the change of the reductive peak potential, which indicated that HSA could interact with [Cup-Cd(II)] complex to form a supramolecular biocomplex. The interaction mechanism was discussed and the decrease of reductive peak current was proportional to the concentration of HSA, which could be further used for the proteins determination. The optimal conditions of the binding reaction and the electrochemical detection were carefully investigated. Under the optimal conditions a new quantitative determination method for different kinds of proteins such as HSA, bovine serum albumin (BSA) and bovine hemoglobin (BHb) etc. was developed. The proposed method was simple, practical and relatively free from the interferences of coexisting substances, and it was further applied to the samples determination with satisfactory results. The binding constant (βs) and the binding number (m) of HSA with [Cup-Cd(II)] complex were calculated by the voltammetric data with the results as βs=1.12×106 and m=1.

The electrochemical behaviors of the interaction of chromotrope 2R (CH2R) with human serum albumin (HSA) are investigated on the hanging mercury drop electrode with linear sweep voltammetry. In the acidic buffer solution (pH 2.5) CH2R has a well-defined voltammetric reductive wave at -0.34 V (SCE). On the addition of HSA into the CH2R solution, the reductive peak current of CH2R decreases with little movement of the peak potential. The voltammetric study shows that the electrochemical parameters of interaction solution do not change and a new electrochemically non-active complex is formed via interaction of CH2R with HSA, which cannot be reduced on the Hg electrode and results in the decrease of the free concentration of CH2R. The decrease of reductive peak current is proportional to HSA concentration and further used for protein detection. The binding ratio and the binding constant are further calculated with the experimental voltammetric data.

The interaction ofphenosafranine (PSF) with a glycosaminoglycan of heparin (Hep) in aqueous solution was characterized by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) in this paper and further used for Hep detection. In pH 1.5 Britton-Robinson (B-R) buffer solution PSF had a well-defined voltammetric reductive peak at -0.256 V (vs SCE), and the electrochemical response was faded by the addition of Hep. Cyclic voltammetric experiments indicated that the electrochemical behaviors of free PSF didn't change no matter whether Hep was presented in PSF solution or not. Based on the decrease of the peak current, a second order derivative linear sweep voltammetry was used to establish a sensitive electroanalytical method for Hep. The peak current was proportional to the concentration of Hep in the range of 0.7∼20.0 mg L -1 , demonstrating that this method was suitable for routine Hep detection. Under optimal conditions, the linear regression equation for the Hep determination was ΔIp"(nA) = 46.30 C (mg L -1 ) + 343.31 (n = 11, γ = 0.991) with a detection limit of 0.08 mg L -1 (3σ). The established method was further successfully applied to heparin sodium injection samples determination. The interaction mechanism was discussed based on the electrostatic attraction of the negatively charged Hep with the positively charged PSF, and the stoichiometry of Hep-PSF was calculated by the voltammetric method.

The tenderization effect of a new elastase from Bacillus sp. EL31410 was investigated on beef meat. Meat tenderization was done by dipping the meat cut in a solution containing proteolytic enzymes after freeze-dehydration. It was found that a marination time of 4 h was enough for enzyme adsorption. The samples were treated for 4 h in different enzyme solutions and then was stored at 4 °C for 24, 48, 72 h, and subjected to texture measurement, sensory evaluations, biochemical analysis and histological observations. A marked decrease in hardness, by texture measurements, was observed in the meats with papain and elastase and higher sensory scores for tenderness were observed in the meats treated with enzymes than in the control. The papain-treated beef meat received the highest score for tenderness, but the scores given for juiciness and taste were lower than that of the control. Rapid increases of fragmentation of myofibrils from the enzyme-treated meat were observed in the first 24 h of storage, especially for papain-treated meat. Meantime, elastin of myofibrilar structure was selectively degraded by elastase compared with the control when stored at 4 °C for 48 h as shown by electron microscopy. These findings suggest that Bacillus elastase (EL31410) is a promising substitute for papain as a favourable meat tenderizer.

The property of carvedilol in acid-alkaline medium was studied by spectrofluorimetry. Effects of organic solvents on carvedilol fluorescence spectra were examined and the reason was discussed. A simple, rapid and high sensitive fluorimetric method for the determination of carvedilol in medicine is developed. The measurement of relative fluorescence intensity was carried out at 356 nm with excitation at 254 nm. Effects of pH, standing time and foreign ions on the determination of carvedilol have been examined. A linear relationship was obtained between the relative fluorescence intensity and concentration of carvedilol in the range of 0.50-270 ng ml(-1). The linear regression equation of the calibration graph is C = 0.000543F - 0.002 (C is concentration (microg ml(-1)) and F is relative fluorescence intensity in the equation), with a correlation coefficient of linear regression of 0.9998 and relative standard deviation of 2.31%. The detection limit of this method is 0.19 ng ml(-1), and recovery is from 98.70 to 102.1%. This method can be used for determination of carvedilol in tablet. The results obtained by this method agreed with those by the official method.