Novel Amperometric Mercury-Selective Sensor Based on Organic Chelator Ionophore.

A novel amperometric sensor for the direct determination of toxic mercury ions, Hg2+, based on the organic chelator ionophore N, N di (2-hydroxy-5-[(4-nitrophenyl)diazenyl]benzaldehyde) benzene-1,2-diamine (NDBD), and multiwalled carbon nanotubes (MWCNT) immobilized on a glassy carbon electrode surface was developed. The parameters influencing sensor performance including the ionophore concentration, the applied potential, and electrolyte pH were optimized. The sensor response to Hg2+ was linear between 1-25 µM with a limit of detection of 60 nM. Interferences from other heavy metal ions were evaluated and the sensor showed excellent selectivity towards Hg2+. The method was successfully applied to the determination of mercury ions in milk and water samples.

Non-enzymatic disposable electrochemical sensors based on CuO/Co3O4@MWCNTs nanocomposite modified screen-printed electrode for the direct determination of urea.

A new electrochemical impedimetric sensor for direct detection of urea was designed and fabricated using nanostructured screen-printed electrodes (SPEs) modified with CuO/Co3O4 @MWCNTs. A facile and simple hydrothermal method was achieved for the chemical synthesis of the CuO/Co3O4 nanocomposite followed by the integration of MWCNTs to be the final platform of the urea sensor. A full physical and chemical characterization for the prepared nanomaterials were performed including Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), contact angle, scanning electron microscope (SEM) and transmission electron microscopy (TEM). Additionally, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to study the electrochemical properties the modified electrodes with the nanomaterials at different composition ratios of the CuO/Co3O4 or MWCNTs. The impedimetric measurements were optimized to reach a picomolar sensitivity and high selectivity for urea detection. From the calibration curve, the linear concentration range of 10-12-10-2 M was obtained with the regression coefficient (R2) of 0.9961 and lower detection limit of 0.223 pM (S/N = 5). The proposed sensor has been used for urea analysis in real samples. Thus, the newly developed non-enzymatic sensor represents a considerable advancement in the field for urea detection, owing to the simplicity, portability, and low cost-sensor fabrication.

A Core-Shell Au@TiO2 and Multi-Walled Carbon Nanotube-Based Sensor for the Electroanalytical Determination of H2O2 in Human Blood Serum and Saliva.

A hydrogen peroxide (H2O2) sensor was developed based on core-shell gold@titanium dioxide nanoparticles and multi-walled carbon nanotubes modified glassy carbon electrode (Au@TiO2/MWCNTs/GCE). Core-shell Au@TiO2 material was prepared and characterized using a scanning electron microscopy and energy dispersive X-ray analysis (SEM/EDX), transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman spectroscopy, X-ray diffraction (XRD) and Zeta-potential analyzer. The proposed sensor (Au@TiO2/MWCNTs/GCE) was investigated electrochemically using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The analytical performance of the sensor was evaluated towards H2O2 using differential pulse voltammetry (DPV). The proposed sensor exhibited excellent stability and sensitivity with a linear concentration range from 5 to 200 µM (R2 = 0.9973) and 200 to 6000 µM (R2 = 0.9994), and a limit of detection (LOD) of 1.4 µM achieved under physiological pH conditions. The practicality of the proposed sensor was further tested by measuring H2O2 in human serum and saliva samples. The observed response and recovery results demonstrate its potential for real-world H2O2 monitoring. Additionally, the proposed sensor and detection strategy can offer potential prospects in electrochemical sensors development, indicative oxidative stress monitoring, clinical diagnostics, general cancer biomarker measurements, paper bleaching, etc.

Simultaneous determination of ascorbic acid, uric acid and dopamine using silver nanoparticles and copper monoamino-phthalocyanine functionalised acrylate polymer.

A silver nanoparticle and copper monoamino-phthalocyanine-acrylate (Cu-MAPA) polymer modified glassy carbon electrode was developed for the simultaneous detection of dopamine (DOP), ascorbic acid (AA) and uric acid (UA) using voltammetric techniques. Silver nanoparticles (AgNPs) were synthesised according to the citrate reduction method. Following synthesis and characterisation the copper phthalocyanine polymer was co-deposited with AgNPs realising a surface with enhanced electron transfer which lowered the overpotential required for analyte electro-oxidation. Differential pulse voltammetry (DPV) was employed for the simultaneous determination of dopamine (DOP), ascorbic acid (AA) and uric acid (UA) at AgNP/Cu-MAPA modified surfaces at <µM ranges. The peak potential separations for DOP-AA and DOP-UA were ca. 181 mV and 168 mV respectively. The chemical sensor was also capable of individual quantitation of DOP, UA and AA with detection limits of 0.7, 2.5 and 5.0 nM respectively. Overall, the approach realised a simple and effective electrode modifier for the selective discrimination and quantitation of DOP in the presence of physiological levels of AA and UA.

Yersinia pestis detection using biotinylated dNTPs for signal enhancement in lateral flow assays.

Due to the extreme infectivity of Yersinia pestis it poses a serious threat as a potential biowarfare agent, which can be rapidly and facilely disseminated. A cost-effective and specific method for its rapid detection at extremely low levels is required, in order to facilitate a timely intervention for containment. Here, we report an ultrasensitive method exploiting a combination of isothermal nucleic acid amplification with a tailed forward primer and biotinylated dNTPs, which is performed in less than 30 min. The polymerase chain reaction (PCR) and enzyme linked oligonucleotide assay (ELONA) were used to optimise assay parameters for implementation on the LFA, and achieved detection limits of 45 pM and 940 fM using SA-HRP and SA-polyHRP, respectively. Replacing PCR with isothermal amplification, namely recombinase polymerase amplification, similar signals were obtained (314 fM), with just 15 min of amplification. The lateral flow detection of the isothermally amplified and labelled amplicon was then explored and detection limits of 7 fM and 0.63 fg achieved for synthetic and genomic DNA, respectively. The incorporation of biotinylated dNTPs and their exploitation for the ultrasensitive molecular detection of a nucleic acid target has been demonstrated and this generic platform can be exploited for a multitude of diverse real life applications.

Determination of prostate cancer biomarker acid phosphatase at a copper phthalocyanine-modified screen printed gold transducer.

In this work, a novel sensor based on immobilised copper phthalocyanine, 2,9,16,23-tetracarboxylic acid-polyacrylamide (Cu(II)TC Pc-PAA) was developed for determination of acid phosphatase (ACP) levels in nanomolar quantities. Detection was based on the measurement of enzymatically generated phosphate, with initial studies focused on phosphate detection at a Cu(II)TC Pc-PAA modified screen-printed gold transducer. The sensor was characterised in relation to operational performance (pH, response time, stability, linearity, and sensitivity) and common anionic interferents (nitrate, sulphate, chloride, and perchlorate). The functionalised surface also facilitated rapid detection of the enzyme bi-product 2-naphthol over the range 5-3000 µM. Quantitation of ACP was demonstrated, realising a linear response range of 0.5-20 nM and LOD of 0.5 nM, which is within the clinical range for this prostate cancer biomarker.

DNA biosensors based on gold nanoparticles-modified graphene oxide for the detection of breast cancer biomarkers for early diagnosis.

Two different DNA (ERBB2c and CD24c) modified gold nanoparticles and graphene oxide loaded on glassy carbon electrodes were prepared for early detection of breast cancer markers by electrochemical detection of HER2. Comparative study of ERBB2c and CD24c for the detection was carried out. A "sandwich-type" detection strategy was employed in this electrochemical DNA biosensor and its response was measured by amperometric detection. The electrochemical signal enhancement achieved via gold nanoparticles and grapheme oxide system allowed for sensitive detection of the breast cancer biomarker ERBB2 and the control marker CD24. The modified graphene oxide was characterised using Raman spectroscopy, UV-visible spectroscopy, Fourier transform infrared spectroscopy transmission electron microscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy. The various steps involved in the modification of a glassy carbon electrode with graphene oxide, gold nanoparticles and DNA probes, target and reporter probe were electrochemically characterised using cyclic voltammetry and electrochemical impedance spectroscopy. Using amperometric detection of a horse radish peroxidase label, detection limits of 0.16nM and 0.23nM were obtained with sensitivity 378nA/nM and 219nA/nM for ERBB2 andCD24 respectively.

Catalase based hydrogen peroxide biosensor for mercury determination by inhibition measurements.

A new amperometric hydrogen peroxide enzyme inhibition biosensor for the indirect determination of toxic mercury ions, Hg2+, based on catalase immobilized on a glassy carbon electrode surface by cross-linking with glutaraldehyde and bovine serum albumin, is reported. The parameters influencing biosensor performance were optimized, including enzyme loading, the amount of hydrogen peroxide, the applied potential and electrolyte pH. It was shown that the inhibition of catalase by Hg2+ species is irreversible, with a linear inhibition response between 5×10-11 and 5×10-10M. The limit of detection calculated as 10% inhibition was 1.8×10-11M and is the lowest reported until now. Electrochemical impedance spectroscopy was successfully used as a diagnostic of inhibition. Interferences from other heavy metal ions and organic pesticides were evaluated and the inhibition showed very good selectivity towards Hg2+. The method was successfully applied to the determination of mercury ions in different types of water sample.

A novel sensitive amperometric choline biosensor based on multiwalled carbon nanotubes and gold nanoparticles.

A novel amperometric biosensor for choline determination has been developed, exploiting the electrocatalytic properties of multiwalled carbon nanotubes (MWCNT) and gold nanoparticles (GNP). Chitosan (Chit), a natural biocompatible polymer, was used to disperse CNT, then Chit-MWCNT was dropped on the surface of a glassy carbon electrode (GCE), followed by GNP; finally, choline oxidase (ChOx) was immobilized by glutaraldehyde crosslinking. The ChOx/(GNP)4/MWCNT/GCE exhibited linear response to choline from 3 to 120µM, the sensitivity was 204µAcm-2mM-1 and the detection limit was 0.6µM. The biosensor exhibited good intra and inter-electrode precision, and excellent selectivity and stability. Electrochemical impedance spectroscopy (EIS) was also used to measure choline at 0.0V and this is the first report on choline determination by EIS. Successful measurement in milk samples was performed.