A ratiometric electrochemical sensor for selectively monitoring monoamine oxidase A in the live brain.

Herein, an electrochemical method for selectively sensing and accurately quantifying monoamine oxidase A (MAO-A) in the cortex and thalamus of a live mouse brain was reported. Using this tool, it was found that MAO-A increased Ca2+ entry into neurons via the TPRM2 channel in the live mouse brain of an AD model.

Development of an electrochemical sensor based on carbon black for the detection of cannabidiol in vegetable extracts.

A glassy carbon electrode chemically modified with a carbon black coating is proposed here for the rapid and portable determination of cannabidiol (CBD) in a commercial Cannabis seed oil and in fibre-type Cannabis sativa L. leaves. The mechanism of CBD oxidation was studied in relation to simpler phenyl derivatives bearing the same electroactive group, namely resorcinol and 2-methylresorcinol. These molecules also allowed us to determine the best conditions for the electrochemical detection of CBD, as to the pH value and to the best solvent mixture to use. Carbon black was chosen among nanostructured carbon-based materials owing to its outstanding features as an electrode modifier for analyte detection. The performance of the modified electrode was determined by flow injection analyses of standard solutions of CBD, obtaining a linear correlation between the oxidation current and the analyte concentration; the sensor response is characterised by suitable repeatability and reproducibility. The analysis of commercial products by the standard addition method allowed us to ascertain the accuracy of the sensor for the detection of CBD in real samples.

High-throughput electrochemical sensing platform for screening nanomaterial-biomembrane interactions.

A high-throughput, automated screening platform has been developed for the assessment of biological membrane damage caused by nanomaterials. Membrane damage is detected using the technique of analyzing capacitance-current peak changes obtained through rapid cyclic voltammetry measurements of a phospholipid self-assembled monolayer formed on a mercury film deposited onto a microfabricated platinum electrode after the interaction of a biomembrane-active species. To significantly improve wider usability of the screening technique, a compact, high-throughput screening platform was designed, integrating the monolayer-supporting microfabricated electrode into a microfluidic flow cell, with bespoke pumps used for precise, automated control of fluid flow. Chlorpromazine, a tricyclic antidepressant, and a citrate-coated 50 nm diameter gold nanomaterial (AuNM) were screened to successfully demonstrate the platform's viability for high-throughput screening. Chlorpromazine and the AuNM showed interactions with a 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) monolayer at concentrations in excess of 1 µmol dm-3. Biological validity of the electrochemically measured interaction of chlorpromazine with DOPC monolayers was confirmed through quantitative comparisons with HepG2 and A549 cytotoxicity assays. The platform also demonstrated desirable performance for high-throughput screening, with membrane interactions detected in <6 min per assay. Automation contributed to this significantly by reducing the required operating skill level when using the technique and minimizing fluid consumption.

Towards improving the electroanalytical speciation analysis of indium.

The geochemical fate of indium in natural waters is still poorly understood, while recent studies have pointed out a growing input of this trivalent element in the environment as a result of its utilisation in the manufacturing of high-technology products. Reliable and easy-handling analytical tools for indium speciation analysis are, then, required. In this work, we report the possibility of measuring the total and free indium concentrations in solution using two complementary electroanalytical techniques, SCP (Stripping chronopotentiometry) and AGNES (Absence of Gradients and Nernstian Equilibrium Stripping) implemented with the TMF/RDE (Thin Mercury Film/Rotating Disk Electrode). Nanomolar limits of detection, i.e. 0.5 nM for SCP and 0.1 nM for AGNES, were obtained for both techniques in the experimental conditions used in this work and can be further improved enduring longer experiment times. We also verified that AGNES was able (i) to provide robust speciation data with the known In-oxalate systems and (ii) to elaborate indium binding isotherms in presence of humic acids extending over 4 decades of free indium concentrations. The development of electroanalytical techniques for indium speciation opens up new routes for using indium as a potential tracer for biogeochemical processes of trivalent elements in aquifers, e.g. metal binding to colloidal phases, adsorption onto (bio)surfaces, etc.

DNA-Hybridization Detection on Si(100) Surfaces Using Light-Activated Electrochemistry: A Comparative Study between Bovine Serum Albumin and Hexaethylene Glycol as Antifouling Layers.

Light can be used to spatially resolve electrochemical measurements on a semiconductor electrode. This phenomenon has been explored to detect DNA hybridization with light-addressable potentiometric sensors and, more recently, with light-addressable amperometric sensors based on organic-monolayer-protected Si(100). Here, a contribution to the field is presented by comparing sensing performances when bovine serum albumin (BSA) and hexaethylene glycol (OEG6) are employed as antifouling layers that resist nonspecific adsorption to the DNA-modified interface on Si(100) devices. What is observed is that both sensors based on BSA or OEG6 initially allow electrochemical distinction among complementary, noncomplementary, and mismatched DNA targets. However, only surfaces based on OEG6 can sustain electroactivity over time. Our results suggest that this relates to accelerated SiO x formation occasioned by BSA proteins adsorbing on monolayer-protected Si(100) surfaces. Therefore, DNA biosensors were analytically explored on low-doped Si(100) electrodes modified on the molecular level with OEG6 as an antifouling layer. First, light-activated electrochemical responses were recorded over a range of complementary DNA target concentrations. A linear semilog relation was obtained from 1.0 × 10-11 to 1.0 × 10-6 mol L-1 with a correlation coefficient of 0.942. Then, measurements with three independent surfaces indicated a relative standard deviation of 4.5%. Finally, selectivity tests were successfully performed in complex samples consisting of a cocktail mixture of four different DNA sequences. Together, these results indicate that reliable and stable light-activated amperometric DNA sensors can be achieved on Si(100) by employing OEG6 as an antifouling layer.

Analysis of phenolic acids by ionic liquid-in-water microemulsion liquid chromatography coupled with ultraviolet and electrochemical detector.

An environmentally friendly ionic liquid-in-water (IL/W) microemulsion was established and applied as mobile phase in microemulsion liquid chromatography (MELC) with ultraviolet (UV) detection or electrochemical detector (ECD) for analysis of phenolic compounds in real samples. The optimal condition of the method was using the best composition of microemulsion (0.2% w/v [HMIM]PF6, 1.0% w/v SDS, 3.0% w/v n-butanol, 95.8% v/v water, pH 2.5) with UV detection. The validation results indicated that the method provided high degree of sensitivity, precision and accuracy with the low limit of detections ranged from 17.9-238ng/mL, satisfactory mean recovery values in the range of 80.1-105% and good linearity (r2>0.9994). Additionally, this method exhibited high selectivity and resolution for the analytes and was more eco-friendly compared with traditional MELC method. Consequently, the established IL/W MELC method was successfully applied to simultaneously separate and determine target compounds in Danshen sample and its preparation.

Impact of electro-stimulation on denitrifying bacterial growth and analysis of bacterial growth kinetics using a modified Gompertz model in a bio-electrochemical denitrification reactor.

This study aimed to investigate the effect of electro-stimulation on denitrifying bacterial growth in a bio-electrochemical reactor, and the growth were modeled using modified Gompertz model under different current densities at three C/Ns. It was found that the similar optimum current density of 250mA/m2 was obtained at C/N=0.75, 1.00 and 1.25, correspondingly the maximum nitrate removal efficiencies were 98.0%, 99.2% and 99.9%. Moreover, ATP content and cell membrane permeability of denitrifying bacteria were significantly increased at optimum current density. Furthermore, modified Gompertz model fitted well with the microbial growth curves, and the highest maximum growth rates (µmax) and shorter lag time were obtained at the optimum current density for all C/Ns. This study demonstrated that the modified Gompertz model could be used for describing microbial growth under different current densities and C/Ns in a bio-electrochemical denitrification reactor, and it provided an alternative for improving the performance of denitrification process.

Validated electrochemical and chromatographic quantifications of some antibiotic residues in pharmaceutical industrial waste water.

Realistic implementation of ion selective electrodes (ISEs) into environmental monitoring programs has always been a challenging task. This could be largely attributed to difficulties in validation of ISE assay results. In this study, the electrochemical response of amoxicillin trihydrate (AMX), ciprofloxacin hydrochloride (CPLX), trimethoprim (TMP), and norfloxacin (NFLX) was studied by the fabrication of sensitive membrane electrodes belonging to two types of ISEs, which are polyvinyl chloride (PVC) membrane electrodes and glassy carbon (GC) electrodes. Linear response for the membrane electrodes was in the concentration range of 10-5-10-2 mol/L. For the PVC membrane electrodes, Nernstian slopes of 55.1, 56.5, 56.5, and 54.0 mV/decade were achieved over a pH 4-8 for AMX, CPLX, and NFLX, respectively, and pH 3-6 for TMP. On the other hand, for GC electrodes, Nernstian slopes of 59.1, 58.2, 57.0, and 58.2 mV/decade were achieved over pH 4-8 for AMX, CPLX, and NFLX, respectively, and pH 3-6 for TMP. In addition to assay validation to international industry standards, the fabricated electrodes were also cross-validated relative to conventional separation techniques; high performance liquid chromatography (HPLC), and thin layer chromatography (TLC)-densitometry. The HPLC assay was applied in concentration range of 0.5-10.0 µg/mL, for all target analytes. The TLC-densitometry was adopted over a concentration range of 0.3-1.0 µg/band, for AMX, and 0.1-0.9 µg/band, for CPLX, NFLX, and TMP. The proposed techniques were successfully applied for quantification of the selected drugs either in pure form or waste water samples obtained from pharmaceutical plants. The actual waste water samples were subjected to solid phase extraction (SPE) for pretreatment prior to the application of chromatographic techniques (HPLC and TLC-densitometry). On the other hand, the fabricated electrodes were successfully applied for quantification of the antibiotic residues in actual waste water samples without any pretreatment. This finding assures the suitability of the fabricated ISEs for environmental analysis.

Simultaneous Electrochemical Detection of Benzimidazole Fungicides Carbendazim and Thiabendazole Using a Novel Nanohybrid Material-Modified Electrode.

In this work, a novel ZnFe2O4/SWCNTs nanohybrid was successfully synthesized as electrode material and applied to the simultaneous quantitative determination of carbendazim (CBZ) and thiabendazole (TBZ). The electrochemical behaviors of CBZ and TBZ on the ZnFe2O4/SWCNTs/GCE were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The electrochemical active area of modified electrode was calculated, which is nearly 5.5 times that of the bare electrode. The influence of various factors such as accumulation time, pH and scan rates, type of surfactant, and the electrochemical reaction mechanism was studied. The results showed that the reaction of CBZ/TBZ was controlled by adsorption/diffusion and was a quasi-reversible/an irreversible process at the ZnFe2O4/SWCNTs/GCE. In the pH 7.0 phosphate-buffered saline (PBS) containing 10.0 µg/mL CTAB, the electrochemical responses of CBZ and TBZ were separately investigated and were linearly dependent on their concentrations ranging from 0.5 to 100.0 µM, with relatively low detection limits of 0.09 and 0.05 µM, respectively. The concentration range for the simultaneous determination of CBZ and TBZ was 1.0-100.0 µM. Furthermore, with satisfactory results, the proposed electrochemical sensor was successfully applied to the determination of CBZ and TBZ in the real samples.

Selective and sensitive electrochemical device for direct VB2 determination in real products.

The developed by us electrochemical device for vitamin B2 (VB2; riboflavin) determination, without preconcentration step, in real products exhibits high sensitivity, selectivity, stability and low detection limit compared to those described in the literature. The determination procedure was based on the monitoring of the reduction current signal of VB2 bound with dsDNA anchored to the electrode surface through intermediary - carboxyphenyl layer. The application of such intermediary layer formed during electroreduction of appropriate diazonium salt at CV peak potential guarantees high efficiency of hybridization process and thus fully available places for VB2 interaction. Moreover, such intermediary layer provides good electrical contact, what is very important in the case of electrochemical sensors. The analytical range of work of the proposed VB2 sensor was between 0.08-1µM (30-377µgL-1) of riboflavin concentration. The obtained detection (LOD) and quantification limits (LOQ) were 24±2 and 55±5µgL-1, respectively. The proposed VB2 detection method was used for determination of riboflavin content in commercially available dietary supplements and yolk of hen egg samples. The accuracy of the obtained data was proved using comparison with an independent method (HPLC FLD).

Electrochemical Sensor Based on Fe Doped Hydroxyapatite-Carbon Nanotubes Composite for L-Dopa Detection in the Presence of Uric Acid.

A novel amperometric sensor based on iron doped hydroxyapatite (Fe-HA) and multiwalled carbon nanotubes (CNT) composite immobilized on a glassy carbon electrode (GCE) has been fabricated. The hybrid composite made of Fe-HA nanoparticles and CNT promotes electron transfer kinetics between the analyte levodopa (L-dopa) and the modified GC electrode. Under optimum conditions, the fabricated sensor gave a linear response range of 1.0 x 10(-7)-1.1 x 10(-6) M with the detection limit as low as 62 nM. The Fe-HA/CNT modified electrode showed good selectivity towards the determination of L-dopa in the presence of ascorbic acid (AA), uric acid (UA) and other common interferents. The sensor displays a high sensitivity, good reproducibility and long-term stability and it was successfully applied for the detection of L-dopa in pharmaceutical and medicinal plant samples.

The novel voltammetric method for determination of hesperetin based on a sensitive electrochemical sensor.

A highly sensitive voltammetric sensor, based on reduced graphene oxide on SWCNTs modified glassy carbon electrode (GCE), was constructed and used for sensitive detection of hesperetin. The electrochemical behavior of hesperetin at this sensor was investigated systematically and a novel voltammetric method for determination of hesperetin was proposed. The redox characters of hesperetin was discussed in detail and a reasonable reaction mechanism was proposed also. As the analytical method, the response currents were linear relationship with the hesperetin concentrations in the range of 5.0 × 10(-8) to 3.0 × 10(-6) mol L-(1), with a detection limit of 2.0 × 10(-8) mol L(-1) (S/N=3). The method was also applied successfully to detect hesperetin in biological samples and Chinese herbal medicine Flos buddlejae with satisfactory results.

Use of array of conducting polymers for differentiation of coconut oil products.

An array of chemiresistors based on conducting polymers was assembled for the differentiation of coconut oil products. The chemiresistor sensors were fabricated through the potentiostatic electrodeposition of polyaniline (PANi), polypyrrole (PPy) and poly(3-methylthiophene) (P-3MTp) on the gap separating two planar gold electrodes set on a Teflon substrate. The change in electrical resistance of the sensors was measured and observed after exposing the array to the headspace of oil samples. The sensor response was found rapid, reversible and reproducible. Different signals were obtained for each coconut oil sample and pattern recognition techniques were employed for the analysis of the data. The developed system was able to distinguish virgin coconut oil (VCO) from refined, bleached & deodorised coconut oil (RBDCO), flavoured VCO, homemade VCO, and rancid VCO.

A new amperometric biosensor based on Fe3O4/polyaniline/laccase/chitosan biocomposite-modified carbon paste electrode for determination of catechol in tea leaves.

In the present study, a new biosensor based on laccase from Paraconiothyrium variabile was developed for catechol. The purified enzyme entrapped into the Fe3O4/polyaniline/chitosan (Fe3O4/polyaniline (PANI)/chitosan (CS)) biocomposite matrix film without the aid of other cross-linking reagents by a one-step electrodeposition on the surface of carbon paste electrode (CPE). The formed layer of biocomposite was characterized with scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The biosensor was optimized with respect to biocomposite composition, enzyme loading, and solution pH by amperometry method. The biosensor exhibited noticeable eletrocatalytic ability toward catechol with a linear concentration range from 0.5 to 80 µM and a detection limit of 0.4 µM. The biosensor showed optimum response within 8 s, at pH 5, and 40 °C. The apparent Michaelis-Menten (K M (app)) was found to be 1.092 µM. The fabricated biosensor could be applied for determination of catechol in tea leaf samples.

Application of multivariate curve resolution alternating least squares method for determination of caffeic acid in the presence of catechin interference.

In the current article, preparation and application of a graphene oxide nanosheets-based sensor for electrochemical determination of caffeic acid (CA) in the presence of catechin is described. This measurement was performed using the differential pulse voltammetry (DPV) technique and chemometric methods such as multivariate curve resolution-alternating least squares (MCR-ALS). The modified sensor was characterized by various techniques such as Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet-visible, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Operating conditions and influencing variables (involving several chemical and instrumental variables) were optimized with central composite rotatable design and response surface methodology. The second-order electrochemical data were generated by changing the pulse height in DPV, and after potential shift correction MCR-ALS was applied. Under the optimized conditions, the dynamic range for CA was from 0.5 to 100.0 µM and the detection limit was found to be 1.1×10(-9) M. The results revealed that the modified electrode shows an improvement in anodic oxidation activity of CA due to a marked enhancement in the current response compared with the bare carbon paste electrode. The modified electrode demonstrated good sensitivity, selectivity, and stability. The proposed method was successfully applied in determination of caffeic acid in the presence of unexpected electroactive interferences with a very high degree of overlapping such as catechin in real samples.

Amperometric cell for subcutaneous detection of hydrogen sulfide in anesthetized experimental animals.

Hydrogen sulfide (H2S) is a toxic gas. It has been recognized that H2S evolving in biochemical reactions in living organisms has an important role in different physiologic processes. Nowadays, H2S is known as an endogenous messenger molecule. Natural sulfurous spring water has been proved beneficial in the therapy of diseases of the skin and other organs (Boros et al 2013). In vivo real-time detection of local H2S concentration is an important but challenging task.We developed a two-electrode amperometric cell for selective subcutaneous detection of H2S in anesthetized mice. The cell is a small size implantable gas sensor containing a platinum disc anode and a silver cathode. The selectivity is provided by a membrane permeable only by gases. There is a buffered reversible electrochemical mediator solution in an oxidized form inside the cell. As gaseous H2S penetrates into the cell the mediator is reduced, and +0.4 V versus the reference is employed on the platinum working electrode. The reduced mediator is oxidized on the anode surface. The current provides an analytical signal representing the concentration of H2S.Appropriate shape, size and membrane material were selected, and optimal working parameters--such as mediator concentration, pH and cell voltage--were determined in vitro. The lower limit of detection in the stirred sample solution at pH = 5.5 was as small as 9.4 × 10(-7) M and a dynamic concentration range of 0-6 × 10(-4) M could be achieved.The detecting surfaces of the cell were covered with freshly dissected mouse skin to test dermal H2S permeability. In other experiments, the cell was implanted subcutaneously in an anesthetized mouse and the animal was submerged in a buffer solution containing different concentrations of H2S so that the skin surface over the sensor was covered by the solution. Measurements of subcutaneous H2S concentration were taken. The experiments clearly proved that H2S diffuses through the skin of the live mouse.

Online electrochemical monitoring of dynamic change of hippocampal ascorbate: toward a platform for in vivo evaluation of antioxidant neuroprotective efficiency against cerebral ischemia injury.

Effective monitoring of cerebral ascorbate following intravenous antioxidant treatment is of great importance in evaluating the antioxidant efficiency for neuroprotection because ascorbate is closely related to a series of ischemia-induced neuropathological processes. This study demonstrates the validity of an online electrochemical system (OECS) for ascorbate detection as a platform for in vivo evaluation of neuroprotective efficiency of antioxidants by studying the dynamic change of hippocampal ascorbate during the acute period of cerebral ischemia and its responses to intravenous administration of antioxidants including ascorbate and glutathione (GSH). The OECS consists of a selective electrochemical detector made of a thin-layer electrochemical flow cell integrated with in vivo microdialysis. With such a system, the basal level of hippocampal ascorbate is determined to be 5.18 ± 0.60 µM (n = 20). This level is increased by 10 min of two-vessel occlusion (2-VO) ischemia treatment and reaches 11.51 ± 3.43 µM (n = 5) at the time point of 60 min after the ischemia. The 2-VO ischemia-induced hippocampal ascorbate increase is obviously attenuated by immediate intravenous administration of ascorbate (2.94 g/kg) or glutathione (5.12 g/kg) within 10 min after ischemia and the ascorbate level remains to be 3.75 ± 1.66 µM (n = 4) and 5.30 ± 0.79 µM (n = 5), respectively, at the time point of 60 min after ischemia. To confirm if the attenuated hippocampal ascorbate increase is attributed to the antioxidant-induced oxidative stress alleviation, we further study the immunoreactivity of 8-hydroxy-2-deoxyguanosine (8-OHdG) in the ischemic hippocampus and find that the 8-OHdG immunoreactivity is decreased by the administration of ascorbate or GSH as compared to the ischemic brain without antioxidant treatment. These results substantially demonstrate that the OECS for ascorbate detection could be potentially used as a platform for evaluating the efficiency of antioxidant neuroprotection in cerebral ischemia treatment.

Real-time monitoring of adipocyte differentiation using a capacitance sensor array.

As obesity and its associated metabolic diseases become a worldwide epidemic, the demand for novel anti-obesity agents is increasing. We report a label-free and real-time monitoring method that uses a capacitance sensor array to screen anti-obesity agents. The results for the real-time capacitance of 3T3-L1 cells treated with 12 different chemicals extracted from natural products were consistent with the biochemical indicators of adipogenesis such as the expression of perilipin, the major protein coating the surface of lipid droplets in adipocytes. The data demonstrate that a capacitance change during adipocyte differentiation is closely associated with lipid accumulation in the cells, suggesting that adipocyte differentiation can be monitored in real time. This capacitance sensor might be used for label-free and real-time monitoring of adipocyte differentiation, and may facilitate the development of high throughput screening methods for anti-obesity drugs.

Label-free impedimetric immunosensor for sensitive detection of fenvalerate in tea.

In this experiment, fenvalerate antibodies were immobilised on the electrode by the crosslinking with glutaraldehyde modified on the glassy carbon electrode (GCE) via chitosan. Fenvalerate was measured by the increase of electron transfer resistance when the immune reaction occurred with Fe(CN)6(3-)/Fe(CN)6(4-) as the probe. Under optimal conditions, the change of resistance is in a linear relationship with the logarithm of the concentration in the range of 1.0×10(-3)∼1.0×10(1)mg/L (R=0.998) with a detection limit of 0.80 µg/L. This method bears such merits as simplicity of operation, high sensitivity, wide linear range, specificity, reproducibility and good stability. The immunosensor was applied in the detection of real samples of tea, achieving satisfactory results, and it could be regenerated after being placed alternately in 0.5 mol/L HCl and 0.5 mol/L NaOH solutions.

The effect of ultrasonic and HNO3 treatment of activated carbon from fruit stones on capacitive and pseudocapacitive energy storage in electrochemical supercapacitors.

The effect of ultrasonic treatment and modification with nitric acid of activated carbon obtained from fruit stones, on the parameters of electric double-layer (EDL) as well as on farad-volt characteristics of its boundary with electrolyte 7.6 m KОН, 4 m KI and 2 m ZnI2 aqueous solutions has been studied by means of precision porometry, cyclic voltamperometry, electrochemical impedance spectroscopy and computer simulation methods. It is shown that HNO3 treatment results in an increase of the electrostatic capacitance up to 202 F/g in 7.6 m KОН-solution as well as pseudocapacitance up to 1250 F/g in 4 m KI. This increase is supposed to be related both with hydrophilicity and with an increase of the density of states on Fermi level. The ultrasonic treatment enables one to significantly increase (more than 200 times) the density of states on Fermi level which in turn causes both quantitative and qualitative changes in farad-volt dependences. A hybrid supercapacitor with specific capacitance of 1100 F/g and specific energy of 49 Wh/kg per active mass of two electrodes was developed.