Effects of sonochemical approach and induced contraction of core-shell bismuth sulfide/graphitic carbon nitride as an efficient electrode materials for electrocatalytic detection of antibiotic drug in foodstuffs.

Ultrasonic-enhanced surface-active bismuth trisulfide based core-shell nanomaterials were developed and used as an efficient modified electrode material to construct a highly sensitive antibiotic sensor. The core-shell Bi2S3@GCN electrode material was directly synthesized by in-situ growth of GCN on Bi2S3 to form core-shell like nanostar (Ti-horn, 30 kHz, and 70 W/cm2). The electrocatalyst of Bi2S3@GCN nanocomposites was efficaciously broadened towards electrochemical applications. As synthesized Bi2S3@GCN promoted the catalytic ability and electrons of GCN to transfer to Bi2S3. The single-crystalline GCN layers were uniformly grown on the surface of the Bi2S3 nanostars. Under the optimal conditions of electrochemical analysis, the CPL sensor exhibited responses directly proportional to concentrations (toxic chemical) over a range of 0.02-374.4 µM, with a nanomolar detection limit of 1.2 nM (signal-to-noise ratio S/N = 3). In addition, the modified sensor has exhibited outstanding selectivity under high concentrations of interfering chemicals and biomolecules. The satisfactory CPL recoveries in milk product illustrated the credible real-time application of the proposed Bi2S3@GCN sensors for real samples, indicating promising potential in food safety department and control. Additionally, the proposed electrochemical antibiotic sensor exhibited outstanding performance of anti-interfering ability, high stability and reproducibility.

Ruthenium oxide nanoparticles immobilized over Citrus limetta waste derived carbon material for electrochemical detection of hexestrol.

Hexestrol is a non-steroidal estrogen which causes carcinogenic effects in animals. It is therefore important to develop sensitive and selective test methods for its early detection. Herein, we report the development of an electrochemical sensor to detect hexestrol in ultralow concentrations. In order to devise a simple and cost-effective hexestrol sensing electrode, attention is paid to the development of biomass-derived porous carbon (PCB) with large surface area and suitable porosity to immobilize ruthenium oxide nanoparticles (RuO2 NPs, 3-4 nm). The leftover Citrus limetta pulp is chosen as waste biomass since it has N and O based chemical species. Structural, morphological and compositional analysis of PCB and RuO2@PCB revealed well-dispersed RuO2 NPs over the PCB surface. High loading (5.27 at%) of Ru content is achieved due to the large surface area of PCB. Cyclic voltammetry, chronoamperometry and differential pulse voltammetry results suggest that the RuO2@PCB/ITO electrode is capable of detecting hexestrol concentration (in the range of 1 × 10-7-2 × 10-5 M). The practical application of hexestrol detection in milk samples demonstrates the recovery from 96.28 to 101%.

Combination of Efficiency with Easiness, Speed, and Cheapness in Development of Sensitive Electrochemical Sensors.

Nowadays, electrochemical techniques can be considered as a suitable alternative technique besides UV/Vis spectroscopy, liquid chromatography, capillary electrophoresis, mass spectroscopy, NMR for evaluation and determination of different electroactive compounds. Solid electrodes such as carbon and metal-based substrates are common for electrochemical applications. Especially, during two past decades, different types of modified electrodes with these solid electrodes have been developed for fast, sensitive, and selective analysis of various important analyses (biomolecules, enzymes, and drugs) in a wide range of real samples. These applications are highly efficient, cost effective and facile fabrication procedures of the electrode modification can be employed. In the present review, at first, some recently developed high performance bare and modified electrodes are evaluated based on their outstanding properties. In the next step, developed new procedures or fabricated modified electrodes with good sensitivity based on simple and cheap protocols are introduced and discussed.

Facile Preparation of Fe3O4/C Nanocomposite and Its Application for Cost-Effective and Sensitive Detection of Tryptophan.

In this study, we reported facile synthesis of Fe3O4/C composite and its application for the cost-effective and sensitive determination of tryptophan (Trp) in human serum samples. Fe3O4/C composites were prepared by a simple one-pot hydrothermal method followed by a mild calcination procedure, using FeCl3∙6H2O as Fe3O4 precursor, and glucose as reducing agent and carbon source simultaneously. The Fe3O4/C composite modified glassy carbon electrode (Fe3O4/C/GCE) was prepared by drop-casting method. The microstructure and morphology of Fe3O4/C composite was characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Due to large specific surface area and synergistic effect from Fe3O4 nanoparticles and carbon coating, Fe3O4/C composite showed excellent electrocatalytic activity toward the oxidation of Trp. As a result, the proposed Fe3O4/C/GCE displayed superior analytical performances toward Trp determination, with two wide detection ranges (1.0-80 µM and 80-800 µM) and a low detection limit (0.26 µM, S/N = 3). Moreover, successful detection of Trp in human serum samples further validate the practicability of the proposed sensor.

Low cost non-electromechanical technique for the purification of giant unilamellar vesicles.

Lipid membranes of giant unilamellar vesicles (GUVs) with diameters greater than 10 µm are promising model membranes for investigating the physical and biological properties of the biomembranes of cells. These are extensively used for the study of the interaction of various membrane-active agents, where purified and similar-size oil-free GUVs are necessary. Although the existing membrane filtering method provides the required quality and quantity of GUVs, it includes a relatively expensive double-headed peristaltic pump. In our proposed non-electromechanical technique, gravity is used to maintain the flow of buffer, wherein the flow rate of buffer with the suspension of GUVs is controlled by a locally available low cost roller clamp regulator. We have characterized the results of this non-electromechanical approach in terms of size distribution, average size, flow rate and efficiency for dioleoylphosphatidylglycerol (DOPG)/dioleoylphosphatidylcholine (DOPC)-GUVs prepared by the natural swelling method. The technique purifies the GUVs by removing the non-entrapped solutes at an optimum flow rate 1.0-2.0 mL/min. In addition, it gives similar results to the pump-driven membrane filtering method. Therefore, it might be a cost effective technique for the purification of GUVs without employing any electromechanical devices.

Rapid voltammetric method for quinine determination in soft drinks.

A novel voltammetric assay for quinine (QN) determination using an electrochemically pretreated pencil graphite electrode is described. The detection limit of QN was 2 × 10-7 M. The method possesses some obvious advantages including extreme simplicity, rapid response, and low cost.

Amperometric Gas Sensors as a Low Cost Emerging Technology Platform for Air Quality Monitoring Applications: A Review.

This review examines the use of amperometric electrochemical gas sensors for monitoring inorganic gases that affect urban air quality. First, we consider amperometric gas sensor technology including its development toward specifically designed air quality sensors. We then review recent academic and research organizations' studies where this technology has been trialed for air quality monitoring applications: early studies showed the potential of electrochemical gas sensors when colocated with reference Air Quality Monitoring (AQM) stations. Spatially dense networks with fast temporal resolution provide information not available from sparse AQMs with longer recording intervals. We review how this technology is being offered as commercial urban air quality networks and consider the remaining challenges. Sensors must be sensitive, selective, and stable; air quality monitors/nodes must be electronically and mechanically well designed. Data correction is required and models with differing levels of sophistication are being designed. Data analysis and validation is possibly the biggest remaining hurdle needed to deliver reliable concentration readings. Finally, this review also considers the roles of companies, urban infrastructure requirements, and public research in the development of this technology.

A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO2.

We introduce a gross-margin model to evaluate the technoeconomic feasibility of producing different C1 -C2 chemicals such as carbon monoxide, formic acid, methanol, methane, ethanol, and ethylene through the electroreduction of CO2 . Key performance benchmarks including the maximum operating cell potential (Vmax ), minimum operating current density (jmin ), Faradaic efficiency (FE), and catalyst durability (tcatdur ) are derived. The Vmax values obtained for the different chemicals indicate that CO and HCOOH are the most economically viable products. Selectivity requirements suggest that the coproduction of an economically less feasible chemical (CH3 OH, CH4 , C2 H5 OH, C2 H4 ) with a more feasible chemical (CO, HCOOH) can be a strategy to offset the Vmax requirements for individual products. Other performance requirements such as jmin and tcatdur are also derived, and the feasibility of alternative process designs and operating conditions are evaluated.

Electrochemistry-based approaches to low cost, high sensitivity, automated, multiplexed protein immunoassays for cancer diagnostics.

Early detection and reliable diagnostics are keys to effectively design cancer therapies with better prognoses. The simultaneous detection of panels of biomarker proteins holds great promise as a general tool for reliable cancer diagnostics. A major challenge in designing such a panel is to decide upon a coherent group of biomarkers which have higher specificity for a given type of cancer. The second big challenge is to develop test devices to measure these biomarkers quantitatively with high sensitivity and specificity, such that there are no interferences from the complex serum or tissue matrices. Lastly, integrating all these tests into a technology that does not require exclusive training to operate, and can be used at point-of-care (POC) is another potential bottleneck in futuristic cancer diagnostics. In this article, we review electrochemistry-based tools and technologies developed and/or used in our laboratories to construct low-cost microfluidic protein arrays for the highly sensitive detection of a panel of cancer-specific biomarkers with high specificity which at the same time has the potential to be translated into POC applications.

Simultaneous determination of three species with a single-injection step using batch injection analysis with multiple pulse amperometric detection.

In this work, the possibility of simultaneous determination of three compounds with a single-injection step using batch injection analysis with multiple pulse amperometric detection (BIA-MPA) is demonstrated for the first time. A sequence of three potential pulses (+1.25 V, +1.60 V, and +1.80 V) was applied with the acquisition of three separate amperograms. 8-Chlorotheophylline was detected selectively at +1.25 V, both 8-chlorotheophylline and pyridoxine at +1.60V and 8-chlorotheophylline, pyridoxine, and diphenhydramine at +1.80 V. Subtraction between the currents detected at the three amperograms (with the help of correction factors) was used for the selective determination of pyridoxine and diphenhydramine. The proposed method is simple, inexpensive, fast (60 injections h(-1)), and present selectivity for the determination of the three compounds in pharmaceutical samples, with results similar to those obtained by HPLC (95% confidence level).

Electrochemical Preparation and Characterization of a Gold Nanoparticles Graphite Electrode: Application to Myricetin Antioxidant Analysis.

Graphite material is abundantly available from recyclable sources. It possesses a good electrical conductance property, which makes it an attractive material as a working electrode. However, due to a high activation overpotential it has limited applications as compared to other solid metal electrodes. In this present work, we obtained a graphite rod from a used battery, and carried out electrochemical improvements by electro-deposition with gold nanoparticles (AuNPs). The heterogeneous electron transfer rate and electron transfer resistance of the fabricated electrode were improved. The electrode overpotential has shown improvement by 50 mV, and the effective surface area has increased by 2 fold. To determine the practicability of the AuNPs/graphite electrode, we used the electrode in the analysis of myricetin. A square-wave voltammetry was used in the analysis, and the detection response increased by 2.5 fold, which suggested an improvement in the electrode sensitivity.

Electrochemical monitoring of the interaction between Temozolamide and nucleic acids by using disposable pencil graphite electrodes.

Temozolomide (TMZ) is an anticancer drug used for the treatment of adult brain tumour and skin cancer. The biomolecular interaction between TMZ and DNA was investigated for the first time in this study using disposable pencil graphite electrodes (PGEs) in combination with electrochemical techniques. The surface confined interactions between TMZ and different type of nucleic acids were performed. Before/after surface confined interaction process, the oxidation signals of TMZ, guanine and adenine were measured using differential pulse voltammetry (DPV) and PGE and accordingly, the changes at the oxidation signals were evaluated. The detection limit (DL) was also estimated based on the oxidation signal of TMZ. The interaction of TMZ with single stranded poly [A], poly [G], or double stranded poly [A]-poly[T] and poly [G]-poly[C] was also explored. Moreover, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques were utilized for detection the interaction between TMZ and DNA. The features of this single-use electrochemical sensor was discussed in comparison to other reports that were developed for TMZ detection.

A high performance nonenzymatic electrochemical glucose sensor based on polyvinylpyrrolidone-graphene nanosheets-nickel nanoparticles-chitosan nanocomposite.

In this report, a new nanocomposite was successfully synthesized by chemical deposition of nickel nanoparticles (NiNPs) on polyvinylpyrrolidone (PVP) stabilized graphene nanosheets (GNs) with chitosan (CS) as the protective coating. The as obtained nanocomposite (PVP-GNs-NiNPs-CS) was characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Benefiting from the synergistic effect of GNs (large surface area and high conductivity), NiNPs (high electrocatalytic activity towards the glucose oxidation) and CS (good film-forming and antifouling ability), a nonenzymatic electrochemical glucose sensor was established. The nanocomposite displays greatly enhanced electrocatalytic activity towards the glucose oxidation in NaOH solution. The PVP-GNs-NiNPs-CS based electrochemical glucose sensor demonstrates good sensitivity, wide linear range (0.1 µM-0.5 mM), outstanding detection limit (30 nM), attractive selectivity, good reproducibility, high stability as well as prominent feasibility for the real sample analysis. The proposed experiment might open up a new possibility for widespread use of non-enzymatic sensors for monitoring blood glucose owing to its advantages of low cost, simple preparation and excellent properties for glucose detection.

In situ electrochemical assessment of cytotoxicity of chlorophenols in MCF-7 and HeLa cells.

An in situ electrochemical method was used to assess the cytotoxicity of chlorophenols using human breast cancer (MCF-7) and cervical carcinoma (HeLa) cells as models. On treatment with different chlorophenols, the electrochemical responses of the selected cells, resulting from the oxidation of guanine and xanthine in the cytoplasm, indicated the cell viability. In addition, the in situ in vitro electrochemical method was further compared with the traditional MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays. Although similar cytotoxicity data were obtained from both methods, the effective concentrations of chlorophenols that inhibited 50% cell growth (EC50 values) from the electrochemical method were only slightly lower than those from the MTT assay. These results indicate that the in situ in vitro electrochemical method paves a simple, rapid, strongly responsive, and label-free way to the cytotoxicity assessment of different chlorophenol pollutants.

Electrocoagulation for the removal of phenol and aldehyde contaminants from resin effluent.

This paper is a report on a study which aimed to investigate the effect of different current density, pH, temperature, and cathode-anode combination on the removal of phenol and aldehyde in two samples of actual resin effluent through the process of electrocoagulation using solar energy. Current density 60 A/m(2) and pH 6 proved to be the best levels for both contaminants. As for the effect of temperature, although the highest degree of phenol and aldehyde removal was achieved at 15 °C, 25 °C was taken to be the optimum temperature for economic reasons. The Fe-Fe combination of electrodes was found to be the best as it led to nearly 93% of phenol removal and approximately 95% of aldehyde removal. Also, the effect of electrode combination on energy consumption was studied. It was observed that the Fe-Fe combination consumed the least amount of energy (0.7-4.3 kWh/m(3) of wastewater in the case of phenol and 0.8-4 kWh/m(3) of wastewater in the case aldehyde). Moreover, the Fe-Fe combination brought about the best results in terms of chemical oxygen demand removal: 93% in both cases. Finally, an economic analysis was performed for the electrocoagulation process.

Comparison of bioanalytical methods for the quantitation of PEGylated human insulin.

PURPOSE: The quality of bioanalytical data is dependent upon selective, sensitive, and reproducible analytical methods. With evolving technologies available, bioanalytical scientists must assess which is most appropriate for their molecule through proper method validation. For an early stage PEGylated insulin program, the characteristics of four platforms, ELISA, ECL, Gyrolab, and LC-MS/MS, were evaluated using fit-for-purpose method development and validation, while also evaluating costs. METHOD: Methods selected for validation required acceptable performance based on satisfaction of a priori criteria prior to proceeding to subsequent stages of validation. LBA pre-validation included reagent selection, evaluation of matrix interference, and range determination. LC-MS/MS pre-validation included selection of a signature peptide; optimization of sample preparation, HPLC, and LC-MS/MS conditions; and calibration range determination. Pre-study validation tested accuracy and precision (mean bias criteria±30%; precision≤30%). Pharmacokinetic (PK) parameters were estimated for an in vivo study with WinNonlin noncompartmental analysis. Statistics were performed with JMP using ANOVA and Tukey-Kramer post hoc analysis. A cost analysis was performed for a 200-sample PK study using the methods from this study. RESULTS: All platforms, except Gyrolab, were taken through validation. However, a typical Gyrolab method was included for the cost analysis. Ranges for the ELISA, ECLA, and LC-MS/MS were 8.52-75, 2.09-125, and 100-1000 ng/mL, respectively, and accuracy and precision fell within a priori criteria. PK samples were analyzed in the 3 validated methods. PK profiles and parameters are similar for all methods, except LC-MS/MS, which differed at t=24h and with AUC0-24. Further investigation into this difference is warranted. The cost analysis identified the Gyrolab platform as the most expensive and ELISA as the least expensive, with method specific consumables attributing significantly to costs. CONCLUSIONS: ECLA had a larger dynamic range and sensitivity, allowing accurate assessment of PK parameters. Although this method was more expensive than the ELISA, it was the most appropriate for the early stage PEGylated insulin program. While this case study is specific to PEGylated human insulin, it highlights the importance of evaluating and selecting the most appropriate platform for bioanalysis during drug development.

Ultrasensitive voltammetric determination of catechol at a gold atomic cluster/poly(3,4-ethylenedioxythiophene) nanocomposite electrode.

A novel gold atomic cluster-poly(3,4-ethylenedioxythiophene) (AuAC/PEDOT/Au) nanocomposite modified gold electrode has been designed for the trace level sensing of catechol. The addition of copper(II) enhanced the electro-catalytic oxidation of catechol via the formation of copper(I). The electrochemically synthesized PEDOT/Au and the AuAC/PEDOT/Au hybrid films were characterized by electrochemical and morphological methods. Under optimal conditions the nanocomposite modified electrode offers a wider calibration range of 1 × 10(-4) to 10 µM with a lowest detection limit of 6.3 pM for catechol. Moreover, the developed electrochemical sensor exhibited good selectivity and acceptable reproducibility (1.23% for 1 nM of catechol) and could be used for the routine detection and quantification of catechol in natural water samples. To gain a better understanding of such an excellent sensor performance achieved with this electrode, studies were undertaken to pinpoint electrode kinetics of charge transfer processes.

Effectiveness of a hybrid process combining electro-coagulation and electro-oxidation for the treatment of domestic wastewaters using response surface methodology.

The performance of a two-stage process combining electro-coagulation (EC) and electro-oxidation (EO) was studied for the treatment of domestic wastewater (DWW) loaded with organic matter. The process was firstly evaluated in terms of its capability of simultaneously producing an oxidant and a coagulant agents using aluminum (Al) (or iron (Fe)) as bipolar and sacrificial electrodes, whereas graphite (Gr) electrodes were used as monopolar electrodes. Relatively high concentrations of chlorine (9.6 mg/min A) and Al (20-40 mg Al/L) or Fe (40-60 mg Fe/L) were produced. Subsequently, the factorial and central composite design methodologies were successively employed to define the optimal operating conditions for total chemical oxygen demand (COD) removal from DWW. Current intensity and treatment time were found to be very meaningful for chemical oxygen demand removal. The effect of these two main factors was around 90% on the investigated response, whereas the type of sacrificial electrode and the other interaction effects represent only 10%. The treatment using aluminum electrode and a current intensity imposed of 0.7 A during 39 min was found to be the optimal conditions in terms of cost/effectiveness. Under these conditions, 78% of COD removal can be obtained for a total cost of 0.78 US $/m(3).

All polymer chip for amperometric studies of transmitter release from large groups of neuronal cells.

We present an all polymer electrochemical chip for simple detection of transmitter release from large groups of cultured PC 12 cells. Conductive polymer PEDOT:tosylate microelectrodes were used together with constant potential amperometry to obtain easy-to-analyze oxidation signals from potassium-induced release of transmitter molecules. The nature of the resulting current peaks is discussed, and the time for restoring transmitter reservoirs is studied. The relationship between released transmitters and potassium concentration was found to fit to a sigmoidal dose-response curve. Finally, we demonstrate how the presented device can be used for simple drug screening purposes, by measuring the increase of transmitter release due to short-term treatment with L-DOPA.

Flow injection simultaneous determination of synthetic colorants in food using multiple pulse amperometric detection with a boron-doped diamond electrode.

A single-line flow injection system and multiple pulse amperometric detection using a boron-doped diamond electrode were employed to develop and optimize a simple, low-cost, and rapid method for the simultaneous determination of two pairs of food colorants: tartrazine and sunset yellow (TT-SY) or brilliant blue and SY (BB-SY). A dual-potential waveform was used: E(det.1)=-150 mV (400 ms duration) and E(det.2)=-450 mV (100 ms duration) vs. Ag/AgCl (3.0 mol L(-1) KCl). Polarization at E(det.1) or E(det.2) causes reduction of SY or the respective pair of colorants, TT-SY or BB-SY; hence, with proper current correction, both colorants in each pair can be determined. The obtained linear response ranges (detection limits) were 5.0-60.0 (2.5) and 1.0-50.0 (0.80) µmol L(-1), for TT and SY, or 5.0-60.0 (3.5) and 1.0-50.0 (0.85) µmol L(-1), for BB and SY, respectively. Investigation of possible interferents (other food colorants or additives) showed no significant interference with the methods here proposed, which were then used to simultaneously determine the pairs of colorants in industrialized food samples, with results that showed good agreement with those obtained using a comparative HPLC method.