Development of cloth-based microfluidic devices for rapid determination of histamine in fish and fishery products.

A cloth-based analytical device combined with electrochemiluminescence detection (CAD-ECL) was described for rapid determination  of histamine (HA). The CAD device was produced by screen-printing a conductive carbon ink onto a patterned hydrophobic electrochemical microfluidic chamber to fabricate the three-carbon electrode system on a single hydrophilic cloth. The introduction of carbon nanodots linked to chitosan on the working carbon electrode surface enhanced the catalytic performance and overcame the resistance of the cotton fiber material. On this basis, the enhancement of the electrochemiluminescence (ECL) signal of the tris(2,2'-bipyridyl) ruthenium(II) complex, caused by HA, was observed in a phosphate buffer solution at pH 7.6. The proposed CAD-ECL sensor was successfully applied to the quantification of HA in fish and fishery samples with good linearity between ECL intensity and the logarithm of HA concentration in the range 1.0 to 1000.0 µg L-1 with a low detection limit of 0.82 µg L-1.

Fabrication of a simple 3D-printed microfluidic device with embedded electrochemiluminescence detection for rapid determination of sibutramine in dietary supplements.

The design and fabrication of a simple 3D-printed platform with embedded electrochemiluminescence (ECL) detection for sibutramine determination is described. The microfluidic platform was fabricated by the fused deposition 3D-printing technique with polylactic acid filament, facilitated by computer-aided design (CAD). A three-electrode system was integrated into the device using graphene carbon paste as a working electrode, Ag/AgCl wire as a reference, and a graphite rod as a counter electrode. A further modification was carried out by applying bimetallic Au-Pt nanoparticle-supported multi-walled carbon nanotubes (MWCNT-Au-Pt) on the working electrode surface to enhance the electrocatalytic performance by exploiting the unique properties of nanomaterials. The analytical feasibility of the CAD-ECL sensor was tested through its application for the determination of sibutramine in dietary supplements. Under the optimized conditions, based on the enhancing effect of luminol emission, the device exhibited a linear calibration curve of the logarithmic sibutramine concentration versus ECL intensity in the range 5 × 10-3 to 1 ng mL-1. The limit of detection was 3 pg mL-1 with a relative standard deviation of 1.7% (n = 15). The 3D-printed prototype can be successfully applied to a small-scale analysis in a simple and cost-effective approach.

A cloth-based electrochemiluminescence sensor for determination of salbutamol residues in pork samples.

The fabrication of a cloth-based analytical device combined with electrochemiluminescence detection was established for the rapid determination of salbutamol in pork samples. A hand-coloring method to pattern the hydrophobic chamber was employed, and a three-carbon electrode system was subsequently screen printed onto the patterned cotton chamber. Further modifications of the working electrode surface were conducted using platinum nanoparticles and chitosan solution. The salbutamol enhanced the electrochemiluminescence signal of tris(2,2'-bipyridyl)ruthenium(II) complex in the Britton-Robinson buffer of pH 9.5 and the potential quantitative assay for SAL detection was exhibited. The proposed sensor illustrated a linear calibration curve of the logarithmic SAL concentration in the range of 5 × 10-2 to 5 × 104 µg L-1 (r2 > 0.996). A limit of detection of 6.8 ng L-1 was observed. The CAD-ECL sensor was successfully applied for the determination of salbutamol residuals in pork samples. The method validation was performed using the LC-MS method.

An integrated microcatheter-based dual-analyte sensor system for simultaneous, real-time measurement of propofol and fentanyl.

According to the American Society of Anesthesiologists Closed Claims Database, one of three drug-related errors is the result administrating an incorrect dose. Directly measuring drug concentration removes the uncertainty in the dose-concentration relationship and addresses inter- and intra-subject variabilities that affect the pharmacokinetics of anesthetics. Here we describe a dual-analyte microcatheter-based electrochemical sensor capable of simultaneous real-time continuous monitoring of fentanyl (FTN) and propofol (PPF) drugs simultaneously in the operating rooms. Such a dual PPF/FTN catheter sensor relies on embedding two different modified carbon paste (CP)-packed working electrodes along with Ag/AgCl microwire reference electrodes within a mm-wide Teflon tube, and uses a square wave voltammetric (SWV) technique. The composition of each working electrode was judiciously tailored to cover the concentration range of interest for each analyte. A polyvinyl chloride (PVC) organic polymer coating on the surface of CP electrode enabled selective and sensitive PPF measurements in µM range. The detection of nM FTN levels was achieved through a multilayered nanostructure-based surface modification protocol, including a CNT-incorporated CP transducer modified by a hybrid of electrodeposited Au nanoparticles and electrochemically reduced graphene oxide (erGO) and a PVC outer membrane. The long-term monitoring capability of the dual sensor was demonstrated in a protein-rich artificial plasma medium. The promising antibiofouling behavior of the catheter-based multiplexed sensor was also illustrated in whole blood samples. The new integrated dual-sensor microcatheter platform holds considerable promise towards real-time, in-vivo detection of the anesthetic drugs, propofol and fentanyl, during surgical procedures towards significantly improved safe delivery of anesthetic drugs.

A new alternative assay for sensitive analysis of ethylenethiourea and propylenethiourea in fruit samples after their separation.

Ultra-high-performance liquid chromatography (UHPLC) coupled with a cobalt phthalocyanine screen-printed carbon electrode (CoPc-SPCE) was developed and validated for quantitative analysis of ethylenethiourea (ETU) and propylenethiourea (PTU). CoPC-SPCE provided high catalytic properties for ETU and PTU oxidation. This fabricated electrode is inexpensive, disposable, and easy to prepare by an in-house screen-printing technique. The chromatographic separation was performed in isocratic mode on a reversed phase C18 (100 mm × 4.6 mm, 3 µm) column, using a 90 : 10 (v/v) ratio of 0.05 M phosphate buffer solution (pH 4) and methanol as the mobile phase with a flow rate of 1.0 mL min-1 at an oxidation potential of +0.7 V vs. Ag/AgCl. The separation could be achieved within 3 min, and a wide linear range of 0.01-100 µg mL-1 (r2 > 0.99) was obtained for both analytes. The limits of detection (3 S/N) were found to be 0.006 and 0.009 µg mL-1 for ETU and PTU, respectively. Furthermore, this proposed method was utilized to determine ETU and PTU in fruit samples with satisfactory results, yielding excellent intra-day and inter-day relative standard deviations and recoveries. These results demonstrated that the proposed assay can be used as a new alternative way for inexpensive, rapid, selective and sensitive determination of ETU and PTU in fruit samples.

Microneedle-Based Detection of Ketone Bodies along with Glucose and Lactate: Toward Real-Time Continuous Interstitial Fluid Monitoring of Diabetic Ketosis and Ketoacidosis.

Diabetic ketoacidosis (DKA), a severe complication of diabetes mellitus with potentially fatal consequences, is characterized by hyperglycemia and metabolic acidosis due to the accumulation of ketone bodies, which requires people with diabetes to monitor both glucose and ketone bodies. However, despite major advances in diabetes management mainly since the emergence of new-generation continuous glucose monitoring (CGM) devices capable of in vivo monitoring of glucose directly in the interstitial fluid (ISF), the continuous monitoring of ketone bodies is yet to be addressed. Here, we present the first use of a real-time continuous ketone bodies monitoring (CKM) microneedle platform. The system is based on the electrochemical monitoring of ß-hydroxybutyrate (HB) as the dominant biomarker of ketone formation. Such real-time HB detection has been realized using the ß-hydroxybutyrate dehydrogenase (HBD) enzymatic reaction and by addressing the major challenges associated with the stable confinement of the enzyme/cofactor couple (HBD/NAD+) and with a stable and selective low-potential fouling-free anodic detection of NADH. The resulting CKM microneedle device displays an attractive analytical performance, with high sensitivity (with low detection limit, 50 µM), high selectivity in the presence of potential interferences, along with good stability during prolonged operation in artificial ISF. The potential applicability of this microneedle sensor toward minimally invasive monitoring of ketone bodies has been demonstrated in a phantom gel skin-mimicking model. The ability to detect HB along with glucose and lactate on a single microneedle array has been demonstrated. These findings pave the way for CKM and for the simultaneous microneedle-based monitoring of multiple diabetes-related biomarkers toward a tight glycemic control.

Enhanced electrogenerated chemiluminescence of tris(2,2'-bipyridyl)ruthenium(II) system by l-cysteine-capped CdTe quantum dots and its application for the determination of nitrofuran antibiotics.

This paper reports a new approach to enhance the electrogenerated chemiluminescence (ECL) of the tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+)) system using resonance energy transfer with l-cysteine-capped cadmium telluride quantum dots (CdTe-QDs) in aqueous solution. The oxidative peak signal of Ru(bpy)3(2+) occurred at a voltage of 1.10V when the potential was cycled between 0.4 and 1.6V using cyclic voltammetry with a carbon screen-printed electrode (SPE) in a 0.11M phosphate buffer at pH 7.50. The l-cysteine-capped CdTe-QDs were synthesized and added into the solution of Ru(bpy)3(2+) to magnify the ECL signal. The ECL emission signal was investigated and the extreme enhancement of the ECL intensity was achieved due to the energy transfer by the l-cysteine-capped CdTe-QDs. It was found that the induced ECL from the Ru(bpy)3(2+) CdTe-QDs system was inhibited by the presence of selected nitrofurans. This quenching effect of nitrofuran antibiotics on the anodic ECL of Ru(bpy)3(2+) CdTe-QDs was found to be selective and concentration dependent and was observed to have a linear relationship over the concentration range 10-100×10(-6)M. The detection limits were found to be 0.40, 0.73 and 0.60µM for furaltadone (FTD), furazolidone (FZD) and nitrofurantoin (NFT). In addition, the proposed ECL method was successfully applied to detect the total residuals of selected nitrofuran residues in animal feed samples with satisfactory results.

Determination of sulfite by pervaporation-flow injection with amperometric detection using copper hexacyanoferrate-carbon nanotube modified carbon paste electrode.

A pervaporation-flow injection (PFI) method was developed for the determination of sulfite in selected food samples using a copper hexacyanoferrate-carbon nanotube (CuHCF-CNT)-modified carbon paste electrode. The electrochemical behavior of the modified electrode was observed using cyclic voltammetry in comparison to a CuHCF-modified carbon paste electrode and a bare carbon paste electrode at a scan rate of 100mVs(-1) in 0.10M KNO(3). The bare carbon paste electrode gave the lowest response to sulfite, while the presence of CuHCF made the detection of sulfite possible through electrocatalytic oxidation by the hexacyanoferrate in the modified electrodes. The presence of CNT in the CuHCF-CNT-modified sensor gave the most remarkable current for the detection of sulfite and was then used as a working electrode in the amperometric flow-through cell in the pervaporation flow injection system. The PFI method involves the injection of a standard or sample sulfite solution into a sulfuric acid donor stream to generate sulfur dioxide gas and evaporate into the headspace of the pervaporation unit. The sulfur dioxide diffuses through the PTFE hydrophobic membrane into a potassium nitrate acceptor stream and reverts to the sulfite form, which, subsequently, is transported to the electrochemical flow cell where it is analyzed amperometrically at a CuHCF-CNT-modified electrode at +0.55V (vs. Ag/AgCl). The detection was determined to be applicable in the sulfite concentration range of 0.5-50mgL(-1). The sensitivity, detection limit, and sample throughput were determined to be 2.105nALmg(-1), 0.40mgL(-1) and 11h(-1), respectively. The developed PFI method, coupled with the CuHCF-CNT-modified carbon paste electrode, was applied in the determination of sulfite content in sulfite-containing food products. The results agreed well with those obtained through the officially recommended differential pulse polarographic method.

Electrocatalytic detection of insulin at RuOx/carbon nanotube-modified carbon electrodes.

A bilayer surface coating, prepared by electrodepositing ruthenium oxide (RuOx) onto a carbon nanotube (CNT) layer, offers dramatic improvements in the stability and sensitivity of voltammetric and amperometric measurements of insulin compared to the individual (CNT or RuOx) coated electrodes. The enhanced electrocatalytic activity towards insulin is indicated from lowering the potential of the oxidation process (starting around 0.35 versus Ag/AgCl) and the substantially higher sensitivity over the entire potential range. A wide linear dynamic range (10-800 nM) was achieved with a detection limit of 1 nM. The marked electrocatalytic activity of the RuOx/CNT coating towards insulin is coupled with a greatly enhanced stability. For example, the insulin amperometric response of the RuOx/CNT-coated electrodes is highly stable, with 97% of the initial activity remaining after 60 min stirring of 2 x 10(-6) M solution (compared to significantly faster current diminutions at the RuOx- or CNT-coated surfaces). The results suggest great promise for miniaturized sensors and detectors for monitoring insulin.

Design and development of a highly stable hydrogen peroxide biosensor on screen printed carbon electrode based on horseradish peroxidase bound with gold nanoparticles in the matrix of chitosan.

The design and development of a screen printed carbon electrode (SPCE) on a polyvinyl chloride substrate as a disposable sensor is described. Six configurations were designed on silk screen frames. The SPCEs were printed with four inks: silver ink as the conducting track, carbon ink as the working and counter electrodes, silver/silver chloride ink as the reference electrode and insulating ink as the insulator layer. Selection of the best configuration was done by comparing slopes from the calibration plots generated by the cyclic voltammograms at 10, 20 and 30 mM K(3)Fe(CN)(6) for each configuration. The electrodes with similar configurations gave similar slopes. The 5th configuration was the best electrode that gave the highest slope. Modifying the best SPCE configuration for use as a biosensor, horseradish peroxidase (HRP) was selected as a biomaterial bound with gold nanoparticles (AuNP) in the matrix of chitosan (HRP/AuNP/CHIT). Biosensors of HRP/SPCE, HRP/CHIT/SPCE and HRP/AuNP/CHIT/SPCE were used in the amperometric detection of H(2)O(2) in a solution of 0.1M citrate buffer, pH 6.5, by applying a potential of -0.4V at the working electrode. All the biosensors showed an immediate response to H(2)O(2). The effect of HRP/AuNP incorporated with CHIT (HRP/AuNP/CHIT/SPCE) yielded the highest performance. The amperometric response of HRP/AuNP/CHIT/SPCE retained over 95% of the initial current of the 1st day up to 30 days of storage at 4 degrees C. The biosensor showed a linear range of 0.01-11.3mM H(2)O(2), with a detection limit of 0.65 microM H(2)O(2) (S/N=3). The low detection limit, long storage life and wide linear range of this biosensor make it advantageous in many applications, including bioreactors and biosensors.

Highly sensitive electrochemical detection of trace liquid peroxide explosives at a Prussian-blue 'artificial-peroxidase' modified electrode.

A highly sensitive electrochemical assay of the peroxide-based explosives triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) at a Prussian-blue (PB) modified electrode is reported. The method involves photochemical degradation of the peroxide explosives and a low potential (0.0 V) electrocatalytic amperometric sensing of the generated hydrogen peroxide at the PB transducer and offers nanomolar detection limits following a short (15 s) irradiation times. The electrochemical sensing protocol should facilitate rapid field screening of peroxide explosives.

Sensitive and rapid electrochemical bioassay of glycosidase activity.

Here we present a highly sensitive, rapid and simple electrochemical assay for glycosidases based on treatment of the glycosidase with the appropriate p-nitrophenyl glycoside and anodic detection of released p-nitrophenol. The attractive characteristics of the new bioassay should facilitate advanced glycomic research and routine clinical diagnostics since glycosidases are associated with various diseases.