Determination of promethazine in forensic samples using multi-walled carbon nanotube-gold nanoparticle electrochemical sensor.

An electrochemical sensor was developed based on a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs) and gold nanoparticles (AuNPs) for the determination of promethazine (PMZ) in 'purple drank', pharmaceutical formulations, and synthetic saliva. The oxidation of PMZ at the modified electrode occurred at a higher cathodic potential and produced a higher sensitivity compared to the unmodified GCE. The morphology of the modified electrode was characterized using field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). The presence of MWCNTs and AuNPs was confirmed. The optimized parameters included the concentration and pH of the supporting electrolyte, amount of modifiers used to fabricate the electrode, deposition potential, and time. Using these optimized conditions, the method has a linear range from 0.5 to 100 µmol L-1, with a R2 value of 0.9991. The limit of detection (3SDblank/slope) was 0.13 µmol L-1. The proposed electrochemical sensor was successfully applied for the determination of PMZ in 'purple drank', pharmaceutical formulations, and spiked synthetic saliva samples. The results obtained from this sensor were in statistical agreement with the values obtained using the reference gas chromatography-flame ionization method.

A microplate spectrophotometric method for analysis of indole-3-carbinol in dietary supplements using p-dimethylaminocinnamaldehyde (DMACA) as a chromogenic reagent.

This work presents the development of a microplate spectrophotometric method for determination of indole-3-carbinol in dietary supplements. The colorimetric procedure is based on the reaction of indole-3-carbinol with the p-dimethylaminocinnamaldehyde (DMACA) reagent under acidic conditions. The absorbance of the colored product measured at 675 nm was used to determine the target analyte. To achieve optimal spectrophotometric performance, the DMACA reagent concentration, the hydrochloric acid concentration, and the reaction time were optimized. The developed technique performed well under the optimal conditions, with a linear calibration range of 30 to 300 mg L-1 and a high correlation coefficient (r2 = 0.9954). The limit of detection and limit of quantification were 7.8 mg L-1 and 26.2 mg L-1, respectively. This approach demonstrated good repeatability (intra- and inter-day precision) with a % RSD lower than 9.4%, good accuracy with acceptable relative recoveries in the range of 98 to 106%, and high sample throughput (24 detection per min). This simple, rapid, and multi-sample analysis approach for routine analysis of indole-3-carbinol has the potential to be used for the quality control of dietary supplements.

A stir bar sorptive extraction device coupled with a gas chromatography flame ionization detector for the determination of abused prescription drugs in lean cocktail samples.

A lean cocktail is a mixed drink for the non-medical use of prescription medications that has emerged in recent years as a drug of abuse and is related to drug-facilitated crimes. The determination of active ingredients in a lean cocktail is necessary for forensic investigations. This work presents an in-house developed stir bar sorptive extraction (SBSE) device with an XAD-2 adsorbent followed by analysis using GC-FID for the extraction and determination of the five main abused prescription drugs (diphenhydramine, tramadol, chlorpheniramine, dextromethorphan and promethazine) in lean cocktail samples. Under optimized conditions, the developed method provided linearity for 1.0-250 µg mL-1 of each of the five abused prescription drugs. The limits of detection and limits of quantitation were in the respective ranges of 0.25-0.5 µg mL-1 and 1.0-1.5 µg mL-1. The percentage of extraction was 85.0-94.9%. The intra-day and inter-day precisions were 1.2-14.4% RSD and 1.4-15.8% RSD, respectively. Good relative recoveries in the range of 86.7-110.3% and 88.5-107.9% were obtained when the proposed method was applied for extraction and analysis of abused prescription drugs in five lean cocktail samples. The developed method can be a useful tool for measuring the levels of abused prescription drugs in a lean cocktail and the data could also be used as evidence in a forensic investigation.

Dual-Purpose Photometric-Conductivity Detector for Simultaneous and Sequential Measurements in Flow Analysis.

This work presents a new dual-purpose detector for photometric and conductivity measurements in flow-based analysis. The photometric detector is a paired emitter-detector diode (PEDD) device, whilst the conductivity detection employs a capacitively coupled contactless conductivity detector (C4D). The flow-through detection cell is a rectangular acrylic block (ca. 2 × 2 × 1.5 cm) with cylindrical channels in Z-configuration. For the PEDD detector, the LED light source and detector are installed inside the acrylic block. The two electrodes of the C4D are silver conducting ink painted on the PEEK inlet and outlet tubing of the Z-flow cell. The dual-purpose detector is coupled with a sequential injection analysis (SIA) system for simultaneous detection of the absorbance of the orange dye and conductivity of the dissolved oral rehydration salt powder. The detector was also used for sequential measurements of creatinine and the conductivity of human urine samples. The creatinine analysis is based on colorimetric detection of the Jaffé reaction using the PEDD detector, and the conductivity of the urine, as measured by the C4D detector, is expressed in millisiemens (mS cm-1).

Electrochemical quantification of piperine in black pepper.

A simple, rapid method of the detection of piperine in black pepper is reported using a voltammetric sensor based on a glassy carbon (GC) electrode with analysis following a short one-step extraction using ethanol. The method is based on a novel potential sweep designed to maximise signal sizes and shown with context of the present analytical challenge to be essential for gathering data allowing the construction of a linear calibration curve for the analysis in the relevant range namely 0.25-5.0 mM.

Optimising amperometric pH sensing in blood samples: an iridium oxide electrode for blood pH sensing.

Amperometric pH sensing in blood samples has been studied using iridium oxide electrodes. The iridium oxide electrodes are made by electrodeposition of iridium oxide onto an iridium micro-disc electrode from an alkaline solution of iridium(iii) oxide. The response of the electrode is studied in aqueous solutions and authentic samples of sheep's blood employing both cyclic voltammetry and square wave voltammetry. Uncertainties of pH measurement in blood samples via cyclic voltammetry (±0.07 pH units) were improved by a factor of two using square wave voltammetry (±0.03 pH units). Limitations of amperometric pH sensing in blood samples are considered as caused by the uncertainty of the required reference measurements (via a conventional glass electrode) and also the use of matrix-free and low ionic strength buffers to calibrate a standard glass electrode for the measurement of blood pH.

Singlet Oxygen and the Origin of Oxygen Functionalities on the Surface of Carbon Electrodes.

The generation of oxygen-containing functionalities on pristine carbon surfaces is investigated and shown to be light sensitive, specifically to infra-red radiation. A mechanistic route involving singlet oxygen, 1 O2 , is proposed and evidenced.

Correction: Chemical analysis in saliva and the search for salivary biomarkers - a tutorial review.

Correction for 'Chemical analysis in saliva and the search for salivary biomarkers - a tutorial review' by Kamonwad Ngamchuea, et al., Analyst, 2018, 143, 81-99.

Chemical analysis in saliva and the search for salivary biomarkers - a tutorial review.

Biomarkers refer to analytes that can be used in the diagnosis of diseases or disorders. In saliva, there are many components that are potential biomarkers, and increasing research has focussed on the development of saliva as a diagnostic fluid. This review summarizes the existing uses of salivary biomarkers and highlights the importance of the choice of saliva collection as well as the storage procedures. A case study on the effect of collection tools on the concentrations of one of the potential biomarkers, glutathione, is highlighted. Moreover, molecular diagnosis requires reliable measurement assays. This review presents electroanalytical methods for the detection of salivary biomarkers. It further reviews approaches that can be taken to improve the selectivity of electroanalytical assays without the use of biologically selective materials, notably without the use of enzymes or antibodies.

Improving Single-Carbon-Nanotube-Electrode Contacts Using Molecular Electronics.

We report the use of an electroactive species, acetaminophen, to modify the electrical connection between a carbon nanotube (CNT) and an electrode. By applying a potential across two electrodes, some of the CNTs in solution occasionally contact the electrified interface and bridge between two electrodes. By observing a single CNT contact between two microbands of an interdigitated Au electrode in the presence and absence of acetaminophen, the role of the molecular species at the electronic junction is revealed. As compared with the pure CNT, the current magnitude of the acetaminophen-modified CNTs significantly increases with the applied potentials, indicating that the molecule species improves the junction properties probably via redox shuttling.

Amperometric micro pH measurements in oxygenated saliva.

An amperometric micro pH sensor has been developed based on the chemical oxidation of carbon fibre surfaces (diameter of 9 µm and length of ca. 1 mm) to enhance the population of surface quinone groups for the measurement of salivary pH. The pH analysis utilises the electrochemically reversible two-electron, two-proton behaviour of surface quinone groups on the micro-wire electrodes. A Nernstian response is observed across the pH range 2-8 which is the pH range of many biological fluids. We highlight the measurement of pH in small volumes of biological fluids without the need for oxygen removal and specifically the micro pH electrode is examined by measuring the pH of commercial synthetic saliva and authentic human saliva samples. The results correspond well with those obtained by using commercial glass pH electrodes on large volume samples.

Electrochemical detection and quantification of gingerol species in ginger (Zingiber officinale) using multiwalled carbon nanotube modified electrodes.

We demonstrate the potential of electrochemical detection for the analysis of the 'strength' of ginger in ginger sample. This facile and fast detection method is aimed at the quality control in food industry. Specifically, we report adsorptive stripping voltammetry (AdsSV) as a technique for detection of gingerol compounds, the pungent components of ginger rhizome. Among the gingerols, 6-gingerol is the most abundant and is chosen as a model to characterise the behaviour of a wider range of related compounds. Multiwalled carbon nanotube modified basal plane pyrolytic graphite electrodes (MWCNT-BPPG electrode) are employed to enhance the sensitivity of the measurement. A linearity range from 1 µM to 50 µM with limit of detection of 0.21 µM and limit of quantification of 0.71 µM is obtained. Further, the simple and rapid extraction procedure by simply vortexing the ginger sample with ethanol is developed for extraction of gingerol related species.