Voltammetric co-determination of lead and copper in gunshot residue based on iron oxide particle/spent coffee grounds-modified electrode.

A novel electrochemical sensor was developed for the detection of lead (Pb) and copper (Cu) ions using spent coffee grounds decorated with iron oxide particles (FeO/SCG). The FeO-decorated SCG was used to modify a glassy carbon electrode (GCE). FeO, SCG, and FeO/SCG were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The electrochemical properties of the modified electrode were characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electrode modifications increased the active surface area and electron transfer and enhanced the accumulation of the target analyte. In the optimal condition, the developed sensor showed linear ranges of 1.0 µg L-1-0.05 mg L-1 and 0.05 mg L-1-0.8 mg L-1 for Pb2+ and 5.0 µg L-1-0.1 mg L-1 and 0.1 mg L-1-0.8 mg L-1 for Cu2+. The limit of detection (LOD) was 1.0 µg L-1 for Pb2+ and 2.4 µg L-1 for Cu2+. The developed sensor was successfully applied to determine Pb2+ and Cu2+ in bullet holes. The results were in good agreement with those obtained by inductively coupled plasma optical emission spectrometry (ICP/OES).

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.

An irreversible paper-based profluorescent nitroxide probe for the selective detection of ascorbic acid.

Ascorbic acid (AA) or vitamin C plays multiple crucial roles, particularly as an antioxidant. This essentially biologically active molecule was selectively detected over other reductants by the synthesized profluorescent nitroxide probe ProN6via a switch-on method. After either a hydrogen atom or single electron transfer from AA to nitroxide, the resulting diamagnetic hydroxylamine was rapidly cyclized to form a fluorescent O-acylalkoxyamine. This cyclization prevented the reoxidation of the corresponding hydroxylamine to the nitroxide, leading to a high precision of detection. A kinetic fluorescence study indicated that ProN6 exhibited higher reactivity than ProN7. Density functional theory (DFT) calculations indicated that the Gibbs free energy of the AA-induced cascade reductive lactonization of ProN6 was lower than that of ProN5 and ProN7. The designed probe achieved the sensitive and specific detection of AA with detection limits of 77.9 nM and 195.9 µM in solution and on paper, respectively. The utilization of the probe as a paper-based fluorescent sensor demonstrated the good accuracy of the quantitative analysis of AA in commercial supplements.

Detection and discrimination of sedative-hypnotics in spiked beverage dry residues using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy combined with chemometrics.

Drugs-facilitated crimes (DFCs) involve the incapacitation of victims under the influence of drugs. Conventionally, a drug administration act is often determined through the examination of biological samples; however, dry residues from any surface, such as drinking glass if related to a DFC could be a potential source of evidence. This study was aimed to establish an attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy coupled with chemometrics for the determination of spiked sedative-hypnotics from dry residues of a drug-spiked beverage. In this study, four sedative-hypnotics, namely diazepam, ketamine, nimetazepam, and xylazine were examined using ATR-FTIR spectroscopy. Subsequently, the ATR-FTIR profiles were compared and decomposed by principal component analysis (PCA) followed by linear discriminant analysis (LDA) for their detection and discrimination. Visual comparison of ATR-FTIR profiles revealed distinct spectra among the tested drugs. An initial unsupervised exploratory PCA model indicated the separation of four main sedative-hypnotics clusters, and the proposed PCA score-LDA model had allowed for a 100% accurate classification. Discrimination of sedative-hypnotics from a dry beverage previously spiked with these drugs was also possible upon an additional extraction procedure. In conclusion, ATR-FTIR coupled with PCA score-LDA model was useful in detecting and discriminating sedative-hypnotics, including those that had been previously spiked into a beverage.

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.

Nanocoral-like Polyaniline-Modified Graphene-Based Electrochemical Paper-Based Analytical Device for a Portable Electrochemical Sensor for Xylazine Detection.

A portable electrochemical device for xylazine detection is presented for the first time. An electrochemical paper-based analytical device (ePAD) was integrated with a smartphone. The fabrication of the ePAD involved wax printing, low-tack transfer tape, and cutting and screen-printing techniques. Graphene ink was coated on the substrate and modified with nanocoral-like polyaniline, providing an electron transfer medium with a larger effective surface area that promoted charge transfer. The conductive ink on the ePAD presented a thickness of 25.0 ± 0.9 µm for an effective surface area of 0.374 cm2. This sensor was then tested directly on xylazine using differential pulse voltammetry. Two linear responses were obtained: from 0.2 to 5 µg mL-1 and from 5 to 100 µg mL-1. The detection limit was 0.06 µg mL-1. Reproducibility was tested on 10 preparations. The relative standard deviation was less than 5%. The applicability of the sensor was evaluated with beverage samples spiked with trace xylazine. Recoveries ranged from 84 ± 4 to 105 ± 2%. The developed sensor demonstrated excellent accuracy in the detection of trace xylazine. It would be possible to develop the portable system to detect various illicit drugs to aid forensic investigations.

A novel colorimetric indicator for ethanol detection in preserved baby mangoes.

A colorimetric indicator cube for use in smart packaging was designed and fabricated to detect ethanol produced by microbial fermentation in preserved baby mangoes. The presence and level of ethanol was indicated by color variations of the indicator cube, which consists of porous melamine foam (MF) that entraps an indicator solution of potassium dichromate and sulfuric acid. Within the packaging, the cube sits behind a gas-permeable membrane. The morphological structure of MF was studied by digital microscope and X-ray fluorescence analysis. In the optimal condition, the indicator cube exhibited distinct color changes from yellow to brown, green and blue over an ethanol concentration range from 0.25% to 5.0%. Color changes were clearly visible to the naked eye. The repeatability of the ethanol indicator cube was good and storage stability was maintained for up to 19 and 74 days at room and refrigeration temperatures, respectively. The smart packaging was applied to detect ethanol in preserved baby mangoes at different storage times.

The Development of Digital Image Colorimetric Quantitative Analysis of Multi-Explosives Using Polymer Gel Sensors.

Polymer gel sensors on 96-well plates were successfully used to detect four different multi-explosives, including 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), nitrite, and perchlorate. The products of reactions between the explosives and the polymer gel sensors were digitally captured, and the images were analyzed by a developed Red-Green-Blue (RGB) analyzer program on a notebook computer. RGB color analysis provided the basic color data of the reaction products for the quantification of the explosives. The results provided good linear range, sensitivity, limit of detection, limit of quantitation, specificity, interference tolerance, and recovery. The method demonstrated great potential to detect explosives by colorimetric analysis of digital images of samples on 96-well plates. It is possible to apply the proposed method for quantitative on-site field screening of multi-explosives.

Adsorptive Cathodic Stripping Voltammetry for Quantification of Alprazolam.

A simple and highly sensitive electrochemical sensor was developed for adsorptive cathodic stripping voltammetry of alprazolam. Based on an electrochemically pretreated glassy carbon electrode, the sensor demonstrated good adsorption and electrochemical reduction of alprazolam. The morphology of the glassy carbon electrode and the electrochemically pretreated glassy carbon electrode were characterized by scanning electron microscopy/energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical behaviors of alprazolam were determined by cyclic voltammetry, and the analytical measurements were studied by adsorptive cathodic stripping voltammetry. Optimized operational conditions included the concentration and deposition time of sulfuric acid in the electrochemical pretreatment, preconcentration potential, and preconcentration time. Under optimal conditions, the developed alprazolam sensor displayed a quantification limit of 0.1 mg L-1, a detection limit of 0.03 mg L-1, a sensitivity of 67 µA mg-1 L cm-2 and two linear ranges: 0.1 to 4 and 4 to 20 mg L-1. Sensor selectivity was excellent, and repeatability (%RSD < 4.24%) and recovery (82.0 ± 0.2 to 109.0 ± 0.3%) were good. The results of determining alprazolam in beverages with the developed system were in good agreement with results from the gas chromatography-mass spectrometric method.

A portable electrochemical sensor for detection of the veterinary drug xylazine in beverage samples.

A portable electrochemical sensor was developed to determine xylazine in spiked beverages by adsorptive stripping voltammetry (AdSV). The sensor was based on a graphene nanoplatelets-modified screen-printed carbon electrode (GNPs/SPCE). The electrochemical behavior of xylazine at the GNPs/SPCE was an adsorption-controlled irreversible oxidation reaction. The loading of graphene nanoplatelets (GNPs) on the modified SPCE, electrolyte pH, and AdSV accumulation potential and time were optimized. Under optimal conditions, the GNPs/SPCE provided high sensitivity, linear ranges of 0.4-6.0 mg L-1 (r = 0.997) and 6.0-80.0 mg L-1 (r = 0.998) with a detection limit of 0.1 mg L-1 and a quantitation limit of 0.4 mg L-1. Repeatability was good. The accuracy of the proposed sensor was investigated by spiking six beverage samples at 1.0, 5.0, and 10.0 mg L-1. The recoveries from this method ranged from 80.8 ± 0.2-108.1 ± 0.3 %, indicating the good accuracy of the developed sensor. This portable electrochemical sensor can be used to screen for xylazine in beverage samples as evidence in cases of sexual assault or robbery.

A portable sol-gel urea colorimetric method for the determination of urea in feedstuffs.

A sol-gel urea colorimetric method was developed for the determination of urea in feedstuffs. The sol-gel platform contained p-dimethylaminobenzaldehyde (p-DMAB) as the reagent entrapped within polymer network. The urea analysis relied on the formation of Schiff base under acidic conditions. The colorimetric product was imaged with a Smartphone. Under optimized conditions, the calibration curve for urea was linear over the concentration range of 2.5-100 and 100-1000 mg L-1 with a good coefficient of determination (r2 > 0.99). The limit of detection (LOD) and limit of quantification (LOQ) were 0.1 and 0.5 mg L-1, respectively. The intra-day and inter-day precisions were 0.83-3.01%RSD and 2.20-5.47%RSD, respectively. Accuracy of urea analysis ranged from -1.15 to 2.76%. The proposed method was stable for at least 90 days. The amount of urea in feedstuff sample was determined. The developed method is easy to use with small samples and reagent consumption in field conditions for monitoring the quality of feedstuff.

Rapid measurement of indole levels in Brassica vegetables using one millilitre binary organic extraction solvent and capillary electrophoresis-UV analysis.

INTRODUCTION: Brassica vegetables contain high levels of indole compounds which have been found to provide health benefits, especially as cancer-preventive agents. An efficient and rapid method using solvent extraction with capillary electrophoresis (CE) and ultraviolet (UV) detection was developed for the determination of four major indoles from four types of Brassica vegetables. MATERIALS AND METHODS: Freeze-dried samples of four Brassica vegetables, i.e. broccoli, cauliflower, Chinese cabbage and cabbage, were selected. Hence, 1 mL of the binary solvent dimethylformamide (DMF)-methanol, 4:1 (v/v), was used for sample extraction. The extracts were diluted with the running buffer and directly analysed using CE with UV detection of four indole compounds. RESULTS: The binary solvent DMF-methanol, 4:1 (v/v) was selected from studies of the extraction efficiency of standard indoles spiked in ivy gourd (as the negative control sample) and using diphenylamine as the internal standard. Recovery was 80(±10)-120(±3)% for the four indoles: indole-3-carbinol (I3C), indole-3-acetonitrile (I3A), indole-3-acetic acid (IAA), and 3,3'-diindolylmethane (DIM). For direct analysis suitable dilution of the extract with the running buffer was required. The linear range of the quantitation is 0.75-25.0 µg/mL, limit of detection (LOD) of 0.14-0.52 µg/mL and r2 > 0.998. The amount of indole in the Brassica vegetables are in the order I3C > > IAA, I3A > DIM. CONCLUSION: A rapid method for extraction and quantitation of four indoles in four Brassica vegetables using CE with UV detection was developed. It has the potential as an efficient technique for generating data for use in agricultural and nutritional studies.

Development of a solid-phase extraction method with simple MEKC-UV analysis for simultaneous detection of indole metabolites in human urine after administration of indole dietary supplement.

This work presents the development of a solid phase extraction method with simple MEKC-UV analysis for the simultaneous determination of indole-3-carbinol (I3C) and its metabolites (3, 3'-diindolylmethane (DIM), indole-3-carboxaldehyde (I3CAL), indole-3-acetonitrile (I3A)) in human urine after oral administration of an indole dietary supplement. Solid phase extraction (SPE) method was applied for the first time for simultaneous analysis of these indole metabolites. The MEKC separation method was developed in a previous work. Three commercial SPE cartridges, each with different sorbent materials, were investigated: Sep-Pak® C18, Oasis® HLB and Oasis® WCX. The Sep-Pak® C18 material provided the highest extraction recovery of 88-113% (n = 9), for the four target indole metabolites (I3C, DIM, I3CAL and I3A). The optimal washing and elution solutions were 40% methanol/water (v/v) and 100% methanol, respectively, and optimal elution volume was 2.0mL. The specificity of the proposed SPE method was evaluated with negative control urine samples (n = 10) from healthy volunteers who had not taken the dietary supplement or vegetables known to contain indole compounds. Linear calibration curves were in the range of 0.2-25µgmL-1 (r2 > 0.998) using diphenylamine (DPA) as the internal standard. Intra-day and inter-day precisions were 3.5-12.3%RSD and 2.7-14.1%RSD, respectively. Limits of detection and quantification were 0.05-0.10µgmL-1 and 0.10-0.50µgmL-1, respectively. The four target indole compounds were separated within only 5min by MEKC-UV analysis. Urine from 5 subjects who had taken a dietary supplement containing I3C and DIM were found to contain only the DIM metabolite at concentrations ranging from 0.10 to 0.35µgmL-1. Accuracy of the proposed method based on the percentage recovery of spiked urine samples were 70-108%, 82-116%, 82-132% and 80-100% for I3C, I3CAL, I3A and DIM, respectively. The Sep-Pak®C18 cartridge was highly effective in extraction and sample cleanup for the downstream simultaneous detection of urinary indole metabolites by MEKC-UV method.

Lab-on-a-disc for simultaneous determination of total phenolic content and antioxidant activity of beverage samples.

In this paper, we present a fully integrated and automated lab-on-a-disc for the rapid determination of the total phenolic content (TPC) and antioxidant activity (AA) of beverage samples. The simultaneous determinations of TPC and AA on a spinning disc were achieved by integrating three independent analytical techniques: the Folin-Ciocalteu method that is used to measure TPC, the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) method and the ferric reducing antioxidant power method that are used to measure AA. The TPC and AA of 8 different beverage samples, including various fruit juices, tea, wine and beer, were analyzed. Unlike conventional labor-intensive processes for measuring TPC and AA, our fully automated platform offers one-step operation and rapid analysis.