Rapid sequential determination of the explosives 2,4,6-trinitrotoluene and cyclotrimethylenetrinitramine in forensic samples employing a graphite sheet sensor and cyclic square-wave stripping voltammetry.

The development of a portable analytical procedure is described for rapid sequential detection and quantification of the explosives 2,4,6-trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX) in forensic samples using a graphite sheet (GS). A single GS platform works as a collector of explosive residues and detector after its assembly into a 3D-printed cell. The detection strategy is based on cyclic square-wave stripping voltammetry. The cathodic scan from + 0.1 to -1.0 V with accumulation at 0.0 V enables the TNT detection (three reduction peaks), and the anodic scan from + 0.2 to + 1.55 V with accumulation at -0.9 V provides the RDX detection (two oxidation processes). Low detection limit values (0.1 µmol L-1 for TNT and 2.4 µmol L-1 for RDX) and wide linear ranges (from 1 to 150 µmol L-1 for TNT and from 20 to 300 µmol L-1 for RDX) were obtained. The sensor did not respond to pentaerythritol tetranitrate (PETN), which was evaluated as a potential interferent, because plastic explosives contain mixtures of TNT, RDX, and PETN. The GS electrode was also evaluated as a collector of TNT and RDX residues spread on different surfaces to simulate forensic scenarios. After swiping over different surfaces (metal, granite, wood, cloths, hands, money bills, and cellphone), the GS electrode was assembled in the 3D-printed cell ready to measure both explosives by the proposed method. In all cases, the presence of TNT and RDX was confirmed, attesting the reliability of the proposed device to act as collector and sensor.

Sandpaper-based electrochemical devices assembled on a reusable 3D-printed holder to detect date rape drug in beverages.

This study describes the development of a new electrochemical paper-based analytical device (ePAD) on alumina sandpaper substrate through a pencil-drawing process for square wave voltammetry measurements of midazolam maleate used as a "date rape drug" in beverages. The proposed ePAD was assembled on a reusable 3D printed holder to delimit its geometric area and ensure better robustness. The ePAD was characterized by scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and Raman spectroscopy. The direct drawing of ePADs on sandpaper platforms through a graphite pencil has offered suitable repeatability (RSD = 1.0%) and reproducibility (RSD = 4.0%) using [Fe(CN)6]4- as redox probe. The proposed ePAD provided linear behaviour in the midazolam maleate concentration range between 2.5 and 150 mg L-1 and a limit of detection of 2.0 mg L-1. The feasibility of the ePAD for forensic application was successfully demonstrated through the detection of midazolam in different beverages (water, beer, liquor, and vodka). The intended application revealed low interference of other compounds present in beverages. Based on the achieved results, the proposed ePAD has offered great accuracy with no statistical difference at 95% confidence level from the data recorded by high performance liquid chromatography. The operational simplicity and the robustness ensured by the assembling on a reusable 3D printed holder make the ePAD drawn on sandpaper platform a powerful and promising analytical tool for the analysis of "date rape drugs" opening new possibilities for on-site forensic investigations.

3D-printing for forensic chemistry: voltammetric determination of cocaine on additively manufactured graphene-polylactic acid electrodes.

Cocaine is probably one of the most trafficked illicit drugs in the world. For this reason, police forces require fast, selective, and sensitive methods for cocaine detection at crime scenes. Taking benefit of additive manufacturing, we demonstrate that 3D-printed graphene-polylactic acid (G-PLA) electrodes using the affordable fused deposition modelling technique can identify and quantify cocaine in seized drugs. The detection of cocaine based on its electrochemical oxidation on such electrodes was dramatically improved after an electrochemical surface treatment that generates reduced graphene oxide (anodic followed by a cathodic treatment). Square-wave voltammetric determination of cocaine was achieved in the concentration range between 20 and 100 µmol L-1, with a detection limit of 6 µmol L-1, and free from the interference of paracetamol, caffeine, phenacetin, lidocaine, benzocaine and levamisole, which are common adulterants found in seized drugs. The analytical characteristics obtained using 3D-printed G-PLA electrodes were comparable with those of previously reported electrochemical sensors, but presented the inherent advantages of the 3D-printing technology that enables low-cost, reproducible, and large-scale production of such electrodes in remote areas combined with the use of an environmentally-friendly biopolymer.

Simultaneous determination of lead and antimony in gunshot residue using a 3D-printed platform working as sampler and sensor.

3D-printing is an emerging technique that enables the fast prototyping of multiple-use devices. Herein we report the fabrication of a 3D-printed graphene/polylactic acid (G-PLA) conductive electrode that works as a sampler and a voltammetric sensor of metals in gunshot residue (GSR) using a commercially-available G/-PLA filament. The 3D-printed surface was used as swab to collect GSR and next submitted to a square-wave voltammetric scan for the simultaneous detection of Pb2+ and Sb3+. The proposed sensor presented excellent analytical performance, with limit of detection values of 0.5 and 1.8 µg L-1 to Pb2+ and Sb3+, respectively, and linear ranges between 50 and 1500 µg L-1. Sampling was performed through the direct contact of G-PLA electrode in hands and clothes of shooters, followed by immersion in the electrochemical cell in the presence of supporting electrolyte for the SWASV scan. The proposed method showed a great performance in the recovery, identification and semi-quantification of Pb2+ and Sb3+ in the evaluated samples without the need for sample preparation. Moreover, the device can be reused as sampler and sensor (until three times without loss of electrochemical performance) and the fabrication is reproducible (RSD = 7%, for three different devices). Hence, this 3D-printed material is an excellent candidate for the analysis of GSR, an indispensable analysis in the forensic field.

Investigation of midazolam electro-oxidation on boron doped diamond electrode by voltammetric techniques and density functional theory calculations: Application in beverage samples.

Midazolam (MID) is a sedative drug which can be added in beverage samples as drug-facilitated-sexual assault (date rape drug). This type of drug has short half-life in biological fluids (not detectable) which often prevents the correlation between drug abuse and crime. In this work, we described a simple and low-cost method for fast screening and selective determination of MID in beverage samples (vodka, whiskey and red wine). For the first time, the electrochemical oxidation of MID was used for this purpose. The oxidation mechanism was studied using electrochemical techniques (cyclic and square-wave voltammetry) and computational simulations (density functional theory calculations). Differential-pulse voltammetry, boron-doped diamond electrode (BDDE), and Britton-Robinson (BR) buffer (pH = 2) were selected as electrochemical analysis technique, working electrode and supporting electrolyte, respectively. Different linear response ranges (4-25 µmol L-1 with r = 0.9972; 1-10 µmol L-1 with r = 0.9951; 1-15 µmol L-1 with r = 0.9982) and limits of detection (0.46, 0.43 and 0.33 µmol L-1) were obtained for the analysis of vodka, whisky, and red wine solutions, respectively. The precision and accuracy were satisfactory considering the low relative standard deviation values (RSD < 6.3%, n = 15) and minimal sample matrix effects (recovery values between 87 and 103%).

Graphite sheet as a novel material for the collection and electrochemical sensing of explosive residues.

This work presents the use of a graphite sheet (graphite papers) as a new platform for the collection and sensing of explosive residues. This material offers a lightweight, highly conductive, flexible platform that can be cut in several ways, enabling for the collection of explosive residues at the place of interest, without any further sample preparation steps. As a proof-of-concept, the device was utilised for the collection and electrochemical sensing of 2,4,6-trinitrotoluene (TNT) residues. The GS has a remarkable performance for the sensing of TNT within the supporting electrolyte (0.1 mol dm-3 HCl) resulting in a linear range between 1 and 1300 µmol dm-3 and detection limit of 0.06 µmol dm-3 using square-wave voltammetry (SWV). Five surfaces (granite, gloved and bare hands, metal and cash banknotes) were contaminated with traces of TNT and the collection was performed using the graphite sheet (1 cm2 square pieces were swiped over the different surfaces). The results obtained using SWV enabled the identification of TNT residues, at quantities of 0.01-0.23 ng (quantification by the measured coulometric charge of the SWV scan), demonstrating that this novel material can be used as a promising device at crime scene investigations.

Highly-sensitive voltammetric detection of trinitrotoluene on reduced graphene oxide/carbon nanotube nanocomposite sensor.

This work presents the highly-sensitive detection of 2,4,6-trinitrotoluene (TNT) on reduced graphene oxide/multi-walled carbon nanotube (rGO/MWCNT) nanocomposite sensor. The formation of a thin film of this nanocomposite occurred at the cyclohexane/water immiscible interface of a mixture of MWCNT and rGO in the biphasic solution. The film was transferred to a boron-doped diamond (BDD) electrode for the square-wave voltammetric detection of TNT, which presented improved analytical characteristics in comparison with bare BDD and after modification with precursors. Electrochemical impedance spectroscopy also revealed the faster electron transfer for a redox probe on the nanocomposite modified surface. The synergistic properties of both carbon nanomaterials in the thin film modified surface resulted in a TNT sensor with a detection limit of 0.019 µmol L-1 within a wide linear range (0.5-1100 µmol L-1), with superior performance in comparison with other electrochemical sensors produced with carbon nanomaterials. This new material provides great promises for the highly-sensitive detection of other nitroaromatic explosives as well as other analytes. Moreover, the interfacial method enables the production of homogeneous and stable films on large coated areas as well as the large-scale production of electrochemical sensors.

Portable analytical platforms for forensic chemistry: A review.

This current review article focuses on recent contributions to on-site forensic investigations. Portable and potentially portable methods are presented and critically discussed about (bio)chemical trace analysis and studies performed outside the controlled laboratory environment to rapidly help in crime scene inquiries or forensic intelligence purposes. A wide range of approaches including electrochemical sensors, microchip electrophoresis, ambient ionization on portable mass spectrometers, handheld Raman and NIR instruments as well as and point-of-need devices, like paper-based platforms, for in-field analysis of latent evidences, controlled substances, drug screening, hazards, and others to assist in law enforcements and solving crime more efficiently are highlighted. The covered examples have successfully demonstrated the huge potential of portable devices for on-site applications. Future investigations should consider analytical validation to compete equality and even replace current gold standard methods.

Screening of seized cocaine samples using electrophoresis microchips with integrated contactless conductivity detection.

This study describes the development of a new analytical method for the separation and detection of cocaine (COC) and its adulterants, or cutting agents, using microchip electrophoresis (ME) devices coupled with capacitively coupled contactless conductivity detection (C4 D). All the experiments were carried out using a glass commercial ME device containing two pairs of integrated sensing electrodes. The running buffer composed of 20 mmol/L amino-2-(hydroxymethyl) propane-1,3-diol and 10 mmol/L 3,4-dimethoxycinnamic acid provided the best separation conditions for COC and its adulterants with baseline resolution (R > 1.6), separation efficiencies ranging from (2.9 ± 0.1) to (3.2 ± 0.2) × 105 plates/m, and estimated LOD values between 40 and 150 µmol/L. The quantification of COC was successfully performed in four samples seized by the Brazilian Federal Police Department and all predicted values agree with values estimated by the reference method. Some other interfering species were detected in the seized samples during the screening procedure on ME-C4 D devices. While lidocaine was detected in sample 3, the presence of levamisole was observed in samples 2 and 4. However, their concentrations were estimated to be below the LOQ. ME-C4 D devices have proved to be quite efficient for the identification and quantification of COC with errors lower than 10% when compared to the data obtained by a reference method. The approach herein reported offers great potential to be used for on-site COC screening in seized samples.

Simple and Sensitive Paper-Based Device Coupling Electrochemical Sample Pretreatment and Colorimetric Detection.

We report the development of a simple, portable, low-cost, high-throughput visual colorimetric paper-based analytical device for the detection of procaine in seized cocaine samples. The interference of most common cutting agents found in cocaine samples was verified, and a novel electrochemical approach was used for sample pretreatment in order to increase the selectivity. Under the optimized experimental conditions, a linear analytical curve was obtained for procaine concentrations ranging from 5 to 60 µmol L(-1), with a detection limit of 0.9 µmol L(-1). The accuracy of the proposed method was evaluated using seized cocaine samples and an addition and recovery protocol.

Application of electrochemically generated ozone to the discoloration and degradation of solutions containing the dye Reactive Orange 122.

Aqueous solutions containing the commercial azo dye Reactive Orange 122 (RO122) were ozonated in acid and alkaline conditions. Ozone was electrochemically generated using a laboratory-made electrochemical reactor and applied using semi-batch conditions and a column bubble reactor. A constant ozone application rate of 0.25gh(-1) was used throughout. Color removal and degradation efficiency were evaluated as function of ozonation time, pH and initial dye concentration by means of discoloration kinetics and COD-TOC removal. Experimental findings revealed that pH affects both discoloration kinetics and COD-TOC removal. A single pseudo-first-order kinetic rate constant, k(obs), for discoloration was found for ozonation carried out in alkaline solutions, contrary to acidic solutions where k(obs) depends on ozonation time. COD-TOC removal supports degradation of RO122 is more pronounced for alkaline conditions. Evaluation of the oxidation feasibility by means of the COD/TOC ratio indicates that the ozonation process in both acid and alkaline conditions leads to a reduction in recalcitrance of the soluble organic matter.