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.

A 3D Printer Guide for the Development and Application of Electrochemical Cells and Devices.

3D printing is a type of additive manufacturing (AM), a technology that is on the rise and works by building parts in three dimensions by the deposit of raw material layer upon layer. In this review, we explore the use of 3D printers to prototype electrochemical cells and devices for various applications within chemistry. Recent publications reporting the use of Fused Deposition Modelling (fused deposition modeling®) technique will be mostly covered, besides papers about the application of other different types of 3D printing, highlighting the advances in the technology for promising applications in the near future. Different from the previous reviews in the area that focused on 3D printing for electrochemical applications, this review also aims to disseminate the benefits of using 3D printers for research at different levels as well as to guide researchers who want to start using this technology in their research laboratories. Moreover, we show the different designs already explored by different research groups illustrating the myriad of possibilities enabled by 3D printing.

Production of 3D-printed disposable electrochemical sensors for glucose detection using a conductive filament modified with nickel microparticles.

Three-dimensional printing techniques have been widely used in the fabrication of new materials applied to energy, sensing and electronics due to unique advantages, such as fast prototyping, reduced waste generation, and multiple fabrication designs. In this paper, the production of a conductive 3D-printing filament composed of Ni(OH)2 microparticles and graphene within a polylactic acid matrix (Ni-G-PLA) is reported. The nanocomposite was characterized by thermogravimetric, energy-dispersive X-ray spectroscopic, scanning electronic microscopic, Raman spectroscopic and electrochemical techniques. Characteristics such as printability (using fused deposition modelling), electrical conductivity and mechanical stability of the polymer nanocomposite were evaluated before and after 3D printing. The novel 3D-printed disposable electrode was applied for selective detection of glucose (enzyme-less sensor) with a detection limit of 2.4 µmol L-1, free from the interference of ascorbic acid, urea and uric acid, compounds typically found in biological samples. The sensor was assembled in a portable electrochemical system that enables fast (160 injection h-1), precise (RSD < 5%) and selective determination of glucose without the need of enzymes (electrocatalytic properties of the Ni-G-PLA nanocomposite). The obtained results showed that Ni-G-PLA is a promising material for the production of disposable sensors for selective detection of glucose using a simple and low-cost 3D-printer.

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.

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.