A Multi-Pump Magnetohydrodynamics Lab-On-A-Chip Device for Automated Flow Control and Analyte Delivery.

This article shows the development of a computer-controlled lab-on-a-chip device with three magnetohydrodynamic (MHD) pumps and a pneumatic valve. The chip was made of a stack of layers of polymethylmethacrylate (PMMA), cut using a laser engraver and thermally bonded. The MHD pumps were built using permanent magnets (neodymium) and platinum electrodes, all of them controlled by an Arduino board and a set of relays. The implemented pumps were able to drive solutions in the open channels with a flow rate that increased proportionally with the channel width and applied voltage. To address the characteristic low pressures generated by this kind of pump, all channels were interconnected. Because the electrodes were immersed in the electrolyte, causing electrolysis and pH variations, the composition and ionic strength of the electrolyte solution were controlled. Additionally, side structures for releasing bubbles were integrated. With this multi-pump and valve solution, the device was used to demonstrate the possibility of performing an injection sequence in a system that resembles a traditional flow injection analysis system. Ultimately, the results demonstrate the possibility of performing injection sequences using an array of MHD pumps that can perform fluid handling in the 0-5 µL s-1 range.

Complete Additively Manufactured (3D-Printed) Electrochemical Sensing Platform.

Herein, we report a complete additively manufactured (AM) electrochemical sensing platform. In this approach, a fully AM/3D-printed electrochemical system, using a conventional low-cost 3D printer (fused deposition modeling) fabricating both the conductive electrodes and the nonconductive/chemically inert electrochemical cell is reported. The electrodes (working, counter, and pseudo-reference) are AM using a conductive fused-filament comprised of a mixture of carbon black nanoparticles and polylactic acid (CB/PLA). AM components partially coated with silver ink presented a similar behavior to a conventional Ag/AgCl reference electrode. The performance of the AM working electrode was evaluated after a simple and fast polishing procedure on sandpaper and electrochemical activation in a NaOH solution (0.5 mol L-1). Following the electrochemical activation step, a considerable improvement in the electrochemical behavior (current intensity and voltammetric profile) was obtained for model analytes, such as dopamine, hexaammineruthenium(III) chloride, ferricyanide/ferrocyanide, uric acid, and ascorbic acid. Excellent repeatability (RSD = 0.4%, N = 10) and limit of detection (0.1 µmol L-1) were obtained with the all complete AM electrochemical system for dopamine analysis. The electrochemical performance of the developed system (after simple electrochemical activation of the working electrode) was similar or better than those obtained using commercial glassy carbon and screen-printed carbon electrodes. The results shown here represents a significant advance in AM (3D printing) technology for analytical chemistry.

Pyrolyzed cotton balls for protein removal: Analysis of pharmaceuticals in serum by capillary electrophoresis.

Because of the inherent affinity of proteins for bare, fused silica capillaries, the analysis of protein-containing samples has proven a challenging task for capillary electrophoresis. The adsorption of proteins to the capillary walls effectively changes the zeta potential and thus affects the electro-osmotic flow leading to significant shifts in migration time, peak broadening, and poor reproducibility. While there are several well-known methods to remove proteins from samples prior to the analysis (including precipitation) or to prevent their adsorption to the capillary (semi-permanent coatings), those approaches are often expensive, time consuming, or simply unreliable. Aiming to address these needs, this manuscript reports on the use of pyrolyzed cotton balls, as a simple and widely accessible hydrophobic material to remove proteins from serum samples. The material retains enough flexibility so it can be placed directly into the sample vials and has enough capacity to capture more than 75% of the proteins in the sample (1% dilution of 1 mL of serum). The advantages of the material are demonstrated by performing the analysis of five representative drugs (in serum) by capillary electrophoresis obtaining a change in migration time of only 5 ± 1%, after 10 consecutive runs.

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.

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.

3D-printing pen versus desktop 3D-printers: Fabrication of carbon black/polylactic acid electrodes for single-drop detection of 2,4,6-trinitrotoluene.

The fabrication of carbon black/polylactic acid (PLA) electrodes using a 3D printing pen is presented and compared with electrodes obtained by a desktop fused deposition modelling (FDM) 3D printer. The 3D pen was used for the fast production of electrodes in two designs using customized 3D printed parts to act as template and guide the reproducible application of the 3D pen: (i) a single working electrode at the bottom of a 3D-printed cylindrical body and (ii) a three-electrode system on a 3D-printed planar substrate. Both devices were electrochemically characterized using the redox probe [Fe(CN)6]3-/4- via cyclic voltammetry, which presented similar performance to an FDM 3D-printed electrode or a commercial screen-printed carbon electrode (SPE) regarding peak-to-peak separation (ΔEp) and current density. The surface treatment of the carbon black/PLA electrodes fabricated by both 3D pen and FDM 3D-printing procedures provided substantial improvement of the electrochemical activity by removing excess of PLA, which was confirmed by scanning electron microscopic images for electrodes fabricated by both procedures. Structural defects were not inserted after the electrochemical treatment as shown by Raman spectra (iD/iG), which indicates that the use of 3D pen can replace desktop 3D printers for electrode fabrication. Inter-electrode precision for the best device fabricated using the 3D pen (three-electrode system) was 4% (n = 5) considering current density and anodic peak potential for the redox probe. This device was applied for the detection of 2,4,6-trinitrotoluene (TNT) via square-wave voltammetry of a single-drop of 100 µL placed upon the thee-electrode system, resulting in three reduction peaks commonly verified for TNT on carbon electrodes. Limit of detection of 1.5 µmol L-1, linear range from 5 to 500 µmol L-1 and RSD lower than 4% for 10 repetitive measurements of 100 µmol L-1 TNT were obtained. The proposed devices can be reused after polishing on sandpaper generating new electrode surfaces, which is an extra advantage over chemically-modified electrochemical sensors applied for TNT detection.

Electrochemical synthesis of Prussian blue from iron impurities in 3D-printed graphene electrodes: Amperometric sensing platform for hydrogen peroxide.

This communication shows the electrochemical synthesis of Prussian blue (PB) films on additive manufactured (3D-printed) electrodes from iron impurities found at the graphene-polylactic acid (G/PLA) substrate and its application as a highly selective sensor for H2O2. The 3D-printed G/PLA electrode was immersed in dimethylformamide for 30 min to exposure the iron impurities within the PLA matrix. Next, cyclic voltammograms (200 cycles) in the presence of potassium ferricyanide in 0.1 mol L-1 KCl + 0.01 mol L-1 HCl were performed to grow the PB films. The sensing properties of this novel PB/G/PLA platform were evaluated for the amperometric detection of H2O2 using batch-injection analysis, with a limit of detection of 0.56 µmol L-1 under the application of 0.0 V (vs Ag/AgCl/KClsat.). The applicability of the sensor was demonstrated for the analysis of milk samples (10-fold diluted in the supporting electrolyte), resulting in proper recovery values (94-101%).

Additive-manufactured (3D-printed) electrochemical sensors: A critical review.

Additive manufacturing or three-dimensional (3D)-printing is an emerging technology that has been applied in the development of novel materials and devices for a wide range of applications, including Electrochemistry and Analytical Chemistry areas. This review article focuses on the contributions of 3D-printing technology to the development of electrochemical sensors and complete electrochemical sensing devices. Due to the recent contributions of 3D-printing within this scenario, the aim of this review is to present a guide for new users of 3D-printing technology considering the required features for improved electrochemical sensing using 3D-printed sensors. At the same time, this is a comprehensive review that includes most 3D-printed electrochemical sensors and devices already reported using selective laser melting (SLM) and fused deposition modeling (FDM) 3D-printers. The latter is the most affordable 3D-printing technique and for this reason has been more often applied for the fabrication of electrochemical sensors, also due to commercially-available conductive and non-conductive filaments. Special attention is given to critically discuss the need for the surface treatment of FDM 3D-printed platforms to improve their electrochemical performance. The insertion of biochemical and chemical catalysts on the 3D-printed surfaces are highlighted as well as novel strategies to fabricate filaments containing chemical modifiers within the polymeric matrix. Some examples of complete electrochemical sensing systems obtained by 3D-printing have successfully demonstrated the enormous potential to develop portable devices for on-site applications. The freedom of design enabled by 3D-printing opens many possibilities of forthcoming investigations in the area of analytical electrochemistry.

Neutrophils recruited to the site of Mycobacterium bovis BCG infection undergo apoptosis and modulate lipid body biogenesis and prostaglandin E production by macrophages.

Neutrophil influx to sites of mycobacterial infections is one of the first events of tuberculosis pathogenesis. However, the role of early neutrophil recruitment in mycobacterial infection is not completely understood. We investigated the rate of neutrophil apoptosis and the role of macrophage uptake of apoptotic neutrophils in a pleural tuberculosis model induced by BCG. Recruited neutrophils were shown to phagocyte BCG and a large number of neutrophils undergo apoptosis within 24 h. Notably, the great majority of apoptotic neutrophils were infected by BCG. Increased lipid body (lipid droplets) formation, accompanied by prostaglandin E(2) (PGE(2)) and TGF-beta1 synthesis, occurred in parallel to macrophage uptake of apoptotic cells. Lipid body and PGE(2) formation was observed after macrophage exposure to apoptotic, but not necrotic or live neutrophils. Blockage of BCG-induced lipid body formation significantly inhibited PGE(2) synthesis. Pre-treatment with the pan-caspase inhibitor zVAD inhibited BCG-induced neutrophil apoptosis and lipid body formation, indicating a role for apoptotic neutrophils in macrophage lipid body biogenesis in infected mice. In conclusion, BCG infection induced activation and apoptosis of infected neutrophils at the inflammatory site. The uptake of apoptotic neutrophils by macrophages leads to TGF-beta1 generation and PGE(2)-derived lipid body formation, and may have modulator roles in mycobacterial pathogenesis.

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.

3D printing for electroanalysis: From multiuse electrochemical cells to sensors.

This work presents potential applications of low-cost fused deposition modeling 3D-printers to fabricate multiuse 3D-printed electrochemical cells for flow or batch measurements as well as the 3D-printing of electrochemical sensing platforms. Electrochemical cells and sensors were printed with acrylonitrile butadiene styrene (ABS) and conductive graphene-doped polylactic acid (G-PLA) filaments, respectively. The overall printing operation time and estimated cost per cell were 6 h and $ 6.00, respectively, while the sensors were printed within minutes (16 sensor strips of 1 × 2 cm in 10 min at a cost of $ 1.00 each sensor). The cell performance is demonstrated for the amperometric detection of tert-butylhydroquinone, dipyrone, dopamine and diclofenac by flow-injection analysis (FIA) and batch-injection analysis (BIA) using different working electrodes, including the proposed 3D-printed sensor, which presented comparable electroanalytical performance with other carbon-based electrodes (LOD of 0.1 µmol L-1 for dopamine). Raman spectroscopy and scanning electron microscopy of the 3D-printed sensor indicated the presence of graphene nanoribbons within the polymeric matrix. Electrochemical impedance spectroscopy and heterogeneous electron transfer constants (k0) for the redox probe Ru(NH3)6+3 revealed that a glassy-carbon electrode presented faster electron transfer rates than the 3D-printed sensor; however, the latter presented lower LOD values for dopamine and catechol probably due to oxygenated functional groups at the G-PLA surface.