Multi-walled carbon nanotubes/carbon black/rPLA for high-performance conductive additive manufacturing filament and the simultaneous detection of acetaminophen and phenylephrine.

The combination of multi-walled carbon nanotubes (MWCNT) and carbon black (CB) is presented to produce a high-performance electrically conductive recycled additive manufacturing filament. The filament and subsequent additively manufactured electrodes were characterised by TGA, XPS, Raman, and SEM and showed excellent low-temperature flexibility. The MWCNT/CB filament exhibited an improved electrochemical performance compared to an identical in-house produced bespoke filament using only CB. A heterogeneous electrochemical rate constant, [Formula: see text] of 1.71 (± 0.19) × 10-3 cm s-1 was obtained, showing an almost six times improvement over the commonly used commercial conductive CB/PLA. The filament was successfully tested for the simultaneous determination of acetaminophen and phenylephrine, producing linear ranges of 5-60 and 5-200 µM, sensitivities of 0.05 µA µM-1 and 0.14 µA µM-1, and limits of detection of 0.04 µM and 0.38 µM, respectively. A print-at-home device is presented where a removable lid comprised of rPLA can be placed onto a drinking vessel and the working, counter, and reference components made from our bespoke MWCNT/CB filament. The print-at-home device was successfully used to determine both compounds within real pharmaceutical products, with recoveries between 87 and 120% over a range of three real samples. This work paves the way for fabricating new highly conductive filaments using a combination of carbon materials with different morphologies and physicochemical properties and their application to produce additively manufactured electrodes with greatly improved electrochemical performance.

Mixed Graphite/Carbon Black Recycled PLA Conductive Additive Manufacturing Filament for the Electrochemical Detection of Oxalate.

Mixing of graphite and carbon black (CB) alongside recycled poly(lactic acid) and castor oil to create an electrically conductive additive manufacturing filament without the use of solvents is reported herein. The additively manufactured electrodes (AMEs) were electrochemically benchmarked against a commercial conductive filament and a bespoke filament utilizing only CB. The graphite/CB produced a heterogeneous rate constant, k0, of 1.26 (±0.23) × 10-3 cm s-1 and resistance of only 155 ± 15 Ω, compared to 0.30 (±0.03) × 10-3 cm s-1 and 768 ± 96 Ω for the commercial AME. Including graphite within the filament reduced the cost of printing each AME from £0.09, with the CB-only filament, to £0.05. The additive manufacturing filament was successfully used to create an electroanalytical sensing platform for the detection of oxalate within a linear range of 10-500 µM, achieving a sensitivity of 0.0196 µA/µM, LOD of 5.7 µM and LOQ of 18.8 µM was obtained. Additionally, the cell was tested toward the detection of oxalate within a spiked synthetic urine sample, obtaining recoveries of 104%. This work highlights how, using mixed material composites, excellent electrochemical performance can be obtained at a reduced material cost, while also greatly improving the sustainability of the system.

Novel Additive Manufactured Multielectrode Electrochemical Cell with Honeycomb Inspired Design for the Detection of Methyl Parathion in Honey Samples.

The development and increase in the number of crops recently have led to the requirement for greater efficiency in world food production and greater consumption of pesticides. In this context, the widespread use of pesticides has affected the decrease in the population of pollinating insects and has caused food contamination. Therefore, simple, low-cost, and quick analytical methods can be interesting alternatives for checking the quality of foods such as honey. In this work, we propose a new additively manufactured (3D-printed) device inspired by a honeycomb cell, with 6 working electrodes for the direct electrochemical analysis of methyl parathion by reduction process monitoring in food and environmental samples. Under optimized parameters, the proposed sensor presented a linear range between 0.85 and 19.6 µmol L-1, with a limit of detection of 0.20 µmol L-1. The sensors were successfully applied in honey and tap water samples by using the standard addition method. The proposed honeycomb cell made of polylactic acid and commercial conductive filament is easy to construct, and there is no need for chemical treatments to be used. These devices based on 6 working electrodes array are versatile platforms for rapid, highly repeatable analysis in food and environment, capable of performing detection in low concentrations.

Circular Economy Electrochemistry: Creating Additive Manufacturing Feedstocks for Caffeine Detection from Post-Industrial Coffee Pod Waste.

The recycling of post-industrial waste poly(lactic acid) (PI-PLA) from coffee machine pods into electroanalytical sensors for the detection of caffeine in real tea and coffee samples is reported herein. The PI-PLA is transformed into both nonconductive and conductive filaments to produce full electroanalytical cells, including additively manufactured electrodes (AMEs). The electroanalytical cell was designed utilizing separate prints for the cell body and electrodes to increase the recyclability of the system. The cell body made from nonconductive filament was able to be recycled three times before the feedstock-induced print failure. Three bespoke formulations of conductive filament were produced, with the PI-PLA (61.62 wt %), carbon black (CB, 29.60 wt %), and poly(ethylene succinate) (PES, 8.78 wt %) chosen as the most suitable for use due to its equivalent electrochemical performance, lower material cost, and improved thermal stability compared to the filaments with higher PES loading and ability to be printable. It was shown that this system could detect caffeine with a sensitivity of 0.055 ± 0.001 µA µM-1, a limit of detection of 0.23 µM, a limit of quantification of 0.76 µM, and a relative standard deviation of 3.14% after activation. Interestingly, the nonactivated 8.78% PES electrodes produced significantly better results in this regard than the activated commercial filament toward the detection of caffeine. The activated 8.78% PES electrode was shown to be able to detect the caffeine content in real and spiked Earl Grey tea and Arabica coffee samples with excellent recoveries (96.7-102%). This work reports a paradigm shift in the way AM, electrochemical research, and sustainability can synergize and feed into part of a circular economy, akin to a circular economy electrochemistry.

Adjusting the Connection Length of Additively Manufactured Electrodes Changes the Electrochemical and Electroanalytical Performance.

Changing the connection length of an additively manufactured electrode (AME) has a significant impact on the electrochemical and electroanalytical response of the system. In the literature, many electrochemical platforms have been produced using additive manufacturing with great variations in how the AME itself is described. It is seen that when measuring the near-ideal outer-sphere redox probe hexaamineruthenium (III) chloride (RuHex), decreasing the AME connection length enhances the heterogeneous electrochemical transfer (HET) rate constant (k0) for the system. At slow scan rates, there is a clear change in the peak-to-peak separation (ΔEp) observed in the RuHex voltammograms, with the ΔEp shifting from 118 ± 5 mV to 291 ± 27 mV for the 10 and 100 mm electrodes, respectively. For the electroanalytical determination of dopamine, no significant difference is noticed at low concentrations between 10- and 100-mm connection length AMEs. However, at concentrations of 1 mM dopamine, the peak oxidation is shifted to significantly higher potentials as the AME connection length is increased, with a shift of 150 mV measured. It is recommended that in future work, all AME dimensions, not just the working electrode head size, is reported along with the resistance measured through electrochemical impedance spectroscopy to allow for appropriate comparisons with other reports in the literature. To produce the best additively manufactured electrochemical systems in the future, researchers should endeavor to use the shortest AME connection lengths that are viable for their designs.

Exploration of defined 2-dimensional working electrode shapes through additive manufacturing.

In this work, the electrochemical response of different morphologies (shapes) and dimensions of additively manufactured (3D-printing) carbon black (CB)/poly-lactic acid (PLA) electrodes are reported. The working electrodes (WE) are printed using standard non-conductive PLA based filament for the housing and commercial Protopasta (carbon black/PLA) filament for the electrode and connection parts. Discs, squares, equilateral triangles and six-point stars with varying working electrode (WE) widths from 2 to 10 mm are evaluated herein towards the well-known near-ideal outer sphere redox probe hexaamineruthenium(III) chloride (RuHex). The results obtained show that triangular and squared electrodes exhibit a faster heterogeneous electron transfer (HET) rate constant (k°) than those of discs and stars, the latter being the slowest one. The results reported here also show a trend between the WE dimension and the reversibility of the electrochemical reaction, which decreases as the WE size increases. It is also observed that the ratio of the geometrical and electroactive area (%realarea) decreases as the overall WE size increases. On the other hand, these four WE shapes were applied toward the well-known and benchmarking detection of ascorbic acid (AA), uric acid (UA), ß-nicotinamide adenine dinucleotide (NADH) and dopamine (DA). Moreover, electroanalytical detection of real acetaminophen (ACOP) samples is also showcased. The different designs for the working electrode proposed in this manuscript are easily changed to any other desired shapes thanks to the additive manufacturing methodology, these four shapes being just an example of what additive manufacturing can offer to experimentalists and to electrochemists in particular. Additive manufacturing is shown here as a versatile and rapid prototyping tool for the production of novel electrochemical sensing platforms, with scope for this work to be able to impact a wide variety of electroanalytical applications.

Additively Manufactured Rotating Disk Electrodes and Experimental Setup.

This manuscript details the first report of a complete additively manufactured rotating disk electrode setup, highlighting how high-performing equipment can be designed and produced rapidly using additive manufacturing without compromising on performance. The additively manufactured rotating disk electrode system was printed using a predominantly acrylonitrile butadiene styrene (ABS) based filament and used widely available, low-cost electronics, and simplified machined parts to create. The additively manufactured rotating disk electrode system costs less than 2% of a comparable commercial solution (£84.47 ($102.26) total). The rotating disk electrode is also additively manufactured using a carbon black/polylactic acid (CB/PLA) equivalent, developing a completely additively manufactured rotating disk electrode system. The electrochemical characterization of the additively manufactured rotating disk electrode setup was performed using hexaamineruthenium(III) chloride and compared favorably with a commercial glassy carbon electrode. Finally, this work shows how the additively manufactured rotating disk electrode experimental system and additive manufactured electrodes can be utilized for the electroanalytical determination of levodopa, a drug used in the treatment of Parkinson's disease, producing a limit of detection of 0.23 ± 0.03 µM. This work represents a step-change in how additive manufacturing can be used in research, allowing the production of high-end equipment for hugely reduced costs, without compromising on performance. Utilizing additive manufacturing in this way could greatly enhance the research possibilities for less well-funded research groups.

Influence of design and material characteristics on 3D printed flow-cells for heat transfer-based analytical devices.

Redesigning 3D-printed flow cells is reported used for heat transfer based detection of biomolecules from a flow-through system to an addition-type measurement cell. The aim of this study is to assess the performance of this new measurement design and critically analyse the influence of material properties and 3D printing approach on thermal analysis. Particular attention is paid to reduce the time to stabilisation, the sample volume in order to make the technique suitable for clinical applications, and improving the sensitivity of the platform by decreasing the noise and interference of air bubbles. The three different approaches that were studied included a filament polylactic acid cell using only fused filament fabrication (FFF), a resin cell printed using stereolitography (SLA), and finally a design made of copper, which was manufactured by combining metal injection moulding (MIM) with fused filament fabrication (FFF). Computational fluid dynamic (CFD) modelling was undertaken using ANSYS Fluent V18.1 to provide insight into the flow of heat within the measurement cell, facilitating optimisation of the system and theoretical response speed.It was shown that the measurement cells using SLA had the lowest noise (~ 0.6%) and shortest measurement time (15 min), whereas measurement cells produced using other approaches had lower specificity or suffered from voiding issues. Finally, we assessed the potential of these new designs for detection of biomolecules and amoxicillin, a commonly used beta lactam antibiotic, to demonstrate the proof of concept. It can be concluded that the resin addition-type measurement cells produced with SLA are an interesting affordable alternative, which were able to detect amoxicillin with high sensitivity and have great promise for clinical applications due to the disposable nature of the measurement cells in addition to small sample volumes.

All-in-One Single-Print Additively Manufactured Electroanalytical Sensing Platforms.

This manuscript provides the first report of a fully additively manufactured (AM) electrochemical cell printed all-in-one, where all the electrodes and cell are printed as one, requiring no post-assembly or external electrodes. The three-electrode cell is printed using a standard non-conductive poly(lactic acid) (PLA)-based filament for the body and commercially available conductive carbon black/PLA (CB/PLA, ProtoPasta) for the three electrodes (working, counter, and reference; WE, CE, and RE, respectively). The electrochemical performance of the cell is evaluated first against the well-known near-ideal outer-sphere redox probe hexaamineruthenium(III) chloride (RuHex), showing that the cell performs well using an AM electrode as the pseudo-RE. Electrochemical activation of the WE via chronoamperometry and NaOH provides enhanced electrochemical performances toward outer-sphere probes and for electroanalytical performance. It is shown that this activation can be completed using either an external commercial Ag|AgCl RE or through simply using the internal AM CB/PLA pseudo-RE and CE. This all-in-one electrochemical cell (AIOEC) was applied toward the well-known detection of ascorbic acid (AA) and acetaminophen (ACOP), achieving linear trends with limits of detection (LODs) of 13.6 ± 1.9 and 4.5 ± 0.9 µM, respectively. The determination of AA and ACOP in real samples from over-the-counter effervescent tablets was explored, and when analyzed individually, recoveries of 102.9 and 100.6% were achieved against UV-vis standards, respectively. Simultaneous detection of both targets was also achieved through detection in the same sample exhibiting 149.75 and 81.35% recoveries for AA and ACOP, respectively. These values differing from the originals are likely due to electrode fouling due to the AA oxidation being a surface-controlled process. The cell design produced herein is easily tunable toward different sample volumes or container shapes for various applications among aqueous electroanalytical sensing; however, it is a simple example of the capabilities of this manufacturing method. This work illustrates the next step in research synergising AM and electrochemistry, producing operational electrochemical sensing platforms in a single print, with no assembly and no requirements for exterior or commercial electrodes. Due to the flexibility, low-waste, and rapid prototyping of AM, there is scope for this work to be able to span and impact a plethora of research areas.

Electrochemical Improvements Can Be Realized via Shortening the Length of Screen-Printed Electrochemical Platforms.

Screen-printed electrodes (SPEs) are ubiquitous within the field of electrochemistry and are commonplace within the arsenal of electrochemists. Their popularity stems from their reproducibility, versatility, and extremely low-cost production, allowing their utilization as single-shot electrodes and thus removing the need for tedious electrode pretreatments. Many SPE studies have explored changing the working electrode composition and/or size to benefit the researcher's specific applications. In this paper, we explore a critical parameter of SPEs that is often overlooked; namely, we explore changing the length of the SPE connections. We provide evidence of resistance changes through altering the connection length to the working electrode through theoretical calculations, multimeter measurements, and electrochemical impedance spectroscopy (EIS). We demonstrate that changing the physical length of SPE connections gives rise to more accurate heterogeneous electrode kinetics, which cannot be overcome simply through IR compensation. Significant improvements are observed when utilized as the basis of electrochemical sensing platforms for sodium nitrite, ß-nicotinamide adenine dinucleotide (NADH), and lead (II). This work has a significant impact upon the field of SPEs and highlights the need for researchers to characterize and define their specific electrode performance. Without such fundamental characterization as the length and resistance of the SPE used, direct comparisons between two different systems for similar applications are obsolete. We therefore suggest that, when using SPEs in the future, experimentalists report the length of the working electrode connection alongside the measured resistance (multimeter or EIS) to facilitate this standardization across the field.