Electrochemical sensor based on 3D-printed substrate by masked stereolithography (MSLA): a new, cheap, robust and sustainable approach for simple production of analytical platforms.

The development of miniaturized, sustainable and eco-friendly analytical sensors with low production cost is a current trend worldwide. Within this idea, this work presents  the innovative use of masked stereolithography (MSLA) 3D-printed substrates for the easy fabrication of pencil-drawn electrochemical sensors (MSLA-3D-PDE). The use of a non-toxic material such as pencil (electrodes) together with a biodegradable 3D printing resin (substrate) allowed the production of devices that are quite cheap (ca. US$ 0.11 per sensor) and with low environmental impact. Compared to paper, which is the most used substrate for manufacturing pencil-drawn electrodes, the MSLA-3D-printed substrate has the advantages of not absorbing water (hydrophobicity) or becoming crinkled and weakened when in contact with solutions. These features provide more reproducible, reliable, stable, and long-lasting sensors. The MSLA-3D-PDE, in conjunction with the custom cell developed, showed excellent robustness and electrochemical performance similar to that observed of the glassy carbon electrode, without the need of any activation procedure. The analytical applicability of this platform was explored through the quantification of omeprazole in pharmaceuticals. A limit of detection (LOD) of 0.72 µmol L-1 was achieved, with a linear range of 10 to 200 µmol L-1. Analysis of real samples provided results that were highly concordant with those obtained by UV-Vis spectrophotometry (relative error ≤ 1.50%). In addition, the greenness of this approach was evaluated and confirmed by a quantitative methodology (Eco-Scale index). Thus, the MSLA-3D-PDE appears as a new and sustainable tool with great potential of use in analytical electrochemistry.

Improving the performance and versatility of microfluidic thread electroanalytical devices by automated injection with electronic pipettes: a new and powerful 3D-printed analytical platform.

Microfluidic cotton thread-based electroanalytical devices (µTEDs) are analytical systems with attractive features such as spontaneous passive flow, low cost, minimal waste production, and good sensitivity. Currently, sample injection in µTEDs is performed by hand using manual micropipettes, which have drawbacks such as inconstant speed and position, dependence of skilled analysts, and need of physical effort of operator during prolonged times, leading to poor reproducibility and risk of strain injury. As an alternative to these inconveniences, we propose, for the first time, the use of electronic micropipettes to carry out automated injections in µTEDs. This new approach avoids all disadvantages of manual injections, while also improving the performance, experience, and versatility of µTEDs. The platform developed here is composed by three 3D-printed electrodes (detector) attached to a 3D-printed platform containing an adjustable holder that keeps the electronic pipette in the same x/y/z position. As a proof-of-concept, both injection modes (manual and electronic) were compared using three model analytes (nitrite, paracetamol, and 5-hydroxytryptophan) on µTED with amperometric detection. As result, improved analytical performance (limits of detection between 2.5- and 5-fold lower) was obtained when using electronic injections, as well as better repeatability/reproducibility and higher analytical frequencies. In addition, the determination of paracetamol in urine samples suggested better precision and accuracy for automated injection. Thus, electronic injection is a great advance and changes the state-of-art of µTEDs, mainly considering the use of more modern and versatile electronic pipettes (wider range of pre-programmed modes), which can lead to the development of even more automated systems.

Simple, fast, and instrumentless fabrication of paper analytical devices by novel contact stamping method based on acrylic varnish and 3D printing.

A new contact stamping method for fabrication of paper-based analytical devices (PADs) is reported. It uses an all-purpose acrylic varnish and 3D-printed stamps to pattern hydrophobic structures on paper substrates. The use of 3D printing allows quickly prototyping the desired stamp shape without resorting to third-party services, which are often expensive and time consuming. To the best of our knowledge, this is the first report regarding the use of this material for creation of hydrophobic barriers in paper substrates, as well as this 3D printing-based stamping method. The acrylic varnish was characterized and the features of the stamping method were studied. The PADs developed here presented better compatibility with organic solvents and surfactants compared with similar protocols. Furthermore, the use of this contact stamping method for fabrication of paper electrochemical devices was also possible, as well as multiplexed microfluidic devices for lateral flow testing. The analytical applicability of the varnish-based PADs was demonstrated through the image-based colorimetric quantification of iron in pharmaceutical samples. A limit of detection of 0.61 mg L-1 was achieved. The results were compared with spectrophotometry for validation and presented great concordance (relative error was < 5% and recoveries were between 104 and 108%). Thus, taking into account the performance of the devices explored here, we believe this novel contact stamping method is a very interesting alternative for production of PADs, exhibiting great potentiality. In addition, this work brings a new application of 3D printing in analytical sciences.

Design of novel, simple, and inexpensive 3D printing-based miniaturized electrochemical platform containing embedded disposable detector for analytical applications.

This paper describes the development of a novel, simple, and inexpensive electrochemical device containing an integrated and disposable three-electrode system for detection. The base of this platform consists on a PDMS structure containing microchannels which were prototyped using 3D-printed molds. Pencil graphite leads were inserted into these microchannels and utilized as working, counter and reference electrodes in a novel design. Morphological analysis and electrochemical experiments with benchmark redox probes were carried out in order to evaluate the performance and characterize the miniaturized device proposed. Even using inexpensive materials and a simple fabrication protocol, the electrochemical platform developed provided good repeatability and reproducibility over a low cost (ca. $2 per device), acceptable lifetime (ca. 250 voltammetric runs) and extremely reduced consumption of samples and reagents (order of µL). As proof of concept, the analytical feasibility of the platform was investigated through the simultaneous determination of dopamine (DOPA) and acetaminophen (AC). The two analytes showed linear dependence on the concentration range from 1 to 15 µM and the LODs achieved were 0.21 µM for DOPA and 0.29 µM for AC. Moreover, the platform was successfully applied on the determination of DOPA and AC in spiked blood serum and urine samples. The results obtained with the device described here were better than some reports in literature that use more costly electrodic materials and complex modification steps for the detection of the same analytes.

Rapid and inexpensive method for the simple fabrication of PDMS-based electrochemical sensors for detection in microfluidic devices.

The fabrication of PDMS microfluidic structures through soft lithography is widely reported. While this well-established method gives high precision microstructures and has been successfully used for many researchers, it often requires sophisticated instrumentation and expensive materials such as clean room facilities and photoresists. Thus, we present here a simple protocol that allows the rapid molding of simple linear microchannels in PDMS substrates aiming microfluidics-based applications. It might serve as an alternative to researchers that do not have access to sophisticated facilities such as clean rooms. The method developed here consists on the use of pencil graphite leads as template for the molding of PDMS channels. It yields structures that can be used for several applications, such as housing support for electrochemical sensors or channels for flow devices. Here, the microdevices produced through this protocol were employed for the accommodation of carbon black paste, which was utilized for the first time as amperometric sensor in microchip electrophoresis. This platform was successfully used for the separation and detection of model analytes. Ascorbic acid and iodide were separated within 45 s with peak resolution of 1.2 and sensitivities of 198 and 492 pA/µM, respectively. The background noise was ca. 84 pA. The analytical usefulness of the system developed was successfully tested through the quantification of iodide in commercial pharmaceutical formulations. It demonstrates good efficiency of the microfabrication protocol developed and enables its use for the easy and rapid prototyping of PDMS structures over a low fabrication cost.

Electrodeposition of reduced graphene oxide on a Pt electrode and its use as amperometric sensor in microchip electrophoresis.

This report describes the development and application of a novel graphene-modified electrode to be used as amperometric sensor in microchip electrophoresis (ME) devices. The modified electrode was achieved based on electroreduction of graphene oxide on an integrated Pt working electrode of a commercial ME device. The surface modification was characterized by SEM and cyclic voltammetry techniques. The results indicated that graphene sheets were successfully deposited exhibiting higher surface conductivity and greater electrode sensitivity. The performance of the modified electrode for the amperometric detection on ME devices has been demonstrated by the separation and detection of an anionic mixture containing iodide and ascorbate. The graphene-modified electrode provided significantly higher sensitivity (896.7 vs. 210.9 pA/µM for iodide and 217.8 vs. 127.8 pA/µM for ascorbate), better separation efficiencies (3400 vs. 700 plates/m for iodide and 10 000 vs. 2400 plates/m for ascorbate), enhanced peak resolutions (1.6 vs. 1.0), and LODs (1.5 vs. 5.3 µM for iodide and 3.1 vs. 7.3 µM for ascorbate) in comparison with the unmodified Pt electrode. The proposed amperometric sensor was successfully applied for the analysis of ascorbic acid (through its anionic form) in a commercial medicine sample, and the results achieved were in agreement with the value provided by the supplier. Based on the data here presented, the modified graphene electrode shows great promise for ME applications.

Separation of natural antioxidants using PDMS electrophoresis microchips coupled with amperometric detection and reverse polarity.

This report describes the use of PDMS ME coupled with amperometric detection for rapid separation of ascorbic, gallic , ferulic, p-coumaric acids using reverse polarity. ME devices were fabricated in PDMS by soft lithography and detection was accomplished using an integrated carbon fiber working electrode aligned in the end-channel configuration. Separation and detection parameters were investigated and the best conditions were obtained using a run buffer consisting of 5 mM phosphate buffer (pH 6.9) and a detection voltage of 1.0 V versus Ag/AgCl reference electrode. All compounds were separated within 70 s using gated injection mode with baseline resolution and separation efficiencies between 1200 and 9000 plates. Calibration curves exhibited good linearity and the LODs achieved ranged from 1.7 to 9.7 µM. The precision for migration time and peak height provided maximum values of 4% for the intrachip studies. Lastly, the analytical method was successfully applied for the analysis of ascorbic and gallic acids in commercial beverage samples. The results achieved using ME coupled with amperometric detection were in good agreement with the values provided by the supplier. Based on the data reported here, the proposed method shows suitability to be applied for the routine analysis of beverage samples.

Electrochemical study and forensic electroanalysis of fungicide benzovindiflupyr using disposable graphite pencil electrode.

Nowadays, the use of pesticides in world agriculture is fundamental. However, it leads to an increase in the illegal sale and smuggling of these products in various parts of the world, mainly in Brazil. Therefore, the development of new analytical methods for screening and analysis of these kind of substances is a relevant issue. We present in this work, for the first time, an electrochemical study and a novel electroanalytical method for determination of fungicide benzovindiflupyr (BENZO). According to our knowledge, the electrochemical behavior of BENZO, as well as its voltammetric determination, have never been reported before. The sensors used here consisted of disposable pencil graphite electrodes (PGEs). On this electrode surface and at optimal pH, BENZO behaved according to a quasi-reversible system and showed two voltammetric peaks, one anodic at Ep = +0.59 V and another cathodic at Ep = +0.43 V. The analytical studies utilized BENZO anodic sweep and square-wave adsorptive stripping voltammetry (SWAdSV). All experimental and instrumental parameters were fully investigated and optimized. Under the best conditions, a calibration plot was obtained in the concentration range from 0.10 to 12.5 µmol L-1. The limits of detection (LOD) and quantification (LOQ) achieved were 0.023 and 0.076 µmol L-1, respectively. An electrochemical mechanism for BENZO oxidation was also proposed. The method developed here was successfully employed for the qualitative and quantitative forensic analysis of BENZO in smuggled products, showing good accuracy (recoveries ca. 104%) and precision (relative standard deviation < 5%). These data attest the potential for use of this method in forensic area.

Exploring the coating of 3D-printed insulating substrates with conductive composites: a simple, cheap and versatile strategy to prepare customized high-performance electrochemical sensors.

The development of 3D-printed electrochemical sensors by fused deposition modeling (FDM) has been increasing exponentially in the last five years. In this context, commercial conductive filaments composed of a blend of carbon particles (e.g., graphene or carbon black (CB)) and insulating thermoplastic polymers (e.g., polylactic acid (PLA) or acrylonitrile butadiene styrene (ABS)) have been widely used for electrode fabrication. However, such materials may be expensive and the electrodes when used "as-printed" exhibit poor electrochemical performance as a function of the low content of conductive particles in the composition (∼10 to 20 wt%), which requires one or more post-treatment steps (e.g. polishing, chemical, electrochemical, and photochemical) to reach good electrochemical performance. In this technical note a less used approach to produce "ready-to-use" electrochemical platforms based on 3D printing is explored, which consists of the coating of 3D-printed insulating substrates with homemade conductive composites. To demonstrate the potentiality of this alternative protocol, 3D-printed ABS insulating substrates at two geometries were coated in a highly loaded graphite (55 wt%) homemade composite (G-ABS) and evaluated for the detection of the ferri/ferrocyanide redox probe and model analytes in stationary and hydrodynamic 3D-printed systems (nitrite in micro-flow injection analysis/µFIA and paracetamol in batch injection analysis/BIA, respectively). The analytical parameters acquired with the coated electrodes were comparable to those obtained using conventional electrodes (glassy carbon, boron-doped diamond and carbon screen-printed) and 3D-printed sensors fabricated with commercial filaments. Moreover, the inclusion of carbon black in the fluid conductive composite was demonstrated as a perspective to obtain modified coated 3D-printed surfaces easily for the first time. This alternative "do it yourself" strategy is promising for the large-scale production of very cheap (US$ 0.08) and high-performance electrodes based on FDM 3D printing. Moreover, this approach dispenses the acquisition of commercial conductive filaments and the laborious development of homemade filaments.

A novel all-3D-printed thread-based microfluidic device with an embedded electrochemical detector: first application in environmental analysis of nitrite.

A microfluidic thread electroanalytical device (µTED) containing an embedded electrochemical detector is presented for the first time in this work. This novel device was entirely produced in an automated way using the fused deposition modeling (FDM) 3D printing technique. The main platform was fabricated with acrylonitrile butadiene styrene (ABS) filament, while the integrated electrochemical detector was produced using a commercial conductive filament composed of carbon black and polylactic acid (CB/PLA). The microfluidic channels consisted of cotton threads, which act as passive pumps, and the µTED was used for microflow injection analysis (µFIA). As a proof of concept, this µFIA system was utilized for the amperometric sensing of nitrite in natural waters. This is the first report on the use of both µTEDs and 3D-printed CB/PLA electrodes to determine this species. This fully 3D-printed µTED was characterized and all experimental and instrumental parameters related to the method were studied and optimized. Using the best conditions, the proposed approach showed a linear response in the concentration range from 8 to 200 µmol L-1 and a limit of detection (LOD) of 2.39 µmol L-1. The LOD obtained here was ca. ten-fold lower than the maximum contaminant level for nitrite in drinking water established by the Brazilian and US legislation. Moreover, the platform presented good repeatability and reproducibility (relative standard deviations (RSDs) were 2.1% and 2.5%, respectively). Lastly, the 3D-printed µTED was applied for the quantification of nitrite in well water samples and the results obtained showed good precision (RSD < 3%) and excellent concordance (relative error was ca.±3%) with those achieved by ion chromatography, used for validation.

Development of highly sensitive electrochemical sensor using new graphite/acrylonitrile butadiene styrene conductive composite and 3D printing-based alternative fabrication protocol.

Here, a novel electrically conductive thermoplastic material composed of graphite/acrylonitrile butadiene styrene (G/ABS) is reported for the first time. This material was explored on the production of 3D printing-based electrochemical sensors with enhanced sensitivity using a novel fabrication approach. The developed G/ABS electrodes showed lower charge transfer resistance (157 vs. 3279 Ω), higher electroactive area (0.61 vs. 0.19 cm2) and peak currents ca. 69% higher when compared with electrodes fabricated using carbon black/polylactic acid (CB/PLA) commercial filament, which has been widely explored in recent literature. Moreover, the G/ABS sensor provided satisfactory repeatability, reproducibility and stability (relative standard deviations (RSDs) were 1.14%, 6.81% and 10.62%, respectively). This improved performance can be attributed to the fabrication protocol developed here, which allows the incorporation of greater amounts of conductive material in the polymeric matrix. The G/ABS electrode also required a simpler and quicker protocol for activation when compared to CB/PLA. As proof of concept, the G/ABS sensor was employed for electroanalytical quantification of paracetamol (PAR) in pharmaceutical products. The linear concentration range was observed from 0.20 to 30 µmol L-1 and the limit of detection achieved was 54 nmol L-1, much lower than several recent studies dealing with the same analyte. The sensitivity of the G/ABS electrode regarding PAR was also far better when compared to CB/PLA sensor (0.50 µA/µmol L-1 vs. 0.12 µA/µmol L-1). Analyses in commercial pill samples showed good accuracy (recoveries ca. 108%) and precision (RSDs < 5%), suggesting great potential for use of this novel conductive thermoplastic in electroanalytical applications based on 3D printing.

Multi sensor compatible 3D-printed electrochemical cell for voltammetric drug screening.

3D printing is a hot topic in electroanalytical chemistry, allowing the construction of custom cells and sensors at affordable prices. In this work, we describe a novel small and practical 3D-printed electrochemical cell. The cell's body, manufactured in ABS on a 3D printer, is composed by three parts easily screwed: solution vessel, stick and cover with two embedded 3D-pen-printed carbon black-polylactic acid (CB-PLA) electrodes (counter and pseudo-reference). The cell is compatible with any planar working electrode, in which boron-doped diamond, graphite sheet (GS) and 3D-printed CB-PLA were shown as examples. A new alternative protocol to quickly produce 3D-printed sensors using a 3D pen and other low-cost apparatus is also proposed. The voltammetric performance of each evaluated sensor was carried out in the presence of redox probe ferricyanide and paracetamol as model analyte, and the surfaces were characterized by electrochemical impedance spectroscopy and scanning electrochemical microscopy. To present an analytical application of the 3D-printed cell, low-cost flexible sensors (GS and CB-PLA) were used as integrated platforms for sampling and detection of solid drugs. As a proof-of-concept, traces of drugs with a historic of counterfeit or adulteration (sildenafil citrate, tadalafil, losartan and 17α-ethinylestradiol) were abrasively sampled over the sensor and assembled on 3D-printed cell to perform a fast voltammetric scan in the presence of only 500 µL of electrolyte. This protocol is attractive for pharmaceutical and forensic sciences as a simple preliminary screening method which could identify the presence or absence of the suspicious drug as well as impurities or adulterants. The 3D-printed cell was also used for the determination of 17α-ethinylestradiol in a contraceptive pill to demonstrate a quantitative analysis. The cell is quickly printed (90 min), cheap (US$ 0.30) and requires low electrolyte volumes (0.5-3.0 mL), being suitable to be used in several other electroanalyses, especially for on-site applications.

Electrochemical study and simultaneous voltammetric determination of contraceptives ethinylestradiol and cyproterone acetate using silver nanoparticles solid amalgam electrode and cationic surfactant.

In this work we propose the voltammetric analysis of contraceptive hormones ethinylestradiol (EE) and cyproterone acetate (CPA) using solid amalgam electrode fabricated with silver nanoparticles. To the best of our knowledge, this is the first report describing the simultaneous determination of these two compounds and also the first report of the use of amalgam electrode for analysis of EE and CPA. The voltammetric behavior of both substances was investigated by their reduction. An irreversible electrochemical process involving two protons and two electrons was found for each compound. The analytical assays were carried out using staircase voltammetry (SCV). Due to this, aiming to improve the analytical sensitivity, the cationic surfactant cetyltrimethylammonium bromide was also used. The instrumental and experimental parameters were studied and optimized to achieve the best conditions for the analysis. Under the optimum conditions, the voltammetric signals of EE and CPA showed dependence on the concentration range from 6.4 × 10-7 to 7.8 × 10-6 mol L-1 and from 1.0 × 10-6 to 1.0 × 10-5 mol L-1, respectively. The limits of detection obtained were 1.03 × 10-7 mol L-1 for EE and 2.99 × 10-7 mol L-1 for CPA. The analytical usefulness of the method was evaluated through its application on the simultaneous determination of EE and CPA in pharmaceutical formulations and urine samples. The two analytes were successfully quantified in these samples with good precision and the values found presented satisfactory concordance with the reference values, suggesting acceptable analytical efficiency for the approach described here.

Easy and rapid pen-on-paper protocol for fabrication of paper analytical devices using inexpensive acrylate-based plastic welding repair kit.

This work describes a novel, simple and inexpensive pen-on-paper (PoP) method for patterning hydrophobic structures in paper substrates aiming the production of paper-based analytical devices (PADs). This fabrication protocol uses a commercially available plastic welding kit that can be easily acquired and is sold as a repair tool. It consists of an acrylate-based resin which is deposited on the paper and then cured using a UV led, or even the sunlight, for creation of the hydrophobic barriers. The protocol is instrument-free and can be easily implemented in any laboratory. To the best of our knowledge, this is the first report of the use of this material for production of analytical devices. The developed PADs were fully characterized and exhibited better chemical resistance than other recently reported PoP approaches regarding organic media and surfactants. Moreover, the fabrication method demonstrated good analytical versatility since it allowed the production of flexible devices, flow-based devices and pencil-drawn electrochemical devices. These findings are very interesting since overcome some limitations related by other PoP reports and expand the possibilities of using this technology in several aqueous and non-aqueous applications. Lastly, the analytical usefulness of the developed devices was successfully explored through colorimetric determination of nitrite. A detection limit of 0.14 mg L-1 was achieved and several samples of natural waters were analyzed. The results showed good agreement when compared with a reference technique. So, considering the simplicity and the results presented here, this fabrication method shows great potential for use in analytical chemistry.

Simple approach for the fabrication of screen-printed carbon-based electrode for amperometric detection on microchip electrophoresis.

This paper describes a simple method for the fabrication of screen-printed based electrodes for amperometric detection on microchip electrophoresis (ME) devices. The procedure developed is quite simple and does not require expensive instrumentation or sophisticated protocols commonly employed on the production of amperometric sensors, such as photolithography or sputtering steps. The electrodes were fabricated through manual deposition of home-made conductive carbon ink over patterned acrylic substrate. Morphological structure and electrochemical behavior of the carbon electrodes were investigated by scanning electron microscopy and cyclic voltammetry. The produced amperometric sensors were coupled to polydimethylsiloxane (PDMS) microchips at end-channel configuration in order to evaluate their analytical performance. For this purpose, electrophoretic experiments were carried out using nitrite and ascorbic acid as model analytes. Separation of these substances was successfully performed within 50s with good resolution (R = 1.2) and sensitivities (713.5 pA/µM for nitrite and 255.4 pA/µM for ascorbate). The reproducibility of the fabrication method was evaluated and revealed good values concerning the peak currents obtained (8.7% for nitrite and 9.3% for ascorbate). The electrodes obtained through this method exhibited satisfactory lifetime (ca. 400 runs) over low fabrication cost (less than $1 per piece). The feasibility of the proposed device for real analysis was demonstrated through the determination of nitrite concentration levels in drinking water samples. Based on the results achieved, the approach proposed here shows itself as an interesting alternative for simple fabrication of carbon-based electrodes. Furthermore, the devices indicate great promise for other kind of analytical applications involving ME devices.