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.
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•We review the contributions of 3D-printing to fabricate electrochemical sensors.•Different 3D-printing methods are compared highlighting fused deposition modeling (FDM).•Surface treatment and modification with (bio)chemical mediators for improved performance.•Strategies for fabrication of conductive filaments are presented for future applications.•3D-printing of all-in-one electrochemical devices in different designs are assessed.
A sensor based on glassy carbon electrode (GCE) modified within reduced graphene oxide (RGO) and carbon black (CB) in a chitosan film (CTS) is presented. The combination of the nanomaterials with CTS ...provided a stable dispersion and could be successfully used as electroactive layer. By using the Nicholson method and the results obtained by cyclic voltammetry with the proposed RGO-CB-CTS/GCE, the heterogeneous electron transfer rate constant (k0) of 5.6×10−3cms−1 was obtained. The proposed electrode was applied for the simultaneous determination of dopamine (DA) and paracetamol (PAR). Employing square-wave voltammetry, DA presented an anodic peak at 0.25V and PAR at 0.50V vs. Ag/AgCl (3.0molL−1 KCl). The analytical curves obtained were linear in the range from 3.2×10−6 to 3.2×10−5molL−1 and from 2.8×10−6 to 1.9×10−5molL−1 for DA and PAR, respectively, with detection limits of 2.0×10−7 for DA and 5.3×10−8molL−1 for PAR. The developed sensor presented advantages such as simple preparation, low cost of the nanomaterials employed and a fast response. Besides, it could successfully apply in the determination of DA and PAR in biological samples.
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•A thin film using reduced graphene oxide and carbon black in a chitosan film is proposed.•The proposed electrode is easy to prepare, presents low cost and fast response.•It was applied the simultaneous determination of dopamine and paracetamol.
In this study, we report an electrochemical study based on nanocellulose (NC) and single-walled carbon nanohorns (SWCNH). SWCNH and NC ensure large surface area, good conductivity, high porosity and ...chemical stability, becoming attractive for electrodes. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Scanning Electron Micrograph (SEM), Transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential. Using XRD and FTIR it was possible to observe particular characteristics of NC and SWCNH. The presence of dahlia-like assemblies on the NC surface was observed by MEV and TEM. Then, we investigated the electrochemical behavior of NC-SWCNH, which showed the excellent results when it was used guanine and adenine, as proof of concept, by using cyclic and linear sweep voltammetry (LSV). LSV was also employed for simultaneous detection resulting in limits of detection of 1.7 × 10−7 mol L−1 and 1.4 × 10−6 mol L−1, for guanine and adenine, respectively. In addition, the proposed electrode was applied for determination of both bases in synthetic human serum and fish sperm. We demonstrate that it is possible to use NC, a renewable material, in conducting thin films with SWCNH, and due to simplicity in the preparation and high conductivity, this new thin film could be extended for others electrochemical purposes such as sensing and biosensing.
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•Water-based conductive ink based on chitosan, graphite powder, and glycerol.•Low-cost and easy construction of a biosensor of Tyrosinase.•Reliable quantification of uric acid and catechol using only ...70 µL of solution.•Environmentally friendly platform for electrochemical sensing and biosensing purposes.
This paper presents a novel water-based conductive ink obtained by proper combination of chitosan (C) biopolymer, graphite (G) powder, and glycerol (G), and its subsequent use in the screen-printing of disposable electrodes on polyethylene terephthalate (PET) plastic obtained from recyclable soda bottles (CGG/PET electrodes). The electrode was used in two directions, as a sensor for the quantification of uric acid and as a biosensor for the enzymatic quantification of catechol. The linear sweep voltammetry-detection of uric acid (UA), showed a linear range between 8.0 and 500 μmol L−1 and a limit of detection (LOD) of 0.36 μmol L−1. Additionally, the performance of the resulting electrodes for biosensing purposes was evaluated through the development of a catechol biosensor by the modification of the GCG/PET surface with the tyrosinase (Tyr) enzyme, multiwalled carbon nanotubes (MWCNTs), and dyhexadecyl phosphate (DHP) (Tyr-MWCNT-CGG/PET). Using the chronoamperometry technique a linear relationship from 0.5 to 50 μmol L−1 and LOD of 0.3 μmol L−1 were achivied for catechol. The proposed electrode has demonstrated outstanding analytical characteristics, proving its potential as a disposable, low-cost, and environmentally friendly platform for electrochemical sensing and biosensing purposes.
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Simple, low-cost, and sensitive new platforms for electrochemical immunosensors for virus detection have been attracted attention due to the recent pandemic caused by a new type of coronavirus ...(SARS-CoV-2). In the present work, we report for the first time the construction of an immunosensor using a commercial 3D conductive filament of carbon black and polylactic acid (PLA) to detect Hantavirus Araucaria nucleoprotein (Np) as a proof-of-concept. The recognition biomolecule was anchored directly at the filament surface by using N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and N-Hydroxysuccinimide (EDC/NHS). Conductive and non-conductive composites of PLA were characterized using thermal gravimetric analysis (TGA), revealing around 30% w/w of carbon in the filament. Morphological features of composites were obtained from SEM and TEM measurements. FTIR measurement revealed that crosslinking agents were covalently bonded at the filament surface. Electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used for the evaluation of each step involved in the construction of the proposed immunosensor. The results showed the potentiality of the device for the quantitative detection of Hantavirus Araucaria nucleoprotein (Np) from 30 μg mL−1 to 240 μg mL−1 with a limit of detection of 22 μg mL−1. Also, the proposed immunosensor was applied with success for virus detection in 100x diluted human serum samples. Therefore, the PLA conductive filament with carbon black is a simple and excellent platform for immunosensing, which offers naturally carboxylic groups able to anchor covalently biomolecules.
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•Commercial 3D conductive filament of polylactic acid (PLA) to construction of immunosensors.•Sensor construction based on carboxylic group naturally present at filament without any additional pre-treatment.•Immunosensor for diagnosis of Hantavirus disease.•Feasible, simple, and low-cost alternative strategy to detect viral diseases.
This work presents a novel procedure involving the sequential chemical treatment to generate reduced graphene oxide (rGO) within 3D-printed polylactic acid (PLA) electrodes and their potential ...applications for sensing and biosensing. A new configuration of a compact all-3D-printed electrochemical device containing the three electrodes is presented, in which the working electrode was treated to generate rGO within PLA (rGO-PLA) after treatment within NaBH4. The rGO-PLA electrodes presented a notable current increase for the redox probe ferrocene-methanol in comparison with the same surface treated by dimethylformamide immersion. Also, the electrochemical impedance spectroscopic data that presented the lowest resistance to electron transfer for the proposed electrode. The electrochemical experiments were in accordance with Raman spectra and surface roughness obtained by atomic force microscopy images. As proofs-of-concept, the rGO-PLA electrode was applied for serotonin determination in synthetic urine using differential-pulse voltammetry with a limit of detection of 0.032 μmol L−1. Also, the second application involved the fabrication of a tyrosinase-based biosensor capable of determining catechol in natural water samples with a limit of detection of 0.26 μmol L−1. Based on both applications, the 3D-printed rGO-PLA showed to be an excellent platform for sensing and biosensing purposes.
•A new platform using reduced graphene oxide is proposed.•The electrochemical cell, sensors, and biosensors were produced by 3D-printing.•The proposed electrode could be applied for other electrochemical sensing and biosensing.•The 3D-printed sensor and biosensor were applied for the determination of phenolic compounds.
Disposable electrochemical sensors using sustainable and cheap materials are an exciting alternative to produce new kinds of sensing platforms. Waterproof paper (WP) is a biodegradable and ...biocompatible material that allows dropped of the sample on its surface without absorption by fibers. Also, WP can be used for miniaturized sensors construction. In this work, a conductive ink was produced with nail polish and graphite powder, using the WP as the sensor substrate for paracetamol (PAR) and melatonin (MEL) voltammetric determination. PAR is a pharmaceutical commonly used in high doses for the relief of pain and fever, and MEL is a hormone related to several diseases besides a direct relation to sleep quality. Using differential pulse voltammetry for PAR determination, the WP sensor showed a linear response in the concentration ranging from 0.50 μmol L−1 to 100 μmol L−1 with a limit of detection (LOD) of 53.6 nmol L−1. Square wave voltammetry was applied for MEL determination, and the proposed electrode presented linear response ranging from 0.80 μmol L−1 to 100 μmol L−1 and LOD of 32.5 nmol L−1. The sensor showed excellent repeatability and reproducibility for consecutive measurements. Then, the disposable WP sensor was successfully applied in the determination of PAR and MEL in pharmaceutical and biological samples, with recovery values, above 91.1%. The described architecture allowed the manufacture of a disposable, simple, and low-cost electroanalytical device that can be used for electrochemical sensing.
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•Waterproof paper showed an excellent platform for GPT-WPE sensor construction.•Waterproof paper allows the construction of a sensor with hydrophobic characteristic.•Low-cost and easy construction of a sensor based on graphite and nail polish ink.•Accurate method for paracetamol and melatonin determination in pharmaceutical and biological samples.
Additive manufacturing is a technique that allows the construction of prototypes and has evolved a lot in the last 20 years, innovating industrial fabrication processes in several areas. In ...chemistry, additive manufacturing has been used in several functionalities, such as microfluidic analytical devices, energy storage devices, and electrochemical sensors. Theophylline and paracetamol are important pharmaceutical drugs where overdosing can cause adverse effects, such as tachycardia, seizures, and even renal failure. Therefore, this paper aims at the development of miniaturized electrochemical sensors using 3D printing and polylactic acid-based conductive carbon black commercial filament for theophylline and paracetamol detection. Electrochemical characterizations of the proposed sensor were performed to prove the functionality of the device. Morphological characterizations were carried out, in which chemical treatment could change the surface structure, causing the improvement of the analytical signal. Thus, the detection of theophylline at a linear range of 5.00–150 μmol L−1 with a limit of detection of 1.2 μmol L−1 was attained, and the detection of paracetamol at a linear range of 1.00–200 μmol L−1 with a limit of detection of 0.370 μmol L−1 was obtained, demonstrating the proposed sensor effectively detected pharmaceutical drugs.
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•A simple and easy printing miniaturized electrochemical device has been developed.•A 3D-printed sensor based on PLA and carbon black filament is constructed.•DMF chemical treatment was effective for exposing carbon black agglomerates.•The optimized method was applied for theophylline detection.•Drug monitoring is performed in pharmaceutical and artificial biological samples.
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•The Carbon Black was characterized by MEV, MET, EDX, DRX and RAMAN.•An ultrathin CB film was applied in the development of an electrochemical sensor.•AA, DA, UA and PAR were ...simultaneously determined using a CB/GCE electrode.•The new DPV method was used in the determination of these analytes in biological fluids.
A novel material for the simultaneous electrochemical determination of ascorbic acid (AA), dopamine (DA), uric acid (UA) and paracetamol (PAR) using a composite based on carbon black film at glassy carbon electrode (CB/GC) has been evaluated. The morphology, structure and electrochemical performance of the composite electrodes were characterized by transmission electron microscopy, scanning electron microscopy, Raman spectra and cyclic voltammetry. The transmission electron microscopy and scanning electron microscopy images showed good distribution of the carbon black with a nanoscale particle size. The electrochemical measurements demonstrated the high-performance electrocatalytic of CB/GC electrode. Differential pulse voltammetry was applied to simultaneously detect AA, DA, UA and PAR levels in biological samples.
Disposable electrochemical sensors by using recyclable materials are an interesting alternative to produce electrochemical sensors with an extreme low cost. In addition, the screen-printing technique ...has been widely used to propose electrochemical devices with new conductive inks for different applications. In this context, we develop a disposable eco-friend sensor with relative cost low and easy production. A conductive ink was produced with nail polish and graphite powder. As a sensor substrate, we reuse polyethylene terephthalate (PET) from drink bottles. The characterizations of the proposed electrode were performed by using scanning electron microscopy, infrared microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The determination of hydroquinone (HQ), epinephrine (EP) and serotonin (5-HT) were chosen as proof of concept. Using square wave voltammetry, for HQ, the PET sensor showed a linear response in the concentration range of 5.0 to 100μmolL−1 with a detection limit (LOD) of 0.01μmolL−1. Differential pulse voltammetry was applied for EP and 5-HT detection, and the proposed electrode presented linear response in the range of 5.0 to 100μmolL−1 and 1.0 to 50μmolL−1 and LODs of 0.3 and 0.1μmolL−1 for EP and 5-HT, respectively. Then, the disposable PET sensor was applied in the determination of HQ in environmental and pharmaceutical samples and, EP and 5-HT in biological samples. The proposed electrode is simple to prepare and can be easily used for electrochemical sensing and biosensing.
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•A new disposable sensor is made from PET bottles.•A new conductive ink is prepared with nail polish and graphite.•The hydroquinone is used as proof of concept.
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