► Highly rapid, selective and sensitive amperometric detection of H2O2 in milk. ► Prussian-blue modified electrode with improved stability and precision. ► Association with batch-injection analysis ...provided high analytical frequency. ► Satisfactory recovery values for milk analysis.
We report a highly rapid, precise, selective and sensitive analytical method for the determination of hydrogen peroxide in milk using a batch-injection analysis (BIA) with amperometric detection at a Prussian-blue bulk modified graphite-composite electrode. An electronic micropipette injected 100μL aliquots of 10-fold diluted samples (high and low-fat milk) directly onto the modified electrode immersed in the BIA cell. The analytical features of our proposed method includes low RSD between injections (0.76%, n=9), low detection limit (10μmolL−1), elevated analytical frequency (up to 80h−1) and satisfactory recovery values for spiked samples. A fresh and highly reproductive electrode surface can be easily obtained by simple mechanical polishing (RSD=1.6%, n=5). The storage stability of the PB-modified graphite-composite surpassed 1year keeping equivalent performance as initially presented. The association of BIA with an improved amperometric detector provides great promise for routine monitoring of hydrogen peroxide in milk and other beverages.
The storage stability and corrosive character of soybean biodiesel stabilised with tert-butylhydroquinone (TBHQ) was investigated through static immersion corrosion tests. Coupons of carbon steel and ...galvanised steel were immersed in soybean biodiesel with and without TBHQ for 12 weeks. Measurements of total acid number, peroxide value, oxidation stability (Rancimat induction period), metal release, and TBHQ consumption at different stages of corrosion were performed. After 12 weeks of the static immersion test with both steels, the non-stabilised biodiesels presented induction times below the EN 14214 limit (6 h); these results were in agreement with increase in the peroxide values. Zinc release was only detected in the non-stabilised biodiesel exposed to galvanised steel, whilst iron was not detected in any biodiesel samples exposed to carbon steel. The absence of zinc in the TBHQ-doped biodiesel exposed to galvanised steel indicates that TBHQ may have acted as a corrosion inhibitor. Additionally, TBHQ was rapidly consumed in the first 3 days of experiments, providing evidence of its activity. For a storage period of up to 56 days, both galvanised and carbon steels were shown to be compatible with biodiesel even in the absence of an antioxidant. The presence of zinc (>2 (mu)g g(-1) after 28 days of immersion) due to corrosion did not promote biodiesel deterioration.
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.
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•Low-cost fused deposition modeling (FDM) 3D-printers to produce cells and electrodes.•Multiuse cells for flow- (FIA) and batch-injection analysis (BIA) as well for batch condition.•Designs and printing conditions accessible for any FDM 3D-printers.•Graphene-doped PLA printed sensors for voltammetric and amperometric detection.•Electroanalytical performance similar to GCE modified with carbon nanomaterials.
Paracetamol is an active ingredient commonly found in pharmaceutical formulations in combination with one of the following compounds: codeine, orphenadrine, promethazine, scopolamine, and tramadol. ...In this work, we propose a unique analytical method for determination of these active ingredients in pharmaceutical samples. The method is based on capillary electrophoresis with capacitively coupled contactless conductivity detection. The separation was achieved on a fused silica capillary (50 cm total length, 40 cm effective length, and 50 μm id) using an optimized background electrolyte composed of 20 mmol/L β‐alanine/4 mmol/L sodium chloride/4 μmol/L sodium hydroxide (pH 9.6). Each sample can be analyzed in a single run (≤2 min) and the limits of detection were 2.5, 0.62, 0.63, 2.5, 15, and 1.6 μmol/L for scopolamine, tramadol, orphenadrine, promethazine, codeine, and paracetamol, respectively. Recovery values for spiked samples were between 94 and 104%.
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.
We show that fused deposition modelling (FDM) 3D-printed electrodes can be used for quality control of fuel bioethanol. 3D-printing using carbon black/polylactic acid (CB-PLA) filaments resulted in ...conductive and biodegradable electrodes for biofuel analysis. As a proof-of-concept, copper determination in fuel bioethanol was performed, as such ions catalyse oxidation processes during storage and transport. Square-wave anodic-stripping voltammetry (SWASV) of copper was achieved after sample dilution in 0.1 mol L
−1
HCl as supporting electrolyte (resulting in 30:70%
v
/
v
ethanol:water). The linear responses were in the range between 10 and 300 μg L
−1
(
R
= 0.999), inter-day precision was lower than 8% (
n
= 10, for 20 μg L
−1
) and limits of detection (LOD) and quantification (LOQ) using 180 s as deposition time were 0.097 μg L
−1
and 0.323 μg L
−1
, respectively. Recovery values between 95 and 103% for the analysis of bioethanol spiked with known amounts of copper were obtained. These results show great promise of the application of 3D-printed sensors for the quality control of biofuels.
Graphical abstract
We report the development of a simple, portable, low-cost, high-throughput visual colorimetric paper-based analytical device for the detection of procaine in seized cocaine samples. The interference ...of most common cutting agents found in cocaine samples was verified, and a novel electrochemical approach was used for sample pretreatment in order to increase the selectivity. Under the optimized experimental conditions, a linear analytical curve was obtained for procaine concentrations ranging from 5 to 60 μmol L(-1), with a detection limit of 0.9 μmol L(-1). The accuracy of the proposed method was evaluated using seized cocaine samples and an addition and recovery protocol.
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•Low-cost fused deposition modeling 3D-printed device for sampling and detection of TNT.•Graphene-doped polylacic acid (G-PLA) filament to fabricate the 3D-printed device.•Nanograms ...of TNT sampled from metallic, granite and glove surfaces were quantified.•Mechanical polishing of the 3D-printed surface improved the electrochemical properties.•Metal determination on the device was also shown; promising for gunshot residue analysis.
Fused deposition modelling 3D printing of a flexible, conductive, disposable and biodegradable platform using graphene-doped polylactic acid (G-PLA) was demonstrated as an integrated device for sampling and detection of explosives. As a proof-of-concept, traces of 2,4,6-Trinitrotoluene (TNT) impregnated on different surfaces were abrasively sampled using the 3D-printed device and readily assembled in a portable electrochemical cell for rapid square-wave voltammetry scans in the presence of 0.1 mol L–1 HCl electrolyte. Nanogram amounts of TNT sampled from metallic, granite and glove surfaces were detected and quantified using the Faraday equation applied to the voltammetric response of TNT immobilised on the electrode surface. Identification of TNT was possible due to the unique voltammetric behaviour obtained on the G-PLA sensor and efficient sampling due to the rough surface and flexibility of the device. Lead and copper determination by stripping voltammetry was also demonstrated on the same device, highlighting the possibility of detecting gunshot residues. Moreover, we demonstrated that simple mechanical polishing of the 3D-printed surface improved the electrochemical sensing properties of the sensor by exposing graphene nanoribbons within the PLA matrix. Hence, this 3D-printed integrated platform holds promise as a rapid and low-cost approach for on-site crime scene investigations.
This work shows that the electrochemical activity of a 3D-printed electrode fabricated using a conductive composite of polylactic acid (PLA) containing carbon black (CB) can be substantially improved ...through a simple and fast chemical/electrochemical pretreatment in 0.5 mol L−1 NaOH. Scanning electron microscopy and infrared spectroscopy data showed that the pretreatment process promotes the removal of the non-conductive PLA material, providing greater exposure of the conductive particles. Cyclic voltammetry of the redox probe ferricyanide/ferrocyanide indicated faster electron transfer on the treated 3D-printed surface and increase in electroactive area. Moreover, electrochemical impedance spectroscopic results also confirmed faster electron transfer after surface pretreatment. As a proof-of-concept, a low-cost and sensitive method for the determination of cadmium and lead in real urine and saliva samples by square-wave anodic stripping voltammetry was developed. The chemical/electrochemical treatment provided an impressive 30-fold current increase in the detection of both metals. Acceptable limits of detection (2.9 μg L−1 for Cd2+ and 2.6 μg L−1 for Pb2+), wide linear ranges for both metals (30 μg L−1 to 270 μg L−1; R = 0.997), high stability (RSD lower than 4.5%; n = 10), and adequate recovery values (between 93% and 112%) for the analysis of spiked samples were achieved. Additionally, interday (n = 3), intra-day (n = 3), inter-electrode (n = 2) and inter-treatment (n = 2) experiments revealed RSD values lower than 6.5%, which indicates high reproducibility of the proposed treated 3D-printed electrode. The strategy here proposed opens up new applications for 3D-printed electrode in analytical electrochemistry with improved electrochemical sensing properties in comparison to screen-printed electrodes.
► Simultaneous determination of ethanol and methanol in fuel ethanol. ► Fast cyclic voltammetric method identifies adulteration of fuel ethanol. ► The proposed method can be applied for on-site ...analysis.
A new and simple strategy for the simultaneous determination of ethanol and methanol in fuel ethanol using cyclic voltammetry at a gold electrode is reported. A fuel ethanol aliquot was added into an electrochemical cell containing 0.5molL−1 NaOH and 0.1% (v/v) of methanol as the electrolyte and both analytes were determined using cyclic voltammetry. Ethanol was selectively detected at +0.19V and both compounds were detected at +1.20V. Current subtraction (using a correction factor) could be used for the selective determination of methanol. The limits of detection were estimated to be 0.028% and 0.045% (v/v) for ethanol and methanol, respectively. The proposed method presented similar results to those obtained by gas chromatography at a 95% confidence level.
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