Lab-made 3D-printed accessories for spectroscopy and spectroelectrochemistry: a proof of concept to investigate dynamic interfacial and surface phenomena.

3D printing is presented as an auspicious additive manufacturing technique for diverse interesting applications coupling electrochemistry and spectroscopy techniques, proposing as utilities: a general-purpose module for specular spectroscopy and spectroelectrochemical (SEC) cells for in situ UV-VIS and Raman measures capable of acting in flux or a stationary regime. As a proof of concept, UV-VIS absorption and middle-infrared spectra of an azo dye thin film were collected with the specular module showing characteristic bands according to the literature data. SEC investigations related to the Prussian Blue (PB) film growth on the platinum electrode surface were also investigated. By applying appropriate potentials, the PB film growth was accompanied by a proportional increase in the absorption signal at 700 nm in the UV-VIS region. This signal was related to the intervalence charge transfer from the Fe(II)-C to Fe(III)-N. Moreover, the Raman SEC experiment presented scattering intensity at 2092 and 2156 cm-1, related to the (CN) mode associated with the Fe(II) and Fe(III) cations, which was observed during the thin film growth. In addition, the conversion to the Berlin Green (BG) and Prussian White (PB) forms was monitored while applying the suitable potential and in situ spectroscopic observations of structural changes during the redox processes were also detected as described in the literature. Thus, it is possible to state that the accessories successfully validated in situ spectroelectrochemical dynamic investigations unlocking many other applications in this research field.

Cost-effective smartphone-based method for low range chemical oxygen demand analysis.

Aiming the decentralization of monitoring policies and to facilitate the work of researchers, mainly in developing countries, the present method deals with the explanation of a simple and rapid protocol for chemical oxygen demand (COD) analysis through the use of digital smartphone devices coupled with a camera and a free app available for Android operating system that recognizes HSV (hue, saturation, value). The calibration of the method is done based on the theoretical values of potassium hydrogen phthalate for a proper and reliable build of the calibration curve by using the smartphone-based technique and the digested samples of COD. The coefficient of determination (R2) attained a value upper than 0.99, providing a high confidence levels, and the method achieved 97% of average accuracy in samples with COD values ranging from 0 to 150 mg L-1. Finally, the procedure here presented can be a great support for scientific laboratories and monitoring policies, once it can efficiently substitute expensive spectrophotometers and can improve and ensure the sustainable management of water sanitation, which is one of the sustainable goals proposed by the United Nations.•COD measurements, based on the use of a simple smartphone with a camera, can be a promising way for environmental analysis when spectrophotometers are not available, such as decentralized approaches.•The use of smartphone protocol is a novel initiative to fulfill sustainable development goal 6 on clean water and sanitation.•The smartphone is capable to read the difference of HSV values efficiently and can substitute the use of expensive spectrophotometers.

Biosorption process using Cereus jamacaru DC, Cactaceae for Pb2+ removal from aqueous systems.

Lead is a highly toxic metal associated with many human health diseases that can be caused by several environmental changes. Innovative sustainable solutions for water remediation have been recently encouraged by using renewable, low-cost and earth-abundant biomass materials to ensure public health conditions. In this article, Cereus jamacaru DC (popularly known as Mandacaru) was investigated as a biosorbent in the Pb2+ removal from aqueous solution using a two-level factorial design. The analysis of variance suggested a significant and predictive model (R2 = 0.9037). The maximum efficacy of Pb2+ removal in the experimental design was 97.26%, being the optimized conditions: pH 5.0, contact time 4 h without adding NaCl. The Mandacaru was divided into three types according to the plant structure and this parameter did not present a significant interference in the biosorption process. This result corroborates with slight differences in the total soluble proteins, carbohydrates and phenolic compounds found in the Mandacaru types investigated. FT-IR analysis revealed the presence of O-H, C-O and C = O groups that were responsible for the ion biosorption process. The optimized procedure was capable to remove 97.28% of the Pb2+ added in the Taborda river water sample. The kinetic adsorption results show the pseudo-second-order model, suggesting chemisorption process. Thus the treated water sample can be considered in accordance with technical standards issued by CONAMA Resolution Num. 430/2011 and Ordinance GM/MS Num.888/2021 of WHO. In this way, the Mandacaru proved to be an efficient, fast and easy-to-apply bioadsorbent in Pb2+ removal and has great environmental application potential.

Development of recycled and miniaturized electroanalytical sensor: Probing isoniazid determination in environmental water matrices.

Surface water pollution has become relevant because growing population and intense industrial activities. Thus, to protect the environment from contamination, recently the electroanalytical sensors that require small sample volume and easy preparation have shown a prominent performance for pharmaceuticals monitoring. For this purpose, a miniaturized electrochemical platform was developed based on recycling obsolete computer integrated circuits (microchips), fitting with the ideals of green chemistry and circular economy. The gold microelectrodes array (Au-µEA) was easily exposed by polishing the device surface and then characterized by optical microscopy, scanning electron microscopy and cyclic voltammetry. To enhance the analytical performance for isoniazid detection, the Au-µEA was modified with electrochemically reduced graphene oxide (ERGO). The developed sensor presented a linear range between 5 and 100 µmol L-1 and a limit of detection of 1.38 µmol L-1 demonstrating a reliable performance. Looking to its environmental application, the ERGO/Au-µEA sensor was used for isoniazid quantification in lagoon, river, tap water and synthetic effluent spiked samples with recovery values between 92.5 and 108.4%. Thus, this research field opens up new possibilities in global water-related issues contributing with innovative sustainable solutions.

Probing the Use of Homemade Carbon Fiber Microsensor for Quantifying Caffeine in Soft Beverages.

In the development of electrochemical sensors, carbon micro-structured or micro-materials have been widely used as supports/modifiers to improve the performance of bare electrodes. In the case of carbon fibers (CFs), these carbonaceous materials have received extensive attention and their use has been proposed in a variety of fields. However, to the best of our knowledge, no attempts for electroanalytical determination of caffeine with CF microelectrode (µE) have been reported in the literature. Therefore, a homemade CF-µE was fabricated, characterized, and used to determine caffeine in soft beverage samples. From the electrochemical characterization of the CF-µE in K3Fe(CN)6 10 mmol L-1 plus KCl 100 mmol L-1, a radius of about 6 µm was estimated, registering a sigmoidal voltammetric profile that distinguishes a µE indicating that the mass-transport conditions were improved. Voltammetric analysis of the electrochemical response of caffeine at the CF-µE clearly showed that no effects were attained due to the mass transport in solution. Differential pulse voltammetric analysis using the CF-µE was able to determine the detection sensitivity, concentration range (0.3 to 4.5 µmol L-1), limit of detection (0.13 µmol L-1) and linear relationship (I (µA) = (11.6 ± 0.09) × 10-3 [caffeine, µmol L-1] - (0.37 ± 0.24) × 10-3), aiming at the quantification applicability in concentration quality-control for the beverages industry. When the homemade CF-µE was used to quantify the caffeine concentration in the soft beverage samples, the values obtained were satisfactory in comparison with the concentrations reported in the literature. Additionally, the concentrations were analytically determined by high-performance liquid chromatography (HPLC). These results show that these electrodes may be an alternative to the development of new and portable reliable analytical tools at low cost with high efficiency.

Real time monitoring of in situ generated hydrogen peroxide in electrochemical advanced oxidation reactors using an integrated Pt microelectrode.

This work propose the fabrication and characterization of a Pt microelectrode integrated with a silver quasi-reference counter electrode (Pt/AgQRCE) for real time amperometric measurements of hydrogen peroxide electrochemically generated by water oxidation on Nb-supported boron doped diamond (Ni/BDD) anode. The developed electroanalytical method requires a very small sample volume and has higher sensitivity when compared to the conventional spectrophotometric analysis using ammonium metavanadate. The experiments were performed with Nb/BDD anode applying current densities of 30, 60, 90 and 120 mA cm-2 in 0.10 mol L-1 HClO4 supporting electrolyte showed that H2O2 production increase in the first 90 min of electrolysis and then reaches a plateau in both off-line and real time measurements. For the first 90 min, the electrogeneration of H2O2 exhibited a pseudo zero-order kinetics. The results obtained by the electrochemical amperometric analysis were compared to a spectrophotometric methodology reported on the literature and, at 95% confidence level the two methods do not demonstrated significant difference.