RESUMEN

The chemical stability of azithromycin (AZM) may be compromised depending on the imposed thermo-oxidative conditions. This report addresses evidence of this process under varying conditions of temperature (20-80 °C), exposure time to UV radiation (1-3 h irradiation at 257 nm), and air saturation (1-3 h saturation with atmospheric air at 1.2 L min-1 and 15 kPa) through electrochemical measurements performed with a thermoactivated cerium molybdate (Ce2(MoO4)3)/multi-walled carbon nanotubes (MWCNT)-based composite electrode. Thermal treatment at 120 °C led to coordinated water elimination in Ce2(MoO4)3, improving its electrocatalytic effect on antibiotic oxidation, while MWCNT were essential to reduce the charge-transfer resistance and promote signal amplification. Theoretical-experimental data revealed remarkable reactivity for the irreversible oxidation of AZM on the working sensor using phosphate buffer (pH = 8) prepared in CH3OH/H2O (10:90%, v/v). Highly sensitive (230 nM detection limit) and precise (RSD < 4.0%) measurements were recorded under these conditions. The results also showed that AZM reduces its half-life as the temperature, exposure time to UV radiation, and air saturation increase. This fact reinforces the need for continuous quality control of AZM-based pharmaceuticals, using conditions closer to those observed during their transport and storage, reducing impacts on consumers' health.

RESUMEN

Fungal lectins have enormous biotechnological potential, but limited knowledge about their biochemical and biophysical features prevents their proper use. Herein, we report an innovative alternative to use Ganoderma applanatum lectin (GAL) as a glucose biorecognition element, after identifying the ideal electroanalytical conditions by machine learning studies performed with a homologous agglutinin from the same macrofungus. The research revealed that GAL has moderate resistance to pH (4-8) and temperature (20-60 °C) variations, but its hemagglutinating activity (376.5 HU mg-1 GAL at 20 °C) was better conserved under physiological conditions. Integrating electrochemical data and semi-empirical molecular modeling, biocompatible and electrostatically favorable conditions were found to immobilize the lectin on Prussian blue-modified glassy carbon electrode, after thermal activation of the metal-complex film. The glucose dose-response relationship obtained with the developed biosensor, defined as GAL/ta-PB/GCE, showed a typical Hill equation correlation, suggesting electrodic interactions represented by a sigmoidal mathematical function. GAL/ta-PB/GCE achieved remarkable electroanalytical performance, with emphasis on the detection limit (10.2 pM) and sensitivity (0.012 µA µM-1cm-2). The biosensor was successfully used to quantify glucose in pharmaceutical formulations, reiterating that the association of theoretical and experimental information drives important advances in bioelectrochemical studies.

Asunto(s)

RESUMEN

Agaricus bisporus mushroom biomass contains a lectin, ABL, with remarkable specificity for lactose biorecognition; in this work, this feature was explored to develop a photoelectrochemical biosensor. The high lectin activity found in saline extracts of this macrofungus (640 HU mL-1), even at critical pH values (4-10) and temperatures (20-100 °C), allowed its direct use as an ABL source. Theoretical and experimental evidence revealed favorable electrostatic and biocompatible conditions to immobilize ABL on a poly(methylene blue)/fluorine-doped tin oxide-coated glass platform, giving rise to the ABL/PMB/FTO biosensor. The conducting polymer added further photoactivity to the device, allowing the identification of lectin-carbohydrate interactions with even greater sensitivity. The dose-response curves studied by electrochemical impedance spectroscopy showed a sigmoidal profile that was well-fitted by Hill's equation, expanding the working dynamic range (15-540 nmol L-1 lactose; 20.2 pmol L-1 detection limit) and avoiding undesirable sample dilution or preconcentration procedures. Under the optimized photoelectrochemical conditions, the ABL/PMB/FTO biosensor showed remarkable signal stability, accuracy, specificity, and selectivity to analyze lactose in commercial food products. This research raises interest in ABL-based biosensors and the added value of the crude Agaricus bisporus extract toward the development of greener and more sustainable biotechnological approaches.

Asunto(s)

RESUMEN

The giant extracellular hemoglobin of the annelid Glossoscolex paulistus (HbGp; 3.6 MDa) is a valuable and underexplored supramolecular hemoprotein system for the biorecognition of reactive oxygen species. In this work, an efficient and simple electrochemical platform was designed for analyzing H2O2, using HbGp covalently immobilized on Nafion®-modified glassy carbon electrode, named as HbGp/Nafion/GCE. Voltammetric and spectroscopic studies revealed the importance of prior modification of the electrodic support with the conducting polymer to obtain satisfactory hemoglobin electroactivity, as well as a biocompatible microenvironment for its immobilization. In terms of biological activity, it was observed a greater reactivity of the biomolecule in acidic medium, enabling the detection of the analyte by a quasi-reversible mechanism, whose kinetics was limited by analyte diffusion. In the presence of H2O2, the native structure of hemoglobin (oxy-HbGp (Fe2+)) oxidizes to ferryl-HbGp (Fe4+) and this redox reaction can be monitored on HbGp/Nafion/GCE with a detection limit of 8.5 × 10‒7  mol L-1. In addition to high sensitivity, the electrochemical biosensor also provided reproducible, consistent, and accurate measurements. The electroanalytical method showed an appropriate performance to quantify different levels of H2O2 in milk samples, proving the potential of HbGp/Nafion/GCE for this purpose.

Asunto(s)

RESUMEN

Carbohydrates and glycoconjugates are involved in numerous natural and pathological metabolic processes, and the precise elucidation of their biochemical functions has been supported by smart technologies assembled with lectins, i.e., ubiquitous proteins of nonimmune origin with carbohydrate-specific domains. When lectins are anchored on suitable electrochemical transducers, sensitive and innovative bioanalytical tools (lectin-based biosensors) are produced, with the ability to screen target sugars at molecular levels. In addition to the remarkable electroanalytical sensitivity, these devices associate specificity, precision, stability, besides the possibility of miniaturization and portability, which are special features required for real-time and point-of-care measurements. The mentioned attributes can be improved by combining lectins with biocompatible 0-3D semiconductors derived from carbon, metal nanoparticles, polymers and their nanocomposites, or employing labeled biomolecules. This systematic review aims to substantiate and update information on the progress made with lectin-based biosensors designed for electroanalysis of clinically relevant carbohydrates and glycoconjugates (glycoproteins, pathogens and cancer biomarkers), highlighting their main detection principles and performance in highly complex biological milieus. Moreover, particular emphasis is given to the main advantages and limitations of the reported devices, as well as the new trends for the current demands. We believe that this review will support and encourage more cutting-edge research involving lectin-based electrochemical biosensors.

Asunto(s)

RESUMEN

An electroanalytical method for determining dienestrol (DNL) in bovine urine samples is described. A glassy carbon electrode (GCE) modified with silver nanoparticles and functionalized multi-walled carbon nanotubes was used as working sensor. The modified GCE displays substantial analytical improvements including an amplified signal, fast electron transfer kinetics, and resistance to fouling. The irreversible oxidation signal of DNL is pH-dependent. Best reactivity is found at pH 3.0, where a typical anodic peak is recorded at 0.8 V (vs. Ag/AgCl). Square-wave voltammetry revealed a 8.4 nM detection limit (1.9 µg L-1), good repeatability and reproducibility (RSDs <5.0%), and good accuracy (93.2-99.4% recovery from spiked samples). The modified electrode is highly stable even in the presence of ions (Na+ and K+), urea and uric acid. The electrochemical sensor fulfills all requisites to be used as forensic device in surveillance of illegal livestock practices. Graphical abstract Schematic presentation of the construction of a glassy carbon electrode modified with silver nanoparticles and functionalized multi-walled carbon nanotubes. This sensor exhibited a remarkable performance for voltammetric detection of the illicit growth promoter dienestrol in animal urine.

Asunto(s)

RESUMEN

Environmental heavy-metals contamination is a worldwide concern and the treatment of their sources constitutes a sustainable and efficient alternative. This work investigated the performance of Malpighia emarginataD.C. seed fibers microparticles (Me-SFMp) as biosorption platform for heavy metal ions. Integrated physicochemical analyses (FAAS, FTIR, SEM/EDS and XRF) showed that such ability was associated with the high microstructural porosity, wide surface area and diversity of functional groups on Me-SFMp structures, which favored the high and fast uptake of the target-substances (Cd, Zn, Cr, Pb, Cu and Ni ions). In terms of reactional kinetics, the pseudo-second order model showed better data correlation (R2 from 0.9992 to 0.9998) and suggested the chemisorption as limiting step of the reaction mechanisms. From the Langmuir isotherms (R2 from 0.9993 to 0.9998), it was observed that these phenomena occurred non-linearly on a homogeneous biosorbent monolayer. Me-SFMp can also be reused after desorption processes conducted in acid medium and, under ideal conditions (0.8 g biosorbent dosage; 100 mL of 1.00 mg L-1 multi-metal solution adjusted to pH = 8.0; 300 rpm stirring speed; and 60 min contact time), the following maximum removal percentages order was observed for the first cycle: Cd (100%) = Zn (100%) > Cr (95.1%) > Pb (86.8%) > Cu (84.2%) > Ni (81.0%). The procedure was successfully applied to remove the studied heavy metal ions from raw landfill leachate, even in the presence of several (in)organic interferers, reinforcing the strong biosorbent-adsorbate interaction and the viability of this proposal.

RESUMEN

The yeast Saccharomyces cerevisiae, a microorganism with cell walls resistant to many types of treatments, was chosen as a model to study electrochemical disinfection process using dimensionally stable anodes (DSA). DSA electrodes with nominal composition of Ti/RuO2TiO2 and Ti/RuO2TiO2IrO2 were evaluated in 0.05 mol L-1 Na2SO4 containing yeast. The results showed inactivation about of 100 % of the microorganisms at Ti/RuO2TiO2 by applying 20 and 60 mA cm-2 after 120 min of electrolysis, while a complete inactivation at Ti/RuO2IrO2TiO2 electrode was achieved after 180 min at 60 mA cm-2. When chloride ions were added in the electrolyte solution, 100 % of the yeast was inactivated at 20 mA cm-2 after 120 min of electrolysis, independent of the anode used. In the absence of chloride, the energy consumption (EC) was of 34.80 kWh m-3, at 20 mA cm-2 by using Ti/RuO2TiO2 anode. Meanwhile, in the presence of chloride, EC was reduced, requiring 30.24 and 30.99 kWh m-3 at 20 mA cm-2, for Ti/RuO2TiO2 and Ti/RuO2IrO2TiO2 electrodes, respectively, The best performance for cell lysis was obtained in the presence of chloride with EC of 88.80 kWh m-3 (Ti/RuO2TiO2) and 91.85 kWh m-3 (Ti/RuO2IrO2TiO2) to remove, respectively, 92 and 95 % of density yeast. The results clearly showed that yeast, as a model adopted, was efficiently inactivated and lysed by electrolysis disinfection using DSA-type electrodes.

Asunto(s)