Maria Fidalgo de Cortalezzi

Water quality is threatened by numerous pollutants, among which antibiotics are of great concern due to their widespread use and unaltered excretion, leading to water contamination and fostering antibiotic resistance. To comprehensively address sustainable water remediation, herein, the susceptibility to non-thermal plasma degradation of two veterinary antibiotics (Oxytetracycline (OTC) and Lincomycin (LNC)) are compared in an integral approach, including computational analyses, plasma irradiation assays, and a byproduct toxicity assessment. The computational assessment was performed by evaluating the ionization potential (IP) obtained from Density Functional Theory calculations and determining the antibiotics’ susceptible sites for radical attack. Plasma irradiation achieved nearly complete degradation (~100%) of both compounds with the initial concentration of 1 mg L⁻¹, while 60% degradation was observed when the starting concentration was 10 mg L⁻¹. The mineralization rates were 21% and 31% for OTC and LNC, respectively. The degradation profiles followed similar trends, as expected from their comparable IP values. After treatment, the solution exhibited lower biotoxicity compared to the original antibiotics. Therefore, this work represents a step forward in addressing one of the key environmental challenges of our time and encourages further extending the analysis towards the remediation of water polluted with many other organic compounds.

A novel approach to the fabrication of thin-film supported metal oxide membranes was investigated. Nanocoatings were obtained by the condensed layer deposition of TiO₂ on tubular microporous supports, applying multiple consecutive layers of TiO₂/polyaniline. The surface, cross-sectional structure, and morphology of the materials were investigated by electron microscopy. Their membrane-related properties were explored by permeability measurements, rejection, and fouling analysis, using polyethylene glycol (PEG) as test molecules. The SEM images showed that TiO₂ was successfully deposited on the surface, creating a layer with partial coverage of the support after each layer was deposited; consequently, the permeability of the membranes decreased gradually. Overall, the results of the flux and permeability of the membranes confirmed the coating. The transmembrane pressure (TMP) increased with each coating layer, while the rejection of the membrane showed gradual improvement.

Chitosan was subjected to a crosslinking reaction with three polyhydroxylated diacids (glucaric (GlcA), mannaric (ManA), and mucic (MucA) acids) that only differ in the spatial orientation of their hydroxyl groups. This work aimed to obtain experimental evidence of the impact of the three-dimensional arrangement of the crosslinkers on the resulting properties of the products. In all the cases, the products were hydrogels, and their chemical structures were fully elucidated by FT-IR spectroscopy and conductometric titration. Thermogravimetric and morphological studies were also carried out. The specific surface area of all the products was similar and higher than that of native chitosan. Moreover, all hydrogels were characterized in terms of viscoelastic properties and long-term stability under external perturbation. Furthermore, their lead adsorption efficiency and swelling capacity were assessed. Despite the resemblant chemical structure in all the hydrogels, Ch/ManA exhibited the highest lead adsorption capacity, (Ch/ManA: 93.8 mg g⁻¹, Ch/GlcA: 82.9 mg g⁻¹, Ch/MucA: 79.2 mg g⁻¹), while Ch/GlcA exhibited a remarkably higher swelling capacity (i.e., ~30% more than Ch/MucA and ~40% more than Ch/ManA). The results obtained herein evidenced that the selection of the polyhydroxylated crosslinker with the appropriate three-dimensional structure could be crucial to finely adjust the final materials’ features.

It has been well established that natural organic matters (NOMs) are precursors for the formation of disinfection by-products (DBPs) in drinking water supplies, thus the removal of NOMs is often used as an effective approach to limit DBPs production. In this study, we evaluated the application of oxidized multi-walled carbon nanotubes (OMWNTs)/polysulfone (PSU) nanocomposite hollow fiber membranes (HFM) for the removal of NOMs and its impact on the production of DBPs following water chlorination. Analysis of source water samples by fluorescence excitation/emission matrix (EEM) spectrometry indicated that the dominant dissolved organic matters were humic acid. Evaluation of the fabricated nanocomposite HFMs showed improved water fluxes (30~50%), better fouling resistance, and a comparable solute rejection rate when compared with the conventional PSU membranes. The flux increase was attributed to the increased surface hydrophilicity and porosity of the membrane after embedding the hydrophilic OMWNTs. The membrane filtration resulted in a reduction of UV254 by approximately 52%, 48%, and 38% for three water samples from Missouri River, Eagle Bluffs Conservation Area, and Columbia Water Treatment Plant, respectively. The corresponding reduction in trihalomethane formation potential (THMFP) reached 40%, 70%, and 27%, respectively. Overall, this study demonstrated that proper OMWNTs/PSU ultrafiltration membranes could remove a portion of NOMs from water at a relatively low cross-membrane pressure. It also illustrates the innovative concept that membrane design could be tailored for specific water quality conditions and regulatory requirements; in this particular case, to fabricate a membrane to reduce the THMFP to a level that meets the regulatory standards for trihalomethanes when the water was disinfected by chlorine.

Titanium dioxide nanoparticles (TiO₂NPs) are found in a wide range of products such as sunscreen, paints, toothpaste and cosmetics due to their white pigment and high refractive index. These wide-ranging applications could result in direct or indirect exposure of these NPs to humans and the environment. Accordingly, conflicting levels of toxicity has been associated with these NPs. Therefore, the risk associated with these reports and for TiO₂NPs produced using varying methodologies should be measured. This study aimed to investigate the effects of various media on TiO₂NP properties (hydrodynamic size and zeta potential) and the effects of TiO₂NP exposure on human colorectal adenocarcinoma (Caco-2) epithelial cell viability, inflammatory and cell stress biomarkers and angiogenesis proteome profiles. The NPs increased in size over time in the various media, while zeta potentials were stable. TiO₂NPs also induced cell stress biomarkers, which could be attributed to the NPs not being cytotoxic. Consequently, TiO₂NP exposure had no effects on the level of inflammatory biomarkers produced by Caco-2. TiO₂NPs expressed some anti-angiogenic properties when exposed to the no-observed-adverse-effect level and requires further in-depth investigation.

In a previous study, photonic-based molecularly imprinted polymers (MIPs) were fabricated using atrazine (ATZ) and its metabolites, desethylatrazine (DEA) and desisopropylatrazine (DIA), as templates in separate matrices. For the purposes of monitoring the abovementioned molecules in natural waters, the effect of natural waters—featuring ionic strength and natural organic matter (NOM) on atrazine MIP—were studied in this work, and the photonic MIP was implemented for monitoring the target molecules in natural water samples collected from land in nearby farms in northeast of Columbia MO. Non-imprinted polymers (NIP) were also fabricated and applied in the experiments as a control test. In presence of NaCl, CaCl₂, and NOM, MIPs presented lower responses by 26%, higher responses by 23%, and higher responses by 35%, respectively. NIPs response in terms of an increase or decrease was consistent with those of MIPs, but only for a lower percentage. MIPs response in natural waters—which were characterized for their physicochemical characteristics such as conductivity, total organic carbon content, etc.—provided a good approximation of the real concentrations obtained from the LCMS instrument; in general, they showed a good concordance, although large discrepancies occurred for some samples, which can be related to reproducibility issues in the manufacturing process or the presence of unknown interfering compounds in the real samples.

A label-free molecular imprinted polymer (MIP) sensor was fabricated for the detection of progesterone in aqueous solutions, by polymerization inside the void spaces of colloidal crystals, which gave them photonic properties. The prepolymerization mixture was prepared from acrylic acid as the functional monomer, ethylene glycol as the cross-linker agent, ethanol as solvent, and progesterone as the imprinted template. After polymerization, the colloidal crystal was removed by acid etching and the target eluted with a solvent. Material characterization included as follows: attenuated total reflectance-Fourier-transform infrared spectroscopy, dynamic light scattering, swelling experiments, and environmental scanning electron microscopy. MIPs were investigated by equilibrium binding, kinetics experiments, and UV–visible spectra to investigate Bragg diffraction peak shift that occurs with the rebinding at different progesterone concentrations in deionized water and 150-mM NaCl solutions. The MIP response was investigated with progesterone concentration in the 1–100 μg L⁻¹ range, with LOD of 0.5 μg L⁻¹, reaching the detected range of hormone in natural waters. Furthermore, hydrogel MIP films were successfully tested in various real water matrices with satisfactory results. Moreover, the MIP film exhibited good selectivity toward the progesterone hormone evidenced by a larger response than when exposed to structurally similar molecules. Computational studies suggested that size along with surface potential influenced the binding of analog compounds. Due to their ease of use and low cost, the sensors are promising as screening tools for the presence of progesterone in aqueous samples. Graphical abstract

Molecular imprinted polymers are custom made materials with specific recognition sites for a target molecule. Their specificity and the variety of materials and physical shapes in which they can be fabricated make them ideal components for sensing platforms. Despite their excellent properties, MIP-based sensors have rarely left the academic laboratory environment. This work presents a comprehensive review of recent reports in the environmental and biomedical fields, with a focus on electrochemical and optical signaling mechanisms. The discussion aims to identify knowledge gaps that hinder the translation of MIP-based technology from research laboratories to commercialization.