Publications

Plastics are omnipresent in the environment and degrade into smaller fragments in time. This study shows how plastics could reach nanometer sizes under specific conditions and the interaction of the nanofragments with prokaryotic cells. Imaging and spectroscopy techniques were employed to determine the modifications induced in artificially aged low-density polyethylene (LDPE). Scanning electron microscopy indicated that nanometer-scale LDPE could be obtained after ultraviolet-C (UVC) exposure for 10 days. Raman and Fourier-transformed infrared spectroscopy confirmed the chemical changes within the UVC-exposed LDPE are consistent with the increase of crystallinity. Moreover, the interaction between the degraded LDPE and chemo- and photosynthetic organisms was observed through fluorescence, confocal, electron microscopy techniques, and electron paramagnetic resonance spectroscopy. The results showed how micro/nano-LDPE could influence the development of Escherichia coli and Arthrospira platensis after only 72 h of interaction. This fundamental study indicates the environmental presence and effects of nanometer-sized LDPE resulting from light exposure.

A novel scaffold for in situ electrochemical detection of cell biomarkers was developed using electrospun nanofibers and commercial adhesive polymeric membranes. The electrochemical sensing of cell biomarkers requires the cultivation of the cells on/near the (bio)sensor surface in a manner to preserve an appropriate electroactive available surface and to avoid the surface passivation and sensor damage. This can be achieved by employing biocompatible nanofiber meshes that allow the cells to have a normal behavior and do not alter the electrochemical detection. For a better mechanical stability and ease of handling, nylon 6/6 nanofibers were collected on commercial polymeric membranes, at an optimal fiber density, obtaining a double-layered platform. To demonstrate the functionality of the fabricated scaffold, the screening of cellular stress has been achieved integrating melanoma B16-F10 cells and the (bio)sensor components on the transducer whereas the melanin exocytosis was successfully quantified using a commercial electrode. Either directly on the surface of the (bio)sensor or spatially detached from it, the integration of cell cultures in biosensing platforms based on electrospun nanofibers represents a powerful bioanalytical tool able to provide real-time information about the biomarker release, enzyme activity or inhibition, and monitoring of various cellular events.

Infections related to orthopedic/stomatology surgery are widely recognized as a significant health concern. Therefore, the development of new materials with superior biological properties and good stability could represent a valuable alternative to the classical treatments. In this paper, the fluorine-substituted hydroxyapatite (FHAp) suspension, with the chemical formula Ca10(PO4)6(OH)2-2xF2x (where x = 0.05), was prepared using a modified coprecipitation technique. Stability studies were conducted by zeta potential and ultrasound measurements for the first time. The X-ray diffraction (XRD) patterns of FHAp powders displayed a hexagonal structure akin to that of pure hydroxyapatite (HAp). The XPS general spectrum revealed peaks corresponding to the constituent elements of fluorine-substituted hydroxyapatite such as calcium, phosphorus, oxygen, and fluorine. The purity of the obtained FHAp samples was confirmed by energy-dispersive X-ray spectroscopy (EDS) studies. The FHAp morphology was evaluated by scanning electron microscopy (SEM) measurements. Fourier-transform infrared spectroscopy (FTIR) studies were performed in order to study the vibrational properties of the FHAp samples. The FHAp suspensions were tested for antibacterial activity against reference strains such as Staphylococcus aureus 25923 ATCC, Escherichia coli ATCC 25922, and Candida albicans ATCC 10231. Additionally, the biocompatibility of the FHAp suspensions was assessed using human fetal osteoblastic cells (hFOB 1.19 cell line). The results of our biological tests suggest that FHAp suspensions are promising candidates for the future development of new biocompatible and antimicrobial agents for use in the biomedical field.

We model the equilibrium properties of a two-dimensional electron gas in a square lateral superlattice of quantum dots in a GaAs heterostructure subject to an external homogeneous perpendicular magnetic field and a far-infrared circular cylindrical photon cavity with one quantized mode, the TE011 mode. In a truncated linear basis constructed by a tensor product of the single-electron states of the noninteracting system and the eigenstates of the photon number operator, a local spin density approximation of density functional theory is used to compute the electron-photon states of the two-dimensional electron gas in the cavity. The common spatial symmetry of the vector fields for the external magnetic field and the cavity photon field in the long wavelength approximation enhances higher order magnetic single- and multiphoton processes for both the para- and the diamagnetic electron-photon interactions. The electron-photon coupling introduces explicit photon replicas into the band structure and all subbands gain a photon content, constant for each subband, that can deviate from an integer value as the coupling is increased or the photon energy is varied. The subbands show a complex Rabi anticrossing behavior when the photon energy and the coupling bring subbands into resonances. The complicated energy subband structure leads to photon density variations in reciprocal space when resonances occur in the spectrum. The electron-photon coupling polarizes the charge density and tends to reduce the Coulomb exchange effects as the coupling strength increases.

Tri-layered heterojunction devices based on oxide thin films are attracting significant attention for ultra-fast visible photodetection. However, the responsivity of these devices is still low. In this work, high performance photodetectors based on a tri-layered heterojunction of n-Si/p-Co3O4/n-ZnO were fabricated. Under no applied bias, a maximum responsivity and detectivity of 14.2 mA W-1 and 1.34 x 10(12) Jones were achieved respectively, for a power density of 9.35 mW cm(-2). Remarkably, a significant increase in the responsivity of approximately 864% was found when the device was biased at -2 V. This effect is understood based on the coupling of the photovoltaic and pyroelectric effects. Also, upon applying an external bias of -2 V, at a laser power density of 9.35 mW cm(-2) and at a chopper frequency of 10 Hz, the device exhibits a detectivity and sensitivity of 3.4 x 10(11) Jones and 2.2, respectively, together with a rise and fall time of 4 and 2 mu s, respectively. Compared to high performance Al/Si/SnO/ZnO/ITO and Au/pCuI/ZnO devices, our voltage-biased Al/Si/Co3O4/ZnO/ITO devices exhibit a >40% increase in R and >10x higher D*. Furthermore, an important advantage of our PDs is the p-type component, Co3O4, which is more stable and stoichiometric than CuI and SnO, ensuring PD performance that is stable with time. Therefore, n-Si/p-Co3O4/n-ZnO heterojunction devices shows great promise for ultrafast visible photodetection.

Plastics are indispensable materials for packaging and many products from our daily life, and their recycling is essential to ensure a circular economy. In this study, -SO3H-modified, Ti3C2-MXene was used as a recoverable solid acid catalyst for upcycling of polyethylene terephthalate (PET) to terephthalic acid (TPA) and ethylene glycol by hydrolysis. For the grafting of -SO3H groups to the Ti3C2Tx surface (where T-x represents the surface moieties, such as -OH or -O), sulfonation with an aryl diazonium salt obtained from sulfanilic acid was employed. X-ray photoelectron and Fourier transform infrared spectroscopy analyses provided a direct indication that sulfonation of the Ti3C2Tx was successfully performed, while X-ray diffraction and transmission electron microscopy analyses evidence the presence of -SO3H groups between the Ti3C2Tx layers due to the increases of the interlayer spacing through the intercalation of functional groups. The higher the concentration of acid groups, the higher the interlayer spacing. The depolymerization of PET in water occurred with a very good isolated yield in TPA (99%) for the MXene with the highest amount of sulfonic acid groups. We conclude that the acidity is mandatory to perform the hydrolysis reaction, in agreement with the acidity measurements, which show that the MXenes modified with the highest amount of derived sulfonic acids are the most active. Nevertheless, the accessibility to the acidic sites is a key factor that promotes the 2D acid-modified MXene materials as important catalysts for PET upcycling to TPA.

This paper describes the electrical and dielectric behavior of the nCdS/pZnTe HJ by current-voltage, capacitance-voltage characteristics, and impedance spectroscopy in a temperature interval 220-350 K. A microcrystalline p-ZnTe layer and n-CdS were grown on glass/ZnO substrate by closed space sublimation method. As frontal contact to CdS, the transparent ZnO and as a back contact to ZnTe, silver conductive paste (Ag) treated at 50 degrees C in vacuum were used. The current-voltage results of nCdS/pZnTe HJ show a rectifying behavior. The junction ideality factor, barrier height, and series resistance values were extracted from the rectifying curves at different temperatures. The built-in voltage, carrier concentration and depletion width were obtained from the capacitance-voltage measurements. Analysis of the J-V-T and C-V-T characteristics shows that the thermionic emission and recombination current flow mechanisms dominate in the nCdS/pZnTe HJ. The dielectric study reveals that the experimental values of the AC conductivity, dielectric constant, dielectric loss, the imaginary part of the electric modulus are found to be very sensitive to frequency and temperature. The dielectric constant and dielectric loss are observed to be high at the low frequency region. The increase in the values of electric modulus with the frequency implies an increase in the interfacial polarization at the interface of nCdS/pZnTe HJ. Jonscher's universal power law shows that with increasing frequency, AC conductivity increased. The results conductivity show that the ionic conductivity and interfacial polarization are the main parameters affecting the dielectric properties of the device when the temperature changes.

In this study, molybdenum doped iron cobaltite and cobalt ferrite catalysts were prepared by coprecipitation, and their structural, morphological, and optical, properties were evaluated by XRD, BET, SEM, FTIR, Raman, XPS and UV-VIS techniques. Their catalytic behavior evaluated in the malic acid oxidative decarboxylation reaction underlined the importance of the incorporation of Mo into the structure of iron cobaltite and cobalt ferrite catalysts. The catalysts with the highest molybdenum content forming cobaltite and iron molybdate phases showed better activity, with cobaltite-based catalysts being more active than ferrite-based ones.

Our study focuses on disclosing the mechanisms standing behind the improved photocatalytic performance of SrTiO3, where Al modification of the perovskite structure boosts the photocatalytic O2 evolution activity of the Al:SrTiO3 system. By adapting the synthesis method that produces well-crystallized materials with low defect density and employing surface modification techniques, we aim to enhance the photocatalytic efficiency of SrTiO3 via Al2O3 nanoceramic oxide doping at concentrations ranging from 0 to 10% and further examining of the relationship between doping process and the changes in the electronic and crystalline structure of SrTiO3. The prepared Al-based SrTiO3 perovskite samples (Al3%:SrTiO3, Al7%:SrTiO3, Al10%:SrTiO3) were thoroughly characterized to understand their structural, electronic, and morphological properties. Complementary X-ray techniques were employed to assess the stoichiometry (X-ray photoelectron spectroscopy - XPS), local environment, and chemical state (X-ray absorption spectroscopy - XAS in both total electron yield (TEY) and fluorescence yield (TFY). The comprehensive characterization enables us to understand the changes in the electronic properties and morphological features of the modified samples elucidating the surface formation mechanism while providing insights into the structural modifications induced by Al doping in the SrTiO3 perovskite lattice. Our findings give new perspectives for the development of Al-modified SrTiO3 perovskite materials with enhanced photocatalytic performance providing rich insights into the optimization of photocatalytic processes for applications in environmental remediation and sustainable energy production.

TiO2-based mixed oxide-carbon composite support for Pt electrocatalysts provides higher stability and CO tolerance under the working conditions of polymer electrolyte membrane fuel cells compared to traditional carbon supports. Non-traditional carbon materials like graphene nanoplatelets and graphite oxide used as the carbonaceous component of the composite can contribute to its affordability and/or functionality. Ti(1-x)MoxO2-C composites involving these carbon materials were prepared through a sol-gel route; the effect of the extension of the procedure through a solvothermal treatment step was assessed. Both supports and supported Pt catalysts were characterized by physicochemical methods. Electrochemical behavior of the catalysts in terms of stability, activity, and CO tolerance was studied. Solvothermal treatment decreased the fracture of graphite oxide plates and enhanced the formation of a reduced graphene oxide-like structure, resulting in an electrically more conductive and more stable catalyst. In parallel, solvothermal treatment enhanced the growth of mixed oxide crystallites, decreasing the chance of formation of Pt-oxide-carbon triple junctions, resulting in somewhat less CO tolerance. The electrocatalyst containing graphene nanoplatelets, along with good stability, has the highest activity in oxygen reduction reaction compared to the other composite-supported catalysts.