Open Access
Visible-light-driven photocatalytic degradation of organic dyes using a TiO2 and waste-based carbon dots nanocomposite
(Elsevier, 2025-05-20) Sendão, Ricardo M.S.; Algarra González, Manuel; Lázaro-Martínez, Juan; Brandão, Ana T.S.C.; Gil Bravo, Antonio; Pereira, Carlos; Esteves da Silva, Joaquim C.G.; Pinto da Silva, Luís; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Herein we report a visible-light-active photocatalytic nanocomposite (NC50:50) prepared from carbon dots (CDs) and TiO2 nanoparticles, which was applied to the photodegradation of organic dyes in water. The CDs incorporated corn stover, a major agricultural waste, and were prepared via hydrothermal treatment. Using a visible-light irradiation source and the dye methylene blue as a representative of the organic dyes class, we observed that a 374% enhancement of the catalytic performance was achieved by adding CDs relative to bare TiO2. This was possible due to increased visible-light absorption and better photonic efficiency. Tests using reactive species scavengers indicated that three active species (superoxide anion, hydroxyl radicals, and electrons) were responsible for the photodegradation process, differing from bare TiO2 in which only the hydroxyl radical has a relevant role. Photocatalytic degradation was also observed toward Rhodamine B, Orange II and Methyl Orange. Finally, we performed a life cycle assessment (LCA) study to assess and analyse the associated environmental impacts of NC50:50 compared with other alternatives, which revealed that NC50:50 is the alternative resulting in the least environmental impacts. In summary, NC50:50 could, under visible-light irradiation, efficiently remove different organic dyes while incorporating organic waste materials and reducing the impacts associated with their use. We expect that this study provides a base for a more environmentally sustainable design of visible-light-active photocatalysts via waste upcycling.
Open Access
Synergistic enhancement of targeted wound healing by near-infrared photodynamic therapy and silver metal-organic frameworks combined with S- or N-doped carbon dots
(MDPI, 2024) Nesic, Maja D.; Popovic, Iva; Zakula, Jelena; Koricanac, Lela; Filipovic Trickovic, Jelena; Valenta Šobot, Ana; Jiménez, María Victoria; Algarra González, Manuel; Dučić, Tanja; Stepic, Milutin; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
The literature data emphasize that nanoparticles might improve the beneficial effects of near-infrared light (NIR) on wound healing. This study investigates the mechanisms of the synergistic wound healing potential of NIR light and silver metal–organic frameworks combined with nitrogen- and sulfur-doped carbon dots (AgMOFsN-CDs and AgMOFsS-CDs, respectively), which was conducted by testing the fibroblasts viability, scratch assays, biochemical analysis, and synchrotron-based Fourier transform infrared (SR-FTIR) cell spectroscopy and imaging. Our findings reveal that the combined treatment of AgMOFsN-CDs and NIR light significantly increases cell viability to nearly 150% and promotes cell proliferation, with reduced interleukin-1 levels, suggesting an anti-inflammatory response. SR-FTIR spectroscopy shows this combined treatment results in unique protein alterations, including increased α-helix structures and reduced cross-β. Additionally, protein synthesis was enhanced upon the combined treatment. The likely mechanism behind the observed changes is the charge-specific interaction of N-CDs from the AgMOFsN-CDs with proteins, enhanced by NIR light due to the nanocomposite’s optical characteristics. Remarkably, the complete wound closure in the in vitro scratch assay was achieved exclusively with the combined NIR and AgMOFsN-CDs treatment, demonstrating the promising application of combined AgMOFsN-CDs with NIR light photodynamic therapy in regenerative nanomedicine and tissue engineering.
Open Access
Low-cost Titania-Hydroxyapatite (TiHAp) nanocomposites were synthesized for removal of methylene blue under solar and UV irradiation
(Elsevier, 2025-07-01) Latifi, Souhayla; Saoiabi, Sanaa ; Alanazi, Mohammed M. ; Boukra, Omar ; Krime, Anas ; El Hammari, Larbi; Azzaoui, Khalil; Hammouti, Belkheir; Hanbali, Ghadir; Jodeh, Shehdeh; Saoiabi, Ahmad ; Sabbahi, Rachid ; Algarra González, Manuel; Abidi, Noureddine ; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Water pollution from industrial dyes like methylene blue (MB) poses significant environmental and health risks due to their toxicity and persistence. In this study, we synthesized a novel titania-hydroxyapatite (TiHAp) nanocomposite via a low-cost, scalable sol-gel method to address these challenges. The composite was comprehensively characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Photocatalytic degradation of MB under both solar and UV irradiation was evaluated using kinetic (pseudo-first-order and pseudo-second-order) and isotherm (Langmuir and Freundlich) models, demonstrating hydroxyapatite's key role in enhancing adsorption and facilitating effective interactions with the catalyst. Under optimized conditions, the TiHAp nanocomposite achieved 96.58 % degradation of MB at an initial concentration of 120 mg/L and retained over 95 % activity after five reuse cycles. These results illustrate that the synergistic combination of TiO₂'s photocatalytic activity and HAp's adsorptive capacity produces a highly effective composite for degrading organic pollutants. The study underscores the potential of TiHAp nanocomposites as sustainable materials for wastewater treatment applications, while future work will explore their performance against a broader range of contaminants under realistic environmental conditions.
Open Access
Nitrogen doped carbon dots as a photocatalyst based on biomass: a life cycle assessment
(Elsevier, 2023) Rodríguez-Carballo, Gabriela; Moreno-Tost, Ramón; Fernandes, Sónia; Esteves da Silva, Joaquim C.G.; Pinto da Silva, Luís; Castro Galiano, Eulogio; Algarra González, Manuel; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
The effectiveness of various transition metal phosphate-based acid catalysts, including vanadium and niobium, in the hydrothermal synthesis of carbon dots (CDs), has been assessed. Two sources of carbohydrates were employed for this: commercial xylose and liquor of xylose produced by processing olive pits. Catalysts were identified using the NH3-TPD, DTA/TG, XRD, and XPS techniques. The reaction was conducted for 4 h at a temperature of 180 °C. The existence of such nanoparticles, regardless of the carbohydrate source, was confirmed by an analysis of the features and characteristics of CDs nanoparticles. N-doped CDs with increased fluorescence were also created at the same time using a similar hydrothermal technique, and their photocatalytic activity was investigated. A Life Cycle Assessment (LCA) was conducted for both syntheses with the goal of comparing the environmental effects of the synthesis from commercial xylose to the synthesis from biomass. It was revealed that, although energy is the primary driver of both synthesis pathways' effect categories, the fundamental variations that seem to determine their relative sustainability are connected to the nature of the carbon precursor. Regarding the latter, it is determined that electricity has the greatest environmental impact.
Open Access
Green chitosan: thiourea dioxide cleaning gel for manganese stains on granite and glass substrates
(Springer Nature, 2021) Campos, Bruno; Marco, Alexandra; Cadeco, Guilhermina; Freire-Lista, David M.; Silvestre-Albero, Joaquín; Algarra González, Manuel; Vieira, Eduarda; Pintado, Manuela; Moreira, Patricia; Ciencias; Zientziak
The cleaning or removal of manganese stains on Cultural Heritage has not been much tested or successful so far. The aim of this article was to assess a new green cleaning gel for Mn-rich black-blue stains on different substrates. The black-blue stains were characterized at optical and chemical level through colour-related data, optical microscope, FTIR, XRF and XPS. Mn-stained granite found on historical churches at Vila Real (North of Portugal) and glass jars of Leclanché cells, belonging to the ISEP's Museum (Portugal) collection, were the ideal case studies to test the efficiency of chitosan: thiourea dioxide (TD) cleaning gel. TD proved to be the best candidate to reduce insoluble manganese oxides, over Hydroxylamine Hydrochloride and Hydroxymethanesulfinic Acid. Cleaning assays performed on stained granite samples collected at a historical quarry and in situ application on stained granite churches allowed removal of the stains to a satisfactory level. Similar results were obtained on stained glass jars.
Open Access
One-pot synthesis of green-emitting nitrogen-doped carbon dots from xylose
(MDPI, 2023) Rodríguez-Carballo, Gabriela; García-Sancho, Cristina; Algarra González, Manuel; Castro, Eulogio; Moreno-Tost, Ramón; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Carbon dots (CDs) are interesting carbon nanomaterials that exhibit great photoluminescent features, low cytotoxicity, and excellent water stability and solubility. For these reasons, many fields are starting to integrate their use for a variety of purposes. The catalytic performance of VOPO4 has been evaluated in the synthesis of nitrogen-doped carbon dots (N-CDs). The synthesis reaction was carried out at 180 °C using VOPO4 as a heterogeneous catalyst for 2 to 4 h of reaction time. After reaction, the N-CDs were purified using a novel method for the protection of the functional groups over the surfaces of the N-CDs. The morphological, superficial, and photoelectronic properties of the N-CDs were thoroughly studied by means of TEM, HRTEM, XPS, and photoluminescence measurements. The conversion of the carbon precursor was followed by HPLC. After three catalytic runs, the catalyst was still active while ensuring the quality of the N-CDs obtained. After the third cycle, the catalyst was regenerated, and it recovered its full activity. The obtained N-CDs showed a great degree of oxidized groups in their surfaces that translated into high photoluminescence when irradiated under different lasers. Due to the observed photoelectronic properties, they were then assayed in the photocatalytic degradation of methyl orange.
Open Access
Synthesis of hydroxyapatite/polyethylene glycol 6000 composites by novel dissolution/precipitation method: optimization of the adsorption process using a factorial design: DFT and molecular dynamic
(BMC, 2023) Azzaoui, Khalil; Jodeh, Shehdeh; Mejdoubi, E.; Hammouti, B.; Taleb, M.; Ennabety, G.; Berisha, Avni; Aaddouz, M.; Youssouf, M. H.; Shityakov, S.; Sabbahi, Rachid; Algarra González, Manuel; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
In this work, we presented a synthesis of a composite based on HAp and PEG 6000 using a new method of synthesis dissolution precipitation to be applied for application of wastewater purification from toxic metal ions. Multiple characterization methods were used to analyze the morphology and the structure of the well-prepared compounds including FT-IR, Raman, XRD, XPS, TGA and SEM were used to conduct a composite analysis. The adsorption effectiveness of this analysis towards Pb2+ and various other hazardous metal ions found in sewage was assessed. Batch experiments were conducted to optimize the various operational parameters including adsorbent dose, temperature, pH, contact time, and initial concentration. The Langmuir isotherm was used to fit the data, and it predicted monolayer adsorption with a maximum capacity of 67 mg g−1 for HAP PEG600 and 60 mg g−1 for HAp. A pseudo-second-order equation fits the adsorption process well (0.961–0.971). The thermodynamic data support the spontaneous metal bonding to the composite receptor sites. Theoretical calculations showed that the interaction strength is very strong and gets stronger when the PEG6000 is deprotonated. The results presented here are supported by evidence acquired from experiments. Theoretical computation using Monte Carlo (MC) and Molecular Dynamic (MD) simulation models showed excellent affinity of prepared foams for the model ion Pb2+ with highly negative adsorption energy values indicating vigorous interactions of Pb2+ with the adsorbate surfaces.
Open Access
Micro sized interdigital capacitor for gases detection based on graphene oxide coating
(Springer, 2023) Vitoria Pascual, Ignacio; Armas, Dayron; Coronel Camones, Carlos Manuel; Algarra González, Manuel; Ruiz Zamarreño, Carlos; Matías Maestro, Ignacio; Mukhopadhyay, Subhas C.; Institute for Advanced Materials and Mathematics - INAMAT2; Institute of Smart Cities - ISC
A micro sized interdigital capacitor sensible to CO2 and NO is studied in this work. The photolithography technique enables to obtain fingers with dimensions of 10 × 500 µm and separated 7 µm between them. The deposition of a film composed of graphene oxide particles as the dielectrics of the capacitor allows to measure the gas concentration of CO2 and NO mixed with N2. The sensors were characterized in a gas chamber with a constant flow, obtaining promising results in changes of capacitance at 100 Hz. The sensors have a good linearity and sensitivity with a R2 = 0.996 and 5.026·10-1 pF/ % v/v for CO2 and R2=0.972 and 1.433·10-1 pF/ppb for NO.
Open Access
Diverse methods with stereoselective induction in the asymmetric Biginelli reaction
(MDPI Publishing, 2024-08-15) Díaz Fernández, Marcos; Algarra González, Manuel; Calvo Losada, Saturnino; Quirante, José Joaquín; Sarabia, Francisco; Pino-González, María Soledad; Institute for Advanced Materials and Mathematics - INAMAT2
The relevance of the asymmetric Biginelli reaction (ABR) has been increased in this century, due to the pharmacological application of its products. This review focuses predominantly on articles published in the period from 2015 to 2024 on asymmetric synthetic advances in the formation of dihydropyrimidinones (DHPMs), dihydropyrimidinethiones (DHPMTs), and related compounds. The relevant bibliography on general processes in the Biginelli reaction and some methods of separation of isomers have also been referenced.
Open Access
UV-photoelectron spectroscopy and MS-CASPT2/CASSCF study of the thermolysis of azidoethyl-methyl sulfide: Characterization and mechanism of the formation of S-methyl-N-sulfenylethanimine
(American Institute of Physics (AIP), 2025-05-16) Algarra González, Manuel; Labat, Stephane; Rodríguez-Borges, José Enrique; Pino-González, María Soledad; Sotiropoulos, Jean Marc; Soto, Juan; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
The thermal decomposition of azidoethyl methyl sulfide was studied by real-time UV-photoelectron spectroscopy (UV-PES) at temperatures ranging from 773 to 1023 K. Different ionization energies were obtained using density functional theory calculations to assign UV-PES spectra. The complete active space self-consistent field and multistate second-order perturbation methods were used to predict the formation of different species present in the thermal decomposition process. N2 and S-methyl-N-sulfenylethanimine are generated at 773 K. The first step of the reaction is the dissociation of the molecule into nitrene and nitrogen. The spin state (singlet or triplet) of nitrene formed in the first step of the reaction is temperature-dependent. At low temperatures (T ≤ 650 K), both states are formed with almost the same probability; in contrast, at high temperatures (T ≤ 1000 K), singlet nitrene is the majority intermediate. From this singlet nitrene, three stable reaction products were detected in the experiments: an imine derivative, a four-member cyclic derivative, and a sulfenyl derivative.