Open Access
Cellulose polymers with β-amino ester pendant group: design, synthesis, molecular docking and application in adsorption of toxic metals from wastewater
(BioMed Central, 2022) Nairat, Noor; Hamed, Othman; Berisha, Avni; Jodeh, Shehdeh; Algarra González, Manuel; Azzaoui, Khalil; Dagdag, Omar; Samhan, Subhi; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
Background: Cellulose polymers with multidentate chelating functionalities that have high eficiency for toxic metal ions present in water were designed, synthesized, and analyzed. The synthesis was carried out by reacting microcrystalline cellulose extracted from the solid waste of the olive industry with tert-Butyl acetoacetate (Cell-AA), produced cellulose with β-ketoester functionality was then reacted with aniline and the amino acid glycine to produce Cellβ-AN and Cell-β-GL, respectively. Results: The adsorption efciency of the three polymers toward Pb(II) and various toxic metal ions present in sewage was evaluated as a function of adsorbent dose, time, temperature, pH value, and initial ion concentration to determine optimum adsorption conditions. The three polymers showed excellent efciency toward about 20 metal ions present in a sewage sample collected from the sewer. The adsorption process follows the Langmuir adsorption isotherm model with a second-order of adsorption rate, the calculated qe values (2.675, 15.252, 20.856 mg/g) were close to the experimental qe values (2.133, 13.91, 18.786 mg/g) for the three polymers Cell-AA, Cell-β-AG and Cell-β-AN, respectively. Molecular Dynamic (MD) and Monte Carlo (MC) simulations were performed on the three polymers complexed with Pb(II). Conclusion: The waste material of the olive industry was used as a precursor for making the target cellulose polymers with β-Amino Ester Pendant Group. The polymer was characterized by SEM, proton NMR, TGA, and FT-IR spectroscopy. The efcacy of adsorption was quantitative for metal ions present in a real sample of wastewater and the efciency didn’t drop even after 7 cycles of use. The results indicate the existence of strong complexation. The thermodynamic study results showed a spontaneous bonding between of Pb(II) and the polymers pendant groups expressed by the negative value of the Gibbs free energy.
Open Access
Catalyzed methods to synthesize pyrimidine and related heterocyclic compounds
(MDPI, 2023) Díaz Fernández, Marcos; Calvo Losada, Saturnino; Quirante, José Joaquín; Sarabia, Francisco; Algarra González, Manuel; Pino-González, María Soledad; Institute for Advanced Materials and Mathematics - INAMAT2
This review covers articles published in the period from 2010 to mid-2022 on synthetic advances in the formation of pyrimidine and related heterocyclic compounds. Special emphasis has been given to the different types of cycloadditions, taking into account the number of their components and leading to the formation of the pyrimidine ring. Due to the large number of publications on the Biginelli reaction and related reactions, this will be dealt with in a separate review in the near future.
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
Efficient and scalable gene delivery method with easily generated cationic carbon dots
(BMC, 2024) Algarra González, Manuel; González-Muñoz, Elena; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Gene delivery is a complex process with several challenges when attempting to incorporate genetic material efficiently and safely into target cells. Some of the key challenges include not only efficient cellular uptake and endosomal escape to ensure that the genetic material can exert its effect but also minimizing the toxicity of the delivery system, which is vital for safe gene delivery. Of importance, if gene delivery systems are intended for biomedical applications or clinical use, they must be scalable and easy and affordable to manufacture to meet the demand. Here, we show an efficient gene delivery method using a combination of carbon dots coated by PEI through electrostatic binding to easily generate cationic carbon dots. We show a biofunctional approach to generate optimal cationic carbon dots (CCDs) that can be scaled up to meet specific transfection demands. CCDs improve cell viability and increase transfection efficiency four times over the standard of PEI polyplexes. Generated CCDs enabled the challenging transfection protocol to produce retroviral vectors via cell cotransfection of three different plasmids into packing cells, showing not only high efficiency but also functionality of the gene delivery, tested as the capacity to produce infective retroviral particles.
Open Access
Multifunctionalized carbon dots as an active nanocarrier for drug delivery to the glioblastoma cell line
(American Chemical Society, 2024) Algarra González, Manuel; Soto, Juan; Pino-González, María Soledad; González-Muñoz, Elena; Dučić, Tanja; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Nanoparticle-based nanocarriers represent a viable alternative to conventional direct administration in cancer cells. This advanced approach employs the use of nanotechnology to transport therapeutic agents directly to cancer cells, thereby reducing the risk of damage to healthy cells and enhancing the efficacy of treatment. By approving nanoparticle-based nanocarriers, the potential for targeted, effective treatment is greatly increased. The so-called carbon-based nanoparticles, or carbon dots, have been hydrothermally prepared and initiated by a polymerization process. We synthesized and characterized nanoparticles of 2-acrylamido-2-methylpropanesulfonic acid, which showed biocompatibility with glioblastoma cells, and further, we tested them as a carrier for the drug riluzole. The obtained nanoparticles have been extensively characterized by techniques to obtain the exact composition of their surface by using Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and nuclear magnetic resonance (NMR) spectroscopy, as well as cryo-transmission electron microscopy. We found that the surface of the synthesized nanoparticles (NPs) is covered mainly by sulfonated, carboxylic, and substituted amide groups. These functional groups make them suitable as carriers for drug delivery in cancer cells. Specifically, we have successfully utilized the NPs as a delivery system for the drug riluzole, which has shown efficacy in treating glioblastoma cancer cells. The effect of nanoparticles as carriers for the riluzole system on glioblastoma cells was studied using live-cell synchrotron-based FTIR microspectroscopy to monitor in situ biochemical changes. After applying nanoparticles as nanocarriers, we have observed changes in all biomacromolecules, including the nucleic acids and protein conformation. These findings provide a strong foundation for further exploration into the development of targeted treatments for glioblastoma.
Open Access
Nanoporous alumina support covered by imidazole moiety-based ionic liquids: optical characterization and application
(MDPI, 2022) Algarra González, Manuel; López Escalante, María Cruz; Martínez de Yuso, María Valle; Soto, Juan; Cuevas, Ana L.; Benavente, Juana; Institute for Advanced Materials and Mathematics - INAMAT2
This work analyzes chemical surface and optical characteristics of a commercial nanoporous alumina structure (NPAS) as a result of surface coverage by different imidazolium-based ionic liquids (1-butyl-3-metylimidazolium hexafluorophosphate, 3-methyl-1-octylimidazolium hexafluorophosphate, or 1-ethyl-3-methylimidazolium tetrafluoroborate). Optical characteristics of the IL/NPAS samples were determined by photoluminescence (at different excitation wavelengths (from 300 nm to 400 nm), ellipsometry spectroscopy, and light transmittance/reflectance measurements for a range of wavelengths that provide information on modifications related to both visible and near-infrared regions. Chemical surface characterization of the three IL/NPAS samples was performed by X-ray photoelectron spectroscopy (XPS), which indicates almost total support coverage by the ILs. The IL/NPAS analyzed samples exhibit different photoluminescence behavior, high transparency (<85%), and a reflection maximum at wavelength ~380 nm, with slight differences depending on the IL, while the refractive index values are rather similar to those shown by the ILs. Moreover, the illuminated I–V curves (under standard conditions) of the IL/NPAS samples were also measured for determining the efficiency energy conversion to estimate their possible application as solar cells. On the other hand, a computational quantum mechanical modeling method (DFT) was used to establish the most stable bond between the ILs and the NPAS support.
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.
Open Access
CASPT2 study of the electronic structure and photochemistry of protonated N-nitrosodimethylamine (NDMA-H+) at 453 nm
(American Institute of Physics, 2023) Soto, Juan; Peláez, Daniel; Algarra González, Manuel; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
In this work, we have studied the photodissociation of the protonated derivatives of N-nitrosodimethylamine [(CH3)2N–NO] with the CASPT2 method. It is found that only one of the four possible protonated species of the dialkylnitrosamine compound absorbs in the visible region at 453 nm, that is, N-nitrosoammonium ion [(CH3)2NH-NO]+ . This species is also the only one whose first singlet excited state is dissociative to directly yield the aminium radical cation [(CH3)2NHN⋅] + and nitric oxide. In addition, we have studied the intramolecular proton migration reaction {[(CH3)2N–NOH] + → [(CH3)2NH–NO]+ } both in the ground and excited state (ESIPT/GSIPT); our results indicate that this process is not accessible neither in the ground nor in the first excited state. Furthermore, as a first approximation, MP2/HF calculations on the nitrosamine–acid complex indicate that in acidic solutions of aprotic solvents, only [(CH3)2NH–NO]+ is formed.
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.