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- Development of paper-immobilized molecularly imprinted polymers by laser pointer activation for methamphetamine extraction with analysis by ion mobility spectrometry(2023) Muñoz-Bartual, Miguel; Herrero-Martínez, José Manuel; Esteve-Turrillas, Francesc A.A fast, simple, cheap, and versatile strategy has been proposed for the synthesis of paper-immobilized molecularly imprinted polymers (MIPs) by photoactivated bulk polymerization over a piece of nitro- cellulose using a 405 nm laser pointer. Polymerization was carried out using a mixture of methacrylic acid and ethylene glycol dimethacrylate, using methamphetamine as template molecule and bis(2,4,6- trimethylbenzoyl)phenylphosphine oxide as radical initiator. After investigation of different polymeriza- tion parameters, the following experimental conditions were found to give best results: size of nitro- cellulose strip (13.5 ×4.0 ×0.8 mm), type of porogen (acetonitrile), polymerization mixture volume (75 μL), and irradiation times (10 min). Experimental conditions (such as sample pH, extraction and desorp- tion time, and type and volume of desorption solvent) were also adjusted for the extraction of metham- phetamine using the proposed paper-MIP. Methamphetamine determination was carried out by ion mo- bility spectrometry providing a limit of detection of 14 μg L −1 and quantitative recoveries from 81 to 95% using spiked urine and oral fluid samples. The proposed paper-immobilized MIP device allows a sim- ple and selective sample extraction procedure for the determination of methamphetamine in oral fluids and urine with a high portability, minimal solvent consumption, and reduced costs compared to other conventional approaches.
- Rational design and structure-controlled tuning of antioxidant activity in substituted nanocellulose schiff base derivatives: A systematic study of electronic and conjugation effects(2026) Agren, Soumaya; Hassouna, Chaima; Salek, Abir; Mehdaoui, Rahma; El Haskouri, Jamal; Ghédira, Leila Chekir; Baouab, Mohamed Hassen V.Fine-tuning antioxidant performance of sustainable biomaterials remains a challenge for several researchers, mainly because of limited reported investigations of the impact of structural (substitution and/or conjugation extension) on polysaccharide-based frameworks. In this contribution, we describe the first systematic conceptualization and structure-activity study of a series of tetra-aza-substituted nanocellulose Schiff base derivatives (A-F), where we concomitantly control π-conjugation length and/or substituent effects with precisely moderated characteristics. X-ray characterization shows crystallinity indices spanning from 3.09% in pristine dialdehydenanocellulose to 62.67% for naphthol-substituted Schiff base derivatives, showing that hydroxyl donor substitution fused with naphthalene ring favor structural organization. The optical study elucidates advanced red-shifts ranging from 265 nm to 368 nm (nitro derivative), proving controllable photophysical properties. In addition, antioxidant activity assessment through DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)), and FRAP (Ferric Reducing Antioxidant Power) tests reveals an excellent performance: the hydroxyl-naphthalene derivative (D) exhibits the best antioxidant activity; 75% DPPH inhibition (IC 50 = 52 μg/mL), 86% ABTS scavenging (IC 50 = 57 μg/mL), and 265 μM TE reducing strength. Conversely, the electron-acceptor nitro derivative (E) decreases scavenging activity (29% DPPH inhibition). The gathered structure-activity relationship shows that OH-donor group coupled with extended conjugation outranks halogen and withdrawing substitution, di-imine/amine as well as solo conjugation extension, providing a rational conceptualization platform for antioxidant nano-cellulosic agents. Based on the observed structureactivity relationship, the hydroxyl-naphthalene Schiff base derivative shows particular promise for sustainable antioxidant applications in active food packaging, wound healing hydrogels, and ROS-scavenging biomedical materials.
- Highly efficient removal of Cr(III) and Ni(II) ions from aqueous solutions using a new hybrid [magnetic graphene oxide/Dialdehyde Nanocellulose] adsorbent(2026) Hassouna, Chaima; Agren, Soumaya; El Haskouri, Jamal; Baouab, Mohamed Hassen V.A novel ternary magnetic nanocomposite, DANC-[GO@Fe3O4], was successfully synthesized via co-precipitation and demonstrated exceptional adsorption performance for Cr(III) removal from water. Characterization confirmed the successful integration of dialdehyde nanocellulose, graphene oxide, and Fe3O4 into a stable, magnetically recoverable adsorbent. Under optimized adsorption parameters (pH 6, 25 ◦C, 6 h, 0.025 g adsorbent in 0.05 L of 250 mg/L Cr(III) solution), DANC-[GO@Fe3O4] attains a notable 98.72% removal efficacity in addition to a high adsorption capacity of 493.60 mg/g, remarkably outperforming non-combined magnetic graphene oxide and dialdehyde nanocellulose adsorbents. Cr(III) adsorption procedure follows pseudo-second- order kinetics (k2 =0.0226 g⋅mg 1⋅h 1, R2 =0.989) and displayed spontaneous character (ΔG◦= 12.48 kJ/mol at 298 K). The equilibrium findings are better fitted by the Freundlich isotherm model (R2 =0.985, KF = 84.0 mg/g, n =1.03), demonstrating multilayer adsorption on a heterogeneous surface. Moreover, DANC- [GO@Fe3O4] exhibits remarkable recyclability, retaining approximately 90% of its primary adsorption performance after six successive runs. Compared to Ni(II), DANC-[GO@Fe3O4] demonstrates better affinity for Cr(III) associated with its relatively reduced ionic radius (62 pm vs 69 pm) and higher coordination capacity with oxygen-containing functional moieties. The collected data highlights the magnetic material's promising capability as a competent, recoverable adsorbent for the depollution Cr(III)-contaminated wastewater. Environmental Implication: The synthesized DANC-[GO@Fe3O4] nanocomposite presents significant environmental benefits by enabling highly efficient removal of Cr(III) from contaminated water, thereby reducing heavy metal pollution and associated ecological risks. Its high adsorption capacity and reusability minimize secondary waste generation and lower treatment costs. The magnetic recoverability further simplifies separation processes, reducing energy and chemical inputs. By integrating sustainable components such as nanocellulose, this material supports greener remediation strategies and offers a promising, eco-friendly solution for wastewater treatment and environmental protection
- Design and DFT Study of π-Rich Boron Complexes of Tetraphenyl Imidazole: Correlation between Photophysical Properties and Binding Affinity toward p38α MAP Kinase(2026) Agren, Soumaya; Chaabene, Marwa; Hassouna, Chaima; El Haskouri, Jamal; Lahcini, Mohammed; Baouab, Mohamed Hassen V.In this study, we designed and synthesized a novel phenanthro-imidazole derivative (Ph-IMI, a) and its tetracoordinated boron complexes Ph-IMI-BF2 (b) and Ph-IMI-BPh2 (c) in good yields (96%, 72%, and 68%, respectively). All compounds were characterized experimentally (1 H NMR, FTIR, UV-Vis, fluorescence, TGA) and theoretically (DFT/TD-DFT at B3LYP-D3/6-311 + G(d, p) level). Boron complexation dramatically enhanced thermal stability: T5% increased from 74 °C (a) to 147 °C (b) and 328 °C (c). Optically, BF₂ coordination produced a green emission with a large Stokes shift (11700 cm⁻¹) and a reduced HOMO-LUMO gap (3.30 eV vs. 3.72 eV for a), while BPh2 coordination afforded an unusual white emission (two bands at 464 and 571 nm) with a Stokes shift of 9161 cm⁻¹ and a gap of 3.31 eV. Frontier molecular orbital analysis revealed pronounced intramolecular charge transfer, consistent with the observed bathochromic shifts. Preliminary docking against p38α MAP kinase (PDB:1A9U) showed that boron complexation progressively improves binding affinity, with c exhibiting the strongest predicted binding energy (-10.0 kcal/mol) due to additional π-π stacking and polar interactions. These findings demonstrate that coordination with BF2 and especially BPh2 enables systematic tuning of thermal stability, fluorescence color (blue → green → white), and receptor binding, establishing boron-phenanthro-imidazole complexes as promising scaffolds for optoelectronic and bioimaging applications
- Nuclearity and coordination-mode control in Copper-Diphosphine complexes: From Cu(I)-BINAP to Cu(II)-BINAPO(2026) Rodríguez, Humberto A.; Fernández, Israel; Padrón, Juan I.; Olmos Vergé, Andrea; Lorenzo-Luis, Pablo; González-Platas, JavierCopper(I) diphosphine complexes are known to exhibit a strong tendency toward aggregation, often forming halide-bridged dinuclear species that hinder the isolation of well-defined mononuclear structures. Herein, we report a pyridine-driven strategy for nuclearity control in Cu(I)-BINAP halide systems, enabling the selective formation of mononuclear complexes of the type [CuX(L)(py)]. This pyridine effect is further supported by density functional theory (DFT) calculations, which indicate that pyridine coordination and Cu-X bond cleavage proceed in a concerted manner through two consecutive SN2-like reactions. The methodology is applicable to both racemic and enantiopure BINAP, and extends to alternative diphosphine ligands such as DPEphos, revealing a clear correlation between ligand rigidity, bite angle, and deviation from ideal tetrahedral geometry (τ4). Furthermore, the corresponding square-planar Cu(II)-BINAPO complex can be obtained either from BINAP under open-atmosphere Cu(OTf)2 conditions or directly from preformed BINAPO, highlighting a coordinationmode switch from κ2P,P′ to κ2O,O′ binding. This result expands the limited examples of BINAPO coordination to first-row transition metals and provides new insight into the coordination versatility of oxidized diphosphine ligands in copper chemistry.
- Nuclearity and coordination-mode control in Copper-Diphosphine complexes: From Cu(I)-BINAP to Cu(II)-BINAPO(2026) Rodríguez, Humberto A.; Fernández, Israel; Padrón, Juan I.; Olmos Vergé, Andrea; Lorenzo-Luis, Pablo; González-Platas, JavierCopper(I) diphosphine complexes are known to exhibit a strong tendency toward aggregation, often forming halide-bridged dinuclear species that hinder the isolation of well-defined mononuclear structures. Herein, we report a pyridine-driven strategy for nuclearity control in Cu(I)-BINAP halide systems, enabling the selective formation of mononuclear complexes of the type [CuX(L)(py)]. This pyridine effect is further supported by density functional theory (DFT) calculations, which indicate that pyridine coordination and Cu-X bond cleavage proceed in a concerted manner through two consecutive SN2-like reactions. The methodology is applicable to both racemic and enantiopure BINAP, and extends to alternative diphosphine ligands such as DPEphos, revealing a clear correlation between ligand rigidity, bite angle, and deviation from ideal tetrahedral geometry (τ4). Furthermore, the corresponding square-planar Cu(II)-BINAPO complex can be obtained either from BINAP under open-atmosphere Cu(OTf)2 conditions or directly from preformed BINAPO, highlighting a coordinationmode switch from κ2P,P′ to κ2O,O′ binding. This result expands the limited examples of BINAPO coordination to first-row transition metals and provides new insight into the coordination versatility of oxidized diphosphine ligands in copper chemistry.
- Preparation, Characterization, and Keratinocyte Cell Viability of a β-Cyclodextrin-Myrcene Complex Intended for Skin Application(2026) Felipe Mota Tashiro; Lobato Duarte, Jonatas; Martínez-Navarrete, Miquel; Guillot García, Antonio José; Melero Zaera, Ana; Chorilli, MarlusContext: Myrcene has biomedical potential; however, due to its environmental instability and low water solubility, novel approaches, such as inclusion complex formation, can overcome these disadvantages and improve its applicability in cosmetics. Objective: This research investigated the formation of a β-cyclodextrin:myrcene complex using an experimental design approach, followed by physicochemical characterization. The inclusion complex was also evaluated for cytocompatibility in HaCaT keratinocytes for use in skin formulations. Materials and methods: Inclusion complexes were obtained by coprecipitation and optimized using response surface design. The complexes were characterized by FTIR spectroscopy, thermal behavior (TGA and DSC), XRD, and SEM. Cell viability in HaCaT cells was assessed using the MTT assay. Results: The β-cyclodextrin:myrcene complex exhibited a 75.88% inclusion efficacy. FTIR results indicated changes in the band position/intensity consistent with host-guest interactions. Thermal analyses revealed reduced water loss events and the disappearance of the β-CD thermal transition. The X-ray diffraction results suggest a reduction in crystallinity, as indicated by changes in the sample peaks. Scanning electron microscopy data reveal the formation of cubic/rhomboid structures. Cytocompatibility assays demonstrated that free myrcene maintained viability above 70% across most tested concentrations, whereas the formed inclusion complex reduced apparent viability at higher concentrations, consistent with limited aqueous solubility. Conclusions: β-CD effectively entrapped myrcene through coprecipitation, as confirmed by complementary solid-state and thermal analyses. Cytocompatibility results highlighted a reduction in cell viability after the formation of inclusion complexes when compared to myrcene and β-CD controls, possibly due to solubility-related effects. These findings reveal the need for the application of new methods to evaluate the in vitro compatibility and safety of intended skin use.
- Halogen substituted g-C3N4@Fe3O4 Schiff base derivatives: A comparative study of halogen type on structural properties and in vitro anticancer and antioxidant activity(2026) Abbassi, Kaouther; Salek, Abir; Agren, Soumaya; Hedhili, Lassaad; Beyou, Emmanuel; El Haskouri, Jamal; Chekir-Ghedira, Leila; Baouab, Mohamed Hassen V.This study reports the synthesis of advanced hybrid nanomaterials through the functionalization of graphitic carbon nitride (g-C3N4) with halogen-substituted benzaldehydes (F, Cl, Br) via Schiff base condensation, followed by grafting with magnetite nanoparticles to form g-Ald-X@Fe3O4 composites. FTIR reveals the emergence of C--N bonds, whose frequencies are modulated by halogen-specific electronic effects and hydrogen bonding. However, subsequent Fe3O4 coordination overrides these substituent influences. XRD indicates that functionalization reduces interlayer stacking but enhances in-plane crystallinity, while the presence of magnetite diffraction patterns verifies successful Fe3O4 integration. SEM reveals distinct, halogen-dependent morphological evolution, which is further altered by nanoparticle grafting. TGA demonstrates a synergistic enhancement in thermal stability and residual char yield. Optically, Schiff base formation induces a redshift due to extended conjugation and the heavy-atom effect, which is subsequently reversed by a magnetite coating-induced blueshift attributed to disrupted pi-conjugation. Biological assays demonstrate that the structural modifications confer significant, halogen-dependent bioactivity. The bromine and chlorine composites exhibit superior antioxidant capacity, outperforming standard antioxidants, while all derivatives show potent, halogen-modulated cytotoxicity against breast cancer cells, with g-Ald-Br@Fe3O4 displaying the highest potency (IC50 = 12.5 mu g/mL). These results underscore a direct link between halogen identity and enhanced bioactivity.
- Adsorption Kinetics, Isotherm Models, and Thermodynamics: A Brief Review(2026) Yazidi, Imane; Ziat, Khadija; El Bardiji, Naoual; El Boundati, Youssef; Naji, Ahmed; El Haskouri, Jamal; Saidi, MohamedThe study of adsorption kinetics provides significant insight into the rate at which solutes are adsorbed and the duration of adsorbate interaction at the solid-liquid interface. Similarly, adsorption isotherms are fundamental to understanding the interaction dynamics between adsorbates and adsorbents and to determining the maximum adsorption capacity of the adsorbent. Thermodynamic analyses serve to complement these studies by evaluating the feasibility, spontaneity, and energy changes involved in the adsorption process. This article presents an overview of the main models of adsorption kinetics, isotherms, and thermodynamics, as well as their optimization and validation. The models of adsorption kinetics reviewed in this article include the pseudo-first-order, pseudo-second order, Elovich and intra-particular diffusion models. These models are based on the assumption of heterogeneous reactions at the solid-liquid interface. The linearised forms of these equations facilitate the calculation of important parameters, including adsorption capacity, rate constants, adsorption rates, and intraparticle diffusion coefficients, using the slopes and intercepts derived from graphical representations. Optimization and validation of these models are performed using statistical metrics such as the coefficient of determination (R2), sum of squared errors (SSE), and residual root mean square error (RMSE) to ensure the reliability of the models in describing adsorption behavior. Isotherm models review include Langmuir, Freundlich, Temkin, Redlich-Peterson, and Dubinin-Radushkevich. These models provide insight into the following aspects of adsorption: affinity, mean free energy, and the nature of the adsorption process, including whether it involves physisorption or chemisorption, and whether it occurs in single or multi-layer adsorption. Furthermore, thermodynamic parameters such as Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) are discussed, as they provide crucial details about the spontaneity, feasibility, and energy profile of the adsorption process. The values and signs of these parameters indicate whether the adsorption is exothermic or endothermic, thus providing deeper insights into the energetic aspects of the system. This review of adsorption kinetics, isotherms, and thermodynamics and the optimization and validation of adsorption models provides a solid basis for the understanding and optimizing of the adsorption process in a wide variety of applications.
- A Mechanistic Study of Bio-Based Nanotemplated Carbon Nanofibers Derived From Water Processable Lignin Blends for Sustainable Energy Storage Applications(2026) Miralda Jalle, Judith; El Haskouri, Jamal; Bhattacharya, Shayon; Beaucamp, Anne; Kennedy, Tadhg; Culebras, Mario; Collins, Maurice N.This article studies the process for obtaining sustainable and environmentally friendly, carbon nanofibers via an electrospinning process using water without the need for organic solvents or synthetic polymers/binders. Lignosulfonate, gelatin, and alginate are selected for water solubility, ability to produce templated carbon nanostructures and for sustainability. Gelatin and alginate are sacrificial templates during thermal processing, allowing the production of engineered high surface area hollow nanostructures. A mechanistic study is performed to elucidate the relationship between carbon hybridization and electrochemical performance. The as-spun carbon materials were further characterized for potential applications in sodium-ion batteries.
- Tunable dispersion of cobalt oxide nanoclusters grafted on mesoporous SBA-15 for efficient pharmaceutical removal from wastewater(2026) Tallouzt, Hajar; Nayral, Céline; El Haskouri, Jamal; Anis, Khalil; Kherbeche, Abdelhak; El Kadib, AbdelkrimPharmaceutical contaminants are an emerging threat, driving antibiotic resistance and environmental risk. Here, we harness the high surface area and tunable chemistry of mesoporous SBA-15 silica to engineer hybrid adsorbents by confining ultra-small metal oxide clusters (<1 nm; NiO: 0.47 ± 0.15 nm, Co3O4: 0.63 ± 0.17 nm, Fe2O3: 0.73 ± 0.18 nm) within its mesostructured network. Consistent with its strong Lewis acidity, cobalt oxide-loaded SBA-15 exhibited exceptional tetracycline removal efficiency, outperforming pristine SBA-15, aminopropyl/mercaptopropyl-functionalized silicas, bulk cobalt oxide, and other nanomaterials. Through benchmarking and accurate comparison, several key points can be made: (i) residual pluronic was pivotal for stabilizing the burst and keeping the metallic phase well dispersed and with an ultra-small size, which consequently enabled the retention of the mesostructure, (ii) thermal annealing treatment was essential for strengthening the interfacial grafting and for structural integrity, (iii) surface polarity imparted by terminal hydroxyl groups promoted strong interaction with the pharmaceutical pollutant. The photoactivatable Co-O-Si sites, reached through atomic cobalt dispersion on the silica matrix, provide an additional means for photo-oxidation, enabling near-complete degradation of highly concentrated tetracycline (10−3 mol L−1) under visible light. Mechanistic studies reveal the involvement of hole-mediated surface reactions in the photo-triggered degradation pathway. This multifunctional, cobalt oxide decorated mesostructured SBA-15-type silica hybrid offers a promising platform for advanced water purification technologies.
- Bi3O4Br nanosheets immobilized in chitosan microspheres as efficient and recyclable hybrid catalysts for water treatment(2026) Ait Yachou, Hassan; Brik, Abdelmalik; El Kadiri, Mustapha; El Assimia, Taha; Ben Youcef, Hicham; Gouhier, Géraldine; El Haskouri, Jamal; El Meziane, Abdellatif; El Kadib, Abdelkrim; Lahcini, MohammedAccess to clean water is a critical global priority. Thus, photocatalysis using semiconducting materials has emerged as a promising technology for wastewater treatment. Herein, a novel Bi3O4Br@Chitosan hybrid composite was successfully prepared by immobilizing Bi3O4Br in chitosan (CS) beads. First, Bi3O4Br was prepared via a solvothermal process, followed by its physical embedding in the CS matrix via a simple coprecipitation method. The surface morphology, elemental composition, crystal structure, and optical properties of the Bi3O4Br@CS material were comprehensively investigated using SEM, EDS, FTIR, XRD, TGA, zeta potential, Raman, and UV-vis spectroscopy, indicating excellent compatibility, multifunctional structure, and high structural robustness. Consequently, the Bi3O4Br@CS catalyst exhibits high efficiency in the UV-light-driven photodegradation of Rhodamine B (RhB), achieving 88% RhB degradation within 150 minutes and total reduction of 4-nitrophenol (4-NP) in the presence of NaBH4 within 5 min at room temperature. Additionally, the catalyst shows good stability and can be reused over seven successive cycles without significant loss of activity. Therefore, the combination of adsorption capacity and photocatalytic activity within this hybrid catalyst provides an efficient and practical approach for wastewater treatment applications.
- Biomimetic abiotic degradation as a sustainable tool to synthesize Stöber-type silicas with expanded mesopores of modulable size(2026) Garrido Blay, María Dolores; El Haskouri, Jamal; Ros Lis, José Vicente; Amorós, PedroThis paper describes a reproducible methodology for the preparation of spherical St¨ ober-type silica particles with controllable mesopore expansion. The method is based on the use of PBS solution as a degradation agent and generator of expanded pores. Porosity is controlled by easily adjustable parameters, such as reaction time and temperature (in many cases close to room temperature). To accelerate the process, short, consecutive treatments were tested, reducing the synthesis time to 18 h. Pore sizes can be adjusted from small mesopores formed by surfactant micelles (approx. 2-3 nm) to ultra-large mesopores of 14-15 nm. Although the biodegradation of silica particles has been extensively studied in biomedicine, this article presents the first comprehensive use of biocompatible solutions for preparative purposes. Dissolution and reprecipitation progressively transform small mesopores into ultra-large ones without significantly decreasing particle diameter, thus preserving morphological homogeneity. The simplicity of the method, the minimal energy required, and the absence of expensive and hazardous reagents are all clear advantages over other alternatives. Additionally, a Life Cycle Analysis was conducted, encompassing scenarios ranging from laboratory experiments to industrial production. Results show that the use of PBS significantly reduces environmental impact compared to other chemical agents.
- Optical thermometry application based on intensive blue emission of Eu-doped Al2O3 nanoparticles embedded in silica-glass host matrix(2026) Bouri, A.; Bessadok, M.N.; Ihzaz, N.; El Haskouri, Jamal; Martínez-Pastor, Juan P.; Leminec, O.M.; Altoub, Turki; Lassaad Mabrouk El-MirThe effect of europium (Eu) doping on the structural and optical properties of alumina (Al2O3) nanoparticles (NPs) embedded in a silica (SiO2) glass matrix prepared by a modified sol-gel method is reported. The Rietveld refinement of the XRD patterns quantified the crystalline phases. At 1400 ◦C, four-phase regions, cristobalite, mullite and alumina in α and θ allotropic forms were observed. Microstructural and morphological characterisations were performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier Transform Infrared (FTIR) spectroscopy. The nanocomposite of silica enriched by alumina-doped europium (SiO2/Al2O3:Eu3+) exhibited red light emissions with the highest intensity at 617 nm assigned to the 5D0 → 7F2 transition under excitation of 240 nm wavelength, when prepared at 1200 ◦C. A post-heat- treatment at 1400 ◦C involves a reduction of Eu3+ to Eu2+, in parallel with the formation of the mullite Al6Si2O13:Eu2+phase, which XRD and XPS analysis confirmed. As a result, an intense blue emission at 428 nm occurs upon excitation with UV radiation (4F6→4 F7). The composite shows an ability to produce blue light much higher than red light, with a Photoluminescence Quantum Yield (PLQY) of around 50%. The temperature dependence of PL shows an exponential evolution coupling Eu2+and Eu3+ions with a relative sensitivity (Sr %) around 1 at 12 K. These results are promising for low-temperature non-contact luminescence thermometry
- Exploring the Synergistic Effects of Ultrafine Polyaniline Nanofibers and Oxygen-Modified Multi-Walled Carbon Nanotubes on Enhancing Pseudocapacitive Electrochemical Performance for Advanced Supercapacitors(2026) Djefaflia, Fahima; Guellati, Ouanassa; Merzoug, Assia Nait; Harat, Aicha; El Haskouri, Jamal; Janowska, Izabela; Baibarac, MihaelaThis work reports a systematic study concerning the synthesis of pure polyaniline ultrafine nanofibers (PANI-NFs) and their nanocomposites with oxygen-functionalized carbon nanotubes (PANI-NFs/O-MWCNTs) using diluted chemical polymerization and hydrothermal processes. We investigated the synergistic effects of various synthesis parameters, such as the concentration of the ammonium persulfate oxidant agent and growth temperature, on the physical, chemical, and electrochemical properties of the resulting products through structural, morphological, spectroscopic, and electrochemical characterization. Our study revealed the successful synthesis of thermally resistant polyaniline ultrafine nanofibers (PANI-NFs) in the form of emeraldine salt (ES), exhibiting a mean diameter in the range of 8-17 nm. The PANI-NFs and PANI-NFs/O-MWCNT nanocomposites demonstrated excellent electrochemical properties, with specific capacitances of up to 0.94-1.23 F cm−2 and 1410-2074 F/g, respectively, and with good rate capability. These characteristics are confirmed by the relaxation time constant τ0 (41 and 8 ms, respectively) and lower internal R0/interfacial charge transfer RՓ resistances of around 0.2 Ω, as well as diffusion coefficients of around 10−7 and 3.7 × 10−7 cm2/s. This breakthrough in nanofiber synthesis paves the way for practical applications in diverse domains, from high-performance energy storage to biosensing and beyond, where the unique electroactive properties of the nanocomposites can be leveraged to achieve exceptional results.
- Phosphorylation of Pluronic-Filled Silica Mesostructure as a Circular Route for Surfactant Removal and Recycling(2025) El Kaddouri, Malak; Akmach, Dahi; Katir, Nadia; El Haskouri, Jamal; Kaliaguine, Serge; El Kadib, AbdelkrimExpanding the pore size of mesostructured silica above 2 nm has constituted a breakthrough in materials science. Unfortunately, the lack of recyclability of the costly used surfactant impedes large-scale implementation of these precisely calibrated nanoreactors. Unlike the commonly used template-destructive, energy-intensive protocols, we herein report that gentle treatment of the as-prepared silica-surfactant composite with phosphoryl chloride allows for performing two goals in a single action. Concomitant to surface phosphorylation, the released hydrochloric acid disturbs the hydrogen-bonding of the Pluronic to the silica network, triggering, as a consequence, its easy escape from the mesostructure. The presence of the Pluronic limits oligomerization of the phosphorus reagent inside of the mesostructure, thereby providing better site isolation for acid and cooperative acid-base functionalities compared to the phosphorylation undertaken through two-step implying conventional Soxhlet extraction and post-grafting, as substantiated by gas adsorption and catalytic tests. Besides, this nondestructive approach offers additional assets for template recovery and further recycling.
- Design of porous titanium crystals with redox activity(2026) Chinchilla-Garzón, Clara; Martí Gastaldo, Carlos; Muñoz Padial, Natalia; Departament de Química InorgànicaThis thesis investigates the chemical design of titanium-based reticular solids through the rational control of their structure using two complementary components: the organic ligand and the inorganic cluster. Systematic modulation of these elements enables the development of materials with increasing structural precision and functional complexity. Chapter 1 provides an overview of the emergence of chemical design in reticular solids, with particular emphasis on Metal–Organic Frameworks (MOFs). It introduces the fundamental principles of reticular chemistry, including isoreticular expansion, together with the key tools required for the design and synthesis of porous periodic structures. Porous networks are then discussed in order of increasing chemical complexity, beginning with the design of redox-active cores, followed by their influence on material properties, and culminating in the study of photoreactivity. The chapter highlights the importance of structural diversity and intrinsic properties in complex MOFs to broaden their applicability across different fields, with special attention to the photoactivity of Ti(IV). Chapter 2 proposes the use of the persistent Ti₂Ca₂ cluster as a secondary building unit to control the design and assembly of MOFs. This strategy enables the development of the first isoreticular family of Ti-MOFs, allowing systematic tuning of pore size and framework interpenetration. Within the MUV-12(X) and MUV-12(Y) series, MUV-12(2,6-napht) stands out by combining mesoporosity and microporosity, achieving a surface area approximately twice that of previously reported Ti-MOFs. The modular nature of the Ti₂Ca₂ cluster suggests broad applicability in constructing alternative topologies, while its ability to incorporate additional metal ions allows the design of heterobimetallic architectures with tailored functionality. These advances expand the chemical and topological diversity of Ti-MOFs and position them as promising candidates for gas capture, separation, catalysis, and photoredox applications. Chapter 3 reports the synthesis of single crystals of MUV-35, extending the family of flexible titanium-based frameworks. Its two-fold catenated structure undergoes a reversible, thermodynamically driven folding upon DMF desorption, resulting in significant unit cell volume contraction while preserving crystallinity and porosity. This structural transformation creates an efficient through-space charge transport pathway, leading to high photoconductivity with an ON/OFF ratio of four orders of magnitude under visible light. The combination of structural adaptability and enhanced charge mobility highlights the potential of flexible Ti-MOFs for advanced photocatalytic applications. Finally, Chapter 4 presents the heterometallic MUV-1001(M) family, which enables precise modulation of catalytic activity through dual-metal synergistic effects. In particular, MUV-1001(Fe) acts as a heterogeneous photocatalyst under blue light to promote decarboxylative oxidation reactions, facilitating 1,4-addition processes for C–C bond formation across a broad range of carboxylic acid substrates. Unlike conventional Ir- or Ru-based photoredox systems, this material operates via cluster sensitization and single-electron transfer mechanisms, offering a more sustainable and efficient platform for photocatalytic transformations.
- Valorización de glicerol crudo del proceso de obtención de biodiésel mediante su fermentación a butanol y 1,3-propanodiol con Clostridium pasteurianum(2026) Ortega Camino, Stalin Alejandro; Gabaldón García, Carmen; Marzal Doménech, Paula; Escola de DoctoratLa creciente demanda de energía impulsada por el aumento poblacional enfrenta el reto de reducir la dependencia de fuentes fósiles que actualmente representa el 87% del consumo energético en el sector de transporte en la Unión Europea consolidando al biodiésel como un biocombustible estratégico. Sin embargo, la producción de biodiésel genera glicerol crudo en proporciones de 10 al 12% en peso, siendo un subproducto con una alta carga de impurezas que limita su valorización debido a los altos costes de purificación y compromete la sostenibilidad económica y ambiental de la industria de biodiésel. La fermentación de glicerol crudo es una oportunidad estratégica para potenciar la industria de biodiésel. El glicerol como sustrato presenta ventajas frente a los carbohidratos convencionales, como un mayor grado de reducción, lo que favorece la obtención de productos de alto valor añadido. La especie Clostridium pasteurianum, es capaz de metabolizar este sustrato y generar alcoholes de alto interés como el butanol, el 1,3-propanodiol (1,3-PDO) y el etanol, así como ácidos grasos volátiles (butírico, acético y láctico). Sin embargo, la valorización directa del glicerol crudo enfrenta limitaciones debido a la variedad de impurezas que actúan como inhibidores del crecimiento celular. Incluso en la fermentación con glicerol de grado técnico, se observan fenómenos de inhibición por sustrato, por acumulación de ácidos (acid crash) o por producto que restringen el aprovechamiento de glicerol, requiriéndose innovaciones en el pretratamiento del sustrato y en la integración de biorreactores de configuración avanzada. El objetivo general de esta tesis doctoral es desarrollar una alternativa de valorización del glicerol crudo hacia la biosíntesis de butanol y 1,3-PDO empleando la especie C. pasteurianum, integrando técnicas de recuperación in situ mediante arrastre con gas y, con un enfoque innovador, en extracción líquido-líquido utilizando biodiésel como agente extractante. De manera complementaria, se estudia la influencia de los compuestos transportadores de electrones sobre la formación de productos mediante diseño experimental y análisis estadístico. Este trabajo presenta una alternativa para mejorar la economía de la producción de biodiésel fortaleciendo la cadena de valor del glicerol crudo industrial. El glicerol crudo para la realización de esta tesis doctoral fue proporcionado por dos industrias del sector de producción de biodiésel. Se probaron las estrategias de pretratamiento de filtración o adsorción con carbón activado granular (CAG) en una relación de 0.5 gCAG/gglicerol seguida de filtración, siendo esta última la más eficaz para reducir impurezas del glicerol crudo, permitiendo su aprovechamiento hasta concentraciones iniciales de 60 g/L indistintamente de la procedencia industrial. En una segunda fase, se realizaron ensayos para mejorar el medio de fermentación de glicerol. Producto de este estudio se estableció una concentración de FeSO4 de 5 mg/L como factor más determinante para favorecer la producción de butanol. Con la finalidad de prevenir el acid crash, se realizaron fermentaciones en reactores anaerobios con control digital de pH. Bajo condiciones controladas de pH mayores a 6.5, la especie mantuvo su capacidad de producción de butanol (~9 g/L) con todas las fuentes industriales de glicerol crudo ensayadas. No obstante, la toxicidad del butanol limitó el consumo prolongado del sustrato, justificando el acoplamiento de técnicas de recuperación in situ de butanol. El arrastre con gas mejoró la producción acumulada de butanol (~11.5 g/L) y recolectó aproximadamente 15 g/L de butanol en el destilado. Por otro lado, la extracción líquido-líquido en una relación biodiésel: medio de fermentación de 3:1 (v:v) en la unidad de extracción incrementó cerca de un 40% el rendimiento de butanol (0.28 gbutanol/gglicerol consumido) respecto al arrastre con gas, alcanzándose producciones cercanas a 14 g/L de butanol y 6 g/L de 1,3-PDO. Además, se potenció el biodiésel con 1% (p/p) de butanol, dotando a este biocombustible de mejores propiedades de combustión según la bibliografía. Finalmente, la suplementación de compuestos transportadores de electrones reveló un efecto concomitante con las condiciones de pH en el direccionamiento del flujo de carbono del metabolismo de la especie. Particularmente, la suplementación de L-cisteína en condiciones controladas de pH, favoreció la síntesis selectiva de 1,3-PDO logrando 22 g/L con solo 1 g/L de butanol a partir de 60 g/L de glicerol crudo. En conjunto, las investigaciones realizadas en esta tesis doctoral suponen un aporte de datos originales en el área de conocimiento de la Ingeniería Química, Ambiental y de Procesos, sentando las bases para una futura implementación de biorrefinerías sostenibles que integren la fermentación de glicerol crudo con procesos de recuperación de butanol innovadores y económicamente favorables para la industria de biodiésel.
- Accurate modeling of the photophysics of Ir(III) ionic transition-metal complexes(2026) Soriano Díaz, Iván; Giussani, Angelo; Ortí Guillén, Enrique; Escola de DoctoratThis PhD thesis investigates five ionic cyclometalated Ir(III) complexes: [Ir(ppy)2(bpy)]+ (1), [Ir(ppy)2(pbpy)]+ (2), [Ir(ppy)2(dpbpy)]+ (3), [Ir(ppy)2(pyim)]+ (4), and [Ir(diFppy)2(dtb-bpy)]+ (5), which exhibit distinct experimental emission quantum yields 𝛷𝑒𝑚 in solution (19.6, 3.6, 4.9, 20.4, and 71 % for complexes 1–5, respectively). The central aim is to develop reli-able theoretical models to explain their photophysical behavior. The thesis is presented as a compendium of four publications. The first contribution employs DFT calculations to rationalize the different emission efficiencies of complexes 1–3, which differ only in the phenyl rings (0, 1, or 2) attached to the ancillary bipyridine (bpy) ligand. In addition to the commonly assumed axial metal-centered (3MCax) decay pathway, a more fa-vorable nonradiative channel mediated by equatorial 3MC (3MCeq) states is identified, involving an Ir–Nbpy bond elongation. Differences in access to these 3MCeq states provide a better explanation of the observed reduction in 𝛷𝑒𝑚.in passing from 1 to 3. The second contribution focuses on the calculation of the temperature-de-pendent nonradiative decay rate constant for the green-emitting complexes 4 and 5. DFT calculations using B3LYP and PBE0 reveal that B3LYP underesti-mates the energy barriers to the 3MC states and thereby overestimates the nonradiative rate constants. In contrast, PBE0 yields values in good agree-ment with experimental data. The use of B3LYP is therefore discouraged for evaluating the photophysical behavior of cyclometalated Ir(III) complexes. In the third contribution, all radiative and nonradiative decay processes are examined for complexes 4 and 5, which display multiple 3MLCT, 3LC, 3MCax, and 3MCeq minima. The impact of including only the most accessible T1 and 3MC minima or all of them is studied, highlighting the importance and diffi-culty of accurately characterizing these processes for quantitative 𝛷𝑒𝑚 predic-tions. The fourth contribution revisits the role of 3MC states, showing that strong spin–orbit coupling and sloped crossing topographies reduce the efficiency of direct nonradiative decay to the ground state. Consequently, the decay medi-ated by 3MC states is only relevant when the excited population is trapped in them.
- Analytical strategies using aptamer-assisted extraction for food allergens and advanced materials for sensing hazardous compounds(2026) Piqueras García, Natalia; Herrero Martínez, José Manuel; Lerma García, María Jesús; Escola de DoctoratFood safety is essential for protecting public health and ensuring the proper functioning of the food industry, as it guarantees that products intended for human consumption are safe and do not pose risks. This requires strict control of biological, chemical, and physical hazards throughout all stages of the food chain, from production to distribution and storage. Among these risks, food allergens are particularly significant due to their ability to trigger adverse immune responses even at very low concentrations. In recent decades, the incidence of food allergies has increased worldwide due to changes in dietary habits, environmental and genetic factors, and the growing consumption of ultra-processed foods. Milk proteins, such as β-lactoglobulin (β-LG) and α-lactalbumin (α-LA), and egg proteins such as lysozyme (Lyz), are important allergens because of their stability against thermal and digestive treatments, which promotes their persistence in processed foods. Even trace amounts can cause reactions ranging from mild symptoms to severe anaphylaxis. Since there is no cure, prevention relies on avoiding exposure, requiring clear labeling and sensitive, selective analytical methods. Cross-contamination during production, transport, or packaging further increases the risk. Traditional sample preparation techniques, such as liquid-liquid extraction (LLE) and solid-phase extraction (SPE), have limitations including high solvent consumption, long extraction times, and low selectivity. Therefore, more efficient and sustainable microextraction techniques have been developed, such as stir bar sorptive extraction (SBSE), magnetic solid-phase extraction (MSPE), and thin-film microextraction (TFME). Although these techniques offer advantages in terms of efficiency and sustainability, their selectivity may be limited in complex matrices. The use of aptamers immobilized on these supports improves selectivity due to their high affinity and specificity for target analytes. Chemical contaminants also pose risks. Hydrogen peroxide (H₂O₂), widely used in disinfection and technological processes, can be toxic at high levels. Its detection is commonly based on chemiluminescence (CL), where H₂O₂ oxidizes luminol in the presence of a catalyst. While peroxidase enzymes are traditionally used, they present stability and cost limitations. Alternative materials such as metal–organic frameworks (MOFs) have emerged as promising catalysts. This thesis focuses on the development of innovative analytical methodologies for the determination of allergenic proteins and H₂O₂. The objectives include the development of aptamer-based microextraction supports and the evaluation of a Cu-MOF as a catalyst in chemiluminescence sensors. Overall, this work contributes to more sensitive, selective, robust, and sustainable analytical methods for food safety.
