Traditionally, the grafting of vinyl acetate onto chitosan has relied on chemical initiators, such as redox or peroxide systems. Herein, we report for the first time the gamma radiation-induced graft polymerization of vinyl acetate onto chitosan, providing a clean, initiator-free, and controllable route for generating chitosan-graft-poly(vinyl acetate) copolymers. The central hypothesis is that gamma irradiation activates the reactive sites on chitosan, whose selectivity toward hydroxyl or amino groups is modulated by solvent polarity, thereby governing the structural and thermal behavior of the resulting copolymer. The reaction was carried out at 25 kGy in different solvents (ethanol, hexane, ethyl acetate, chloroform, acetone, and acetic acid), and the resulting products were characterized by Fourier transform infrared and solid-state Nuclear magnetic resonance cross-polarization magic angle spinning, confirming the successful grafting of short poly(vinyl acetate) chains onto the chitosan backbone. Thermogravimetric analysis and differential scanning calorimetry revealed solvent-dependent variations in the thermal stability and transition temperatures, indicating distinct polymeric architectures. Viability and scratch assays with human dermal fibroblasts demonstrated the high biocompatibility and enhanced cell proliferation of the copolymers synthesized in hexane or acetic acid. These findings establish gamma radiation as a versatile tool for tailoring chitosan functionalization through solvent-controlled radical mechanisms, thereby providing new opportunities for the rational design of biocompatible carbohydrate-based materials.
The engineering of hybrid nanomaterials that synergistically couple adsorption and photocatalysis represents a transformative frontier in water remediation. Graphene oxide–titanium dioxide (GO–TiO2) hybrids have emerged as the archetypal platform for this goal. However, despite a decade of intense research, progress has often been hampered by empirical trial‒and‒error approaches that obscure fundamental design principles, particularly in the active engineering of the interface for adsorption and reactivity, where structure–property–performance relationships remain poorly understood. In this mini-review, the multifaceted performance of GO–TiO2 hybrids is deconstructed, and a rational design framework is proposed based on three pivotal descriptors: the oxidation degree of GO, the intrinsic electronic structure of the individual components, and the compositional ratio. While these descriptors may not be interdependent in a strict sense, it is contended that their combination exerts a decisive influence on the efficiency and characteristics of the final hybrid material. The literature is critically interrogated through this lens, revealing persistent mechanistic ambiguities—including conflicting reports on bandgap modulation—and reframing the role of adsorption from a passive prelude to an active modulator of interfacial kinetics, demanding advanced surface engineering strategies to actively tune its affinity and selectivity. It is contended that the resolution of these foundational inconsistencies in the binary model is an essential prerequisite for the successful advancement of the field towards more complex ternary and quaternary architectures. By establishing this fundamental design workflow grounded in interfacial descriptors, a paradigm shift is advocated towards rationally designed, multi-component photocatalysts, thereby paving the way for the next generation of sustainable water treatment technologies.
Rapid removal of chemically diverse organic pollutants remains a major challenge in aqueous decontamination. In this study, atmosphere-controlled defect engineering was used to activate anatase TiO2 as a rapid adsorbent operating on the minute scale, exhibiting low charge selectivity under the investigated conditions. A reduced black TiO2 (B-TiO2), produced by inert annealing, achieved approximate to 100% removal of cationic methylene blue within similar to 6 min and approximate to 91% uptake of anionic methyl orange within similar to 3 min, whereas pristine and air-annealed TiO2 showed only marginal adsorption under identical conditions. Correlative structural and surface-sensitive analyses indicated that this behaviour was associated with a chemically activated near-surface region enriched in reduced titanium contributions, defect-associated or non-lattice oxygen environments and a locally perturbed anatase framework, together with finely dispersed carbon-related motifs integrated within the oxide matrix. Adsorption kinetics were described, within experimental resolution, by pseudo-second-order fitting, while intraparticle diffusion analysis supported sequential regimes initiated by rapid interfacial attachment. Equilibrium analysis yielded apparent maximum capacities of 6.116 mg g(-1) for methylene blue and 2.950 mg g(-1) for methyl orange, reflecting adsorption governed by surface heterogeneity for cationic species and an apparent saturation-type response for anionic uptake. Overall, controlled surface non-stoichiometry emerges as a viable strategy to enhance adsorption kinetics in TiO2, providing a transferable design framework for developing oxide-based adsorbents for sustainable water-treatment applications.
In order to reduce climate change rate, sustainable energy sources have emerged as a promising solution. Nevertheless, such energy sources require the use of energy storage systems to match optimal performance. Within this context, the design and synthesis of materials, which can provide enhanced energy storage, stand as a major research field. Herein, we established an eco-friendly method to synthesize a coordination polymer (CP) based on benzene-1,4-diboronic acid (BDBA) and Co(II) atoms, entitled Co-BDBA, using only water in the whole synthetic process. Co-BDBA is a crystalline material comprising a mesoporous structure with specific surface area and a mean pore size of 104.9 m2 g−1 and 3.4 nm, respectively. Remarkably, Co-BDBA features enhanced electrical properties, compared to other reported CPs. Specifically, arguably due to a better orbital overlap in the coordinate bonds, Co-BDBA exhibits a band gap of 3.41 eV. Furthermore, Co-BDBA might transport charge carriers by a band-like mechanism. As a result of the enhanced electrical properties, Co-BDBA shows high electrochemical reversibility with a specific capacitance of 345 F g−1 at 1 A g−1 and superior capacitance retention of 109.7
This work reports the use of the Hot-Filament Chemical Vapor Deposition (HFCVD) technique to synthesize nanostructured molybdenum oxide thin films and to explore their functionality as active layers in conductometric sensor devices. The influence of annealing temperature on the morphology, structure, optical properties, and thermal stability of the synthesized films was analyzed. Morphological characterization by SEM and TEM revealed progressive coalescence, sinterization, and densification of the particles with increasing temperature. Raman and XPS results confirmed the formation of the orthorhombic α-MoO3 phase, while the band gap energies between 2.6–3.0 eV obtained by UV-Vis spectroscopy corroborated its n-type semiconductor nature. TGA analyses showed lower thermal stability than the commercial material, but with more stable behavior at 500 °C. Finally, the electrical evaluation of the sensor device with the active layer corresponding to the film demonstrated a reproducible response to UV excitation and thermal variations, confirming its functional potential for gas-sensing applications.
The urgent need for efficient methods to detect, monitor, and capture toxic and hazardous sulfur dioxide (SO2) has driven the development of new devices for this purpose. Due to its significant corrosiveness and high toxicity, a key requirement for adsorbent materials is their ability to withstand deterioration, alongside possessing high gas sensitivity and selectivity. Within this domain, supramolecular chemistry has made substantial inroads through the development of innovative porous materials formed by the self-assembly of molecular building blocks, driven by diverse interactions. The complex architectures that result can be categorised as either extended networks, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), or as molecular cages, including metal-organic cages (MOCs) and porous organic cages (POCs). These materials have demonstrated high capture capacities, extremely sensitive detection limits, and even active sites for the catalytic transformation of adsorbed molecules. This review aims to highlight the primary contributions of these supramolecular materials to the experimental adsorption of SO2, along with their most remarkable results.
A hybrid MgAlFe-LDH/UiO-66-NH2 material has been developed for the efficient detection of SO2, showing an exceptionally low detection limit of only 0.72 ppm, which is considerably lower in comparison to UiO-66-NH2 (739 ppm). Spectroscopic studies suggest that the preferential oxidation of SO2 to SO42-, catalysed by the Fe3+ centres within MgAlFe-LDH, is the key factor in the enhanced fluorescence response. This process in situ generates Fe2+ sites and favours the interlaminar sequestration of SO2, preventing direct interaction with the active sites of UiO-66-NH2.
Coordination chemistry has garnered significant attention across various domains due to its versatility in both academic research and industrial applications, with catalysis being a particularly prominent area of distinction. The exceptional performance of coordination chemistry-based compounds and materials, such as metal-organic frameworks (MOFs), in catalytic processes is ascribed to their formidable physical and structural attributes. Primarily, possessing accessible vacant active metal sites is crucial for promoting the formation of intermediate or transition states involving the species of interest. This feature facilitates effective interactions between reactant molecules and the active sites of these compounds and supramolecular assembled materials. Professor Tilley's contributions have substantially advanced the field of coordination chemistry for catalysis, as he has consistently aimed to enhance the reactivity and selectivity of these compounds in reactions such as hydrosilylation and water oxidation/evolution. This review aims to summarize the catalytic properties of coordination compounds, in which his contributions have pioneered the incorporation of transition metals into catalysts, and compare them with MOFs applied with the same aim, as heterogeneous catalysts, for these reactions.
MOF-composites are porous materials with a large surface area and functionalized with other types of materials (metallic nanoparticles, oxides, zeolites, quantum dots, etc.), affording optimal and chemically stable structures for wastewater remediation. They are primarily used for the selective adsorption of contaminants such as heavy metals, dyes, pharmaceuticals, and pesticides. Furthermore, they can act as photocatalysts for the degradation of organic compounds under ultraviolet and visible light, as well as serve as supports in advanced oxidation processes. Their adjustable structure allows them to be designed according to the type of contaminant, and they are currently reusable, which favours their sustainability. Due to their efficiency and versatility, they represent an innovative and exciting alternative for the treatment of contaminated water.
The MgAlFe-LDH/UiO-66-NH 2 material demonstrated a low SO 2 detection limit of only 0.72 ppm.
We present an experimental investigation related to a hybrid material comprising a Zr(IV)-based metal-organic framework (UiO-66-NH2) and a layered double hydroxide (NiCo-LDH). This material is designed to address the challenges of SO2 detection and sensing. The NiCo-LDH-(3-chloropropyl)trimethoxysilane (CPTMS)/UiO-66-NH2 composite exhibited moderate SO2 sorption at low pressures (0.8 mmol g(-1) at 0.03 bar) and a detection limit of 21.65 ppm, which is 97% lower than that of unmodified UiO-66-NH2 (739.1 ppm). Furthermore, X-ray photoelectron spectroscopy (XPS), UV-vis and linear voltammetry measurements provided insight into the fluorescence detection mechanism, suggesting that hydrogen bonds and dipole-dipole interactions are the main involved forces of attraction between SO2 molecules and NiCo-LDH-CPTMS/UiO-66-NH2 materials. Additionally, the improved detection was found to be associated with the donation of electron density from the metal-organic framework (MOF) to the LDH, as evidenced by spectroscopic and electrochemical data.
The MFM-300(M) series (M = Al(III), Sc(III), Cr(III), and In(III)) have previously demonstrated excellent sulfur dioxide (SO2) adsorption capabilities, however, their potential as fluorescent SO2 sensors remains unexplored. Here, this work presents a comparative study of their fluorescence response upon SO2 exposure, with a particular focus on the role of the metal centers. MFM-300(Al) exhibits the strongest emission and highest quenching upon SO2 exposure, attributed to localized interactions with µ2-OH functional groups and aromatic sites. In contrast, Sc(III) and In(III) analogues show moderate quenching via charge transfer at the semi-open metal sites, while Cr(III) remains weakly emissive. Density Functional Theory (DFT) calculations employing periodic boundary conditions are conducted to characterize the electronic structure of MFM-300(M), to elucidate the role of metal centers in SO2 retention and to assess the semiconducting nature of these metal- organic frameworks (MOFs).
MUF-16 is a porous metal-organic framework comprising cobalt(II) ions and 5-aminoisophthalate ligands. Here, we measured its reversible SO2 adsorption-desorption isotherm around room temperature and up to 1 bar and observed a high capacity for SO2 (2.2 mmol g(-1) at 298 K and 1 bar). The uptake of SO2 was characterized by Fourier transform infrared (FT-IR) spectroscopy, which indicated hydrogen bonding between the SO2 guest molecules and amino functional groups of the framework. The location and packing of the SO2 molecules were confirmed by computational studies, namely, density functional theory (DFT) calculations of the strongest adsorption site and grand canonical Monte Carlo (GCMC) simulations of the adsorption isotherm. Furthermore, MUF-16 showed a remarkable selective fluorescence response to SO2 compared to other gases (CO2, NO2, N-2, O-2, CH4, and water vapor). The possible fluorescence mechanism was determined by using time-resolved photoluminescence. Also, the limit of detection (LOD) was calculated to be 1.26 mM (similar to 80.72 ppm) in a tetrahydrofuran (THF) solution of SO2.
Diabetes mellitus (DM) prevalence is rising worldwide. Current therapies comprising subcutaneous insulin injections can cause adverse effects such as lipodystrophy, local reactions like redness and swelling, fluid retention, and allergic reactions. Nanoparticle carriers for oral insulin are groundbreaking compared to existing methods because they are non-invasive treatments, showing operational convenience, controlled release profile, and ability to simulate the physiological delivery route into the bloodstream. These systems improve patient adherence and have demonstrated the potential to lower blood glucose levels in DM. We present a systematic review and meta-analysis aimed at compiling relevant data to pave the way for developing innovative nano- and microparticles for the oral delivery of insulin. Our analysis of 85 articles revealed that the diminution of glucose levels is not proportional to the administered insulin dosage, which ranged from 1 to 120 International Units (IU). The meta-analysis data indicated that 25 IU of encapsulated porcine insulin did not produce a statistically significant outcome (p = 0.93). In contrast, a dosage of 30 IU was efficacious in eliciting an optimal hypoglycemic effect compared to excipient controls. Parameters such as a high degree of encapsulation ( 90
Copper deficiency can trigger various diseases such as Amyotrophic Lateral Sclerosis (ALS), Parkinson's disease (PD) and even compromise the development of living beings, as manifested in Menkes disease (MS).
The article focuses on preparing a nanoformulation based on hydrotalcite and glycyrrhizic acid (GA), seeking a hepatoprotective effect. For this purpose, hydrotalcite-GA formulations were prepared by varying the following conditions to obtain optimal systems in terms of size and PDI (the lowest values), and Z potential (the highest values): (i) type of hydrotalcite (obtained by co-precipitation or calcined hydrotalcite); method used (ultrasound or high shear stirring), and (iii) type of stabilizer (Tween®80 or Pluronic® F-127). The best results were obtained using hydrotalcite obtained by co-precipitation, with high shear stirring and adding a stabilizer, either Tween®80 (HT-T80-GA: mean particle size = 315 nm, PDI = 0.18, Z potential = -20.93) or Pluronic® F-127 (HT-PF127-GA: mean particle size = 307 nm; PDI = 0.27, Z potential = -21.03). After stability studies, the HT-T80-GA formulation was chosen to study antioxidant activity, cytotoxicity, and intracellular penetration capacity. Although the hepatoprotective effect of GA in solution allowed a high viability and antioxidant activity, the fact of including GA in the HT-T80-GA formulation favored its penetration into hepatocytes, with a decrease in Caspase-3/7 expression of C-9 hepatocyte cells treated with H2O2, suggesting the capacity to inhibit apoptosis.