Search Results (29)

The pressing issues of organic pollutants contamination of aquatic ecosystems challenges current research. Herein, we prepared three melamine-based POFs, to remove organic dyes from water. Melamine was polymerized with 1,4-dibromobutane (POF-1,4), terephthalaldehyde (POF-TerA) and trimesic acid (POF-TriA), obtaining POFs of different structural order degree and aromaticity. POFs were characterized using FT-IR spectroscopy, thermal gravimetric analysis, BET, powder X-ray diffraction and scanning electron microscopy. They were employed to remove cationic (Rhodamine B, RhB and Methylene Blue, MB) and anionic dyes (Methyl Orange, MO and Eosin Yellow, EY), using UV-vis investigation. The adsorption process was studied from the kinetic and thermodynamic points of view and reusing the best adsorbent was also considered. Data collected evidence that adsorption capacity depends on the POF structure, with maximum adsorption capacity, according to Langmuir isotherm model, of 329 mg/g for POF-1,4/MO and 472 mg/g for POF-TerA/RhB. Interactions involved in the adsorption were also elucidated. Comparison with reported data demonstrates that our materials show comparable performance to some previously reported systems. Furthermore, POF-TriA, is effective for dye mixtures and reusable three times without performance loss, after washing with methanol, avoiding harsh acidic/basic treatments. Results obtained systematically relate the adsorption efficiency to structural features of melamine-based POFs, representing useful support in designing such materials to remove selected classes of contaminants. Full article

Background/Objectives: The use of the drug delivery system is notable for the systemic improvement of low orally bioavailable compounds, such as the bioactive phenolic acid, syringic acid. Innovative techniques are employed to enhance the performance of certain drug delivery systems. In connection with our previously reported journal with the use of MIL-100(Fe) as a drug carrier for syringic acid, this study utilized a mixed-linker synthesis of syringic acid and trimesic acid and characterized the properties in comparison with the unmodified MIL-100(Fe) through a solid solution approach. Methods: Modified MIL-100(Fe) was synthesized by substituting different molar concentrations of syringic acid for trimesic acid through de novo synthesis. Simple impregnation of syringic acid was carried out at 12, 24, 36, and 48 h and at 1:1 and 1:2 molar ratios of MIL-100(Fe) to syringic acid. Characterization was performed via PXRD, FTIR, BET, SEM, and DLS. In vivo studies included acute oral toxicity testing (OECD 425) and bioavailability assessment in Sprague Dawley rats. Results: The optimized amount of syringic acid to be substituted for trimesic acid is 0.10 mmol, as confirmed by the value of the PXRD. Optimized drug loading of 66.85 ± 0.004% was achieved using a 1:2 ratio of syringic acid to MIL-100(Fe)-10% over 36 h. Structural modifications were confirmed via FTIR, specifically through shifts at 1239.2 cm⁻¹, while TGA demonstrated thermal stability up to approximately 350 °C. Morphological analysis by SEM showed octahedral particles (210.70 ± 1.23 nm), and a decrease in BET surface area post-loading verified successful encapsulation. While in vitro release was media-dependent, toxicity studies at 2000 mg/kg showed no adverse effects; notably, SGOT and SGPT levels decreased, though BUN and creatinine levels rose. Compared to pure oral syringic acid, the SYA@MIL-100(Fe)-10% formulation demonstrated a 5.09-fold increase in relative bioavailability. Furthermore, it outperformed intraperitoneal administration of the drug by 1.65-fold. Conclusions: Modification of MIL-100(Fe) by incorporating syringic acid into the framework as a substituted organic linker indicates that SYA@MIL-100(Fe)-10% is a safe and effective delivery system for syringic acid, enhancing oral bioavailability. To the best of our knowledge, this is the first study to investigate the mixed-linker synthesis of MIL-100(Fe) by utilizing syringic acid as a structural co-ligand, rather than solely as an encapsulated guest. While MIL-100(Fe) has been extensively employed as a carrier for various therapeutics, this research uniquely integrates the active agent into the framework lattice itself to modulate porosity and loading capacity, subsequently evaluating its systemic performance in an in vivo model. Full article

The photo-Fenton process is an advanced oxidation method widely employed in environmental remediation. Herein, we developed a novel metal–organic framework@hydrogen-bonded organic framework (MOF/HOF) composite with excellent photo-Fenton-like activity for the efficient degradation of organic dye methylene blue (MB). Cu-based MOF (CuBTC) was firstly prepared via the solvothermal method, then melamine (MA) and trimesic acid (TMA)-based HOF (MA-TMA) was grown in situ on CuBTC with hydrogen bonding interactions to produce the MOF/HOF composite CuBTC-MA. The CuBTC-MA composite could catalyze H₂O₂ to produce active substances for efficient MB degradation. The degradation rate constant of the CuBTC-MA composite was 4.4 times and 16.7 times higher than that of CuBTC and MA-TMA. The remarkably enhanced performance was attributed to the synergistic effect between the efficient separation of electron–holes supported by the type-II heterojunction structure of the CuBTC-MA composite and the Cu(I)/Cu(II) inter-conversion. The CuBTC-MA composite demonstrated exceptional repeatability and maintained a stable performance across a broad pH range. This study provided a novel paradigm for engineering heterogeneous MOF/HOF heterostructures, demonstrating significant potential in advancing photo-Fenton-like catalytic systems for the efficient environmental remediation of organic pollutants through synergistic charge separation and radical generation mechanisms. Full article

Basolite^® F300 and synthetic nano-{Fe-BTC} MOFs, two iron-trimesate MOFs, have been investigated, demonstrating broad pH range adsorption for monomethylarsenate (MMA), cacodylic acid (DMAA), 4-aminophenylarsonate (ASA), and arsenate, while arsenite adsorption was notable at pH > 9.5. A similar uptake trend was found for both MOFs, with Basolite^® F300 being the more effective given its higher porosity and greater surface area. Pseudo-second-order kinetic models were followed by MMA, DMAA, ASA, and As(V), suggesting a chemisorption mechanism with arsenic species diffusion into MOF pores as the controlling step. Equilibrium data for DMAA and ASA fit the Langmuir model whereas MMA adsorption fits the Redlich–Peterson model. The uptake of MMA, DMAA, and ASA by both Fe-MOFs is mainly attributed to their coordination with Fe(III). Aromatic units in ASA enhance adsorption through П-П stacking interactions. The competition between all arsenic species for the sorption sites of the Fe-MOFs led to an uptake decrease of 10% for MMA and ASA and higher than 30% for DMAA and As(V) with respect to the individual uptakes. The Fe-MOFs can be reused for four cycles by washing with acidic methanol. Basolite^® F300 and synthetic nano-{Fe-BTC} effectively removed organic and inorganic arsenic species, exhibiting rapid adsorption, selective uptake, stability, and easy regeneration. Full article

Efficient xylene isomers’ separation remains a challenge due to their similar kinetic diameter and boiling points, particularly for the separation of the immediate size of meta-xylene (MX). A metal–organic framework (MOF) membrane offers the opportunity to realize the isomers’ separation due to the highly tunable pore size and pore environment. Herein, an In-based hierarchic MOF (MIL-100) with a size of 0.77 nm was screened, aiming at the realization for isomer separation through pore size matching. Meanwhile, the polar microenvironment in the MOF channel built through trimesic acid ligands contributes to the higher affinity to the MX relative to the PX. With the equimolar feed mixture of MX/PX, the optimal membrane demonstrated a total flux of 7.6 kg·m⁻²·h⁻¹ and an MX/PX separation factor of 2.54 at room temperature through pervaporation. Such performance highly indicates the possibility for efficient liquid xylene separation in future. Full article

Arsenic contamination of water endangers the health of millions of people worldwide, affecting certain countries and regions with especial severity. Interest in the use of Fe-based metal organic frameworks (MOFs) to remove inorganic arsenic species has increased due to their stability and adsorptive properties. In this study, the performance of a synthesized Nano-{Fe-BTC} MOF, containing iron oxide octahedral chains connected by trimesic acid linkers, in adsorbing As(III) and As(V) species was investigated and compared with commercial Basolite^®F300 MOF. Despite their similarities in composition, they exhibit distinct structural characteristics in their porosity, pore size, and surface areas, which affected the adsorption processes. The kinetic data of the adsorption of As(III) and As(V) by both Fe-MOFs fitted the pseudo second-order model well, with the kinetic constant being higher for Basolite^®F300 given its higher porosity. Intraparticle diffusion was, in both cases, the rate controlling step with the contribution of film diffusion in the adsorption processes, which achieved equilibrium after 1 h. The maximum adsorption capacity for As(V), 41.66 mg g⁻¹, was obtained with Basolite^®F300 at the 6.5–10 pH range, whereas Nano-{Fe-BTC} showed a different behaviour as maximum adsorption (14.99 mg g⁻¹) was obtained at pH 2. However, both adsorbents exhibited the same performance for As(III) adsorption, which is not adsorbed at pH < 9. The Langmuir adsorption isotherm model fitted well for As(III) and As(V) adsorption by Nano-{Fe-BTC} and As(III) by Basolite^®F300, whereas the Freundlich model fitted best for As(V) given its superior structural properties. Full article

This work presents the synthesis and characterization of materials that contain Sn metal clusters formed by ligands of trimesic acid (Sn-BTC) or 5-sulfobenzene-1,3-dicarboxylic acid (Sn-H₃-5-SIP). These catalysts were used to convert levulinic acid with ethanol to produce ethyl levulinate under mild reaction conditions. The characterization results confirmed that Sn is mainly present in the cassiterite crystalline phase with a tetragonal rutile structure in octahedral and tetrahedral coordination in the materials. The assembly of trimesic acid (a hard base) with metal species (Sn) results in the formation of acid and thermally stable metal–organic frameworks. The use of 5-sulfobenzene-1,3-dicarboxylic acid instead of trimesic acid in the synthesis incorporates sulfonic groups in the material, enhancing the total acidity of the Sn-H₃-5-SIP catalyst compared to the Sn-BTC material. The Sn-H₃-5-SIP catalyst exhibited the highest catalytic activity when converting levulinic acid with ethanol, resulting in a turnover frequency (TOF) of 0.0495 s⁻¹, which is a 50% increase compared to the TOF of the Sn-BTC catalyst (0.0329 s⁻¹). This result can be attributed to its higher concentration of acid sites (2.23 ± 0.05 mmol H⁺/g_cat) and specific area (139 m²/g). Thus, materials containing tin metal clusters and sulfonic groups are promising materials that could be used as catalysts for synthesizing ethyl levulinate under mild reaction conditions. Full article

The coordination polymer was obtained based on cobalt trimesinate. It was characterized by elemental analysis, IR spectroscopy, X-ray diffraction analysis and scanning electron microscopy. The polymer was studied as a sorbent for solid-phase extraction of tetracycline antibiotics. Cobalt trimesinate had a high adsorption capacity (400 mg/g). Antibiotic adsorption followed the pseudo-second-order kinetic model and the Freundlich isotherm model. The process proceeded spontaneously, as indicated by the calculated thermodynamic parameters. The resulting coordination polymer has good stability and recyclability. The possibility of using cobalt trimesinate for the determination of tetracycline in various milk samples was investigated. This work holds great promise for the development and application of a cobalt trimesinate-based coordination polymer for use in sample preparation to replace the time-consuming vacuum evaporation procedure with a relatively simple solid-phase extraction procedure. Full article

We designed 0D, 1D, and 2D supramolecular assemblies made of diaryliodonium salts (functioning as double σ-hole donors) and carboxylates (as σ-hole acceptors). The association was based on two charge-supported halogen bonds (XB), which occurred between I^III sites of the iodonium cations and the carboxylate anions. The sequential introduction of the carboxylic groups in the aryl ring of the benzoic acid added a dimension to the 0D supramolecular organization of the benzoate, which furnished 1D-chained and 2D-layered structures when terephthalate and trimesate anions, correspondingly, were applied as XB acceptors. The structure-directing XB were studied using DFT calculations under periodic boundary conditions and were followed by the one-electron-potential analysis and the Bader atoms-in-molecules topological analysis of electron density. These theoretical methods confirmed the existence of the XB and verified the philicities of the interaction partners in the designed solid-state structures. Full article

Rare-earth (RE)-based metal organic frameworks (MOFs) are quickly gaining popularity as flexible functional materials in a variety of technological fields. These MOFs are useful for more than just conventional uses like gas sensors and catalyst materials; in fact, they also show significant promise in emerging technologies including photovoltaics, optical, and biomedical applications. Using yttrium and europium as ionic host centres and dopants, respectively, and 1,3,5-benzenetricarboxylic acid (H₃-BTC) as an organic linker, we describe a simple and green approach for the fabrication of RE-MOFs. Specifically, Y-BTCs and Eu-doped Y-BTCs MOFs have been synthesised in a single step using an eco-friendly method that makes use of ultrasound technology. To establish a correlation between the morphological and structural properties and reaction conditions, a range of distinct reaction periods has been employed for the synthetic processes. Detailed analyses of the synthesised samples through powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM), and Fourier-transform infrared spectroscopy (FT-IR) have confirmed the phase formation. Furthermore, thermal analyses such as thermogravimetric analysis (TGA) have been employed to evaluate the thermal stability and structural modifications of the Y-BTC and Eu-doped Y-BTC samples. Finally, the luminescent properties of the synthesised samples doped with Eu³⁺ have been assessed, providing an evaluation of their characteristics. As a proof of concept, an Eu-doped Y-BTC sample has been applied for the sensing of nitrobenzene as a molecule test of nitro derivatives. Full article

Clinoptilolite (CP) was successfully synthesized via a hydrothermal route in the presence of polyethylene glycol (PEG), and it was then delaminated by washing using Zn²⁺ containing acid. HKUST-1, as one kind of the Cu-based MOFs, showed a high CO₂ adsorption capacity owing to its large pore volume and specific surface area. In the present work, we selected one of the most efficient ways for preparing the HKUST-1@CP compounds via coordination between exchanged Cu²⁺ and ligand (trimesic acid). Their structural and textural properties were characterized by XRD, SAXS, N₂ sorption isotherms, SEM, and TG-DSC profiles. Particularly, the effect of the additive PEG (average molecular weight of 600) on the induction (nucleation) periods and growth behaviors were detailed and investigated in the hydrothermal crystallization procedures of synthetic CPs. The corresponding activation energies of induction (E_n) and growth (E_g) periods during crystallization intervals were calculated. Meanwhile, the pore size of the inter-particles of HKUST-1@CP was 14.16 nm, and the BET specific area and pore volume were 55.2 m²/g and 0.20 cm³/g, respectively. Their CO₂ and CH₄ adsorption capacities and selectivity were preliminarily explored, showing 0.93 mmol/g for HKUST-1@CP at 298 K with the highest selective factor of 5.87 for CO₂/CH₄, and the dynamic separation performance was evaluated in column breakthrough experiments. These results suggested an efficient way of preparing zeolites and MOFs composites that is conducive to being a promising adsorbent for applications in gas separation. Full article

The substrate N¹, N³, N⁵-tris(2-hydroxyphenyl)benzene-1,3,5-tricarboxamide (Sensor A) was prepared in the reaction of 1,3,5-benzenetricarboxylic acid (trimesic acid) and o-aminophenol in ethanol. The prepared organic sensor fulfills the chemiluminescent requirements including a luminophore, spacer, and suitable binding receptor that distress the probe’s luminescent features, providing selective and sensitive detection of mercury and iron ions in aqueous solutions. The sensor selectively detects mercury and iron ions in a water matrix containing various metal ions, including sodium, calcium, magnesium, zinc, and nickel. Strong and immediate binding was observed between mercury ions and the substrate at pH 7.0 with a binding affinity toward Hg²⁺ 9-fold higher than that observed for iron sensor binding affinity, which makes the substrate a distinctive luminescence sensor for mercury detection at ambient conditions. The sensor shows a linear response toward Hg²⁺ in the concentration range from 50 ppb to 100 ppm (2.0 × 10⁻⁸ to 4.2 × 10⁻⁵ M) with a limit of detection of 2 ppb (1.0 × 10⁻⁸ M). Further, Sensor A provides linear detection for iron ions in the range from 10 ppb to 1000 ppm (1.5 × 10⁻⁸ to 1.5 × 10⁻³ M). The measured adsorption capacity of Sensor A toward mercury ions ranged from 1.25 to 1.97 mg/g, and the removal efficiency from water samples reached 98.8% at pH 7.0. The data demonstrate that Sensor A is an excellent probe for detecting and removing mercury ions from water bodies. Full article

PCL-based biodegradable shape-memory polymers (SMPs) are limited in strength, which restricts their practical applications. In this study, a series of novel SMPs, composed of poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), and poly(ε-caprolactone) (PCL), were synthesized and cross-linked using planar (benzene-1,3,5-tricarboxylic acid, BTC) or non-planar (glycerol, GC) cross-linkers via the one-pot method. The influence of different kinds of cross-linkers and hard segments of copolyesters on the thermal properties, crystallization behavior, mechanical properties, shape-memory performance, and degradability was investigated by FT-IR, ¹H-NMR, DSC, DMA, TGA, XRD, tensile test, intrinsic viscosity measurement, and in vitro enzymatic degradation test. The results indicate that the tensile strength of the copolyester can be significantly improved from 27.8 to 53.2 MPa by partially replacing PET with PEN while maintaining its shape-memory characteristics. Moreover, a small amount of cross-linking modification leads to higher temperature sensitivity, improved shape recovery rate at third round (R_r(3) = 99.1%), and biodegradability in the cross-linked PET/PEN/PCL shape-memory polymers. By changing the crystallization morphology and cross-linking forms of the material, we have developed a shape-memory polymer with both high strength and a high shape recovery rate, which provides a new strategy for the development of shape-memory materials. Full article

Chitosan exhibits unique properties making it a suitable material for drug delivery. Considering the rising popularity of hydrogels in this field, this work offers a comprehensive study of hydrogels constituted by chitosan and cross-linked with 1,3,5-benzene tricarboxylic acid (BTC; also known as trimesic acid). Hydrogels were prepared by cross-linking chitosan with BTC in different concentrations. The nature of the gels was studied through oscillatory amplitude strain and frequency sweep tests within the linear viscoelastic region (LVE) limit. The flow curves of the gels revealed shear thinning behavior. High G′ values imply strong cross-linking with improved stability. The rheological tests revealed that the strength of the hydrogel network increased with the cross-linking degree. Hardness, cohesiveness, adhesiveness, compressibility, and elasticity of the gels were determined using a texture analyzer. The scanning electron microscopy (SEM) data of the cross-linked hydrogels showed distinctive pores with a pore size increasing according to increasing concentrations (pore size range between 3–18 µm). Computational analysis was performed by docking simulations between chitosan and BTC. Drug release studies employing 5-fluorouracil (5-FU) yielded a more sustained release profile with 35 to 50% release among the formulations studied in a 3 h period. Overall, this work demonstrated that the presence of BTC as cross-linker leads to satisfactory mechanical properties of the chitosan hydrogel, suggesting potential applications in the sustained release of cancer therapeutics. Full article

Metal–organic frameworks (MOFs) attract growing interest in biomedical applications. Among thousands of MOF structures, the mesoporous iron(III) carboxylate MIL-100(Fe) (MIL stands for the Materials of Lavoisier Institute) is among the most studied MOF nanocarrier, owing to its high porosity, biodegradability, and lack of toxicity. Nanosized MIL-100(Fe) particles (nanoMOFs) readily coordinate with drugs leading to unprecedented payloads and controlled release. Here, we show how the functional groups of the challenging anticancer drug prednisolone influence their interactions with the nanoMOFs and their release in various media. Molecular modeling enabled predicting the strength of interactions between prednisolone-bearing or not phosphate or sulfate moieties (PP and PS, respectively) and the oxo-trimer of MIL-100(Fe) as well as understanding the pore filling of MIL-100(Fe). Noticeably, PP showed the strongest interactions (drug loading up to 30 wt %, encapsulation efficiency > 98%) and slowed down the nanoMOFs’ degradation in simulated body fluid. This drug was shown to bind to the iron Lewis acid sites and was not displaced by other ions in the suspension media. On the contrary, PS was entrapped with lower efficiencies and was easily displaced by phosphates in the release media. Noticeably, the nanoMOFs maintained their size and faceted structures after drug loading and even after degradation in blood or serum after losing almost the totality of the constitutive trimesate ligands. Scanning electron microscopy with high annular dark field (STEM-HAADF) in conjunction with X-Ray energy-dispersive spectrometry (XEDS) was a powerful tool enabling the unraveling of the main elements to gain insights on the MOF structural evolution after drug loading and/or upon degradation. Full article