Iron Trimesate Research Articles

Acetic Acid-Modulated Room Temperature Synthesis of MIL-100 (Fe) Nanoparticles for Drug Delivery Applications.

Due to their flexible composition, large surface areas, versatile surface properties, and degradability, nanoscale metal organic frameworks (nano MOFs) are drawing significant attention in nanomedicine. In particular, iron trimesate MIL-100 (Fe) is studied extensively in the drug delivery field. Nanosized MIL-100 (Fe) are obtained mostly by microwave-assisted synthesis. Simpler, room-temperature (RT) synthesis methods attract growing interest and have scale-up potential. However, the preparation of RT MIL100 is still very challenging because of the high tendency of the nanoparticles to aggregate during their synthesis, purification and storage. To address this issue, we prepared RT MIL100 using acetic acid as a modulator and used non-toxic cyclodextrin-based coatings to ensure stability upon storage. Hydrodynamic diameters less than 100 nm were obtained after RT synthesis, however, ultrasonication was needed to disaggregate the nanoparticles after their purification by centrifugation. The model drug adenosine monophosphate (AMP) was successfully encapsulated in RT MIL100 obtained using acetic acid as a modulator. The coated RT MIL100 has CD-exhibited degradability, good colloidal stability, low cytotoxicity, as well as high drug payload efficiency. Further studies will focus on applications in the field of cancer therapy.

Tailoring MOFs to Biomedical Applications: A Chimera or a Concrete Reality? The Case Study of Fe-BTC by bio-friendly Mechanosynthesis

ABSTRACT We point-out an exceptional tailorability of iron(III) trimesate metal-organic framework to bio-friendly conditions. This is particularly attractive in sight of one-pot immobilization of biomolecules for biomedical applications. Synthesis is carried out via mechanochemical approach under green, biocompatible conditions without additional solvents, in just 1 hour, at room temperature. Solvents are proven to be unnecessary to build the framework, in contrast to solution-based methods. Microstructure and thermal stability of the material are not affected by pH. Conversely, textural properties can be tuned by simply varying the amount of base.

Utilization of lignin separated from pulp and paper wastewater for lead removal

Lignin, which is a major by-product of paper and pulp processing is effectively recovered and repurposed for lead (Pb) removal. This study aimed to extract lignin from real pulp and paper wastewater and then utilized it as an adsorbent for water contaminated-Pb removal. Two types of extracted lignin were compared including 1) lignin precipitated by hydrochloric acid (LP) and 2) lignin separated by the coagulation-flocculation process using iron(III) trimesate, a type of the iron-based metal–organic framework, (LPF). They were characterized using a scanning electron microscope (SEM), nitrogen adsorption–desorption, Fourier transform infrared (FTIR) spectroscopy, X-ray fluorescence (XRF), and thermogravimetric analysis (TGA). LPF showed amorphous characteristics, surface area, and porous increased, and iron oxide appeared compared to LP. Batch experiment results revealed that LPF decreased Pb contamination in water by approximately 65 % in 60 min. Adsorption kinetics had a better fit to the pseudo-second-order model. The adsorption process occurred spontaneously and was endothermic, following the physisorption mechanism. The adsorption isotherm model fitted the Freundlich isotherm well, while parameter (n) as 2.015 implied favorable adsorption. The outcomes of the research might open the door to the creation of lignin-based adsorbents for the elimination of Pb in wastewater.

Cover Feature: Formation of Iron (III) Trimesate Xerogel by Ultrasonic Irradiation (Eur. J. Inorg. Chem. 15/2022)

The Cover Feature shows the ultrasound-assisted formation of Fe-BTC gels, iron carboxylate metal-organic frameworks (MOFs) constructed from iron ions and 1,3,5 benzenetricarboxylic acid linkers. The gels were obtained by two different procedures: ultrasonic irradiation (US) of different water solutions containing the linker and iron nitrate, with or without the additive tetramethylammonium hydroxide. Gelation was observed regardless of the duration of the irradiation, the precursor concentration, the additive, or the US apparatus used. While drying, the wet gels underwent shrinking and cracked into tiny fractions of transparent solid xerogels consisting of interconnected spherical, thermally stable nanoparticles with a permanent microporous structure. The authors acknowledge Prof. Christoph Hartl for gently assisting with the cover′s graphic layout. More information can be found in the Research Article by G. Mannias, M. Pilloni and co-workers.

Formation of Iron (III) Trimesate Xerogel by Ultrasonic Irradiation

AbstractFe−BTC materials have attracted vast attention owing to their high chemical stability, adaptable synthesis, and potential applications. Herein, we describe, for the first time, the preparation of iron trimesate gels by ultrasonic (US) irradiation of an aqueous solution of Iron (III) nitrate and trimesic acid. Two different procedures were used: (1) sonication for 10 or 20 minutes, (2) 3 minutes sonication under controlled pH (pH 3–5). After drying, stable Fe−BTC xerogels were obtained from both procedures. The xerogels consisted of interconnected spherical nanoparticles with similar microstructure when analyzed by FT‐IR and PXRD and similar thermal behavior under oxygen in the range of 25–900 °C. When analyzed by Nitrogen adsorption‐desorption at 77 K, all samples showed a permanent porosity with a narrow micropore distribution below 10 Å. Different textural properties were found among samples obtained with the same procedure. The product of 10 minutes sonication had a specific surface area (SSA) of 1042 m2/g.

Microencapsulated Isoniazid-Loaded Metal-Organic Frameworks for Pulmonary Administration of Antituberculosis Drugs.

Tuberculosis (TB) is an infectious disease that causes a great number of deaths in the world (1.5 million people per year). This disease is currently treated by administering high doses of various oral anti-TB drugs for prolonged periods (up to 2 years). While this regimen is normally effective when taken as prescribed, many people with TB experience difficulties in complying with their medication schedule. Furthermore, the oral administration of standard anti-TB drugs causes severe side effects and widespread resistances. Recently, we proposed an original platform for pulmonary TB treatment consisting of mannitol microspheres (Ma MS) containing iron (III) trimesate metal–organic framework (MOF) MIL-100 nanoparticles (NPs). In the present work, we loaded this system with the first-line anti-TB drug isoniazid (INH) and evaluated both the viability and safety of the drug vehicle components, as well as the cell internalization of the formulation in alveolar A549 cells. Results show that INH-loaded MOF (INH@MIL-100) NPs were efficiently microencapsulated in Ma MS, which displayed suitable aerodynamic characteristics for pulmonary administration and non-toxicity. MIL-100 and INH@MIL-100 NPs were efficiently internalized by A549 cells, mainly localized in the cytoplasm. In conclusion, the proposed micro-nanosystem is a good candidate for the pulmonary administration of anti-TB drugs.

Continuous fixed-bed column studies of arsenite removal via oxidation and adsorption coprocesses

Arsenite (As(III)) was removed via oxidation and adsorption coprocesses in fixed-bed columns. A manganese oxide octahedral molecular sieve (K-OMS2) and iron(III) trimesate (Fe-BTC) were applied as oxidizer and adsorbent, respectively. Before use in the column, K-OMS2 and Fe-BTC powders were coated on ceramic balls, with K-OMS2 and Fe-BTC to ceramic ball ratios of 1 to 50. The As(III) and arsenate (As(V)) removal efficiencies for single fixed-bed columns of K-OMS2 and Fe-BTC, respectively, as well as for the two columns combined, were determined. From the single-column run results, K-OMS2 maintained notable efficiency in oxidizing As(III) to As(V) during a three-round-use cycle, with leached Mn and K concentrations below the groundwater standard. The average As(III) oxidation percentages in K-OMS2 column for 600 min in the 1st, 2nd, and 3rd rounds were 95, 92, and 93%, respectively. In the Fe-BTC single-column run, the Yoon-Nelson model was found to represent the adsorption kinetics model of the run, with a maximum As(V) adsorption capacity of 52.60 mg/g, and more than 75% of As(V) was removed for 600 min. Maximum Fe leaching from Fe-BTC column was 0.23 mg/L, which was lower than Fe concentration range found in natural freshwater. The adsorption behavior can be explained by the fact that the adsorption rate decreased depending on the As(V) breakthrough and Fe-BTC proportion. In the case of two columns combined, more than 62% of the total As was removed over 2200 min of operation time under optimal experimental conditions.

Drug-Loaded Lipid-Coated Hybrid Organic-Inorganic "Stealth" Nanoparticles for Cancer Therapy.

Hybrid porous nanoscale metal organic frameworks (nanoMOFs) made of iron trimesate are attracting increasing interest as drug carriers, due to their high drug loading capacity, biodegradability, and biocompatibility. NanoMOF surface modification to prevent clearance by the innate immune system remains still challenging in reason of their high porosity and biodegradable character. Herein, FDA-approved lipids and poly(ethylene glycol) (PEG)-lipid conjugates were used to engineer the surface of nanoMOFs by a rapid and convenient solvent-exchange deposition method. The resulting lipid-coated nanoMOFs were extensively characterized. For the first time, we show that nanoMOF surface modification with lipids affords a better control over drug release and their degradation in biological media. Moreover, when loaded with the anticancer drug Gem-MP (Gemcitabine-monophosphate), iron trimesate nanoMOFs acted as “Trojan horses” carrying the drug inside cancer cells to eradicate them. Most interestingly, the PEG-coated nanoMOFs escaped the capture by macrophages. In a nutshell, versatile PEG-based lipid shells control cell interactions and open perspectives for drug targeting.

The Application of Ferric-Metal-Organic Framework for Dye Removal: A Mini Review

Dye effluent released from the industries is one of the most severe environmental concerns due to their potential adverse effects on human health. There are many obstacles encountered in degrading dye materials as they are not only very stable to light and heat but also resistant to biodegradation and oxidation reactions. Currently, porous metal-organic frameworks (MOFs), an important class of advanced functional materials due to its novel coordination structures and diverse topologies, have shown potential applications in various fields, including dye removal. Among the highly water stable MOFs, Ferric-based MOFs like iron (III) trimesate, which is also known as MIL-100(Fe), is favorably ascribed by its simple synthesizing method as well as its wide availability. Herein, this paper summarized the recent progress achieved by MIL-100(Fe) in removing different types of dye, together with its sustainable preparation method.

Loading and release of doxorubicin hydrochloride from iron(iii) trimesate MOF and zinc oxide nanoparticle composites.

A significant amount of work has been done in recent years for the development of metal organic framework (MOF) based drug delivery vehicles. Often, nanomaterials such as iron oxide (Fe3O4), zinc oxide (ZnO), and other metal oxides like graphene oxide etc. are incorporated into the structures to impart additional functionality. In this work, an iron(iii) trimesate metal organic framework i.e. MIL-100(Fe) and its composites with ZnO nanoparticles i.e. ZnO@MIL-100(Fe) were investigated as delivery agents for anticancer drug doxorubicin hydrochloride (DOX). The synthesis of the composites was done by two routes viz. a conventional HF route (in the presence of HF as a crystallizing agent) and another one in the absence of HF. The resultant MOF and its composites significantly differ in DOX loading capacity and release rates. The results obtained in this work indicate that the DOX loading capacity increases upon addition of nanoparticles when the original MOF has lower mesopore volume (as in the sample obtained via the HF route). Surprisingly, this increase in the DOX loading was comparable to that of Fe3O4@MIL-100(Fe), although the two pure nanoparticles (ZnO and Fe3O4) have widely different loading capacities. On the other hand, the addition of ZnO nanoparticles reduces the DOX loading capacity, if the MOF has higher mesopore volume (as for the sample obtained via the HF free route). The composites synthesized by the HF route with enhanced loading capacity exhibit slower DOX release rates due to the stronger interaction of the drug with the composite.

Highly Porous Hybrid Metal-Organic Nanoparticles Loaded with Gemcitabine Monophosphate: a Multimodal Approach to Improve Chemo- and Radiotherapy.

Nanomedicine recently emerged as a novel strategy to improve the performance of radiotherapy. Herein we report the first application of radioenhancers made of nanoscale metal-organic frameworks (nanoMOFs), loaded with gemcitabine monophosphate (Gem-MP), a radiosensitizing anticancer drug. Iron trimesate nanoMOFs possess a regular porous structure with oxocentered Fe trimers separated by around 5 Å (trimesate linkers). This porosity is favorable to diffuse the electrons emitted from nanoMOFs due to activation by γ radiation, leading to water radiolysis and generation of hydroxyl radicals which create nanoscale damages in cancer cells. Moreover, nanoMOFs act as "Trojan horses", carrying their Gem-MP cargo inside cancer cells to interfere with DNA repair. By displaying different mechanisms of action, both nanoMOFs and incorporated Gem-MP contribute to improve radiation efficacy. The radiation enhancement factor of Gem-MP loaded nanoMOFs reaches 1.8, one of the highest values ever reported. These results pave the way toward the design of engineered nanoparticles in which each component plays a role in cancer treatment by radiotherapy.

Optimization of Lignin Removal from Synthesized Wastewater by Iron (III) Trimesate

Optimization of Lignin Removal from Synthesized Wastewater by Iron (III) Trimesate

A highly conductive nanostructured PEDOT polymer confined into the mesoporous MIL-100(Fe).

Despite the higher efficiency, larger color range and faster stimulus response of polymeric electrochromic materials, their poor cyclability strongly hampers their application in optoelectronics. As an original strategy to stabilize and further nanostructure these polymers, herein an efficient encapsulation and in situ polymerization inside highly porous metal-organic frameworks (MOFs) is reported. In particular, the successful accommodation of poly(3,4-ethylendioxythiophene) (PEDOT) and its partially oxidized polarons inside the mesopores of the nontoxic iron trimesate MIL-100(Fe) is convincingly proved by a large panel of experimental techniques. Remarkably, the polymer-MOF interaction occurring for entrapped PEDOT within the pores (deeply assessed by experimental and simulation methods) might be responsible for the enhanced electrical conductivity of the resulting PEDOT@MIL-100(Fe) composite when compared to the insulating MIL-100(Fe) and the conductive free PEDOT. Furthermore, it was possible to observe the electrochromic properties of the PEDOT@MIL-100(Fe) composite, achieving an improved stability and good cyclability as a consequence of the effective protection by the MOF matrix.

Biocompatible porous metal-organic framework nanoparticles based on Fe or Zr for gentamicin vectorization

Due to their high porosity and versatile composition and structure, nanoscaled Metal-Organic Frameworks (nanoMOFs) have been recently proposed as novel drug delivery systems, and have been demonstrated to have important capacities and potential for controlled release of different active ingredients. Gentamicin (GM; a broad spectrum aminoglycoside antibiotic indicated in bacterial septicemia therapy) has great therapeutic interest, but the associated bioavailability and toxicity drawbacks accompanying high doses and repeated administration of this free drug make its encapsulation inside new nanocarriers necessary. GM encapsulation within two different porous biofriendly Fe and Zr-carboxylates nanoMOFs was performed by a simple impregnation method, with full characterization of the resulting GM-containing solid using a large panel of techniques (X ray powder diffraction-XRPD, Fourier transform infrared spectroscopy-FTIR, thermogravimetric analysis-TGA, N2 sorption, scanning electron microscopy-SEM, dynamic light scattering-DLS, ζ-potential, fluorescence spectroscopy and molecular simulations). High reproducible encapsulation rates, reaching 600 µg of GM per·mg of formulation, were obtained using the biocompatible mesoporous iron(III) trimesate nanoparticles (NPs) MIL-100(Fe) (MIL: Materials from Institut Lavoisier). In vitro GM delivery studies were also carried out using different oral and intravenous simulated physiological conditions, with complete antibiotic release within 8 h when using protein free media, but lower release rates in the presence of proteins. Furthermore, in vitro toxicity of GM-containing MIL-100(Fe) NPs was investigated on two different cell lines: a monocyte from leukemia (THP-1) and adherent fibroblastoid cells (NIH/3T3). These nanoMOFs had a low cytotoxic profile with IC50 values up to 1 mg·mL−1, ensuring adequate cell proliferation after 24 h. Finally, antibacterial activity studies were carried out on two Gram-positive bacteria and one Gram-negative bacterium: S. aureus, S. epidermidis and P. aeruginosa, respectively. GM-loaded MIL-100(Fe) NPs exhibited the same activity as free GM, confirming that the antibiotic activity of the released GM was conserved.

GraftFast Surface Engineering to Improve MOF Nanoparticles Furtiveness.

Controlling the outer surface of nanometric metal-organic frameworks (nanoMOFs) and further understanding the in vivo effect of the coated material are crucial for the convenient biomedical applications of MOFs. However, in most studies, the surface modification protocol is often associated with significant toxicity and/or lack of selectivity. As an alternative, how the highly selective and general grafting GraftFast method leads, through a green and simple process, to the successful attachment of multifunctional biopolymers (polyethylene glycol (PEG) and hyaluronic acid) on the external surface of nanoMOFs is reported. In particular, effectively PEGylated iron trimesate MIL-100(Fe) nanoparticles (NPs) exhibit suitable grafting stability and superior chemical and colloidal stability in different biofluids, while conserving full porosity and allowing the adsorption of bioactive molecules (cosmetic and antitumor agents). Furthermore, the nature of the MOF-PEG interaction is deeply investigated using high-resolution soft X-ray spectroscopy. Finally, a cell penetration study using the radio-labeled antitumor agent gemcitabine monophosphate (3 H-GMP)-loaded MIL-100(Fe)@PEG NPs shows reduced macrophage phagocytosis, confirming a significant in vitro PEG furtiveness.

Maghemite-nanoMIL-100(Fe) Bimodal Nanovector as a Platform for Image-Guided Therapy

Summary We report here the design of nano-objects (i.e., denoted as MIL/USPIO-cit) that consist of nanoparticles of mesoporous iron trimesate metal-organic framework MIL-100(Fe), whose surface is decorated by maghemite nanoparticles. Not only is this bimodal nanovector produced through a cost-effective and reliable green approach, but it also exhibits excellent colloidal stability under simulated intravenous conditions, and its ability to encapsulate and progressively release drugs (doxorubicin here) is preserved. According to vibrating sample magnetometry and 57 Fe Mossbauer spectrometry, MIL-USPIO-cit presents a superparamagnetic behavior characterized by a high saturation magnetization at room temperature. More importantly, it combines low toxicity with high anti-tumoral activity and can be used in vivo as an efficient MRI contrast agent because of its excellent relaxivity properties. All these properties make this nano-object a potential candidate as a bimodal therapeutic nanovector coupling drug-delivery and MRI properties.

MIL-100(Fe) as a new catalyst for selective catalysis reduction of NOx with ammonia

ABSTRACTA mesoporous iron trimesate MIL-100(Fe) with mixed FeIII/FeII states was successfully employed for selective catalysis reduction with ammonia (NH3-SCR) reaction. The important role played by activation temperature were experimentally evidenced. It was found that the sample dried under vacuum at 473 K for 12 h yielded 100% NO conversion at 300°C. MIL-100(Fe) was characterized by X-ray diffraction, scanning electron microscopy, N2 adsorption, Fourier-transform infrared spectroscopy and thermal analysis. In situ Fourier-transform infrared spectroscopy revealed that NO could obviously adsorb on the Lewis-acid site of MIL-100(Fe), which contributed to the NH3-SCR reaction following Eley-Rideal (E-R) mechanism. In addition, the reusability of MIL-100(Fe) catalyst was also evaluated.

Chitosan-coated mesoporous MIL-100(Fe) nanoparticles as improved bio-compatible oral nanocarriers

Nanometric biocompatible Metal-Organic Frameworks (nanoMOFs) are promising candidates for drug delivery. Up to now, most studies have targeted the intravenous route, related to pain and severe complications; whereas nanoMOFs for oral administration, a commonly used non-invasive and simpler route, remains however unexplored. We propose here the biofriendly preparation of a suitable oral nanocarrier based on the benchmarked biocompatible mesoporous iron(III) trimesate nanoparticles coated with the bioadhesive polysaccharide chitosan (CS). This method does not hamper the textural/structural properties and the sorption/release abilities of the nanoMOFs upon surface engineering. The interaction between the CS and the nanoparticles has been characterized through a combination of high resolution soft X-ray absorption and computing simulation, while the positive impact of the coating on the colloidal and chemical stability under oral simulated conditions is here demonstrated. Finally, the intestinal barrier bypass capability and biocompatibility of CS-coated nanoMOF have been assessed in vitro, leading to an increased intestinal permeability with respect to the non-coated material, maintaining an optimal biocompatibility. In conclusion, the preservation of the interesting physicochemical features of the CS-coated nanoMOF and their adapted colloidal stability and progressive biodegradation, together with their improved intestinal barrier bypass, make these nanoparticles a promising oral nanocarrier.

A non-covalent "click chemistry" strategy to efficiently coat highly porous MOF nanoparticles with a stable polymeric shell.

Metal-organic framework nanoparticles (nanoMOFs) are biodegradable highly porous materials with a remarkable ability to load therapeutic agents with a wide range of physico-chemical properties. Engineering the nanoMOFs surface may provide nanoparticles with higher stability, controlled release, and targeting abilities. Designing postsynthetic, non-covalent self-assembling shells for nanoMOFs is especially appealing due to their simplicity, versatility, absence of toxic byproducts and minimum impact on the original host-guest ability. In this study, several β-cyclodextrin-based monomers and polymers appended with mannose or rhodamine were randomly phosphorylated, and tested as self-assembling coating building blocks for iron trimesate MIL-100(Fe) nanoMOFs. The shell formation and stability were studied by isothermal titration calorimetry (ITC), spectrofluorometry and confocal imaging. The effect of the coating on tritium-labeled AZT-PT drug release was estimated by scintillation counting. Shell formation was conveniently achieved by soaking the nanoparticles in self-assembling agent aqueous solutions. The grafted phosphate moieties enabled a firm anchorage of the coating to the nanoMOFs. Coating stability was directly related to the density of grafted phosphate groups, and did not alter nanoMOFs morphology or drug release kinetics. An easy, fast and reproducible non-covalent functionalization of MIL-100(Fe) nanoMOFs surface based on the interaction between phosphate groups appended to β-cyclodextrin derivatives and iron(III) atoms is presented. This study proved that discrete and polymeric phosphate β-cyclodextrin derivatives can conform non-covalent shells on iron(III)-based nanoMOFs. The flexibility of the β-cyclodextrin to be decorated with different motifs open the way towards nanoMOFs modifications for drug delivery, catalysis, separation, imaging and sensing. This article is part of a Special Issue entitled "Recent Advances in Bionanomaterials" Guest Editors: Dr. Marie-Louise Saboungi and Dr. Samuel D. Bader.

In vivo behavior of MIL-100 nanoparticles at early times after intravenous administration

Metal-organic frameworks have shown interesting features for biomedical applications, such as drug delivery and imaging agents. The benchmarked mesoporous iron(III) trimesate MIL-100 MOF nanocarrier combines progressive release of high drug cargoes with absence of visible in vivo toxicity. Although in a previous study pharmacokinetics and biodistribution of MIL-100 nanoparticles were evaluated in the long term (from 24h to 1 month), the crucial times for drug targeting and delivery applications are shorter (up to 24h). Thus, this work aims to study the blood circulating profile and organ accumulation of MIL-100 nanocarrier at early times after administration. For this purpose, after intravenous administration to rats, both constitutive components of MIL-100 (trimesate and iron) were quantified by high performance liquid chromatography and a spectrophotometric method, respectively. The pharmacokinetic profile suggested that the nanoparticles act as a depot in the blood stream during the first hours before being cleared. Accumulation took mainly place in the liver and, in some extent, in the spleen. Nevertheless, histological studies demonstrated the absence of morphological alterations due to the presence of the particles in these organs. Liver function was however slightly altered as reflected by the increased plasma aspartate aminotransferase concentrations. Finally trimesate was progressively eliminated in urine.