3D-Printed MOF Monoliths: Fabrication Strategies and Environmental Applications.

Metal-organic frameworks (MOFs) have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials, thanks to their large specific surface area, high porosity, tailorable structures and compositions, diverse functionalities, and well-controlled pore/size distribution. However, most developed MOFs are in powder forms, which still have some technical challenges, including abrasion, dustiness, low packing densities, clogging, mass/heat transfer limitation, environmental pollution, and mechanical instability during the packing process, that restrict their applicability in industrial applications. Therefore, in recent years, attention has focused on techniques to convert MOF powders into macroscopic materials like beads, membranes, monoliths, gel/sponges, and nanofibers to overcome these challenges.Three-dimensional (3D) printing technology has achieved much interest because it can produce many high-resolution macroscopic frameworks with complex shapes and geometries from digital models. Therefore, this review summarizes the combination of different 3D printing strategies with MOFs and MOF-based materials for fabricating 3D-printed MOF monoliths and their environmental applications, emphasizing water treatment and gas adsorption/separation applications. Herein, the various strategies for the fabrication of 3D-printed MOF monoliths, such as direct ink writing, seed-assisted in-situ growth, coordination replication from solid precursors, matrix incorporation, selective laser sintering, and digital light processing, are described with the relevant examples. Finally, future directions and challenges of 3D-printed MOF monoliths are also presented to better plan future trajectories in the shaping of MOF materials with improved control over the structure, composition, and textural properties of 3D-printed MOF monoliths.

Fabrication of Bacterial Cellulose/Chitosan-MIL-100(Fe) Composite for Adsorptive Removal of Dacarbazine.

In this research, a polymeric composite based on a chitosan/bacterial cellulose (CS/BC) matrix filled with MIL-100(Fe) particles was prepared to solve the recyclability of issue MIL-100(Fe) particles and utilized as an efficient adsorbent for removing dacarbazine (DTIC) from wastewater. The adsorption capacity of the composite (CS/BC-MIL) was higher than both MIL-100(Fe) and the CS/BC polymeric matrix. The adsorption performance of the fabricated composite was evaluated through kinetics and isotherm studies. While isotherm studies revealed that the adsorption of DTIC onto the adsorbent can be well described by the Freundlich model, kinetics studies indicated that a combination of factors, rather than a single rate-limiting factor, are responsible for the adsorption rate. Thermodynamics investigation showed that the adsorption of DTIC to CS/BC-MIL composite is exothermic and occurs spontaneously. Additionally, due to the negative entropy change, it was established that the adsorption is governed by the enthalpy change. Exploring the solution chemistry revealed that the optimum pH for the adsorption process was about 4. Moreover, the CS/BC-MIL can selectively adsorb DTIC in the presence of other pharmaceuticals like doxorubicin (DOX). Furthermore, regeneration investigations disclosed that the composite holds its structural features and has an acceptable adsorption capacity after several cycles of adsorption/desorption.

Cu-vitamin B3 donut-like MOFs incorporated into TEMPO-oxidized bacterial cellulose nanofibers for wound healing.

In this study, a novel multifunctional nanocomposite wound dressing was developed, consisting of TEMPO-oxidized bacterial cellulose (TOBC) nanofibers functionalized with donut-like copper-based metal-organic frameworks (CuVB3 MOFs). These CuVB3 MOFs were constructed using copper nodes linked by vitamin B3 molecules, resulting in a copper nicotinate crystal structure as confirmed by X-ray diffraction. Electron microscopy confirmed the presence of donut-like microstructures with uniform element distribution in the synthesized MOFs. Through the incorporation of CuVB3 MOFs into the TOBC nanofibers, innovative TOBC-CuVB3 nanocomposites were created. Biocompatibility testing using the MTT assay demonstrated enhanced cell viability of over 115% for the TOBC-CuVB3 nanocomposite. Acridine Orange staining revealed a ratio of 88-92% live cells on the wound dressings. Furthermore, fibroblast cells cultured on TOBC-CuVB3 exhibited expanded morphologies with long filopodia. The agar diffusion method exhibited improved antibacterial activity against both Gram-positive and Gram-negative bacterial strains, correlating with increased CuVB3 concentration in the samples. In vitro cellular scratch assays demonstrated excellent wound healing potential, with a closure rate of over 98% for wounds treated with the TOBC-CuVB3 nanocomposite. These findings underscore the synergistic effects of copper, vitamin B3, and TOBC nanofibers in the wound healing process.

A Novel Silver-Based Metal-Organic Framework Incorporated into Nanofibrous Chitosan Coatings for Bone Tissue Implants.

In this work, new multi-layer nanocomposite coatings comprised of chitosan (CS) nanofibers functionalized using an innovative silver-based metal-organic framework (SOF) were developed. The SOFs were produced via a facile process using green and environmental-friendly materials. The CS-SOF nanocomposites were coated on hierarchical oxide (HO) layers fabricated on titanium substrates by an innovative two-step etching process. X-ray diffraction revealed fruitful production of the SOF NPs and their stable crystalline structure within the nanocomposite coatings. Energy-dispersive x-ray spectroscopy approved uniform SOFs distribution in the CS-SOF nanocomposites. Atomic force microscopy indicated more than 700% increased nanoscale roughness for the treated surfaces compared to the bare sample. In vitro MTT assay revealed proper cell viabilities on the samples, however, high SOFs concentration led to less biocompatibility. All coatings demonstrated positive cell proliferation rates up to 45% after 72 h. Antibacterial studies showed significant inhibition zones against Escherichia coli and Staphylococcus aureus bacteria with 100-200% effective antibacterial activities. Electron microscopy exhibited excellent cell-implant integration for the CS-SOF nanocomposite surfaces due to the attached cells with expanded morphologies and long filopodia. The prepared coatings showed high apatite formation capability and bone bioactivity.

Boosting bone cell growth using nanofibrous carboxymethylated cellulose and chitosan on titanium dioxide nanotube array with dual surface charges as a novel multifunctional bioimplant surface.

One of the most vital aspects of the orthopedic implant field has been the development of multifunctional coatings that improve bone-implant contact while simultaneously preventing bacterial infection. The present study investigates the fabrication and characterization of multifunctional polysaccharides, including carboxymethyl cellulose (CMCn) and carboxymethyl chitosan nanofibers (CMCHn), as a novel implant coating on titania nanotube arrays (T). Field emission scanning electron microscopy (FESEM) images revealed a nanofibrous morphology with a narrow diameter for CMCn and CMCHn, similar to extracellular matrix nanostructures. Compared to the T surface, the roughness of CMCn and CMCHn samples increased by over 250 %. An improved cell proliferation rate was observed on CMCHn nanofibers with a positively charged surface caused by the amino groups. Furthermore, in an antibacterial experiment, CMCn and CMCHn inhibited bacterial colony formation by 80 % and 73 %, respectively. According to the results, constructed modified CMCn and CMCHn increased osteoblast cell survival while inhibiting bacterial biofilm formation owing to their surface charge and bioinspired physicochemical properties.

Synergistic Wound Healing by Novel Ag@ZIF-8 Nanostructures.

In this paper, novel zeolitic imidazolate framework-8 (ZIF-8) functionalized with Ag (Ag@ZIF-8) nanoparticles were synthesized through a green, facile and environmental-friendly process for wound dressing applications. X-ray diffraction revealed that the ZIF-8 and Ag@ZIF-8 were successfully synthesized by green solvents at ambient temperature. Field-emission scanning electron microscopy indicated a homogeneous porous blend of âˆ¼30 nm chitosan/bacterial cellulose (CS/BC) nanofibers embedded with âˆ¼80-110 nm nanoparticles of the ZIF-8 and Ag@ZIF-8. Transmission electron microscopy revealed the Ag@ZIF-8 nanostructures consist of ZIF-8 cores that are covered by 5-20 nm Ag nanoparticles. MTT assay indicated excellent cell viability values of âˆ¼115 and 109% for the CS/BC nanocomposites reinforced by ZIF-8 and Ag@ZIF-8 nanoparticles, respectively. The Ag-containing wound dressings showed 52-300% of effective antibacterial activities. Animal studies demonstrated excellent healing for the wound treated by CS/BC-25%Ag@ZIF-8 nanocomposite with âˆ¼91% of wound closure after 14 days of treatment. Hematoxylin and eosin (H&E) staining revealed successful healing and tissue regeneration for the wounds treated using the CS/BC-Ag@ZIF-8 nanocomposites. This kind of nanocomposites with synergistic antimicrobial and bioactivity properties can be a promising candidate for regenerative medicine.

Green synthesis of PEG-coated MIL-100(Fe) for controlled release of dacarbazine and its anticancer potential against human melanoma cells.

In this study, the potential of using MIL-100(Fe) metal-organic framework (MOF) for loading and controlling the release of dacarbazine (DTIC) was evaluated for in vitro treatment of melanoma. The drug loading was performed during the green synthesis of MIL-100(Fe) in an aqueous media without using any harmful solvents, to obtain MIL-DTIC. The surface of this structure was then coated with polyethylene glycol (PEG) in the same aqueous solution to synthesize MIL-DTIC-PEG. The synthesized samples were characterized using various methods. Their release profile was studied in phosphate-buffered saline (PBS) and simulated cutaneous medium (SCM). The cytotoxicity of DTIC and its nano-MOF formulation were investigated against melanoma A375 cell lines. The results revealed that the PEG coating (PEGylation) changed the surface charge of MOF from -2.8 ± 0.9 mV to -42.8 ± 1.2 mV, which can contribute to the colloidal stability of MOF. The PEGylation showed a significant effect on controlled drug release, especially in SCM, which increases the complete release time from 60 h to 12 days. Moreover, both of the drug-containing MOFs showed more toxicity than DTIC and unloaded MOFs, confirming that the cumulative release of drug and better cellular uptake of NPs lead to increased toxicity.