Anion-Exchange Electrospun Mixed-Matrix Polymer Fibers of Colesevelam for Water Treatment.

Novel anion-exchange electrospun fiber membranes of polycaprolactone doped with the cationic, cross-linked colesevelam polymer are reported. The weight fraction of cross-linked cationic colesevelam polymer, as the active phase within the PCL matrix, can readily be controlled in the synthesis of the mixed-matrix fibers (Cole@PCL), enabling optimization of the ion-exchange properties of the resulted membranes. This approach enabled adaptation of anion-exchange resins to a permeable, flexible membrane form, which is a significant advancement toward futuristic water treatment applications, demonstrated herein for the removal of trace contaminants, including nitrates and phosphates, as well as anionic dyes. The Cole@PCL membranes demonstrated the dependence of contaminant uptake on the weight percentage of colesevelam in the mixed-matrix membrane. An optimal 10 wt % of colesevelam was identified, demonstrating a staggering ion removal capacity of 155.8 mg/g for nitrate, 177.6 mg/g for phosphate, and 70 mg/g for Methyl Orange.

Durable and recyclable MOF@polycaprolactone mixed-matrix membranes with hierarchical porosity for wastewater treatment.

With the fast-growing global water crisis, the development of novel technologies for water remediation and reuse is crucial. Industrial wastewater especially contains various toxic pollutants that pose an additional threat to the environment; thus, efficient removal of such contaminants can ensure safe reprocessing of industrial wastewater, thereby alleviating the demand for fresh water. Herein, we describe a novel and efficient approach for preparing porous polycaprolactone (PCL) membranes with a hierarchical architecture via a simple solvent/non-solvent methodology. A mixed-matrix membrane (MMM) was further constructed utilizing an amine-functionalized metal-organic framework as the sorbent filler nanoparticles and PCL as the polymer support matrix (MOF@PCL) for wastewater treatment applications. The MOF@PCL MMM demonstrated homogeneous morphology as well as exceptional performance towards the removal of both cationic (methylene blue, MB) and anionic (methyl orange, MO) organic dyes, where the maximum adsorption capacities reached 309 mg g-1 and 208 mg g-1, respectively. Kinetic and thermodynamic investigations revealed that the adsorption process was endothermic with a fast intraparticle diffusion rate constant. The MOF@PCL MMM also displayed excellent mechanical stability and recyclability, where the removal efficiency was maintained after 10 cycles.

Nine days extended release of adenosine from biocompatible MOFs under biologically relevant conditions.

Adenosine is a small molecule directly involved in maintaining homeostasis under pathological and stressful conditions. Due to its rapid metabolism, delivery vehicles capable of exhibiting extended release of adenosine are of paramount interest. Herein, we demonstrate a superior long-term (9 days) release profile of adenosine from biocompatible MOFs in a physiologically relevant environment. The key to the biocompatibility of MOFs is their stability under biologically relevant conditions. This study additionally highlights the interplay between the chemical stability of prototypal MOFs, assessed under physiological conditions, and their cytotoxicity profiles. Cytotoxicity of the prototypal Zn-based MOF (ZIF-8) and three Zr-based MOFs (UiO-66, UiO-66-NH2, and MOF-801) on six cell types was assessed. The cell types selected were valve interstitial cells (VICs), valve endothelial cells (VECs), adipose tissue-derived stem cells (ADSCs), and cell lines U937, THP1, and HeLa. Zr-based MOFs demonstrated a wide tolerance range in the cell culture cytotoxicity assays, demonstrating cell viability up to a very high dose of ∼1000 µg mL-1, as compared to ZIF-8 which showed notable cytotoxicity in as little as ∼100 µg mL-1 dose. This study demonstrates, for the first time, the utilization of biocompatible MOFs for adenosine delivery as well as establishes a direct link between structural instability in the cell culture medium and the observed cytotoxicity of the studied MOFs.

Strong Interplay between Polymer Surface Charge and MOF Cage Chemistry in Mixed-Matrix Membrane for Water Treatment Applications.

Despite the large number of reports on the utilization of highly microporous solids, most relevant are metal-organic frameworks (MOFs), in different demanding applications, the successful hybridization of MOFs and moldable polymer matrices into flexible, water-permeable membranes exhibiting strong entanglement of the MOF and the polymer matrix properties is still lacking. We describe herein an efficient pathway to construct a mixed-matrix membrane (MMM) comprising a water-stable metal-organic framework (UiO-66-NH2), as the active sorbent, and cellulose acetate (CA), as the polymer matrix, to construct a flexible membrane for water treatment applications. The MOF@CA MMM demonstrated superior performance in terms of exceptional removal of organic dyes (both cationic and anionic species) as well as hexavalent Cr ions, compared to the control CA membrane. The recorded high uptake of the MOF@CA MMM for this wide array of contaminants demonstrated the accessibility of the MOF nanocages immobilized within the MMM, in contrast to the common perception that the polymer matrix might act as a physical barrier to block the accessibility of the MOF cages. The negative surface charge of the matrix exerted a notable action to affect the diffusion of the negatively charged contaminants to reach the active sorbent filler. Moreover, the formed membrane demonstrated high durability and recyclability with no detected loss of performance over numerous cycles. This approach outlines the ability to formulate one of the most water-stable MOFs, as exceptional microporous sorbent, into a usable membrane form compatible with real-life applications.

Novel Inulin Electrospun Composite Nanofibers: Prebiotic and Antibacterial Activities.

Inspired by the rampant digestive disorders and the vast bacterial infections, this study aimed at fabricating nanofibers made of inulin/polyvinyl alcohol (PVA) composite nanofibers (CNFs) using the electrospinning technique and testing their prebiotic and antibacterial activities. The inulin/PVA CNFs were tested for prebiotic activity with Lactobacillus species while Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were used to assess the antibacterial potentiality. During the fabrication of the CNFs, different electrospinning parameters have been carefully controlled, in order to produce nanofibers with relatively uniform diameter, fewer beads, and high integrity. The different parameters included variable solution concentration (material ratio varied from 14 to 20 wt %), applied voltage (varied from 15 to 25 kV), and solution flow (ranged between 0.005 and 0.5 mL/min). The chemical characteristics, thermal stability, and morphology of the formed CNFs were comprehensively characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Selected CNFs, showing the best diameter uniformity and integrity, were tested for the prebiotic and antimicrobial activity. A 38% increase in prebiotic activity of CNFs, compared to their bulk solution, was observed. The antibacterial activity of the selected CNFs was enhanced, from ∼40% (pure inulin) to 70% (inulin/PVA CNFs) against E. coli and 45% against S. aureus. This study investigates the prebiotic and antibacterial activities of PVA/inulin CNFs and provides the foundation for inulin/PVA CNF use in the healthcare sector, as in disinfectants and/or digestive disorders.

Tuning the Chemical Environment within the UiO-66-NH2 Nanocages for Charge-Dependent Contaminant Uptake and Selectivity.

The remarkable water stability of Zr-carboxylate-based metal-organic frameworks (MOFs) stimulated considerable interest toward their utilization in aqueous phase applications. The origin of such stability is probed here through pH titration and pKa modeling. A unique feature of the Zr6(µ3-OH)4(µ3-O)4(RCO2)12 cluster is the Zr-bridging oxo/hydroxyl groups, demonstrating several pKa values that appear to provide for the water stability at a wide range of pH. Accordingly, the tunability of the cage/surface charge of the MOF can feasibly be controlled through careful adjustment of solution pH. Such high stability, and facile control over cage/surface charge, can additionally be augmented through introducing chemical functionalities lining the cages of the MOF, specifically amine groups in the UiO-66-NH2 presented herein. The variable protonation states of the Zr cluster and the pendant amino groups, their H-bond donor/acceptor characteristics, and their electrostatic interactions with guest molecules were effectively utilized in controlled experiments to demonstrate high uptake of model guest molecules (137 mg/g for Cr(VI), 1275 mg/g for methylene blue, and 909 mg/g for methyl orange). Additionally, a practical form of the silica-supported MOF, UiO-66-NH2@SiO2, constructed in under 2 h reaction time, is described, generating a true platform microporous sorbent for practical use in demanding applications.