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.

Inhibition of Adherence and Biofilm Formation of Pseudomonas aeruginosa by Immobilized ZnO Nanoparticles on Silicone Urinary Catheter Grafted by Gamma Irradiation.

Nosocomial infections caused by microbial biofilm formation on biomaterial surfaces such as urinary catheters are complicated by antibiotic resistance, representing a common problem in hospitalized patients. Therefore, we aimed to modify silicone catheters to resist microbial adherence and biofilm formation by the tested microorganisms. This study used a simple direct method to graft poly-acrylic acid onto silicone rubber films using gamma irradiation to endow the silicone surface with hydrophilic carboxylic acid functional groups. This modification allowed the silicone to immobilize ZnO nanoparticles (ZnO NPs) as an anti-biofilm. The modified silicone films were characterized by FT-IR, SEM, and TGA. The anti-adherence ability of the modified silicone films was evidenced by the inhibition of biofilm formation by otherwise strong biofilm-producing Gram-positive, Gram-negative, and yeast clinical isolates. The modified ZnO NPs grafted silicone showed good cytocompatibility with the human epithelial cell line. Moreover, studying the molecular basis of the inhibitory effect of the modified silicone surface on biofilm-associated genes in a selected Pseudomonas aeruginosa isolate showed that anti-adherence activity might be due to the significant downregulation of the expression of lasR, lasI, and lecB genes by 2, 2, and 3.3-fold, respectively. In conclusion, the modified silicone catheters were low-cost, offering broad-spectrum anti-biofilm activity with possible future applications in hospital settings.

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.

Mixed-metal hybrid ultramicroporous material (HUM) precursor to graphene-supported tetrataenite as a highly active and durable NPG catalyst for the OER.

Current interest in investigating non-precious group (NPG) metals for catalyzing the oxygen evolution reaction (OER) has revealed that doping of Ni hydroxides with Fe results in the dramatic enhancement of catalytic activity. Herein, a facile pathway to construct tetrataenite, an NiFe alloy of extraterrestrial origin and to address the limited electrical conductivity of metal oxides/hydroxides by directly constructing them atop graphene sheets is described. In this approach, a one-pot, bottom-up assembly of hybrid ultramicroporous materials (HUMs) was carried out, in the presence of suspended graphene (G), to homogeneously deposit the HUMs on unmodified graphene sheets, affording HUMs@G. Single metal (SIFSIX-3-Ni@G) and mixed metal (SIFSIX-3-NiFe@G) HUMs can be readily synthesized from their respective metal salts to afford a well-designed catalyst for the OER. The pyrolysis of SIFSIX-3-NiFe@G resulted in the deposition of the nanoalloy tetrataenite on G, demonstrating an exceptionally low OER onset potential of 1.44 V vs. RHE and reduced overpotential at 10 mA cm-2 (η10 = 266 mV). The synergy between the composition of the active catalyst and the electronically conductive support was attained by designing a reaction system encoding the self-assembly of a crystalline pre-catalyst on G sheets.

Probing the Water Stability Limits and Degradation Pathways of Metal-Organic Frameworks.

A comprehensive model to describe the water stability of prototypical metal-organic frameworks (MOFs) is derived by combining different types of theoretical and experimental approaches. The results provide an insight into the early stages of water-triggered destabilization of MOFs and allow detailed pathways to be proposed for the degradation of different MOFs under aqueous conditions. The essential elements of the approach are computing the pKa values of coordinated water molecules and geometry relaxations. Variable-temperature and pH infrared spectroscopy techniques are used to corroborate the main findings. The model developed herein helps to explain stability limits observed for several prototypical MOFs, including MOF-5, HKUST-1, UiO-66, and MIL-101-Cr, in aqueous solutions, and thus, provides an insight into the possible degradation pathways in acidic and basic environments. The formation of a metal hydroxide through the autoprotolysis of metal-coordinated water molecules and the strength of carboxylate-metal interactions are suggested to be two key players that govern stability in basic and acidic media, respectively. The methodology presented herein can effectively guide future efforts, which are especially significant for in silico screening, for developing novel MOFs with enhanced aqueous stability.

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.

Electrically Conductive, Monolithic Metal-Organic Framework-Graphene (MOF@G) Composite Coatings.

We present a novel approach to produce a composite of the HKUST-1 metal-organic framework (MOF) and graphene, which is suited for the fabrication of monolithic coatings of solid substrates. In order to avoid the degradation of graphene electrical properties resulting from chemical functionalization (e.g., oxidation yielding graphene oxide, GO), commercial, nonmodified graphene was utilized. The one-pot synthesis of the moldable composite material allows for a controllable loading of graphene and the tuning of porosity. Potentially, this facile synthesis can be transferred to other MOF systems. The monolithic coatings reported here exhibit high surface areas (1156-1078 m2/g). The electrical conductivity was high (a range of 7.6 × 10-6 S m-1to 6.4 × 10-1 S m-1) and was found to be proportional to the graphene content. The ability to readily attain different forms and shapes of the conductive, microporous composites indicates that the MOF@G system can provide a compelling approach to access various applications of MOFs, specifically in electrochemical catalysis, supercapacitors, and sensors.

Metallic Nanoparticles Assimilation within Metal-Organic Framework Monolith.

A facile and versatile method is reported for the inclusion of gold nanoparticles (AuNPs) within a monolithic metal-organic framework (HKUST-1 MOF). Simple addition of stabilized colloidal AuNPs solution to the reaction mixture at the early stages of the formation of the MOF monolith resulted in quantitative uptake of the AuNPs within the MOF matrix. Several characterization techniques including solution and solid UV-vis spectroscopy, TEM, and XRD indicated the successful immobilization of the AuNPs. Controllable loading of AuNPs was also demonstrated, where gas sorption measurements indicated the maintained microporosity of the AuNPs-containing monoliths. This methodology has wide potential applications in demanding technologies, including sensing and catalysis, where monolithic materials of controllable physicochemical properties can be readily accessible through pore size and guest selectivity of the host MOF matrix controlling access of guest molecules to immobilized AuNPs.

Controlling the Uptake and Regulating the Release of Nitric Oxide in Microporous Solids.

Representative compounds from three classes of microporous solids, namely, metal-organic frameworks (MOFs), hybrid ultra-microporous materials (HUMs), and porous-organic polymers (POPs), were investigated for their nitric oxide gas uptake and release behavior. Low-pressure sorption studies indicated strong chemisorption of NO on the free amine groups decorating the MOF UiO-66-NH2 when compared to its non-amine-functionalized parent. The HUMs demonstrated reversible physisorption within the low-pressure regime, but interestingly in one case there was evidence for chemisorption following pressurization with NO at 10 bar. Significant release of chemisorbed NO from the UiO-66-NH2 and one of the HUMs was triggered by addition of acid to the medium, a pH change from 7.4 to 5.4 being sufficient to trigger NO release. An imidazole-based POP exhibited chemisorption of NO at high pressure wherein the ring basicity facilitated both NO uptake and spontaneous release upon contact with the aqueous release medium.

Tailoring the Oxygen Reduction Activity of Hemoglobin through Immobilization within Microporous Organic Polymer-Graphene Composite.

A facile one-pot, bottom-up approach to construct composite materials of graphene and a pyrimidine-based porous-organic polymer (PyPOP), as host for immobilizing human hemoglobin (Hb) biofunctional molecules, is reported. The graphene was selected because of its excellent electrical conductivity, while the PyPOP was utilized because of its pronounced permanent microporosity and chemical functionality. This approach enabled enclathration of the hemoglobin within the microporous composite through a ship-in-a-bottle process, where the composite of the PyPOP@G was constructed from its molecular precursors, under mild reaction conditions. The composite-enclathrated Fe-protoporphyrin-IX demonstrated electrocatalytic activity toward oxygen reduction, as a functional metallocomplex, yet with a distinct microenvironment provided by the globin protein. This approach delineates a pathway for platform microporous functional solids, where fine-tuning of functionality is facilitated by judicious choice of the active host molecules or complexes, targeting specific application.

The potential of a graphene-supported porous-organic polymer (POP) for CO2 electrocatalytic reduction.

A one-pot, bottom-up assembly of a pyrimidine-containing porous-organic polymer (PyPOP) was conducted to homogenously deposit the PyPOP atop unmodified graphene sheets, affording a composite material PyPOP@G. The PyPOP demonstrated an appreciable affinity toward CO2 capture but was found to be largely insulating, hindering its usage in potential electrochemical conversion of CO2. However, its composite with graphene was found to be microporous, with maintained affinity toward CO2 and furthermore demonstrated significant electrochemical activity toward CO2 reduction (5 mA cm-2 at -1.6 V), not observed in either of its two components separately.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis.

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multitopic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity toward hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited-state lifetime of the covalently immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.