The impact of vaccines extends beyond the improvement of individual health, significantly lowering the burden of infectious disease in healthcare systems and strengthening the societal infrastructure and economic stability of a nation. Unfortunately, the substantial benefits of vaccines are often disproportionately encountered in affluent nations, with the need for cold-chain logistics heavily contributing to this inequity. Here, we describe the biomimetic mineralization of a live viral vaccine using metal-organic frameworks (MOFs) to alleviate stress caused by ambient temperatures. Utilizing a zinc-based MOF (ZIF-8), we demonstrated the advantages of a higher concentration of the ZIF-8 precursor constituents for coverage of viral antigens and recovery of the live viral Newcastle Disease Virus (NDV) vaccine. Using a candidate MOF-based formulation, we identified that ZIF-8 can maintain effective coverage of NDV V4 virions following lyophilization; however, viral titer was negatively impacted if rapid freezing was integrated. As an alternative cost-effective storage technique, we utilized filter paper drying for long-term stabilization of various ZIF-8@NDV formulations. We demonstrated that the presence of ZIF-8 significantly contributed to vaccine stability when stored at 25 or 37 °C compared to NDV in solution. In summary, our findings highlight the potential of utilizing MOFs for stabilization of live viral vaccines at ambient temperatures and demonstrate the viability of filter paper as an alternative to lyophilization for vaccine preservation.

The encapsulation of bacteria in metal-organic frameworks (MOFs) is being studied for use in biomedicine and bioremediation. However, biocompatibility could be improved, as much of the research focuses on ZIF-8 and Escherichia coli. MIL-88A, composed of fumaric acid and iron, offers a safer alternative. This study investigates encapsulation of the probiotic strain Lactiplantibacillus plantarum 299v in a nanocrystalline matrix via a simple one-pot synthesis. The encapsulated bacteria show improved stability in saline, lysozyme and pepsin compared to uncoated cells. These findings highlight the potential of the iron(III) fumarate matrix for bacterial protection and controlled release for biological applications.

The purpose of this study was to design and develop a self-supporting glass MOF membrane (GMM) including its design, fabrication under different heat treatment temperatures, analysis of its physical-chemical properties, and assessment of its separation performance. Glass MOFs preserve metal-ligand bonding structures similar to their crystalline counterparts, providing intrinsic gas separation properties alongside the benefits of amorphous materials, including reduced grain boundaries and ease of processing. In this work, ZIF-62 was melted and then cooled to fabricate GMMs using vitrification to enhance molecular sieving. This study systematically examines the impact of varying thermal treatment temperatures (400-475 °C) on the physical and chemical transformations of GMMs, revealing their effects on the porosity, defect formation, and molecular sieving performance through advanced characterization techniques (e.g., solid-state nuclear magnetic resonance (13C NMR), X-ray photoelectron spectroscopy (XPS), He pycnometry, and positron annihilation lifetime spectroscopy (PALS)). The optimal GMM exhibits an impressive separation performance, particularly for H2 separation. The GMM at 4 bar and 25 °C exhibited He, H2, CO2, N2, and CH4 gas permeations of 576.37, 509.23, 146.07, 3.45, and 2.28 barrer, respectively. The ideal selectivities of H2/CH4, CO2/N2, CO2/CH4, H2/N2, and H2/CO2 gas pairs were 223.47, 42.37, 64.10, 147.71, and 3.49, respectively, which significantly exceed earlier reported values for ZIF-62 membranes, demonstrating the significant potential for GMMs as high-performance molecular sieve membranes, particularly for H2 separation. This work by optimizing the vitrification process through systematic temperature control highlights GMM's ability to achieve high selectivity and permeability, positioning it as a promising candidate for industrial gas separation applications.

Polybenzimidazole (PBI) is a promising membrane material for pre-combustion carbon capture. PBI is highly selective for H2 over CO2 (separation factor of 20-30) and has excellent thermomechanical properties, but its low gas permeabilities limit membrane performance. This study reports blends of Celazole (R) PBI with a highly permeable and thermally rearrangeable triptycene-containing poly(hydroxyimide), TPHI. Relative to H2 permeability of 3.1 f 0.3 Barrer for neat PBI, H2 permeabilities for PBI/TPHI blend films were increased to values as high as 7.5 f 0.5 Barrer with PBI as the majority blend component. PBI/TPHI H2/CO2 selectivity was maintained above 20 for films containing 20 wt % TPHI but decreased substantially with increasing TPHI content. 400 degrees C thermal rearrangement (TR) increased blend H2 permeabilities to values as high as 12 f 1 Barrer with PBI as the majority component, but this was coupled with a pronounced decrease in H2/CO2 selectivity. Selectivity losses beyond those expected for a phase separated polymer blend suggested miscibility between the PBI and TPHI phases. This conclusion was substantiated by scanning and transmission electron microscopy analyses, as well as solid-state nuclear magnetic resonance spectroscopy.

mRNA vaccines have emerged as a highly effective strategy for the prevention and treatment of various diseases. A critical factor driving the success of mRNA vaccines is the development of advanced multicomponent lipid nanoparticles (LNPs) as a delivery system. As mRNA-LNP technology becomes increasingly integral to vaccine and therapeutic development, there is significant potential to enhance LNP efficiency and build upon the first generation of clinically approved mRNA-LNP products. This can lead to the development of superior formulations that achieve higher protein expression and improved therapeutic outcomes. In this study, we present a novel approach to enhance the transfection efficiency of mRNA-LNPs using ZIF-8 metal-organic framework (MOF). We demonstrate effective encapsulation of mRNA-LNPs within ZIF-8, with preserved structural integrity during dissociation and release. Remarkably, following MOF encapsulation and release, we observed a 3-fold and 8-fold increase in transfection efficiency of the mRNA-LNPs at 48 h in HEK-293 and HCT-116 cells, respectively. Our findings suggest that the presence of ZIF-8 materials with the mRNA-LNPs significantly contributes to their improved transfection and translation efficiency.

Metal-organic frameworks (MOFs) are versatile materials, but their synthesis often requires harsh conditions, toxic precursors, or organic solvents. Recently, MOFs have been produced using resonant acoustic mixing (RAM), a form of mechanochemistry that provides a greener alternative to conventional methods. In this study, we demonstrate the solvent-free synthesis of fumarate-based MOFs using RAM at room temperature and atmospheric pressure. Iron fumarate (MIL-88A(Fe)) was successfully produced with a BET surface area of 209 m2 g-1, comparable to mechanochemical grinding. The synthesis was scaled up to a 10.5 g yield using RAM for 20 min and without solvent. Aluminum fumarate (MIL-53(Al)-FA) was also synthesized with a high surface area (790 m2 g-1), while attempts to synthesize the calcium fumarate MOF (CaFu) instead resulted in the non-porous coordination polymer, calcium fumarate trihydrate. These results demonstrate the potential of RAM as a more sustainable approach to MOF synthesis.

The use of polymer or inorganic additives are shown to have a synergistic effect on the gas separation performance of plastic crystal membranes.

Redox flow batteries show promise for large‐scale grid stabilisation. Of these, organic redox flow batteries (ORFBs) harbour the potential for sustainable and economic operation due to the materials deployed. Their long‐term operation requires exquisite transport control of species across the cell, with movement of cations key for high current density, and anionic rejection needed for cycling stability. Nafion, although promising as a commercial separator, faces cost and sustainability limitations due to its fluorinated nature and per‐ and polyfluroralkyl substances (PFAS) generation. Here, we report the tailored combination of a hydrophilic mixed‐matrix membrane, SPEEK‐SX, with sulphonated polydichloroxylene (S p ‐DCX) as the additive and sulphonated poly(ether ether ketone) (SPEEK) as the matrix. Compared to Nafion‐212, the dense aromatic backbone of SPEEK efficiently rejected the crossover of electrolytes, with sulfonate groups housed within S p ‐DCX micropores increasing Na + mobility. SPEEK‐SX2 exhibited 190 times higher Na + / Fe(CN) 6 4− selectivity and 6 times higher Na + / 2,6‐DHAQ 2− selectivity compared to Nafion‐212. This enabled stable operation for 600 cycles at a high current density of 160 mA cm −2 with only 0.00935% per cycle capacity decay. In contrast, the SPEEK membrane exhibited 0.07% per cycle decay, whereas Nafion‐212 failed to run at this high current density.

ABSTRACT Effective sample collection is a pivotal step in environmental DNA (eDNA) workflows. For aquatic eDNA applications, this typically requires water filtration and cold storage, which present logistical challenges in remote or resource‐limited settings. Metal–organic frameworks (MOFs) are porous materials composed of metal ions coordinated with organic linkers that can form around biological molecules in solution. By directly encapsulating and preserving eDNA in situ within a collected water sample, MOFs may simplify field sampling without the need for specialized equipment. In this study, eDNA capture and preservation from seawater samples using the MOF Zeolitic Imidazolate Framework‐8 (ZIF‐8) was compared with the performance of conventional filtration through mixed cellulose ester (MCE) filters. ZIF‐8 samples were stored at ambient temperature for 2 weeks, while MCE filters were either frozen or preserved in a lysis buffer for 5 days. The performance of each method was assessed by high‐throughput DNA sequencing and a metabarcoding assay targeting the 16S rRNA gene of fish. The MCE filter method detected, at present, a greater number of fish amplicon sequence variants (ASVs) and taxa than our trial application of the MOF method. However, community composition analyses (PERMANOVA and NMDS ordination) revealed no significant differences between the methods, demonstrating that despite yielding lower DNA quantities, ZIF‐8 collection effectively replicates the marine fish community structure. Analysis of taxon abundance showed that MOFs captured dominant taxa effectively but were less sensitive to rarer taxa. With further optimisation to enhance eDNA capture efficiency by MOFs beyond this trial application, MOFs could serve as a practical, field‐friendly alternative for eDNA sampling, especially where filtration is difficult.

A facile method of synthesizing flexible thin films of carbon nano dots (CNDs) and Polyvinyl Pyrrolidone (PVP) on cellulose based substrates is developed and their thermoelectric properties are demonstrated through the fabrication of a wearable device. Alongside enhanced thermoelectric performance, the CND thin films are biocompatible, low cost and scalable, all essential criteria for wearable thermoelectric devices. A critical window of the CND loading concentration on the cellulose‐based substrate is observed, with significantly enhanced Seebeck coefficient and Power Factor of thin films, demonstrating that the trade‐off principles for thermoelectric materials must be carefully tuned. The highest Seebeck coefficient of –358.45 µV·K −1 , power factor of 0.03 µW·m −1 ·K −2 and the lowest thermal conductivity of 0.086 W·m −1 ·K −1 at room temperature is achieved with a CND loading concentration of 9.32 g cm −2 . A wearable thermoelectric device is fabricated using n‐type CND films with copper electrodes. When worn, the device can generate voltage and current of ≈70 mV and ≈15 nA, respectively, at ΔT of 10 K.

Mixed matrix materials (MMMs) containing metal-organic framework (MOF) nanoparticles are attractive for membrane carbon capture. Particularly, adding <5 mass % MOFs in polymers dramatically increased gas permeability, far surpassing the Maxwell model's prediction. However, no sound mechanisms have been offered to explain this unusual low-loading phenomenon. Herein, we design an ideal series of MMMs containing polyethers (one of the leading polymers for CO2/N-2 separation) and discrete metal-organic polyhedra (MOPs) with cage sizes of 2-5 nm. Adding 3 mass % MOP-3 in a polyether increases the CO2 permeability by 100% from 510 to 1000 Barrer at 35 degrees C because of the increased gas diffusivity. No discernible changes in typical physical properties governing gas transport properties are detected, such as glass transition temperature, fractional free volume, d-spacing, etc. We hypothesize that this behavior is attributed to fractal-like networks formed by highly porous MOPs, and for the first time, we validate this hypothesis using small-angle X-ray scattering analysis.

Solid polymer electrolytes (SPEs) are long sought after for versatile applications due to their low cost, light weight, flexibility, ease of scale-up, and low interfacial impedance. However, obtaining SPEs with high Li+ conductivity (sigma+) and high voltage stability to avoid concentrated polarization and premature capacity loss has proven challenging. Here a stretchable dry-SPE is reported with a semi-interpenetrating, supermolecular architecture consisting of a cross-linked polyethylene oxide (PEO) tetra-network and an alternating copolymer poly(ethylene oxide-alt-butylene terephthalate). Such a unique supermolecular architecture suppresses the formation of Li+/PEO intermolecular complex and enhances the oxidation stability of PEO-based electrolyte, thus maintaining high chain segmental motion even with high salt loading (up to 50 wt%) and achieving a wide electrochemical stability window of 5.3 V. These merits enable the simultaneous accomplishment of high ionic conductivity and high Li+ transference number (t+) to enhance the energy efficiency of energy storage device, and electrochemical stability. High-performance dry-solid polymer electrolytes (SPEs) are demonstrated using a supramolecular semi-interpenetrating polymer network. These SPEs can accommodate high concentrations of lithium salts without raising their glass transition temperature. This results in high Li+ diffusivity and a high Li+ transference number, as well as excellent mechanical flexibility and optical transmittance.image

Environmental DNA (eDNA) is released by organisms into their surroundings, enabling non-invasive species detection and biodiversity assessments without the need for direct observation. However, collection poses challenges due to the generally low abundance of eDNA and the presence of degradation agents, including enzymes, UV radiation, and microorganisms, rendering samples unstable. Active filtration, which is frequently used to capture eDNA in water, can be time-consuming and cumbersome in field conditions. Herein, a filter-free one-pot procedure for capturing eDNA with the metal-organic framework (MOF), zeolitic imidazolate framework 8 (ZIF-8), is examined. The method is evaluated on 15 mL water samples from diverse sources (aquarium, river, and sea). ZIF-8 forms in all with high capture efficiency (>98%) using spiked salmon DNA to represent eDNA. The DNA is resistant to degradation by endonucleases and UV light. In addition, it remains stable over time as a species-specific salmon quantitative polymerase chain reaction detected genomic DNA in all samples captured with the MOF to a maximum of 28 days at 37 °C while the untreated control samples were below the assay detection limit by day 6. These results highlight the efficacy of ZIF-8 capture in overcoming challenges associated with the preservation of eDNA obtained from aquatic environments.

Microporous glassy polymer membranes suffer from physical aging, which adversely affects their performance in the short time frame. We show that the aging propensity of a model microporous polymer, poly(1-trimethylsilyl-1-propyne) (PTMSP), can be effectively mitigated by blending with as little as 5 wt % porous polymer network (PPN) composed of triptycene and isatin. The aging behavior of these materials was monitored via N2 pure gas permeability measurements over the course of 3 weeks, showing a 14% decline in PTMSP blended with 5 wt % PPN vs a 41% decline in neat PTMSP. Noteworthy, PPNs are 2 orders of magnitude cheaper than the porous aromatic frameworks previously used to control PTMSP aging. A variety of experimental and computational techniques, such as Positron Annihilation Lifetime Spectroscopy (PALS), free volume measurements, cross-polarization/magic angle spinning (CP/MAS) 13C NMR, transport measurements and molecular dynamics (MD) simulations were used to uncover the molecular mechanisms leading to enhanced aging resistance. We show that partial PTMSP chain adsorption into the PPN porosity reduces the PTMSP local segmental mobility, leading to improved aging resistance. Permeability coefficients were broken into their elementary sorption and diffusion contributions, to elucidate the mechanism by which the reduced PTMSP local segmental mobility affects selectivity in gas separation applications. Finally, we demonstrate that in these systems, where both chemical and physical interactions take place, transport coefficients must be corrected for thermodynamic nonidealities to avoid erroneous interpretation of the results.

In light of increasing concerns about climate change, there is a growing need for innovative solutions to address CO2 emissions. Addressing this urgency, this work presents a unique approach to CO2 separation utilizing composite membranes of organic ionic plastic crystals (OIPCs) with ether-functionalized cations and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). Here we report the gas separation performance of OIPC-based membranes of 3,3-dimethyloxazolidinium [C1moxa]+, 4-ethyl-4-methylmorpholinium [C2mmor]+ and 4-isopropyl-4-methylmorpholinium [Ci3mmor]+ cations paired with the bis(fluorosulfonyl)imide [FSI]anion. These composites demonstrated very good gas separation properties, especially [C1moxa][FSI] which produced a permeability of 63 barrer for CO2 and an overall selectivity (CO2/N2) of 205, which is the highest amongst all the OIPCs reported so far. Additionally, a large change in separation performance was observed for the [Ci3mmor][FSI] membrane upon heating above the solid-solid phase transition (II - I) at 48 degrees C; the CO2 permeability increased from 7 to 163 barrer and an approximately 3-fold increase in selectivity was observed. These findings advance the design of composite membranes based on OIPCs towards increased selectivity and sustained effectiveness in the separation of light gases.

Metal-organic frameworks (MOFs) exhibit large surface areas and low thermal conductivity, making them promising for thermoelectric generation. However, their limited electrical conductivity poses a significant hurdle to be practically useful. Traditionally, enhancing the electrical conductivity of MOFs typically comes at the cost of reducing surface area, thereby increasing thermal conductivity. This study introduces an approach to simultaneously boost the electrical conductivity and porosity of a MOF-based material while maintaining remarkably low thermal conductivity. The electrically conductive poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) is deployed to nucleate the growth of Cu-3(BTC)(2) (or simply CuBTC, where BTC = benzene-1,3,5-tricarboxylic acid), resulting in the synthesis of composites labeled CPP-y (where y denotes wt% PEDOT:PSS). Predictably, the CPP-y composites are more electrically conductive than pure CuBTC, achieving an electrical conductivity exceeding 1.40 S cm(-1) at room temperature. Furthermore, the CPP-y composites exhibit consistently high Brunauer-Emmett-Teller (BET) surface areas of approximate to 1600 m(2) g(-1), comparable to pristine CuBTC, while maintaining thermal conductivities below 0.04 W m(-1) K-1 at room temperature. With a high Seebeck coefficient in the range 180-373 mu V K-1, CPP-15 and CPP-23 demonstrate a figure-of-merit (zT) of 0.25 and 0.11, respectively, at 285 K, marking a substantial achievement for MOF-based materials.

Abstract A zeolitic imidazolate framework (ZIF‐8) containing two enzymes that form a cascade biocatalyst has been integrated with 3D structures that are fabricated through a two‐photon polymerization using direct laser writing lithography. Glucose oxidase (GOx) and horseradish peroxidase (HRP) are encapsulated by the biomimetic self‐assembly process of ZIF‐8 to form the GOx/HRP/ZIF‐8 composite which grows in situ on the surface of microprinted carbon‐coated hexagonal substrates (cHS). The GOx/HRP/ZIF‐8/cHS film is applied to glucose detection through enzymatic oxidation of glucose to gluconic acid, forming H2O2, in the presence of GOx and the subsequent reduction of H2O2 to water in the presence of HRP and Amplex Red. This reaction is monitored using fluorimetry as the oxidation of Amplex Red with H2O2 catalyzed by HRP forms red‐emitting resorufin. The GOx/HRP/ZIF‐8/cHS film responds to glucose concentrations with a linear range of 10–200 µm, which correlates to the salivary glucose level in healthy humans. The GOx/HRP/ZIF‐8/cHS film shows more than eight times and 13 times enhanced activity than GOx/HRP/cHS (without ZIF‐8) and GOx/HRP/ZIF‐8 on a non‐3D patterned substrate, respectively. The GOx/HRP/ZIF‐8/cHS film retains more than 80% or 100% of its initial activity after being stored for over 2 months at ≤24 or 4 °C, respectively.

Physical aging rates strongly correlate with the initial free volume of microporous polymers. Introducing hydrogen bonds and crosslinks can reduce the initial free volume and significantly impact gas separation selectivity over time.

Porous liquids (PLs) are attractive materials because of their capability to combine the intrinsic porosity of microporous solids and the processability of liquids. Most of the studies focus on the synthesis of PLs with not only high porosity but also low viscosity by considering their transportation in industrial plants. However, a gap exists between PLs and solid adsorbents for some practical cases, where the liquid characteristics and mechanical stability without leakage are simultaneously required. Here, we fill in this gap by demonstrating a new concept of pore-networked gels, in which the solvent phase is trapped by molecular networks with accessible porosity. To achieve this, we fabricate a linked metal-organic polyhedra (MOPs) gel, followed by exchanging the solvent phase with a bulky liquid such as ionic liquids (ILs); the dimethylformamide solvent trapped inside the as-synthesized gel is replaced by the target IL, 1-butyl-3-methylimidazolium tetrafluoroborate, which in turn cannot enter MOP pores due to their larger molecular size. The remaining volatile solvents in the MOP cavities can then be removed by thermal activation, endowing the obtained IL gel (Gel_IL) with accessible microporosity. The CO2 capacities of the gels are greatly enhanced compared to the neat IL. The exchange with the IL also exerts a positive influence on the final gel performances such as mechanical properties and low volatility. Besides ILs, various functional liquids are shown to be amenable to this strategy to fabricate pore-networked gels with accessible porosity, demonstrating their potential use in the field of gas adsorption or separation.

Engineering different two-dimensional materials into heterostructured membranes with unique physiochemical properties and molecular sieving channels offers an effective way to design membranes for fast and selective gas molecule transport. Here we develop a simple and versatile pyro-layering approach to fabricate heterostructured membranes from boron nitride nanosheets as the main scaffold and graphene nanosheets derived from a chitosan precursor as the filler. The rearrangement of the graphene nanosheets adjoining the boron nitride nanosheets during the pyro-layering treatment forms precise in-plane slit-like nanochannels and a plane-to-plane spacing of ~3.0 Å, thereby endowing specific gas transport pathways for selective hydrogen transport. The heterostructured membrane shows a high H 2 permeability of 849 Barrer, with a H 2 /CO 2 selectivity of 290. This facile and scalable technique holds great promise for the fabrication of heterostructures as next-generation membranes for enhancing the efficiency of gas separation and purification processes.