Metal-organic framework glass composites.

The melting phenomenon in metal-organic frameworks (MOFs) has been recognised as one of the fourth generation MOF paradigm behaviours. Molten MOFs have high processibility for producing mechanically robust glassy MOF macrostructures, and they also offer highly tunable interfacial characteristics when combined with other types of functional materials, such as crystalline MOFs, inorganic glass and metal halide perovskites. As a result, MOF glass composites have emerged as a family of functional materials with dynamic properties and hierarchical structural control. These nanocomposites allow for sophisticated materials science studies as well as the fabrication of next-generation separation, catalysis, optical, and biomedical devices. Here, we review the approaches for designing, fabricating, and characterising MOF glass composites. We determine the key application opportunities enabled by these composites and explore the remaining hurdles, such as improving thermal and chemical compatibility, regulating interfacial properties, and scalability.

Mechanochemically Synthesised Flexible Electrodes Based on Bimetallic Metal-Organic Framework Glasses for the Oxygen Evolution Reaction.

The melting behaviour of metal-organic frameworks (MOFs) has aroused significant research interest in the areas of materials science, condensed matter physics and chemical engineering. This work first introduces a novel method to fabricate a bimetallic MOF glass, through melt-quenching of the cobalt-based zeolitic imidazolate framework (ZIF) [ZIF-62(Co)] with an adsorbed ferric coordination complex. The high-temperature chemically reactive ZIF-62(Co) liquid facilitates the formation of coordinative bonds between Fe and imidazolate ligands, incorporating Fe nodes into the framework after quenching. The resultant Co-Fe bimetallic MOF glass therefore shows a significantly enhanced oxygen evolution reaction performance. The novel bimetallic MOF glass, when combined with the facile and scalable mechanochemical synthesis technique for both discrete powders and surface coatings on flexible substrates, enables significant opportunities for catalytic device assembly.

Hierarchically Porous Biocatalytic MOF Microreactor as a Versatile Platform towards Enhanced Multienzyme and Cofactor-Dependent Biocatalysis.

Metal-organic frameworks (MOFs) have recently emerged as excellent hosting matrices for enzyme immobilization, offering superior physical and chemical protection for biocatalytic reactions. However, for multienzyme and cofactor-dependent biocatalysis, the subtle orchestration of enzymes and cofactors is largely disrupted upon immobilizing in the rigid crystalline MOF network, which leads to a much reduced biocatalytic efficiency. Herein, we constructed hierarchically porous MOFs by controlled structural etching to enhance multienzyme and cofactor-dependent enzyme biocatalysis. The expanded size of the pores can provide sufficient space for accommodated enzymes to reorientate and spread within MOFs in their lower surface energy state as well as to decrease the inherent barriers to accelerate the diffusion rate of reactants and intermediates. Moreover, the developed hierarchically porous MOFs demonstrated outstanding tolerance to inhospitable surroundings and recyclability.

Halogenated Metal-Organic Framework Glasses and Liquids.

The synthesis of four novel crystalline zeolitic imidazolate framework (ZIF) structures using a mixed-ligand approach is reported. The inclusion of both imidazolate and halogenated benzimidazolate-derived linkers leads to glass-forming behavior by all four structures. Melting temperatures are observed to depend on both electronic and steric effects. Solid-state NMR and terahertz (THz)/far-IR demonstrate the presence of a Zn-F bond for fluorinated ZIF glasses. In situ THz/far-IR spectroscopic techniques reveal the dynamic structural properties of crystal, glass, and liquid phases of the halogenated ZIFs, linking the melting behavior of ZIFs to the propensity of the ZnN4 tetrahedra to undergo thermally induced deformation. The inclusion of halogenated ligands within metal-organic framework (MOF) glasses improves their gas-uptake properties.

Intermarriage of Halide Perovskites and Metal-Organic Framework Crystals.

This Review examines how the intermarriage of perovskite and metal-organic framework crystals brings new paradigms for material design and functionality. The strategic combination of halide perovskites and metal-organic frameworks (MOFs) has generated a new family of porous composite materials that will enable new applications, including optoelectronic, catalysis, sensing, and data encryption. This Review surveys the current progress of this exciting new area. Fundamental aspects, including perovskite nucleation and growth, heterojunction electron-hole transfer, electronic structure, and luminescence within confined spaces, are highlighted, with suggestions of approaches by which guest confinement within MOFs can be synthetically designed. We further address the underlying principles and discuss the new insights and tools for the manipulation of these composite materials for the development of synthetic microporous semiconducting composites, as well as new strategies for host-guest interfacial engineering.

Collagen VII deficient mice show morphologic and histologic corneal changes that phenotypically mimic human dystrophic epidermolysis bullosa of the eye.

BACKGROUND: Absence of collagen VII causes blistering of the skin, eyes and many other tissues. This disease is termed dystrophic epidermolysis bullosa (DEB). Corneal fibrosis occurs in up to 41% and vision loss in up to 64% of patients. Standard treatments are supportive and there is no cure. The hypomorphic mouse model for DEB shows production of collagen VII at 10% of wild type levels in skin and spleen, but the eyes have not been described. Our purpose is to characterize the corneas to determine if this is an appropriate model for study of ocular therapeutics. METHODS: Western blot analysis (WB) and immunohistochemistry (IHC) were performed to assess presence and location of collagen VII protein within the hypomorphic mouse cornea. Additional IHC for inflammatory and fibrotic biomarkers transforming growth factor-beta-1 (TGF-ß1), alpha-smooth muscle actin (α-SMA), connective tissue growth factor (CTGF), proteinase 3, tenascin C and collagen III were performed. Clinical photographs documenting corneal opacification were assessed and scored independently by 2 examiners. Histology was then used to investigate morphologic changes. RESULTS: IHC and WB confirmed that hypomorphic mice produce less collagen VII production at the level of the basement membrane when compared with wild-types. IHC showed anomalous deposition of collagen III throughout the stroma. Of the 5 biomarkers tested, TGF-ß1 showed the strongest and most consistently staining. Photographs documented corneal opacities only in mice older than 10 weeks, opacities were not seen in younger animals. Histology showed multiple abnormalities, including epithelial hyperplasia, ulceration, fibrosis, edema, dysplasia, neovascularization and bullae formation. CONCLUSIONS: The collagen VII hypomorphic mouse shows reduced collagen VII production at the level of the corneal basement membrane. Corneal changes are similar to pathology seen in humans with this disease. The presence of anomalous stromal collagen III and TGF-ß1 appear to be the most consistent and strongest staining biomarkers in diseased mice. This mouse appears to mimic human corneal disease. It is an appropriate model for testing of therapeutics to treat EB ocular disease.

Lichen Nitidus of the Eyelids.

Lichen nitidus is a rare, idiopathic inflammatory condition that typically presents as small, flat-topped papules on the chest, abdomen, and upper extremities. The lesions are benign and often asymptomatic and self-resolve. The pediatric population is most often affected. The authors report a case of lichen nitidus presenting as isolated bilateral eyelid lesions increasing in number for several years. Eventual excision and antibiotic/steroid ointment prompted regression.

Single-Enzyme Biofuel Cells.

Herein, we demonstrate that the intramolecular electron transfer within a single enzyme molecule is an important alternative pathway that can be harnessed to generate electricity. By decoupling the redox reactions within a single type of enzyme (for example, Trametes versicolor laccase), we harvested electricity efficiently from unconventional fuels including recalcitrant pollutants (for example, bisphenol A and hydroquinone) in a single-laccase biofuel cell. The intramolecular electron-harnessing concept was further demonstrated with other enzymes, including power generation during CO2 bioconversion to formate catalyzed by formate dehydrogenase from Candida boidinii. The novel single-enzyme biofuel cell is shown to have potential for utilizing wastewater as a fuel as well as for generating energy while driving bioconversion of chemical feedstock from CO2 .

Janus Membranes: Exploring Duality for Advanced Separation.

Janus membranes are an emerging class of materials having opposing properties at an interface. This structure results in selective and often novel transport characteristics. In this Minireview, a definition of the Janus membrane, beyond merely asymmetric materials, is introduced and common fabrication strategies are outlined. Also presented are current and potential applications in directional transport, switchable permeation, and performance optimization with detailed mechanisms.

Formation of Ultrathin, Continuous Metal-Organic Framework Membranes on Flexible Polymer Substrates.

Metal-organic framework (MOF) materials have an enormous potential in separation applications, but to realize their potential as semipermeable membranes they need to be assembled into thin continuous macroscopic films for fabrication into devices. By using a facile immersion technique, we prepared ultrathin, continuous zeolitic imidazolate framework (ZIF-8) membranes on titania-functionalized porous polymeric supports. The coherent ZIF-8 layer was surprisingly flexible and adhered well to the support, and the composite membrane could sustain bending and elongation. The membranes exhibited molecular sieving behavior, close to the theoretical permeability of ZIF-8, with hydrogen permeance up to 201×10(-7)  mol m(-2) s(-1) Pa(-1) and an ideal H2 /CO2 selectivity of 7:1. This approach offers significant opportunities to exploit the unique properties of MOFs in the fabrication of separation and sensing devices.

Assessment of anti-fouling strategies for membrane coupled with upflow anaerobic sludge blanket (MUASB) process.

In this novel process, domestic wastewater was filtered by a hollow-fibre membrane coupled with an upflow anaerobic sludge blanket (MUASB) bioreactor. To improve the process sustainability and decrease energy costs, the membranes were operated under low fluxes with little, or no, shear. The efficiency of anti-fouling strategies, including relaxation, backwashing and supply of low aeration and stir rates, was assessed through detailed characterization of the fouling layers. Results indicated that backwashing was more efficient than relaxation, even when the systems were operated under the same flux productivity. In terms of shear supply, stir provided a better fouling limitation strategy compared to aeration, at similar shear stress values. Physical and chemical cleaning methods were applied to recover three fouling fractions (i.e. cake, residual and irreversible) for better characterization of the fouling layers. Under the sustainable operating conditions used in this study, most of the fouling was easily reversible by simple rinsing. In addition, permanent and irreversible fouling, resulting in the need for frequent chemical cleanings and potential membrane degradation, is limited once small shear stresses are applied. These outcomes are expected to form the basis for the future assessment of trade-off between operation, maintenance and replacement costs of membrane filtration processes used in wastewater treatment.

Advanced characterization of fouling in membrane coupled with upflow anaerobic sludge blanket process.

In this study, an advanced process based on the use of ultrafiltration hollow fibre membranes immersed in the supernatant of an upflow anaerobic sludge blanket bioreactor (MUASB) and operated under low permeate flux was proposed. Process sustainability was assessed under different operating conditions: membranes were immersed either in the supernatant or in the biomass bulk and operated under various permeate fluxes. Additionally, temporal investigation was also proposed through the advanced characterization of fouling behaviour by systematic fractionation (based on level of reversibility) and analysis by liquid chromatography-organic carbon detector. Among the various suspended solids (SS) concentrations in supernatant (10, 25, 100, and 400 mg L(-1)) and in biomass bulk (6500 mg L(-1)), higher fouling levels were observed under low SS concentrations. However, more easily reversible fouling was obtained under MUASB conditions, demonstrating potential long-term sustainability. Results of long-term operation indicated that an increase of flux leads to larger amounts of SS participating in irreversible fouling and higher irreversibility. Temporal change in fouling characteristics revealed that the most easily removable fouling layer (i.e. cake), and its relative fraction of SS, were the two main factors impacting on the overall hydraulic performance. Additionally, the development of microbial population on the membrane surface was closely related to the proteins content and the overall hydraulic resistance. Polysaccharides and other dissolved organic matters (humic substances, building blocks, and low molecular weight compounds) presented low effect on membrane fouling.

Folate and Choline: Does It Take Two to Tango in Early Programming of Disease?

BACKGROUND: The early life period marks a critical time during which the health trajectory of offspring can be shaped by external influences including maternal nutrition. Folate and choline are water-soluble micronutrients important for fetal development and involved in one-carbon metabolism. Intakes above and below the recommendations commonly occur for both of these nutrients including over-consumption of synthetic folic acid due to widespread vitamin supplement uses and discretionary fortification practices, whereas choline is under-consumed by a majority of the populations including pregnant women. Despite these intake patterns, their long-term impact on offspring health is largely unknown. Moreover, limited attention has been on the combined effects of folate and choline despite being metabolically interrelated as methyl nutrients. This review summarizes evidence from animal models and human studies investigating the role of inadequate or supplemental maternal intakes of folic acid, choline and combined effects of folic acid, and choline as modulators of health and disease in offspring. With the recent rise in the prevalence of obesity and metabolic diseases, our primary measures of interest were metabolic outcomes. SUMMARY: Studies examining the role of maternal intakes of folic acid and/or choline in metabolic phenotypes of offspring have mostly been conducted in animal models with a limited number of reports that consider folate and choline together. An interdependent relationship has been demonstrated between folate and choline in studies where a deficiency in one leads to metabolic aberrations in another. Both deficient and excess maternal intakes of folic acid (in varying doses) have been shown to increase risk of obesity and characteristics of the metabolic syndrome in offspring but these findings were restricted to animal studies. Potential metabolic benefits of choline have been suggested in the presence of obesogenic environment but human data were sparse. An imbalanced intake of high folic acid and inadequate choline in the gestational diet created adverse consequences consistent with the obesogenic phenotypes whereas narrowing this imbalance with high choline blocked these effects. Mechanisms by which maternal folate and/or choline influence offspring outcomes may involve epigenetic modification of gene expression with DNA methylation that can be altered globally and gene-specifically. However, the effects of epigenetic programming were inconsistent as compensatory changes in metabolic products may occur and other contributors including the gut microbiota may provide additional insights into the mechanisms. KEY MESSAGES: Maternal intakes of folic acid and/or choline can impact offspring's long-term health, with metabolic consequences that may arise from imbalances between folate and choline. However, there is a paucity of mechanistic understanding as various contributors influence programming effects including those beyond epigenetics. As folate and choline are metabolically interrelated, future studies need to consider both nutrients to better elucidate metabolic programming of health and disease.

Validation and Repeatability of the Epidermolysis Bullosa Eye Disease Index in Dystrophic Epidermolysis Bullosa.

PURPOSE: Dystrophic epidermolysis bullosa (DEB) is a devastating condition that causes painful corneal abrasions and vision loss. Epidermolysis Bullosa Eye Disease Index (EB-EDI) for the first time captures and quantifies EB-specific assessment of ocular symptoms and activities of daily living scales. This survey will become critical in developing new interventions on patients' quality of life. METHODS: Three-part set of the EB-EDI baseline, EB-EDI interval, and Ocular Surface Disease Index (OSDI) survey was distributed to 92 patients with DEB who previously reported eye symptoms on previous surveys. It was then posted online through several EB patient organizations. We compared the EB-EDI with the gold standard OSDI and examined the repeatability of the EB-EDI over a 7- to 15-day interval. RESULTS: Of the 45 individuals who initially responded, 30 of 45 (67%) completed the surveys sent 7 to 15 days later. The age of participants ranged from 6 to 51 years (mean 21 ± 15 years), and 60% (18 of 30) of participants were younger than 18 years. The overall Cronbach alpha values for the subscales of EB-EDI baseline and interval tools presented a good internal consistency (≥0.7). From 2 visits, the domain scores of EB-EDI baseline (0.94) and interval tools (0.83) were shown to have excellent test-retest reliability (intraclass correlation coefficient >0.8). By comparison, OSDI had the intraclass correlation coefficient score of 0.72 ± 0.11. The convergent validation analysis showed that correlations between the domain scores of EB-EDI baseline and interval tools and the subscales of the OSDI reached the hypothesized strength. CONCLUSIONS: Based on a 30-person repeated-measures study, we found that the EB-EDI has excellent reliability and validity specifically in patients with DEB.

Modification of the serotonergic systems and phenotypes by gestational micronutrients.

Micronutrients consumed in excess or imbalanced amounts during pregnancy may increase the risk of metabolic diseases in offspring, but the mechanisms underlying these effects are unknown. Serotonin (5-hydroxytryptamine, 5-HT), a multifunctional indoleamine in the brain and the gut, may have key roles in regulating metabolism. We investigated the effects of gestational micronutrient intakes on the central and peripheral serotonergic systems as modulators of the offspring's metabolic phenotypes. Pregnant Wistar rats were fed an AIN-93G diet with 1-fold recommended vitamins (RV), high 10-fold multivitamins (HV), high 10-fold folic acid with recommended choline (HFolRC), or high 10-fold folic acid with no choline (HFolNC). Male and female offspring were weaned to a high-fat RV diet for 12 weeks. We assessed the central function using the 5-HT2C receptor agonist, 1-(3-chlorophenyl)piperazine (mCPP), and found that male offspring from the HV- or HFolRC-fed dams were less responsive (P < 0.05) whereas female HFolRC offspring were more responsive to mCPP (P < 0.01) at 6 weeks post-weaning. Male and female offspring from the HV and HFolNC groups, and male HFolRC offspring had greater food intake (males P < 0.001; females P < 0.001) and weight gain (males P < 0.0001; females P < 0.0001), elevated colon 5-HT (males P < 0.01; females P < 0.001) and fasting glucose concentrations (males P < 0.01; females P < 0.01), as well as body composition toward obesity (males P < 0.01; females P < 0.01) at 12 weeks post-weaning. Colon 5-HT was correlated with fasting glucose concentrations (males R2=0.78, P < 0.0001; females R2=0.71, P < 0.0001). Overall, the serotonergic systems are sensitive to the composition of gestational micronutrients, with alterations consistent with metabolic disturbances in offspring.

Recent advances in enzymatic biofuel cells enabled by innovative materials and techniques.

The past few decades have seen increasingly rapid advances in the field of sustainable energy technologies. As a new bio- and eco-friendly energy source, enzymatic biofuel cells (EBFCs) have garnered significant research interest due to their capacity to power implantable bioelectronics, portable devices, and biosensors by utilizing biomass as fuel under mild circumstances. Nonetheless, numerous obstacles impeded the commercialization of EBFCs, including their relatively modest power output and poor long-term stability of enzymes. To depict the current progress of EBFC and address the challenges it faces, this review traces back the evolution of EBFC and focuses on contemporary advances such as newly emerged multi or single enzyme systems, various porous framework-enzyme composites techniques, and innovative applications. Besides emphasizing current achievements in this field, from our perspective part we also introduced novel electrode and cell design for highly effective EBFC fabrication. We believe this review will assist readers in comprehending the basic research and applications of EBFCs as well as potentially spark interdisciplinary collaboration for addressing the pressing issues in this field.

Interfacial alloying between lead halide perovskite crystals and hybrid glasses.

The stellar optoelectronic properties of metal halide perovskites provide enormous promise for next-generation optical devices with excellent conversion efficiencies and lower manufacturing costs. However, there is a long-standing ambiguity as to whether the perovskite surface/interface (e.g. structure, charge transfer or source of off-target recombination) or bulk properties are the more determining factor in device performance. Here we fabricate an array of CsPbI3 crystal and hybrid glass composites by sintering and globally visualise the property-performance landscape. Our findings reveal that the interface is the primary determinant of the crystal phases, optoelectronic quality, and stability of CsPbI3. In particular, the presence of a diffusion "alloying" layer is discovered to be critical for passivating surface traps, and beneficially altering the energy landscape of crystal phases. However, high-temperature sintering results in the promotion of a non-stoichiometric perovskite and excess traps at the interface, despite the short-range structure of halide is retained within the alloying layer. By shedding light on functional hetero-interfaces, our research offers the key factors for engineering high-performance perovskite devices.

Lemierre syndrome associated mycotic cavernous sinus thrombosis and carotid aneurysm after COVID-19.

Purpose: The purpose of this article is to report a case of Lemierre syndrome associated mycotic aneurysm of the intracavernous carotid artery leading to cavernous sinus syndrome in an otherwise healthy, young man in the setting of COVID-19 infection. Observations: An 18-year-old, otherwise healthy male athlete developed fever, chills, and headache and was found to be positive for COVID-19 with gram negative bacteremia. While on systemic antibiotic treatment, he developed acute, left-sided, 6th nerve palsy and was found to have bacterial sinusitis, left-sided intracavernous mycotic aneurysm, and cavernous sinus thrombosis on imaging studies. Despite systemic antibiotic and antiplatelet therapy, he developed progressively worsening left-sided ophthalmoplegia and vision decline. He subsequently underwent left internal carotid artery embolization and cervical internal carotid artery sacrifice with excellent outcome. Conclusion and importance: Lemierre syndrome can have atypical presentations and complications, including cavernous sinus thrombosis and mycotic aneurysms. Recognition of signs and symptoms, including progressive multiple cranial neuropathies, can aid in early diagnosis and management, which requires multidisciplinary care tailored to each individual based on risk of intervention.

Corneal Changes and Strategies to Improve Survival of Hypomorphic Collagen VII-Deficient Mice for the Study of Ocular Dystrophic Epidermolysis Bullosa.

Ophthalmic study of collagen CVII hypomorphic mice is uniquely challenging due to the strain's published survival rate to weaning of 24%. Because chronic ocular fibrosis requires time to develop, optimizing the survival rate is of critical importance. In this study, standard husbandry practices were enhanced by the addition of sterilized diet and drug delivery gels, acidified water, irradiated food pellets, cellulose fiber bedding, minimal handling, removal of siblings within 2-3 wk from birth, and a preferred housing location. Survival rates per breeding cycle, sex, weight, and cause of early euthanasia were recorded and analyzed over 43 mo. Overall, 49% of mice survived to weaning and 76% of weaned mice survived to 20 wk of age. Corneal opacities were seen in 65% of mice by 20 wk, but only 10% of eyes showed the sustained opacification that was indicative of fibrosis. Corneal opacities occurred at the same rate as in humans with epidermolysis bullosa. 66% of the mice showed weight loss at 11 wk. Males required early euthanasia 4 times more often than did females. Euthanasia was required for urinary obstruction due to penile prolapse in 88% of males. With our enhanced care protocol, hypomorphic mice in our colony survived at twice the published rate. With this revised husbandry standard, experiments planned with termination endpoints of 14 wk for males and 17 wk for females are more likely to reach completion.