Thermally activated structural phase transitions and processes in metal-organic frameworks.

The structural knowledge of metal-organic frameworks is crucial to the understanding and development of new efficient materials for industrial implementation. This review classifies and discusses recent advanced literature reports on phase transitions that occur during thermal treatments on metal-organic frameworks and their characterisation. Thermally activated phase transitions and procceses are classified according to the temperaturatures at which they occur: high temperature (reversible and non-reversible) and low temperature. In addition, theoretical calculations and modelling approaches employed to better understand these structural phase transitions are also reviewed.

Evidence of Organic Polymeric Behavior in the Glass Transition of Metal-Organic Frameworks.

The origin of the glass transition is still an open debate, especially for the new class of glasses, formed from metal-organic compounds. High-temperature in situ 2H Nuclear Magnetic Resonance (NMR) experiments are performed on deuterated samples of ZIF-62 (Zn(C3H4N2)2-x(C7H6N2)x, with x = 0.25 and x = 0.05), the prototypical metal-organic framework glass former. Using lineshape analysis, frequencies and angular amplitudes of oscillations of the imidazolate ring during heating up to the melt progressively increasing from ≈10 to 150 MHz, and from ≈5° to 25° are found. This behavior is compositionally dependent and points to the origin of the glass transition lying in organic linker movement, in a similar vein to that witnessed in some organics and contrary to the purely inorganic-based view of Metal-Organic Framework (MOF) glasses taken to date. This experimental approach shows the potential to elucidate the melting and/or decomposition process for a wide range of MOFs.

Control of ZIF-62 and agZIF-62 Film Thickness within Asymmetric Tubular Supports through Pressure and Dose Time Variation of Atomic Layer Deposition.

Thin-films of metal-organic frameworks (MOFs) have widespread potential applications, especially with the emergence of glass-forming MOFs, which remove the inherent issue of grain boundaries and allow coherent amorphous films to be produced. Herein, it is established that atomic layer deposition (ALD) of zinc oxide lends excellent control over the thickness and localization of resultant polycrystalline and glass zeolitic imidazole framework-62 (ZIF-62) thin-films within tubular α-alumina supports. Through the reduction of the chamber pressure and dose times during zinc oxide deposition, the resultant ZIF-62 films are reduced from 38 µm to 16 µm, while the presence of sporadic ZIF-62 (previously forming as far as 280 µm into the support) is prevented. Furthermore, the glass transformation shows a secondary reduction in film thickness from 16 to 2 µm.

Observation of a Reversible Order-Order Transition in a Metal-Organic Framework - Ionic Liquid Nanocomposite Phase-Change Material.

Metal-organic framework (MOF) composite materials containing ionic liquids (ILs) have been proposed for a range of potential applications, including gas separation, ion conduction, and hybrid glass formation. Here, an order transition in an IL@MOF composite is discovered using CuBTC (copper benzene-1,3,5-tricarboxylate) and [EMIM][TFSI] (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide). This transition - absent for the bare MOF or IL - provides an extended super-cooling range and latent heat at a capacity similar to that of soft paraffins, in the temperature range of ≈220 °C. Structural analysis and in situ monitoring indicate an electrostatic interaction between the IL molecules and the Cu paddle-wheels, leading to a decrease in pore symmetry at low temperature. These interactions are reversibly released above the transition temperature, which reflects in a volume expansion of the MOF-IL composite.

ZIF-62 glass foam self-supported membranes to address CH4/N2 separations.

Membranes with ultrahigh permeance and practical selectivity could greatly decrease the cost of difficult industrial gas separations, such as CH4/N2 separation. Advanced membranes made from porous materials, such as metal-organic frameworks, can achieve a good gas separation performance, although they are typically formed on support layers or mixed with polymeric matrices, placing limitations on gas permeance. Here an amorphous glass foam, agfZIF-62, wherein a, g and f denote amorphous, glass and foam, respectively, was synthesized by a polymer-thermal-decomposition-assisted melting strategy, starting from a crystalline zeolitic imidazolate framework, ZIF-62. The thermal decomposition of incorporated low-molecular-weight polyethyleneimine evolves CO2, NH3 and H2O gases, creating a large number and variety of pores. This greatly increases pore interconnectivity but maintains the crystalline ZIF-62 ultramicropores, allowing ultrahigh gas permeance and good selectivity. A self-supported circular agfZIF-62 with a thickness of 200-330 µm and area of 8.55 cm2 was used for membrane separation. The membranes perform well, showing a CH4 permeance of 30,000-50,000 gas permeance units, approximately two orders of magnitude higher than that of other reported membranes, with good CH4/N2 selectivity (4-6).

Charged multivesicular body protein 4b forms complexes with gap junction proteins during lens fiber cell differentiation.

Charged multivesicular body protein 4b (CHMP4B) is a core sub-unit of the endosomal sorting complex required for transport III (ESCRT-III) machinery that serves myriad remodeling and scission processes of biological membranes. Mutation of the human CHMP4B gene underlies rare forms of early-onset lens opacities or cataracts, and CHMP4B is required for lens growth and differentiation in mice. Here, we determine the sub-cellular distribution of CHMP4B in the lens and uncover a novel association with gap junction alpha-3 protein (GJA3) or connexin 46 (Cx46) and GJA8 or Cx50. Immunofluorescence confocal microscopy revealed that CHMP4B localized to cell membranes of elongated fiber cells in the outer cortex of the lens-where large gap junction plaques begin to form-particularly, on the broad faces of these flattened hexagon-like cells in cross-section. Dual immunofluorescence imaging showed that CHMP4B co-localized with gap junction plaques containing Cx46 and/or Cx50. When combined with the in situ proximity ligation assay, immunofluorescence confocal imaging indicated that CHMP4B lay in close physical proximity to Cx46 and Cx50. In Cx46-knockout (Cx46-KO) lenses, CHMP4B-membrane distribution was similar to that of wild-type, whereas, in Cx50-KO lenses, CHMP4B localization to fiber cell membranes was lost. Immunoprecipitation and immunoblotting analyses revealed that CHMP4B formed complexes with Cx46 and Cx50 in vitro. Collectively, our data suggest that CHMP4B forms plasma membrane complexes, either directly and/or indirectly, with gap junction proteins Cx46 and Cx50 that are often associated with "ball-and-socket" double-membrane junctions during lens fiber cell differentiation.

Transient intermediate in the formation of an amorphous metal-organic framework.

Amorphous metal-organic frameworks are rarely formed via direct synthesis. Our limited understanding of their atomic assembly in solution prevents full exploitation of their unique structural complexity. Here, we use in situ synchrotron X-ray absorption spectroscopy with sub-second time resolution to probe the formation of the amorphous Fe-BTC framework. Using a combination of spectral fingerprinting, linear combination analysis, and principal component analysis coupled with kinetic analyses, we reveal a multi-stage formation mechanism that, crucially, proceeds via the generation of a transient intermediate species.

Imaging and Segmenting Grains and Subgrains Using Backscattered Electron Techniques.

We present two new methods of processing data from backscattered electron signals in a scanning electron microscope to image grains and subgrains. The first combines data from multiple backscattered electron images acquired at different specimen geometries to (1) better reveal grain boundaries in recrystallized microstructures and (2) distinguish between recrystallized and unrecrystallized regions in partially recrystallized microstructures. The second utilizes spherical harmonic transform indexing of electron backscatter diffraction patterns to produce high angular resolution orientation data that enable the characterization of subgrains. Subgrains are produced during high-temperature plastic deformation and have boundary misorientation angles ranging from a few degrees down to a few hundredths of a degree. We also present an algorithm to automatically segment grains from combined backscattered electron image data or grains and subgrains from high angular resolution electron backscatter diffraction data. Together, these new techniques enable rapid measurements of individual grains and subgrains from large populations.

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.

Interfacial Bonding between a Crystalline Metal-Organic Framework and an Inorganic Glass.

The interface within a composite is critically important for the chemical and physical properties of these materials. However, experimental structural studies of the interfacial regions within metal-organic framework (MOF) composites are extremely challenging. Here, we provide the first example of a new MOF composite family, i.e., using an inorganic glass matrix host in place of the commonly used organic polymers. Crucially, we also decipher atom-atom interactions at the interface. In particular, we dispersed a zeolitic imidazolate framework (ZIF-8) within a phosphate glass matrix and identified interactions at the interface using several different analysis methods of pair distribution function and multinuclear multidimensional magic angle spinning nuclear magnetic resonance spectroscopy. These demonstrated glass-ZIF atom-atom correlations. Additionally, carbon dioxide uptake and stability tests were also performed to check the increment of the surface area and the stability and durability of the material in different media. This opens up possibilities for creating new composites that include the intrinsic chemical properties of the constituent MOFs and inorganic glasses.

Survival of Zirconium-Based Metal-Organic Framework Crystallinity at Extreme Pressures.

Recent research on metal-organic frameworks (MOFs) has shown a shift from considering only the crystalline high-porosity phases to exploring their amorphous counterparts. Applying pressure to a crystalline MOF is a common method of amorphization, as MOFs contain large void spaces that can collapse, reducing the accessible surface area. This can be either a desired change or indeed an unwanted side effect of the application of pressure. In either case, understanding the MOF's pressure response is extremely important. Three such MOFs with varying pore sizes (UiO-66, MOF-808, and NU-1000) were investigated using in situ high-pressure X-ray diffraction and Raman spectroscopy. Partial crystallinity was observed in all three MOFs above 10 GPa, along with some recovery of crystallinity on return to ambient conditions if the frameworks were not compressed above thresholds of 13.3, 14.2, and 12.3 GPa for UiO-66, MOF-808, and NU-1000, respectively. This threshold was marked by an unexpected increase in one or more lattice parameters with pressure in all MOFs. Comparison of compressibility between MOFs suggests penetration of the pressure-transmitting oil into MOF-808 and NU-1000. The survival of some crystallinity above 10 GPa in all of these MOFs despite their differing pore sizes and extents of oil penetration demonstrates the importance of high-pressure characterization of known structures.

The speed and acceleration of the ball carrier and tackler into contact during front-on tackles in rugby league.

The aim was to use a combination of video analysis and microtechnology (10 Hz global positioning system [GPS]) to quantify and compare the speed and acceleration of ball-carriers and tacklers during the pre-contact phase (contact - 0.5s) of the tackle event during rugby league match-play. Data were collected from 44 professional male rugby league players from two Super League clubs across two competitive matches. Tackle events were coded and subject to three stages of inclusion criteria to identify front-on tackles. 10 Hz GPS data was synchronised with video to extract the speed and acceleration of the ball-carrier and tackler into each front-on tackle (n = 214). Linear mixed effects models (effect size [ES], confidence intervals, p-values) compared differences. Overall, ball-carriers (4.73 ± 1.12 m∙s-1) had greater speed into front-on tackles than tacklers (2.82 ± 1.07 m∙s-1; ES = 1.69). Ball-carriers accelerated (0.67 ± 1.01 m∙s-2) into contact whilst tacklers decelerated (-1.26 ± 1.36 m∙s-2; ES = 1.74). Positional comparisons showed speed was greater during back vs. back (ES = 0.66) and back vs. forward (ES = 0.40) than forward vs. forward tackle events. Findings can be used to inform strategies to improve performance and player welfare.

Glass Formation in Hybrid Organic-Inorganic Perovskites.

Crystalline materials have governed the development of hybrid organic-inorganic perovskites (HOIPs), giving rise to a variety of fascinating applications such as solar cells and optoelectronic devices. With increasing interest in non-crystalline systems, the glassy state of HOIPs has recently been identified. Here, the basic building blocks of crystalline HOIPs appear to be retained, though their glasses lack long-range periodic order. The emerging family of glasses formed from HOIPs exhibits diverse properties, complementary to their crystalline state. This mini review describes the chemical diversity of both three-dimensional and two-dimensional crystalline HOIPs and demonstrates how glasses are produced from these materials. Specifically, current achievements in melt-quenched glasses formed from HOIPs are highlighted. We conclude with our perspective on the future of this new family of materials.

Unravelling the Molecular Structure and Confining Environment of an Organometallic Catalyst Heterogenized within Amorphous Porous Polymers.

The catalytic activity of multifunctional, microporous materials is directly linked to the spatial arrangement of their structural building blocks. Despite great achievements in the design and incorporation of isolated catalytically active metal complexes within such materials, a detailed understanding of their atomic-level structure and the local environment of the active species remains a fundamental challenge, especially when these latter are hosted in non-crystalline organic polymers. Here, we show that by combining computational chemistry with pair distribution function analysis, 129 Xe NMR, and Dynamic Nuclear Polarization enhanced NMR spectroscopy, a very accurate description of the molecular structure and confining surroundings of a catalytically active Rh-based organometallic complex incorporated inside the cavity of amorphous bipyridine-based porous polymers is obtained. Small, but significant, differences in the structural properties of the polymers are highlighted depending on their backbone motifs.

Fabrication of Super-Sized Metal Inorganic-Organic Hybrid Glass with Supramolecular Network via Crystallization-Suppressing Approach.

Metal coordination compound (MCC) glasses [e.g., metal-organic framework (MOF) glass, coordination polymer glass, and metal inorganic-organic complex (MIOC) glass] are emerging members of the hybrid glass family. So far, a limited number of crystalline MCCs can be converted into glasses by melt-quenching. Here, we report a universal wet-chemistry method, by which the super-sized supramolecular MIOC glasses can be synthesized from non-meltable MOFs. Alcohol and acid were used as agents to inhibit crystallization. The MIOC glasses demonstrate unique features including high transparency, shaping capability, and anisotropic network. Directional photoluminescence with a large polarization ratio (≈47 %) was observed from samples doped with organic dyes. This crystallization-suppressing approach enables fabrication of super-sized MCC glasses, which cannot be achieved by conventional vitrification methods, and thus allows for exploring new MCC glasses possessing photonic functionalities.

The changing state of porous materials.

Porous materials contain regions of empty space into which guest molecules can be selectively adsorbed and sometimes chemically transformed. This has made them useful in both industrial and domestic applications, ranging from gas separation, energy storage and ion exchange to heterogeneous catalysis and green chemistry. Porous materials are often ordered (crystalline) solids. Order-or uniformity-is frequently held to be advantageous, or even pivotal, to our ability to engineer useful properties in a rational way. Here we highlight the growing evidence that topological disorder can be useful in creating alternative properties in porous materials. In particular, we highlight here several concepts for the creation of novel porous liquids, rationalize routes to porous glasses and provide perspectives on applications for porous liquids and glasses.

Metal-Organic Frameworks: Special Collection 2020.

MOF2020: This Editorial introduces a special collection of review and original research articles, dedicated to the MOF2020 web conference.

Properties of Single-Component Metal-Organic Framework Crystal-Glass Composites.

The formation, and subsequent structural, thermal and adsorptive properties of single-component metal-organic framework crystal-glass composites (MOF-CGCs) are investigated. A series of novel materials exhibiting chemically identical glassy and crystalline phases within the same material were produced, where crystalline ZIF-62(Zn) was incorporated within an ag ZIF-62(Zn) matrix. X-ray diffraction showed that the crystalline phase was still present after heating to above the glass transition temperature of ag ZIF-62(Zn), and interfacial compatibility between the crystalline and glassy phases was investigated using a mixed-metal (ZIF-62(Co))0.5 (ag ZIF-62(Zn))0.5 analogue. CO2 gas adsorption measurements showed that the CO2 uptakes of the MOF-CGCs were between those of the crystalline and glassy phases.

Materials Formed by Combining Inorganic Glasses and Metal-Organic Frameworks.

Here, we propose the combination of glassy or crystalline metal-organic frameworks (MOFs) with inorganic glasses to create novel hybrid composites and blends.The motivation behind this new composite approach is to improve the processability issues and mechanical performance of MOFs, whilst maintaining their ubiquitous properties. Herein, the precepts of successful composite formation and pairing of MOF and glass MOFs with inorganic glasses are presented. Focus is also given to the synthetic routes to such materials and the challenges anticipated in both their production and characterisation. Depending on their chemical nature, materials are classified as crystalline MOF-glass composites and blends. Additionally, the potential properties and applications of these two classes of materials are considered, the key aim being the retention of beneficial properties of both components, whilst circumventing their respective drawbacks.

Mutation of the TRPM3 cation channel underlies progressive cataract development and lens calcification associated with pro-fibrotic and immune cell responses.

Transient-receptor-potential cation channel, subfamily M, member 3 (TRPM3) serves as a polymodal calcium sensor in diverse mammalian cell-types. Mutation of the human TRPM3 gene (TRPM3) has been linked with inherited forms of early-onset cataract with or without other eye abnormalities. Here, we have characterized the ocular phenotypes of germline "knock-in" mice that harbor a human cataract-associated isoleucine-to-methionine mutation (p.I65M) in TRPM3 (Trpm3-mutant) compared with germline "knock-out" mice that functionally lack TRPM3 (Trpm3-null). Despite strong expression of Trpm3 in lens epithelial cells, neither heterozygous (Trpm3+/- ) nor homozygous (Trpm3-/- ) Trpm3-null mice developed cataract; however, the latter exhibited a mild impairment of lens growth. In contrast, homozygous Trpm3-M/M mutants developed severe, progressive, anterior pyramid-like cataract with microphthalmia, whereas heterozygous Trpm3-I/M and hemizygous Trpm3-M/- mutants developed anterior pyramidal cataract with delayed onset and progression-consistent with a semi-dominant lens phenotype. Histochemical staining revealed abnormal accumulation of calcium phosphate-like deposits and collagen fibrils in Trpm3-mutant lenses and immunoblotting detected increased αII-spectrin cleavage products consistent with calpain hyper-activation. Immunofluorescent confocal microscopy of Trpm3-M/M mutant lenses revealed fiber cell membrane degeneration that was accompanied by accumulation of alpha-smooth muscle actin positive (α-SMA+ve) myofibroblast-like cells and macrosialin positive (CD68+ve) macrophage-like cells. Collectively, our mouse model data support an ocular disease association for TRPM3 in humans and suggest that (1) Trpm3 deficiency impaired lens growth but not lens transparency and (2) Trpm3 dysfunction resulted in progressive lens degeneration and calcification coupled with pro-fibrotic (α-SMA+ve) and immune (CD68+ve) cell responses.