Magnetically Responsive Enzyme and Hydrogen-Bonded Organic Framework Biocomposites for Biosensing.

The one-pot synthesis of multicomponent hydrogen-bonded organic framework (HOF) biocomposites is reported. The co-immoblization of enzymes and magnetic nanoparticles (MNPs) into the HOF crystals yielded biocatalysts (MNPs-enzyme@BioHOF-1) with dynamic localization properties. Using a permanent magnet, it is possible to separate the MNPs-enzyme@BioHOF-1 particles from a solution.

Ordered Transfer from 3D-Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns.

Films and patterns of 3D-oriented metal-organic frameworks (MOFs) afford well-ordered pore structures extending across centimeter-scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics.

Fabrication of Oriented Polycrystalline MOF Superstructures.

The field of metal-organic frameworks (MOFs) has progressed beyond the design and exploration of powdery and single-crystalline materials. A current challenge is the fabrication of organized superstructures that can harness the directional properties of the individual constituent MOF crystals. To date, the progress in the fabrication methods of polycrystalline MOF superstructures has led to close-packed structures with defined crystalline orientation.

Water sensitivity of heteroepitaxial Cu-MOF films: dissolution and re-crystallization of 3D-oriented MOF superstructures.

3D-oriented metal-organic framework (MOF) films and patterns have recently emerged as promising platforms for sensing and photonic applications. These oriented polycrystalline materials are typically prepared by heteroepitaxial growth from aligned inorganic nanostructures and display anisotropic functional properties, such as guest molecule alignment and polarized fluorescence. However, to identify suitable conditions for the integration of these 3D-oriented MOF superstructures into functional devices, the effect of water (gaseous and liquid) on different frameworks should be determined.

Atomic-Scale Elucidation of Unusually Distorted Dimeric Complexes Confined in a Zr-Based Metal-Organic Framework.

Nanoconfinement in metal-organic framework (MOF) pores can lead to the isolation of unusual or reactive metal complexes. However, MOFs that support the stabilization and precise structural elucidation of metal complexes and small metal clusters are rare. Here, we report a thermally and chemically stable zirconium-based MOF (University of Adelaide Material-1001, UAM-1001) with a high density of free bis-pyrazolyl units that can confine mono- and dinuclear metal complexes.

Studying manganese carbonyl photochemistry in a permanently porous metal-organic framework.

Mn(diimine)(CO)X (X = halide) complexes are critical components of chromophores, photo- and electrocatalysts, and photoactive CO-releasing molecules (photoCORMs). While these entities have been incorporated into metal-organic frameworks (MOFs), a detailed understanding of the photochemical and chemical processes that occur in a permanently porous support is lacking. Here we site-isolate and study the photochemistry of a Mn(diimine)(CO)Br moiety anchored within a permanently porous MOF support, allowing for not only the photo-liberation of CO from the metal but also its escape from the MOF crystals.

Enhanced Bioactivity of Enzyme/MOF Biocomposite via Host Framework Engineering.

This study reports the successful development of a sustainable synthesis protocol for a phase-pure metal azolate framework (MAF-6) and its application in enzyme immobilization. An esterase@MAF-6 biocomposite was synthesized, and its catalytic performance was compared with that of esterase@ZIF-8 and esterase@ZIF-90 in transesterification reactions. Esterase@MAF-6, with its large pore aperture, showed superior enzymatic performance compared to esterase@ZIF-8 and esterase@ZIF-90 in catalyzing transesterification reactions using both -propanol and benzyl alcohol as reactants.

Charge "mis-matched" hydrogen bonded frameworks for cation exchange and dye sorption.

Anionic hydrogen bonded frameworks were synthesised from di or tetra-amidinium hydrogen bond donor components and a charge "mis-matched" tecton possessing a 5- charge but only four hydrogen bond accepting groups. The net negative charge on the framework skeletons necessitates the presence of a cation in the framework channel. In one of the frameworks, the initially incorporated organic cation was rapidly displaced by smaller inorganic cations, or the cationic dye methylene blue.

Multi-layered ZIF-coated cells for the release of bioactive molecules in hostile environments.

Metal-organic framework (MOF) coatings on cells enhance viability in cytotoxic environments. Here, we show how protective multi-layered MOF bio-composite shells on a model cell system (yeast) enhance the proliferation of living cells exposed to hostile protease-rich environments the dissolution of the shells and release of a protease inhibitor (antitrypsin).

Post-Synthetic Modification of a Porous Hydrocarbon Cage to Give a Discrete Co Organometallic Complex.

A new alkyne-based hydrocarbon cage was synthesized in high overall yield using alkyne-alkyne coupling in the cage forming step. The cage is porous and displays a moderately high BET surface area (546 m  g ). The cage loses crystallinity on activation and thus is porous in its amorphous form, while very similar cages have been either non-porous, or retained crystallinity on activation.

Water Sorption Controls Extreme Single-Crystal-to-Single-Crystal Molecular Reorganization in Hydrogen Bonded Organic Frameworks.

As hydrogen bonded frameworks are held together by relatively weak interactions, they often form several different frameworks under slightly different synthesis conditions and respond dynamically to stimuli such as heat and vacuum. However, these dynamic restructuring processes are often poorly understood. In this work, three isoreticular hydrogen bonded organic frameworks assembled through charge-assisted amidinium⋅⋅⋅carboxylate hydrogen bonds (1 , 1 and 1 ) are studied.

How Reproducible are Surface Areas Calculated from the BET Equation?

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials.

Combining a Genetically Engineered Oxidase with Hydrogen-Bonded Organic Frameworks (HOFs) for Highly Efficient Biocomposites.

Enzymes incorporated into hydrogen-bonded organic frameworks (HOFs) via bottom-up synthesis are promising biocomposites for applications in catalysis and sensing. Here, we explored synthetic incorporation of d-amino acid oxidase (DAAO) with the metal-free tetraamidine/tetracarboxylate-based BioHOF-1 in water. N-terminal enzyme fusion with the positively charged module Z strongly boosted the loading (2.

Insights into the Interaction between Immobilized Biocatalysts and Metal-Organic Frameworks: A Case Study of PCN-333.

The immobilization of enzymes in metal-organic frameworks (MOFs) with preserved biofunctionality paves a promising way to solve problems regarding the stability and reusability of enzymes. However, the rational design of MOF-based biocomposites remains a considerable challenge as very little is known about the state of the enzyme, the MOF support, and their host-guest interactions upon immobilization. In this study, we elucidate the detailed host-guest interaction for MOF immobilized enzymes in the biointerface.

Templated synthesis of zirconium(IV)-based metal-organic layers (MOLs) with accessible chelating sites.

Metal-organic layers (MOLs) are of great interest in heterogeneous catalysis, particularly materials that can accommodate extraneous metal centres. Here, we demonstrate a two-step preorganisation/delamination synthetic strategy using CuI as a template to prepare Zr-based MOLs with accessible 'syn' bis-pyrazolyl chelating sites (named ) that are poised for quantitative post-synthetic metalation with late transition metals.

Use of modulators and light to control crystallisation of a hydrogen bonded framework.

The effect of concentration, organic co-solvent, and salt modulators on the crystallisation of a hydrogen bonded framework was studied. The framework contains ∼1.4 nm wide channels and contains a diazobenzene based dicarboxylate anion.

Self-Assembly of Oriented Antibody-Decorated Metal-Organic Framework Nanocrystals for Active-Targeting Applications.

Antibody (Ab)-targeted nanoparticles are becoming increasingly important for precision medicine. By controlling the Ab orientation, targeting properties can be enhanced; however, to afford such an ordered configuration, cumbersome chemical functionalization protocols are usually required. This aspect limits the progress of Abs-nanoparticles toward nanomedicine translation.

On the completeness of three-dimensional electron diffraction data for structural analysis of metal-organic frameworks.

Three-dimensional electron diffraction (3DED) has been proven as an effective and accurate method for structure determination of nano-sized crystals. In the past decade, the crystal structures of various new complex metal-organic frameworks (MOFs) have been revealed by 3DED, which has been the key to understand their properties. However, due to the design of transmission electron microscopes (TEMs), one drawback of 3DED experiments is the limited tilt range of goniometers, which often leads to incomplete 3DED data, particularly when the crystal symmetry is low.

Single-Crystal-to-Single-Crystal Transformations of Metal-Organic-Framework-Supported, Site-Isolated Trigonal-Planar Cu(I) Complexes with Labile Ligands.

Transition-metal complexes bearing labile ligands can be difficult to isolate and study in solution because of unwanted dinucleation or ligand substitution reactions. Metal-organic frameworks (MOFs) provide a unique matrix that allows site isolation and stabilization of well-defined transition-metal complexes that may be of importance as moieties for gas adsorption or catalysis. Herein we report the development of an in situ anion metathesis strategy that facilitates the postsynthetic modification of Cu(I) complexes appended to a porous, crystalline MOF.

Modulation of metal-azolate frameworks for the tunable release of encapsulated glycosaminoglycans.

Glycosaminoglycans (GAGs) are biomacromolecules necessary for the regulation of different biological functions. In medicine, GAGs are important commercial therapeutics widely used for the treatment of thrombosis, inflammation, osteoarthritis and wound healing. However, protocols for the encapsulation of GAGs in MOFs carriers are not yet available.

Controlling the alignment of 1D nanochannel arrays in oriented metal-organic framework films for host-guest materials design.

Controlling the direction of molecular-scale pores enables the accommodation of guest molecular-scale species with alignment in the desired direction, allowing for the development of high-performance mechanical, thermal, electronic, photonic and biomedical organic devices (host-guest approach). Regularly ordered 1D nanochannels of metal-organic frameworks (MOFs) have been demonstrated as superior hosts for aligning functional molecules and polymers. However, controlling the orientation of MOF films with 1D nanochannels at commercially relevant scales remains a significant challenge.

Influence of the Synthesis and Storage Conditions on the Activity of Lipase B ZIF-8 Biocomposites.

The biomimetic mineralization of zeolitic imidazolate framework-8 (ZIF-8) has been reported as a strategy for enzyme immobilization, enabling the heterogenization and protection of biomacromolecules. Here, we report the preparation of different lipase B biocomposites (CALB@ZIF-8) formed by altering the concentrations of Zn and 2-methylimidazole (2-mIM). The influence of synthetic conditions on the catalytic activity of the lipase CALB was examined by hydrolysis and transesterification assays in aqueous and organic media, respectively.

High-Throughput Electron Diffraction Reveals a Hidden Novel Metal-Organic Framework for Electrocatalysis.

Metal-organic frameworks (MOFs) are known for their versatile combination of inorganic building units and organic linkers, which offers immense opportunities in a wide range of applications. However, many MOFs are typically synthesized as multiphasic polycrystalline powders, which are challenging for studies by X-ray diffraction. Therefore, developing new structural characterization techniques is highly desired in order to accelerate discoveries of new materials.