Mark J. Styles

Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules.

Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules.

Chemical vapour deposition of zeolitic imidazolate framework thin films

Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Suitable film deposition methods are crucial to leverage MOFs in this field. Conventional solvent-based procedures, typically adapted from powder preparation routes, are incompatible with nanofabrication because of corrosion and contamination risks. We demonstrate a chemical vapour deposition process (MOF-CVD) that enables high-quality films of ZIF-8, a prototypical MOF material, with a uniform and controlled thickness, even on high-aspect-ratio features. Furthermore, we demonstrate how MOF-CVD enables previously inaccessible routes such as lift-off patterning and depositing MOF films on fragile features. The compatibility of MOF-CVD with existing infrastructure, both in research and production facilities, will greatly facilitate MOF integration in microelectronics. MOF-CVD is the first vapour-phase deposition method for any type of microporous crystalline network solid and marks a milestone in processing such materials.

Biomimetic Replication of Microscopic Metal–Organic Framework Patterns Using Printed Protein Patterns

It is demonstrated that metal-organic frameworks (MOFs) can be replicated in a biomimetic fashion from protein patterns. Bendable, fluorescent MOF patterns are formed with micrometer resolution under ambient conditions. Furthermore, this technique is used to grow MOF patterns from fingerprint residue in 30 s with high fidelity. This technique is not only relevant for crime-scene investigation, but also for biomedical applications.

Lead(II) uptake by aluminium based magnetic framework composites (MFCs) in water

The recent combination of Metal-Organic Frameworks (MOFs) and magnetic nanoparticles has shown their potential as a composite material in practical applications including drug delivery, catalysis and pollutant sequestration. Here, we report for the first time the preparation of a robust magnetic nanocomposite material based on an aluminium MOF (MIL-53) and iron oxide nanoparticles for the uptake of lead(II) ions. Different aminofunctionalized MIL-53 MOFs were prepared by increasing the 2-aminoterephthalic/terephthalic acid ratio. The composite materials were tested to determine the sequestration capability of heavy metals from various solvents (methanol, DMSO and water), pH (2, 7, 12) and a range of Pb(II) concentrations (10–8000 ppm). The magnetic composite based on MIL-53 showed remarkable capacity to sequester Pb(II) ions from water (up to 492.4 mg g−1 of composite), the highest recorded for a MOF sorbent system to date. While the MOF played a crucial role in the efficient heavy metal uptake, the magnetic nanoparticles allowed the prompt collection of the sorbent from solution. The triggered release of Pb(II) was investigated using an alternating magnetic field. The exceptional adsorption capacity and the response to the magnetic field make this class of innovative functional material a promising candidate for environmental remediation technologies.

Positioning an individual metal–organic framework particle using a magnetic field

For the first time an external magnetic field has been used for the spatial control of a single amino functionalized mixed component metal–organic framework doped with cobalt nanoparticles. The potential applications as an active material for miniaturized devices (e.g. microchannels and microfluidic circuits) are illustrated.

Positioning of the HKUST-1 metal–organic framework (Cu3(BTC)2) through conversion from insoluble Cu-based precursors

A Cu-based metal–organic framework (HKUST-1 or Cu3(BTC)2, BTC = 1,3,5-benzene tricarboxylate) has been synthesized from insoluble Cu-based precursors and positioned on substrates. Patterning of HKUST-1 was achieved through a two-step process: (1) the positioning of the insoluble Cu-based ceramic precursors on substrates using a sol–gel solution, and (2) the subsequent conversion into HKUST-1 by treatments with an alcoholic solution containing 1,3,5-benzene tricarboxylic acid (H3BTC) at room temperature for 10 min. This technique has been found to be suitable for both inorganic and polymeric substrates. The HKUST-1 pattern on a polymer film can be easily bent without affecting the positioned MOFs crystals. This approach would allow for versatile and practical applications of MOFs in multifunctional platforms where the positioning of MOFs is required.

Amino acids as biomimetic crystallization agents for the synthesis of ZIF-8 particles

Biomimetic mineralization of metal–organic frameworks (MOFs) exploits the use of biomolecules to control MOF crystallization processes. Here, we investigate 20 natural amino acids as biomimetic crystallization agents for the synthesis of ZIF-8 particles in aqueous solution. The morphology, size, and particle number of resultant MOF crystals were strongly dependent on the chemical nature of amino acid side chains that match closely the four classes of amino acids: nonpolar, polar neutral, polar negative and polar positive.

High-throughput in-situ characterization and modeling of precipitation kinetics in compositionally graded alloys

The development of new engineering alloy chemistries is a time consuming and iterative process. A necessary step is characterization of the nano/microstructure to provide a link between the processing and properties of each alloy chemistry considered. One approach to accelerate the identification of optimal chemistries is to use samples containing a gradient in composition, ie. combinatorial samples, and to investigate many different chemistries at the same time. However, for engineering alloys, the final properties depend not only on chemistry but also on the path of microstructure development which necessitates characterization of microstructure evolution for each chemistry. In this contribution we demonstrate an approach that allows for the in-situ, nanoscale characterization of the precipitate structures in alloys, as a function of aging time, in combinatorial samples containing a composition gradient. The approach uses small angle x-ray scattering (SAXS) at a synchrotron beamline. The Cu-Co system is used for the proof-of-concept and the combinatorial samples prepared contain a gradient in Co from 0% to 2%. These samples are aged at temperatures between 450°C and 550°C and the precipitate structures (precipitate size, volume fraction and number density) all along the composition gradient are simultaneously monitored as a function of time. This large dataset is used to test the applicability and robustness of a conventional class model for precipitation that considers concurrent nucleation, growth and coarsening and the ability of the model to describe such a large dataset.

Fe3O4@HKUST-1 and Pd/Fe3O4@HKUST-1 as magnetically recyclable catalysts prepared via conversion from a Cu-based ceramic

Nanocomposites obtained by integrating iron oxide magnetic nanoparticles (Fe3O4) into a metal–organic framework (HKUST-1 or Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate) are synthesized through conversion from a composite of a Cu-based ceramic material and Fe3O4. In situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) measurements reveal that the presence of Fe3O4 leads to the fast conversion and synthesis of HKUST-1 with small particle sizes. The prepared MOF composite (Fe3O4@HKUST-1) is found to catalyze the one-pot sequential deacetalization–Knoevenagel condensation reaction as a magnetically collectable and recyclable catalyst. In addition, Pd nanoparticles are also incorporated into the material (Pd/Fe3O4@HKUST-1) by addition of a Pd colloidal solution during the conversion of the precursor composite to HKUST-1. The resulting Pd/Fe3O4@HKUST-1 can be utilized for hydrogenation of 1-octene in the liquid phase.

Metal–Organic Frameworks: Biomimetic Replication of Microscopic Metal–Organic Framework Patterns Using Printed Protein Patterns (Adv. Mater. 45/2015)

K. Liang, P. Falcaro, and co-workers report on page 7293 that metal-organic frameworks (MOFs) can be replicated in a biomimetic fashion from protein patterns on a surface. Bendable, fluorescent MOF patterns are formed with micrometer resolution under ambient conditions. This technique is used to grow MOF patterns from fingerprint residue in 30 s with high fidelity. This technique is not only relevant for crime-scene investigation, but also for biomedical applications.