ORCID Profile
0000-0001-5935-0409
Current Organisations
Osaka Prefecture Univeristy
,
Technische Universität Graz
,
University of Adelaide
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Publisher: American Chemical Society (ACS)
Date: 18-12-2019
DOI: 10.26434/CHEMRXIV.11302478.V1
Abstract: Here, we studied a catalytically active and magnetically responsive porous bio-composite obtained from the synthesis of ZIF-8 in presence of iron oxide magnetic nanoparticles and horseradish peroxidase (HRP) enzyme as guest species. Using a one-pot approach in water the precursors of ZIF-8 (zinc acetate and 2-methylimidazole) spontaneously self-assembles around the guest species. We characterized the composite by means of XRD, SEM, FTIR, AFM, and CLSM. SAXS investigation of the kinetics of crystallization showed how the presence of the guest species can act as nucleation seeds. Moreover, we found that the bio-catalytic activity of the HRP/MNP@ZIF-8 biocomposite is 5 times higher than the analoguous composite without MNPs.
Publisher: Elsevier BV
Date: 03-2018
Publisher: Wiley
Date: 04-12-2013
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CC01620K
Abstract: A facile method to improve the stability of γ-cyclodextrin metal–organic frameworks in an aqueous environment has been developed through the incorporation of hydrophobic C 60 in their matrices.
Publisher: American Chemical Society (ACS)
Date: 21-07-2018
Publisher: American Chemical Society (ACS)
Date: 10-05-2017
DOI: 10.1021/ACS.ACCOUNTS.7B00090
Abstract: Many living organisms are capable of producing inorganic materials of precisely controlled structure and morphology. This ubiquitous process is termed biomineralization and is observed in nature from the macroscale (e.g., formation of exoskeletons) down to the nanoscale (e.g., mineral storage and transportation in proteins). Extensive research efforts have pursued replicating this chemistry with the overarching aims of synthesizing new materials of unprecedented physical properties and understanding the complex mechanisms that occur at the biological-inorganic interface. Recently, we demonstrated that a class of porous materials termed metal-organic frameworks (MOFs) can spontaneously form on protein-based hydrogels via a process analogous to natural matrix-mediated biomineralization. Subsequently, this strategy was extended to functional biomacromolecules, including proteins and DNA, which have been shown to seed and accelerate crystallization of MOFs. Alternative strategies exploit co-precipitating agents such as polymers to induce MOF particle formation thus facilitating protein encapsulation within the porous crystals. In these ex les the rigid molecular architecture of the MOF was found to form a protective coating around the biomacromolecule offering improved stability to external environments that would normally lead to its degradation. In this way, the MOF shell mimics the protective function of a biomineralized exoskeleton. Other methodologies have also been explored to encapsulate enzymes within MOF structures, including the fabrication of polycrystalline hollow MOF microcapsules that preserve the original enzyme functionality over several batch reaction cycles. The potential to design MOFs of varied pore size and chemical functionality has underpinned studies describing the postsynthesis infiltration of enzymes into MOF pore networks and bioconjugation strategies for the decoration of the MOF outer surface, respectively. These methods and configurations allow for customized biocomposites. MOF biocomposites have been extended from simple proteins to complex biological systems including viruses, living yeast cells, and bacteria. Indeed, a noteworthy result was that cells encapsulated within a crystalline MOF shell remain viable after exposure to a medium containing lytic enzymes. Furthermore, the cells can adsorb nutrients (glucose) through the MOF shell but cease reproducing until the MOF casing is removed, at which point normal cellular activity is fully restored. The field of MOF biocomposites is expansive and rapidly developing toward different applied research fields including protection and delivery of biopharmaceuticals, biosensing, biocatalysis, biobanking, and cell and virus manipulation. This Account describes the current progress of MOFs toward biotechnological applications highlighting the different strategies for the preparation of biocomposites, the developmental milestones, the challenges, and the potential impact of MOFs to the field.
Publisher: Wiley
Date: 07-04-2021
Abstract: 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. Here, we report a high‐throughput approach for structural analysis of MOF nano‐ and sub‐microcrystals by three‐dimensional electron diffraction (3DED). A new zeolitic‐imidazolate framework (ZIF), denoted ZIF‐EC1, was first discovered in a trace amount during the study of a known ZIF‐CO 3 ‐1 material by 3DED. The structures of both ZIFs were solved and refined using 3DED data. ZIF‐EC1 has a dense 3D framework structure, which is built by linking mono‐ and bi‐nuclear Zn clusters and 2‐methylimidazolates (mIm − ). With a composition of Zn 3 (mIm) 5 (OH), ZIF‐EC1 exhibits high N and Zn densities. We show that the N‐doped carbon material derived from ZIF‐EC1 is a promising electrocatalyst for oxygen reduction reaction (ORR). The discovery of this new MOF and its conversion to an efficient electrocatalyst highlights the power of 3DED in developing new materials and their applications.
Publisher: Wiley
Date: 03-10-2021
Abstract: Geometrical structuring of monolithic metal‐organic frameworks (MOFs) components is required for their practical implementation in many areas, including electronic devices, gas storage/separation, catalysis, energy storage as well as bio‐medical applications. Despite progress in structuring MOFs, an approach for the precise patterning of MOF functional geometries in the millimeter‐ to micro‐meter depth is lacking. Here, a facile and flexible concept for the microfabrication of complex MOF patterns on large surfaces is reported. The method relies on the engineering of easily‐writable sheets of precursor metal oxide nanoparticles. The gas‐phase conversion of these patterned ceramic nanoparticle sheets results in monolithic MOF objects with arbitrarily shaped geometries and thicknesses of up to hundreds of micrometers. The writing of complex patterns of zeolitic imidazolate framework‐8 (ZIF‐8) is demonstrated by a variety of approaches including ion beam, laser, and hand writing. Nanometer‐scale patterns are achieved by focused ion beam (FIB). Artless handwritings are obtained by using a pen in a similar fashion to writing on a paper. The pure ZIF‐8 composition of the resulting patterns is confirmed by a series of physical and chemical characterization. This facile MOF precursor‐writing approach provides novel opportunities for the design of MOF‐based devices with applications ranging from micro‐fluidics to renewable energy systems.
Publisher: American Chemical Society (ACS)
Date: 10-03-2017
Publisher: Wiley
Date: 13-11-2020
Publisher: American Chemical Society (ACS)
Date: 26-05-2021
DOI: 10.26434/CHEMRXIV.14291644
Abstract: Porosity and surface area analysis play a prominent role in modern materials science, where 123 their determination spans the fields of natural sciences, engineering, geology and medical 124 research. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory,[1] which has been 125 a remarkably successful contribution to the field of materials science. The BET method was 126 developed in the 1930s and is now the most widely used metric for the estimation of surface 127 areas of porous materials.[2] Since the BET method was first developed, there has been an 128 explosion in the field of nanoporous materials with the discovery of synthetic zeolites,[3] 129 nanostructured silicas,[4–6] metal-organic frameworks (MOFs),[7] and others. Despite its 130 widespread use, the manual calculation of BET surface areas causes a significant spread in 131 reported areas, resulting in reproducibility problems in both academia and industry. To probe 132 this, we have brought together 60 labs with strong track records in the study of nanoporous 133 materials. We provided eighteen adsorption isotherms and asked these researchers to 134 calculate the corresponding BET areas, resulting in a wide range of values for each one. We 135 show here that the reproducibility of BET area determination from identical isotherms is a 136 largely ignored issue, raising critical concerns over the reliability of reported BET areas in 137 the literature. To solve this major issue, we have developed a new computational approach 138 to accurately and systematically determine the BET area of nanoporous materials. Our 139 software, called BET Surface Identification (BETSI), expands on the well-known Rouquerol 140 criteria and makes, for the first time, an unambiguous BET area assignment possible.
Publisher: Wiley
Date: 02-05-2019
Publisher: Wiley
Date: 31-05-2012
Abstract: A proof-of-concept for the development of a fast and portable Hendra virus biosensor is presented. Hendra virus, a deadly emerging pathogen in Australia, can be co-localized, concentrated and revealed using simultaneously magnetic and luminescent functional particles. This method should be applicable for the early detection of any other virus by targeting the specific virus with the corresponding antibody.
Publisher: Wiley
Date: 21-12-2009
Abstract: Deep X-ray lithography combined with sol-gel techniques offers facile fabrication of controlled patterned films. Using sol-gel, different functional properties can be induced deep X-ray lithography alters the functionality in the exposed regions. Miniaturized devices based on local property changes are easily fabricated: this technique requires no resist, enabling direct patterning of films in a one-step lithographic process.
Publisher: Wiley
Date: 09-2016
Publisher: Wiley
Date: 19-10-2012
Abstract: The incorporation of highly luminescent core-shell quantum dots (QDs) within a metal-organic framework (MOF) is achieved through a one-pot method. Through appropriate surface functionalization, the QDs are solubilized within MOF-5 growth media. This permits the incorporation of the QDs within the evolving framework during the reaction. The resulting QD@MOF-5 composites are characterized using X-ray fluorescence, cross-sectional confocal microscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and small-angle X-ray scattering. The synergistic combination of luminescent QDs and the controlled porosity of MOF-5 in the QD@MOF-5 composites is harnessed within a prototype molecular sensor that can discriminate on the basis of molecular size.
Publisher: American Chemical Society (ACS)
Date: 08-07-2019
DOI: 10.26434/CHEMRXIV.8792171.V1
Abstract: Copper dicarboxylate metal-organic framework films are deposited via chemical vapour deposition. Uniform films of CuBDC and CuCDC with an out-of-plane orientation and accessible porosity are obtained from the reaction of Cu and CuO with vaporised dicarboxylic acid linkers.
Publisher: IEEE
Date: 07-2010
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9CC09358C
Abstract: A porous model bioreactor is obtained combining zeolitic imidazolate framework ZIF-8 with horseradish peroxidase and iron oxide magnetic nanoparticles in a one-pot process, in water at room temperature.
Publisher: Wiley
Date: 07-2016
Publisher: International Union of Crystallography (IUCr)
Date: 06-2012
Publisher: American Chemical Society (ACS)
Date: 03-2010
DOI: 10.1021/CM902625V
Publisher: Springer Science and Business Media LLC
Date: 12-2004
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2JM31798B
Publisher: Springer Science and Business Media LLC
Date: 10-09-2011
Publisher: American Chemical Society (ACS)
Date: 19-08-2019
DOI: 10.1021/JACS.9B06589
Abstract: Protection of biological assemblies is critical to applications in biotechnology, increasing the durability of enzymes in biocatalysis or potentially stabilizing biotherapeutics during transport and use. Here we show that a porous hydrogen-bonded organic framework (HOF) constructed from water-soluble tetra-amidinium (
Publisher: Wiley
Date: 07-2019
Abstract: Recent work in biomolecule-metal-organic framework (MOF) composites has proven to be an effective strategy for the protection of proteins. However, for other biomacromolecules such as nucleic acids, the encapsulation into nano MOFs and the related characterizations are in their infancy. Herein, encapsulation of a complete gene-set in zeolitic imidazolate framework-8 (ZIF-8) MOFs and cellular expression of the gene delivered by the nano MOF composites are reported. Using a green fluorescent protein (GFP) plasmid (plGFP) as a proof-of-concept genetic macromolecule, successful transfection of mammalian cancer cells with plGFP for up to 4 days is shown. Cell transfection assays and soft X-ray cryo-tomography (cryo-SXT) demonstrate the feasibility of DNA@MOF biocomposites as intracellular gene delivery vehicles. Expression occurs over relatively prolonged time points where the cargo nucleic acid is released gradually in order to maintain sustained expression.
Publisher: Wiley
Date: 05-06-2017
Abstract: A bioactive synthetic porous shell was engineered to enable cells to survive in an oligotrophic environment. Eukaryotic cells (yeast) were firstly coated with a β-galactosidase (β-gal), before crystallization of a metal-organic framework (MOF) film on the enzyme coating thereby producing a bioactive porous synthetic shell. The β-gal was an essential component of the bioactive shell as it generated nutrients (that is, glucose and galactose) required for cell viability in nutrient-deficient media (lactose-based). Additionally, the porous MOF coating carried out other vital functions, such as 1) shielding the cells from cytotoxic compounds and radiation, 2) protecting the non-native enzymes (β-gal in this instance) from degradation and internalization, and 3) allowing for the diffusion of molecules essential for the survival of the cells. Indeed, this bioactive porous shell enabled the survival of cells in simulated extreme oligotrophic environments for more than 7 days, leading to a decrease in cell viability less than 30 %, versus a 99 % decrease for naked yeast. When returned to optimal growth conditions the bioactive porous exoskeleton could be removed and the cells regained full growth immediately. The construction of bioactive coatings represents a conceptually new and promising approach for the next-generation of cell-based research and application, and is an alternative to synthetic biology or genetic modification.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0JM03493B
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B925105G
Publisher: American Chemical Society (ACS)
Date: 28-12-2022
Publisher: American Chemical Society (ACS)
Date: 10-01-2011
DOI: 10.1021/CM101519S
Publisher: American Chemical Society (ACS)
Date: 06-11-2019
DOI: 10.26434/CHEMRXIV.10059935.V1
Abstract: Here we systematically varied the composition of the relative amounts of ligand (2-methylimidazole), metal precursor (Zn(OAc)2∙2H2O, and protein to prepare a series of protein@ZIF biocomposites. The effect of post synthetic treatments (i.e. washes with water or water/ethanol) was investigated. The XRD data of the examined s les were used to construct ternary diagrams. Five different phases were identified. The encapsulation efficiency (of bovine serum albumin and insulin) were phase dependent.
Publisher: Wiley
Date: 14-07-2016
Abstract: The biomimetic mineralization of metal-organic framework (MOF) material on living cells is reported. ZIF-8 can be crystallized on a living cell surface as an exoskeleton that offers physical protection while allowing transport of essential nutrients, thus maintaining cell viability. The MOF shell prevents cell ision, leading to an artificially induced pseudo-hibernation state. Cellular functions can be fully restored upon MOF removal.
Publisher: American Chemical Society (ACS)
Date: 06-02-2020
DOI: 10.26434/CHEMRXIV.11807268.V1
Abstract: Prostate cancer (PC) is the second leading cause of male cancer deaths, the advanced form of which continues to be incurable and nature of the disease being such that it is highly suitable for gene therapy. However, therapy is h ered by lack of appropriate gene delivery agents available. Recently, metal-organic-framework (MOF) biocomposites have seen increasing applications in DNA technologies, including gene delivery. In this work, a polymorph of zeolitic imidazolate framework-8 (ZIF-8) MOF nanoparticles called ZIF-C are used as gene delivery agents to cause knockdown (KD) of a protein overexpressed by the gene ribosomal protein SA in PC. Feasibility of ZIF-C mediated KD at cytoplasmic levels in PC is demonstrated by RNA interference, whereby RPSA specific siRNA is delivered using ZIF-C. Feasibility of ZIF-C mediated KD at genomic levels is demonstrated by CRISPR/Cas9, whereby RPSA specific CRISPR/Cas9 plasmids are delivered using ZIF-C. Specific targeting is further achieved by coating of ZIF-C with epigallocatechin-gallate (EGCG). Cellular transfection assays reveal the gradual expression of ZIF-C delivered RPSA-targeting nucleic acids for up to 96 hours. Quantitative polymerase chain reactions and genomic cleavage detection demonstrate gradual KD, with ~20% reduction in RPSA expression that is almost doubled to ~40% on EGCG-mediated targeted cellular uptake.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CE00390K
Abstract: A Fe 3 O 4 /Cu- ceramic system converted into a magnetic HKUST-1 composite was used as a recyclable catalyst for one-pot cascade and hydrogenation reactions.
Publisher: American College of Physicians
Date: 07-1998
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CC06241C
Abstract: Metal–organic-frameworks for gene therapy in prostate cancer – ZIF-C based delivery of RNA interference and CRISPR/Cas9 causes host gene expression knockdown. Coating with a green tea phytochemical enhances uptake and increases cancer cytotoxicity.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0FD00015A
Abstract: Structure determination by continuous rotation electron diffraction can be as feasible and accurate as single crystal X-ray diffraction without the need for large crystals.
Publisher: Springer Science and Business Media LLC
Date: 14-07-2007
Publisher: American Chemical Society (ACS)
Date: 27-05-2014
DOI: 10.1021/JP501653X
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0SC02958K
Abstract: Orientation-controlled Cu 2 (Linker) 2 DABCO MOF films on macroscopic scales are fabricated for the development of high-performance devices the direction of 1D nanochannels is controllable either perpendicular or parallel to substrates.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CS00089G
Abstract: Methods for permanent localisation, dynamic localisation and spatial control of functional materials within MOF crystals are critical for the development of miniaturised MOF-based devices for a number of technological applications.
Publisher: American Chemical Society (ACS)
Date: 11-11-2013
DOI: 10.1021/AR400130A
Abstract: A critical materials challenge over the next quarter century is the sustainable use and management of the world's natural resources, particularly the scarcest of them. Chemistry's ability to get more from less is epitomized by porous coordination polymers, also known as metal-organic frameworks (MOFs), which use a minimum amount of material to build maximum surface areas with fine control over pore size. Their large specific surface area and tunable porosity make MOFs useful for applications including small-molecule sensing, separation, catalysis, and storage and release of molecules of interest. Proof-of-concept projects have demonstrated their potential for environmental applications such as carbon separation and capture, water purification, carcinogen sequestration, byproduct separation, and resource recovery. To translate these from the laboratory into devices for actual use, however, will require synthesis of MOFs with new functionality and structure. This Account summarizes recent progress in the use of nano- and microparticles to control the function, location, and 3D structure of MOFs during MOF self-assembly, creating novel, hybrid, multifunctional, ultraporous materials as a first step towards creating MOF-based devices. The use of preformed ceramic, metallic, semiconductive, or polymeric particles allows the particle preparation process to be completely independent of the MOF synthesis, incorporating nucleating, luminescent, magnetic, catalytic, or templating particles into the MOF structure. We discuss success in combining functional nanoparticles and porous crystals for applications including molecular sieve detectors, repositionable and highly sensitive sensors, pollutant-sequestering materials, microfluidic microcarriers, drug-delivery materials, separators, and size-selective catalysts. In sections within the Account, we describe how functional particles can be used for (1) heterogeneous nucleation (seeding) of MOFs, (2) preparation of framework composites with novel properties, (3) MOF positioning on a substrate (patterning), and (4) synthesis of MOFs with novel architectures.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CE01030J
Abstract: Metal–organic frameworks are highly crystalline porous materials which present emerging opportunities in biotechnology, catalysis, microelectronics and photonics.
Publisher: Wiley
Date: 03-01-2016
Abstract: Magnetic metal-organic framework (MOF) composites show highly efficient CO2 desorption capacities upon their exposure to an alternating magnetic field, demonstrating a magnetic induction swing strategy for potentially low-energy regeneration of MOF adsorbents.
Publisher: Wiley
Date: 06-05-2019
Abstract: Motile metal-organic frameworks (MOFs) are potential candidates to serve as small-scale robotic platforms for applications in environmental remediation, targeted drug delivery, or nanosurgery. Here, magnetic helical microstructures coated with a kind of zinc-based MOF, zeolitic imidazole framework-8 (ZIF-8), with biocompatibility characteristics and pH-responsive features, are successfully fabricated. Moreover, it is shown that this highly integrated multifunctional device can swim along predesigned tracks under the control of weak rotational magnetic fields. The proposed systems can achieve single-cell targeting in a cell culture media and a controlled delivery of cargo payloads inside a complex microfluidic channel network. This new approach toward the fabrication of integrated multifunctional systems will open new avenues in soft microrobotics beyond current applications.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1NR10404G
Abstract: Mesoporous nanocomposite materials have been fabricated through integration of evaporation-induced self-assembly and deep X-ray lithography. Micropatterned films made using a mesoporous ordered silica matrix which contains silver nanoparticles have been obtained. The exposure of the mesoporous films to high energy X-rays, which are generated by a synchrotron source, produces several effects: the removal of the surfactant, the densification of the silica backbone and the formation of silver nanoparticles. This integrated process produces a nanocomposite material which has a 2D-hexagonal organized porosity and silver nanoparticles with a sharp size distribution around 5 nm. The patterned nanostructured films have been tested as a lab-on-chip device for intrinsic surface enhanced Raman scattering detection using a solution containing rhodamine 6G in ethanol and measuring Raman response as a function of laser power.
Publisher: American Chemical Society (ACS)
Date: 02-12-2013
DOI: 10.1021/AM4027407
Abstract: To fully exploit the potential of self-assembly in a single step, we have designed an integrated process to obtain mesoporous graphene nanocomposite films. The synthesis allows incorporating graphene sheets with a small number of defects into highly ordered and transparent mesoporous titania films. The careful design of the porous matrix at the mesoscale ensures the highest diffusivity in the films. These exhibit an enhanced photocatalytic efficiency, while the high order of the mesoporosity is not affected by the insertion of the graphene sheets and is well-preserved after a controlled thermal treatment. In addition, we have proven that the nanocomposite films can be easily processed by deep X-ray lithography to produce functional arrays.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CC33292B
Abstract: For the first time a top-down process was used to control the spatial location of Metal-Organic Frameworks on a surface. Deep X-ray lithography was utilised to micropattern a Zeolitic Imidazolate Framework layer on a sol-gel surface, with exposure hardening the sol-gel by inducing crosslinking while leaving the frameworks intact.
Publisher: American Chemical Society (ACS)
Date: 23-09-2009
DOI: 10.1021/CM9013859
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B418381A
Publisher: American Chemical Society (ACS)
Date: 31-01-2018
Publisher: IEEE
Date: 08-2011
Publisher: Wiley
Date: 17-03-2020
Publisher: American Scientific Publishers
Date: 09-2014
Abstract: Beta-Glucosidase has been chosen as a model biomolecule to establish a general protocol for binding enzymes on both ferromagnetic and superparamagnetic nano-particles for sensing applications. Using EDC (1-(3-dimethyl-aminopropyl)-3-ethylcarbodiimide) or SMCC (Succinimidyl-4-(N-maleimidomethyl)cyclohexane-1-carboxylate) as coupling agents, we compared two different methods for the fabrication of enzyme-decorated magnetic nanoparticles. We identified the best conditions for the preparation of a responsive bioactive magnetic system comparing different covalent bio-grafting protocols. The enzymatic test has been performed using beta-Glucosidase. The systems were characterized using scanning electron microscopy, infrared spectroscopy, and the enzyme loading was measured by a glucose assay in the presence of the enzyme-decorated magnetic particles. Although the faster response of ferromagnetic particles to the magnetic field, the assay results suggested that the superparamagnetic particles are more efficient carriers. In fact, the best enzymatic activity was measured on superparamagnetic systems that have the further advantage of preventing aggregation induced by the residual magnetization. Hence, beta-Glucosidase coated magnetic nanospheres could provide an attractive system suitable for the cleavage and the rapid evaluation of glycoside levels in natural products, measuring the liberated glucose without the need for specialised instrumentation. Moreover, the magnetic particles allow the subsequent collection of enzymes for further analysis, such as its use in portable fast screening kits or devices.
Publisher: American Chemical Society (ACS)
Date: 20-03-2007
DOI: 10.1021/JP066566C
Publisher: IOP Publishing
Date: 16-12-2011
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CC32081A
Abstract: Titanate nanofunnel brushes were grown on sol-gel derived amorphous TiO(2) thin films, whose shape can be tuned from nanosheets to nanofunnels by changing hydrothermal conditions. A superhydrophobic adhesive surface was achieved by a chemical modification of the brushes.
Publisher: Elsevier BV
Date: 2004
Publisher: Springer Science and Business Media LLC
Date: 07-12-2013
Publisher: American Chemical Society (ACS)
Date: 21-01-2020
DOI: 10.26434/CHEMRXIV.11637759.V1
Abstract: Zeolitic Imidazolate Framework (ZIF) biocomposites show the capacity to protect and deliver bio-therapeutics. To date, the progress in this research area is based on laboratory batch methods. To further explore the potential of ZIF-biocomposites for application to biomedicine and biotechnology, the continuous production of ZIF-biocomposites of specific particle size is desirable. We report the first continuous flow synthetic method for the encapsulation of a model protein (BSA) and a clinical therapeutic (α1-antitrypsin, AAT) in ZIF-8. We studied the in situ kinetics of nucleation, growth and crystallization of BSA-ZIF-8 by SAXS. By controlling the injection time of ethanol, we could quench the particle growth via ethanol-induced crystallization. The particle size of the biocomposite was tuned in the 40-100 nm range by varying residence time prior to introduction of ethanol.
Publisher: American Chemical Society (ACS)
Date: 03-04-2013
DOI: 10.1021/AM4001024
Abstract: Nanocomposite thin films formed by mesoporous titania layers loaded with ceria nanoparticles have been obtained by combining bottom-up self-assembly synthesis of a titania matrix with top-down hard X-ray lithography of nanocrystalline cerium oxide. At first the titania mesopores have been impregnated with the ceria precursor solution and then exposed to hard X-rays, which triggered the formation of crystalline cerium oxides within the pores inducing the in situ growth of nanoparticles with average size of 4 nm. It has been observed that the type of coordinating agent in the solution plays a primary role in the formation of nanoparticles. Different patterns have been also produced through deep X-ray lithography by spatially controlling the nanoparticle growth on the micrometer scale. The radical scavenging role of the nanocomposite films has been tested using as a benchmark the UV photodegradation of rhodamine 6G. After impregnation with a rhodamine 6G solution, s les with and without ceria have shown a remarkably different response upon exposure to UV light. The dye photodegradation on the surface of nanocomposite films appears strongly slowed down because of the antioxidation effect of ceria nanoparticles.
Publisher: Wiley
Date: 17-04-2019
Abstract: The precise alignment of multiple layers of metal-organic framework (MOF) thin films, or MOF-on-MOF films, over macroscopic length scales is presented. The MOF-on-MOF films are fabricated by epitaxially matching the interface. The first MOF layer (Cu
Publisher: American Chemical Society (ACS)
Date: 24-08-2006
DOI: 10.1021/CM060236N
Publisher: Elsevier BV
Date: 2013
Publisher: American Chemical Society (ACS)
Date: 13-01-2021
Publisher: Springer Berlin Heidelberg
Date: 2013
DOI: 10.1007/430_2013_106
Publisher: Springer Science and Business Media LLC
Date: 27-04-2023
DOI: 10.1038/S41467-023-37476-Y
Abstract: Understanding the cause of lithium dendrites formation and propagation is essential for developing practical all-solid-state batteries. Li dendrites are associated with mechanical stress accumulation and can cause cell failure at current densities below the threshold suggested by industry research (i.e., mA/cm 2 ). Here, we apply a MHz-pulse-current protocol to circumvent low-current cell failure for developing all-solid-state Li metal cells operating up to a current density of 6.5 mA/cm 2 . Additionally, we propose a mechanistic analysis of the experimental results to prove that lithium activity near solid-state electrolyte defect tips is critical for reliable cell cycling. It is demonstrated that when lithium is geometrically constrained and local current plating rates exceed the exchange current density, the electrolyte region close to the defect releases the accumulated elastic energy favouring fracturing. As the build-up of this critical activity requires a certain period, applying current pulses of shorter duration can thus improve the cycling performance of all-solid-solid-state lithium batteries.
Publisher: Wiley
Date: 28-02-2013
Abstract: Microchannels are fabricated using a photosensitive polymer to which microporosity is tuned with different X-ray doses. Using hard X-ray irradiation, the micropattern is positioned with various geometries in a multi-level, three-dimensional structure, while controlling the pore size and transport properties of small molecules. This highly reliable fabrication process has potential for use in microfluidic devices with enhanced transport properties through microchannels.
Publisher: American Chemical Society (ACS)
Date: 20-02-2015
DOI: 10.1021/CM504806P
Publisher: American Chemical Society (ACS)
Date: 26-06-2004
DOI: 10.1021/JP037740P
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CE00757A
Abstract: Understanding the stability of zeolitic imidazolate framework-8 (ZIF-8) under physiological conditions is critical in biotechnology and biomedicine for biosensing, biocatalysis, and drug delivery.
Publisher: Elsevier BV
Date: 06-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8MH01611A
Abstract: MOFs have demonstrated outstanding properties for the protection and controlled release of different bio-entities, from proteins to living cells.
Publisher: Wiley
Date: 19-10-2015
Abstract: 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.
Publisher: Wiley
Date: 16-04-2019
Publisher: Elsevier BV
Date: 06-2007
Publisher: American Chemical Society (ACS)
Date: 08-01-2018
Abstract: Metal-organic frameworks (MOFs) are a class of coordination polymers, consisting of metal ions or clusters linked together by chemically mutable organic groups. In contrast to zeolites and porous carbons, MOFs are constructed from a building block strategy that enables molecular level control of pore size/shape and functionality. An area of growing interest in MOF chemistry is the synthesis of MOF-based composite materials. Recent studies have shown that MOFs can be combined with biomacromolecules to generate novel biocomposites. In such materials, the MOF acts as a porous matrix that can encapsulate enzymes, oligonucleotides, or even more complex structures that are capable of replication/reproduction (i.e., viruses, bacteria, and eukaryotic cells). The synthetic approach for the preparation of these materials has been termed "biomimetic mineralization", as it mimics natural biomineralization processes that afford protective shells around living systems. In this Perspective, we focus on the preparation of MOF biocomposites that are composed of complex biological moieties such as viruses and cells and canvass the potential applications of this encapsulation strategy to cell biology and biotechnology.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4QI00215F
Abstract: A Cu-based metal–organic framework (HKUST-1) was synthesized from insoluble precursors and positioned using sol–gel based coatings.
Publisher: American Chemical Society (ACS)
Date: 23-01-2020
DOI: 10.26434/CHEMRXIV.11688270.V1
Abstract: Many framework materials such as metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are synthesized as polycrystalline powders, which are too small for structure determination by single crystal X-ray diffraction (SCXRD). Here, we show that a three-dimensional (3D) electron diffraction method, namely continuous rotation electron diffraction (cRED), can be used for ab initio structure determination of such materials. As an ex le, we present a complete structural analysis of a biocomposite, denoted BSA@ZIF-C, where Bovin Serum Albumin (BSA) was encapsulated in a zeolitic imidazolate framework (ZIF). Low electron dose was combined with ultrafast cRED data collection to minimize electron beam damage of the s le. We demonstrate that the atomic structure obtained by cRED is as reliable and accurate as that obtained by single crystal X-ray diffraction. The high accuracy and fast data collection open new opportunities for investigation of cooperative phenomena in framework structures at atomic level.
Publisher: American Chemical Society (ACS)
Date: 12-01-2019
DOI: 10.1021/JACS.8B10302
Abstract: Encapsulation of biomacromolecules in metal-organic frameworks (MOFs) can preserve biological functionality in harsh environments. Despite the success of this approach, termed biomimietic mineralization, limited consideration has been given to the chemistry of the MOF coating. Here, we show that enzymes encapsulated within hydrophilic MAF-7 or ZIF-90 retain enzymatic activity upon encapsulation and when exposed to high temperatures, denaturing or proteolytic agents, and organic solvents, whereas hydrophobic ZIF-8 affords inactive catalase and negligible protection to urease.
Publisher: Wiley
Date: 05-06-2017
Publisher: Wiley
Date: 19-05-2008
Publisher: Springer Science and Business Media LLC
Date: 04-06-2015
DOI: 10.1038/NCOMMS8240
Abstract: 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 ex le, 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.
Publisher: Elsevier BV
Date: 10-2003
Publisher: Springer Science and Business Media LLC
Date: 30-12-2009
Publisher: Wiley
Date: 04-07-2016
Publisher: Springer Science and Business Media LLC
Date: 26-10-2020
Publisher: International Union of Crystallography (IUCr)
Date: 2015
DOI: 10.1107/S1600577514024047
Abstract: An innovative approach towards the physico-chemical tailoring of zinc oxide thin films is reported. The films have been deposited by liquid phase using the sol–gel method and then exposed to hard X-rays, provided by a synchrotron storage ring, for lithography. The use of surfactant and chelating agents in the sol allows easy-to-pattern films made by an organic–inorganic matrix to be deposited. The exposure to hard X-rays strongly affects the nucleation and growth of crystalline ZnO, triggering the formation of two intermediate phases before obtaining a wurtzite-like structure. At the same time, X-ray lithography allows for a fast patterning of the coatings enabling microfabrication for sensing and arrays technology.
Publisher: American Chemical Society (ACS)
Date: 27-04-2009
DOI: 10.1021/CM802750W
Publisher: Wiley
Date: 22-06-2010
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CC03876H
Abstract: Insoluble fatty acids that trigger the growth of luminescent MOFs on fingerprint residues were employed for the precise positioning of MOFs.
Publisher: International Union of Crystallography (IUCr)
Date: 22-01-2011
Publisher: Wiley
Date: 23-01-2014
Publisher: Springer Science and Business Media LLC
Date: 2007
Publisher: American Chemical Society (ACS)
Date: 26-04-2003
DOI: 10.1021/JP026609Z
Publisher: American Chemical Society (ACS)
Date: 20-07-2011
DOI: 10.1021/AC201337E
Abstract: In industry as well as many areas of scientific research, data collected often contain a number of responses of interest for a chosen set of exploratory variables. Optimization of such multivariable multiresponse systems is a challenge well suited to genetic algorithms as global optimization tools. One such ex le is the optimization of coating surfaces with the required absolute and relative sensitivity for detecting analytes using devices such as sensor arrays. High-throughput synthesis and screening methods can be used to accelerate materials discovery and optimization however, an important practical consideration for successful optimization of materials for arrays and other applications is the ability to generate adequate information from a minimum number of experiments. Here we present a case study to evaluate the efficiency of a novel evolutionary model-based multiresponse approach (EMMA) that enables the optimization of a coating while minimizing the number of experiments. EMMA plans the experiments and simultaneously models the material properties. We illustrate this novel procedure for materials optimization by testing the algorithm on a sol-gel synthetic route for production and optimization of a well studied amino-methyl-silane coating. The response variables of the coating have been optimized based on application criteria for micro- and macro-array surfaces. Spotting performance has been monitored using a fluorescent dye molecule for demonstration purposes and measured using a laser scanner. Optimization is achieved by exploring less than 2% of the possible experiments, resulting in identification of the most influential compositional variables. Use of EMMA to optimize control factors of a product or process is illustrated, and the proposed approach is shown to be a promising tool for simultaneously optimizing and modeling multivariable multiresponse systems.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CE02549D
Publisher: American Scientific Publishers
Date: 07-2014
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2TC00241H
Publisher: American Chemical Society (ACS)
Date: 16-03-2021
DOI: 10.26434/CHEMRXIV.14213966
Abstract: 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 goniometer, which often leads to incomplete 3DED data, particularly when the crystal symmetry is low. This drawback can be overcome by high throughput data collection using continuous rotation electron diffraction (cRED), where data from a large number of crystals can be collected and merged. Here, we investigate the effects of improving completeness on structural analysis of MOFs. We use ZIF-EC1, a zeolitic imidazolate framework (ZIF), as an ex le. ZIF-EC1 crystallizes in a monoclinic system with a plate-like morphology. cRED data of ZIF-EC1 with different completeness and resolution were analyzed. The data completeness increased to 92.0% by merging ten datasets. Although the structures could be solved from in idual datasets with a completeness as low as 44.5% and refined to a high precession (better than 0.04 Å), we demonstrate that a high data completeness could improve the structural model, especially on the electrostatic potential map. We further discuss the strategy adopted during data merging. We also show that ZIF-EC1 doped with cobalt can act as an efficient electrocatalyst for oxygen reduction reaction.
Publisher: Wiley
Date: 07-04-2021
Publisher: American Scientific Publishers
Date: 07-2014
Publisher: American Chemical Society (ACS)
Date: 22-02-2021
DOI: 10.26434/CHEMRXIV.13725817
Abstract: 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. Here, we report a high-throughput approach for structural analysis of MOF nano- and sub-microcrystals by three-dimensional electron diffraction (3DED). A new zeolitic-imidazolate framework (ZIF), denoted ZIF-EC1 a , /a was first discovered in a trace amount during the study of a known ZIF-CO sub /sub -1 material by 3DED. The structures of both ZIFs were solved and refined using 3DED data. ZIF-EC1 has a dense 3D framework structure, which is built by linking mono- and bi-nuclear Zn clusters and 2-methylimidazolates (mIm sup - /sup ). With a composition of Zn sub /sub (mIm) sub /sub (OH), ZIF-EC1 exhibits high N and Zn densities. We show that the N-doped carbon material derived from ZIF-EC1 is a promising electrocatalysis for oxygen reduction reaction (ORR). The discovery of this new MOF and its conversion to an efficient electrocatalyst highlights the power of 3DED in developing new materials and their applications.
Publisher: SPIE
Date: 21-12-2011
DOI: 10.1117/12.904854
Publisher: American Chemical Society (ACS)
Date: 15-12-2007
DOI: 10.1021/CM071784J
Publisher: Wiley
Date: 17-03-2020
Publisher: American Chemical Society (ACS)
Date: 11-2011
DOI: 10.1021/CG200717A
Publisher: Elsevier BV
Date: 2016
Publisher: The Electrochemical Society
Date: 23-11-2020
DOI: 10.1149/MA2020-02301999MTGABS
Abstract: One of the key challenges that the field of metal-organic frameworks (MOFs) faces today is the possibility of processing these materials as thin films to enable their integration into existing technologies [1-4]. This is particularly important for devices that exploit anisotropic properties obtained from highly oriented materials. Based on a previously described procedure to obtain centimetre-scale oriented MOF films [5], we hereby report the optimization and extension of this procedure into an automated, operator-independent method that affords higher yields without compromising the long-range orientation. The procedure is based on the deposition of crystalline copper hydroxide nanobelts that can be aligned to obtain substrates with preferential orientation. The influence of different deposition parameters on the coverage and orientation of the films was studied and tuned in order to obtain reproducible s les with higher yields. With applications in fields such as gas storage, catalysis and light harvesting, among others, these oriented ceramic substrates can be converted on demand to different MOFs by exploiting a rapid heteroepitaxial growth [6]. This automatic method introduces the attractive prospect of the potential implementation of MOFs in large-scale thin-film processing. Figure 1: Comparison between manual and automated procedures for the deposition of oriented copper hydroxide films on silicon substrates. Left: Azimuthal angle dependence of intensity profiles of the (020) reflection of Cu(OH) 2 at a diffraction angle of 23.8°corresponding to a typical s le obtained by each method, showing the superior alignment of the automatic procedure. Right: Optical images showing the surface coverage and long range (centimetre-scale, top) and micro alignment of the substrate (by polarized-light optical microscopy, bottom). References: [1] Bétard, A. Fischer, R.A. Chemical reviews 2011 , 112, 1055 [2] Falcaro, P. Ricco, R. Doherty, C.M. Liang, K. Hill, A.J. Styles, M.J. Chemical Society Reviews 2014 , 43, 5513 [3] Stassen, I. Burtch, N. Talin, A. Falcaro, P. Allendorf, M. Ameloot, R. Chemical Society Reviews 2017 , 46, 3185 [4] Liu, J. Wöll, C. Chemical Society Reviews 2017 , 46, 5730 [5] Falcaro, P. Okada, K. Hara, T. Ikigaki, K. Tokudome, Y. Thornton, A. W. Hill, A. J. Williams, T. Doonan, C. Takahashi, M. Falcaro, P. Nature materials 2017 , 16, 342. [6] Ikigaki, K. Okada, K. Tokudome, Y. Toyao, T. Falcaro, P. Doonan, C.J. Takahashi, M. Angewandte Chemie 2019 , 131, 6960. Figure 1
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2CC03072A
Abstract: Living cells are coated with a multi-layered MOF biocomposite shell: the shell dissolution releases a biotherapeutic (antitrypsin) that provides artificial adaptability to protease-rich environments.
Publisher: American Chemical Society (ACS)
Date: 23-09-2016
Publisher: American Chemical Society (ACS)
Date: 14-06-2017
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3SC04135B
Publisher: American Chemical Society (ACS)
Date: 19-11-2015
Publisher: American Chemical Society (ACS)
Date: 08-09-2005
DOI: 10.1021/CM050850J
Publisher: Wiley
Date: 06-07-2016
Abstract: Adsorbents for CO2 capture need to demonstrate efficient release. Light-induced swing adsorption (LISA) is an attractive new method to release captured CO2 that utilizes solar energy rather than electricity. MOFs, which can be tailored for use in LISA owing to their chemical functionality, are often unstable in moist atmospheres, precluding their use. A MOF is used that can release large quantities of CO2 via LISA and is resistant to moisture across a large pH range. PCN-250 undergoes LISA, with UV flux regulating the CO2 desorption capacity. Furthermore, under UV light, the azo residues within PCN-250 have constrained, local, structural flexibility. This is dynamic, rapidly switching back to the native state. Reusability tests demonstrate a 7.3 % and 4.9 % loss in both adsorption and LISA capacity after exposure to water for five cycles. These minimal changes confirm the structural robustness of PCN-250 and its great potential for triggered release applications.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5TA04154F
Abstract: MIL-53(Al) based magnetic framework composites with iron oxide nanoparticles exhibit high uptake of lead( ii ) from aqueous solution.
Publisher: Springer Science and Business Media LLC
Date: 13-04-2021
DOI: 10.1038/S41467-021-22285-Y
Abstract: Artificial native-like lipid bilayer systems constructed from phospholipids assembling into unilamellar liposomes allow the reconstitution of detergent-solubilized transmembrane proteins into supramolecular lipid-protein assemblies called proteoliposomes, which mimic cellular membranes. Stabilization of these complexes remains challenging because of their chemical composition, the hydrophobicity and structural instability of membrane proteins, and the lability of interactions between protein, detergent, and lipids within micelles and lipid bilayers. In this work we demonstrate that metastable lipid, protein-detergent, and protein-lipid supramolecular complexes can be successfully generated and immobilized within zeolitic-imidazole framework (ZIF) to enhance their stability against chemical and physical stressors. Upon immobilization in ZIF bio-composites, blank liposomes, and model transmembrane metal transporters in detergent micelles or embedded in proteoliposomes resist elevated temperatures, exposure to chemical denaturants, aging, and mechanical stresses. Extensive morphological and functional characterization of the assemblies upon exfoliation reveal that all these complexes encapsulated within the framework maintain their native morphology, structure, and activity, which is otherwise lost rapidly without immobilization.
Publisher: TMS
Date: 2019
Publisher: Springer Science and Business Media LLC
Date: 07-06-2011
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2MA00004K
Abstract: Honeycomb structured copper indium sulfide layers are successfully realized via a nanosphere lithography route employing polystyrene nanosphere array templates and metal xanthates or a nanocrystal ink.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2SC02405E
Abstract: By using a structurally responsive and oriented DMOF-1-on-MOF film, we successfully fabricated the first photo-switchable crystalline MOF film that experiences crystal lattice deformations reversibly within seconds.
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3TA13140H
Publisher: American Chemical Society (ACS)
Date: 10-01-2011
DOI: 10.1021/AM100901M
Abstract: A phenyl-based hybrid organic - inorganic coating has been synthesized and processed by hard X-ray lithography. The overall lithography process is performed in a two-step process only (X-rays exposure and chemical etching). The patterns present high aspect ratio, sharp edges, and high homogeneity. The coating has been doped with a variety of polycyclic aromatic hydrocarbon functional molecules, such as anthracene, pentacene, and fullerene. For the first time, hard X-rays have been combined with thick hybrid functional coatings, using the sol-gel thick film directly as resist. A new technique based on a new material combined with hard X-rays is now available to fabricate optical devices. The effect due to the high-energy photon exposure has been investigated using FT-IR and Raman spectroscopy, laser scanner, optical profilometer, and confocal and electron microscope. High-quality thick hybrid fullerene-doped microstructures have been fabricated.
Publisher: American Chemical Society (ACS)
Date: 14-04-2010
DOI: 10.1021/AM100149E
Abstract: The photocatalytic activity of TiO(2) films synthesized via the sol-gel process has been measured as a function of UV irradiation time and substrate temperature. Fourier-transform infrared spectroscopy has been used to address the chemical changes in stearic acid and block copolymer Pluronic F127 films deposited on the photocatalytic surface. When the temperature of the photocatalytic substrate was raised above 50 degrees C, the removal of stearic acid from the surface was strongly affected by a process involving evaporation, whereas Pluronic F127 revealed a superior stability. Our study shows that heat enhances the photocatalytic activity, suggesting the importance of an accurate temperature control in photocatalytic efficiency measurements.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0SC01204A
Abstract: Clinical and pre-clinical GAG-based biotherapeutics were encapsulated within three metal-azolate frameworks (ZIF-8, ZIF-90, and MAF-7). The resulting MOF biocomposites show different loading capacity, biopreservation properties and release profiles.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CE00416H
Abstract: Metal–organic framework (MOF) coatings were prepared on gold electrodes through the conversion from Cu(OH) 2 nanobelts to Cu 3 (BTC) 2 MOFs.
Publisher: American Chemical Society (ACS)
Date: 27-08-2018
DOI: 10.26434/CHEMRXIV.7012007.V1
Abstract: The ability to align porous metal–organic frameworks (MOFs) on substrate surfaces on a macroscopic scale is a vital step towards integrating MOFs into functional devices. But macroscale surface alignment of MOF crystals has only been demonstrated in a few cases. To accelerate the materials discovery process, we have developed a high-throughput computational screening algorithm to identify MOFs that are likely to undergo macroscale aligned heterepitaxial growth on a substrate. Screening of thousands of MOF structures by this process can be achieved in a few days on a desktop workstation. The algorithm filters MOFs based on surface chemical compatibility, lattice matching with the substrate, and interfacial bonding. Our method uses a simple new computationally efficient measure of the interfacial energy that considers both bond and defect formation at the interface. Furthermore, we show that this novel descriptor is a better predictor of aligned heteroepitaxial growth than other established interface descriptors, by testing our screening algorithm on a s le set of copper MOFs that have been grown heteroepitaxially on a copper hydroxide surface. Application of the screening process to several MOF databases reveals that the top candidates for aligned growth on copper hydroxide comprise mostly MOFs with rectangular lattice symmetry in the plane of the substrate. This result indicates a substrate-directing effect that could be exploited in targeted synthetic strategies. We also identify that MOFs likely to form aligned heterostructures have broad distributions of in-plane pore sizes and anisotropies. Accordingly, this suggests that aligned MOF thin films with a wide range of properties may be experimentally accessible.
Publisher: Wiley
Date: 10-10-2021
Abstract: Processing oriented metal–organic frameworks (MOFs) as thin films is a key challenge for their application to device fabrication. However, typical fabrication methods cannot generate precisely oriented crystals on commercially relevant scales (i.e., cm 2 ). This limits access to applications that require anisotropic functional properties (e.g., separation, optics, and electronics). Currently, highly oriented copper‐based MOFs are synthesized via the addition of the organic MOF component to an ethanolic solution of manually aligned Cu(OH) 2 nanobelt films. In this work, the optimization of a semi‐automatic method for the fabrication of precisely oriented MOF films that affords a 100% yield of high quality ceramic films at the centimeter scale is reported. This improved fabrication protocol will facilitate the progress of heteroepitaxially grown MOFs for molecular separators and micro‐opto‐electronic devices.
Publisher: Springer Science and Business Media LLC
Date: 05-12-2016
DOI: 10.1038/NMAT4815
Abstract: The fabrication of oriented, crystalline films of metal-organic frameworks (MOFs) is a critical step toward their application to advanced technologies such as optics, microelectronics, microfluidics and sensing. However, the direct synthesis of MOF films with controlled crystalline orientation remains a significant challenge. Here we report a one-step approach, carried out under mild conditions, that exploits heteroepitaxial growth for the rapid fabrication of oriented polycrystalline MOF films on the centimetre scale. Our methodology employs crystalline copper hydroxide as a substrate and yields MOF films with oriented pore channels on scales that primarily depend on the dimensions of the substrate. To demonstrate that an anisotropic crystalline morphology can translate to a functional property, we assembled a centimetre-scale MOF film in the presence of a dye and showed that the optical response could be switched 'ON' or 'OFF' by simply rotating the film.
Publisher: Wiley
Date: 02-05-2019
Publisher: Elsevier BV
Date: 03-2018
Publisher: American Chemical Society (ACS)
Date: 22-12-2014
DOI: 10.1021/CM502882A
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9SC05433B
Abstract: We report two ternary phase diagrams that show the synthesis conditions to prepare protein@ZIF biocomposites with different phases, including BSA@ZIF-C and insulin@ZIF-C. For each biocomposite, we measured distinct encapsulation efficiency and release profile properties.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CC05161A
Abstract: Vapour-phase deposition of copper dicarboxylate metal–organic framework thin films with an out-of-plane orientation and accessible porosity.
Publisher: Springer Science and Business Media LLC
Date: 15-03-2011
DOI: 10.1038/NCOMMS1234
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8RA04969F
Abstract: Pinna and co-workers report the design of a MOF-based magnetic composite for long-term release of dopamine in the PC12 cell line.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5CC07577G
Abstract: Recent studies have demonstrated that metal–organic frameworks can be employed as protective coatings for enzymes.
Publisher: Wiley
Date: 21-08-2015
Publisher: American Chemical Society (ACS)
Date: 07-02-2020
DOI: 10.26434/CHEMRXIV.11821731.V1
Abstract: In this work, selected GAG-based biotherapeutics, including one proteoglycan, were successfully encapsulated with high efficiency in three different pH-responsive metal-azolate frameworks (ZIF-8, ZIF-90, and MAF-7). The GAG@MOF biocomposites obtained present significant differences in terms of crystallinity, particle size, and spatial distribution of the cargo, which enables to modulate their performance as drug delivery systems.
Publisher: Wiley
Date: 04-07-2012
Abstract: Space ision with red cubes: Doping metal-organic frameworks with another metal component gives a further opportunity to tune their properties. Recent work successfully introduced europium into the inorganic nodes of frameworks. Although the doping element does not affect the framework topology, highly improved emissive performance was measured thanks to the intrinsic red emission of europium.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6TA09826F
Abstract: A dual stimuli-responsive metal–organic framework exhibits a cooperatively enhanced gas desorption capacity upon simultaneously exposing it to both UV light and an alternating magnetic field, highlighting a low-energy yet highly efficient strategy to regenerate MOF adsorbents.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1FD00020A
Abstract: We investigate the effects of improving the completeness of structural analysis of MOFs using three-dimensional electron diffraction.
Publisher: American Chemical Society (ACS)
Date: 02-12-2021
DOI: 10.1021/JACS.1C09740
Abstract: Synthesis of covalent organic framework (COF) thin films on different supports with high crystallinity and porosity is crucial for their potential applications. We have designed a new synchronized methodology, residual crystallization (RC), to synthesize sub 10 nm COF thin films. These residual crystallized COF thin films showcase high surface area, crystallinity, and conductivity at room temperature. We have used interfacial crystallization (IC) as a rate-controlling tool for simultaneous residual crystallization. We have also ersified the methodology of residual crystallization by utilizing two different crystallization pathways: fiber-to-film (F-F) and sphere-to-film (S-F). In both cases, we could obtain continuous COF thin films with high crystallinity and porosity grown on various substrates (the highest surface area of a TpAzo COF thin film being 2093 m
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B401916D
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8SC00825F
Abstract: The surface charge and chemistry of a protein determines its ability to facilitate biomimetic mineralisation.
Publisher: IOP Publishing
Date: 02-2011
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2JM32863A
Publisher: American Chemical Society (ACS)
Date: 26-02-2005
DOI: 10.1021/JA0427956
Abstract: One-pot self-assembled hybrid films were synthesized by the cohydrolysis of methyltriethoxysilane and tetraethoxysilane and deposited via dip-coating. The films show a high "defect-free" mesophase organization that extends throughout the film thickness and for domains of a micrometer scale, as shown by scanning transmission electron microscopy. We have defined these films defect-free to describe the high degree of order that is achieved without defects in the pore organization, such as dislocations of pores or stacking faults. A novel mesophase, which is tetragonal I4/mmm (space group), is observed in the films. This phase evolves but retains the same symmetry throughout a wide range of temperatures of calcination. The thermal stability and the structural changes as a function of the calcination temperature have been studied by small-angle X-ray scattering, scanning transmission electron microscopy, and Fourier transform infrared spectroscopy. In situ Fourier transform infrared spectroscopy employing synchrotron radiation has been used to study the kinetics of film formation during the deposition. The experiments have shown that the slower kinetics of silica species can explain the high degree of organization of the mesostructure.
Publisher: Elsevier BV
Date: 06-2018
Publisher: Springer Science and Business Media LLC
Date: 12-2017
Publisher: International Union of Crystallography (IUCr)
Date: 18-10-2005
Publisher: Elsevier BV
Date: 08-2005
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2SM07028F
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CS00122C
Abstract: This review highlights the steps needed to bring the properties of MOFs from the chemical lab to the microelectronics fab.
Publisher: Wiley
Date: 29-05-2012
Abstract: The tuneable pore size and architecture, chemical properties and functionalization make metal organic frameworks (MOFs) attractive versatile stimuli-responsive materials. In this context, MOFs hold promise for industrial applications and a fervent research field is currently investigating MOF properties for device fabrication. Although the material properties have a crucial role, the ability to precisely locate the functional material is fundamental for device fabrication. In this progress report, advancements in the control of MOF positioning and precise localization of functional materials within MOF crystals are presented. Advantages and limitations of each reviewed technique are critically investigated, and several important gaps in the technological development for device fabrication are highlighted. Finally, promising patterning techniques are presented which are inspired by previous studies in organic and inorganic crystal patterning for the future of MOF lithography.
Publisher: American Chemical Society (ACS)
Date: 04-03-2011
DOI: 10.1021/LA103863D
Abstract: Ordered mesoporous silica micrometer-sized structures have been fabricated via selective dewetting of the coating sol on a hydrophilic/hydrophobic fluorinated silica substrate, which had been pre-patterned using deep X-ray lithography with a synchrotron radiation source. We have observed that deposition of mesoporous films on the pre-patterned areas can be used as a design tool for obtaining regions of specific geometry and dimensions. The evaporation of the solution in constrained conditions because of pinning at the pattern edges gives layers with thicker edges. This edge effect appears dependent upon the dimension of the pre-patterned hydrophilic/hydrophobic layer in smaller patterns, the evaporation is too fast and thickening of the edges is not observed. We have used infrared imaging, optical profilometry, and atomic force microscopy to characterize the patterned layers and the edge effect, produced by pinning at the border of the microstructures.
Publisher: Elsevier BV
Date: 02-2021
Publisher: Wiley
Date: 23-05-2016
Publisher: American Chemical Society (ACS)
Date: 17-08-2016
Publisher: American Chemical Society (ACS)
Date: 07-05-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3TA04707E
Publisher: Wiley
Date: 02-05-2023
Abstract: Micropatterning crystalline materials with oriented pores is necessary for the fabrication of devices with anisotropic properties. Crystalline and porous metal–organic frameworks (MOFs) are ideal materials as their chemical and structural mutability enables precise tuning of functional properties for applications ranging from microelectronics to photonics. Herein, a patternable oriented MOF film is designed: by using a photomask under X‐ray exposure, the MOF film decomposes in the irradiated areas, remaining intact in the unexposed regions. The MOF film acts simultaneously as a resist and as functional porous material. While the heteroepitaxial growth from aligned Cu(OH) 2 nanobelts is used to deposit oriented MOF films, the sensitivity to radiation is achieved by integrating a brominated dicarboxylate ligand (Br 2 BDC) into a copper‐based MOF Cu 2 L 2 DABCO (DABCO = 1,4‐diazabicyclo[2.2.2]octane L = BDC/Br 2 BDC). The lithographed s les act as diffraction gratings upon irradiation with a laser, thus confirming the quality of the extended MOF micropattern. Furthermore, the oriented MOF patterns are functionalized with fluorescent dyes. As a result, by rotating the polarization angle of the laser excitation, the alignment of the dye in the MOF is demonstrated. By controlling the functional response to light, this MOF patterning protocol can be used for the microfabrication of optical components for photonic devices.
Publisher: Springer Science and Business Media LLC
Date: 2002
Abstract: Silica mesoporous thin films have been synthesised with a self-assembling process employing cetyltrimethylammonium bromide as the organic template and tetraethyl orthosilicate as the silica source. Mesoporous films with Pm3n cubic phase phases have been obtained and the films have been thermally treated in air with a progressive heating schedule from asdeposited up to 1000°C. The evolution of the microstructure has been studied with transmission Fourier transformed infrared (FTIR) spectroscopy. FTIR spectra of the as-deposited films have shown the presence of cyclic species, which at temperatures larger than 350°C have been no more observed. In the 1000-1300 cm -1 region several overlapped absorption bands have been detected. In particular, the pair LO 3 -TO 3 , the cyclic species absorption bands and the pair LO 4 -TO 4 have been resolved. These last bands, in particular, are associated with disorder-order transitions in the silica microstructure. These disorder-induced optical modes are due to the large interface area and related to bond strains. The evolution of the bands in the 1000-1300 cm -1 region has been followed with the Berreman configuration, performing the transmission FTIR analysis at 45° with respect to the normal incidence angle. The LO 3 band, which in silica sol-gel films is indicative of the network condensation and is activated by scattering of the light in the pores, was resolved as a single sharp band from 250°C.
Publisher: Wiley
Date: 07-2008
Publisher: Wiley
Date: 24-07-2013
Abstract: Thin metal-organic framework (MOF) films are patterned using UV lithography and an imprinting technique. A UV lithographed SU-8 film is imprinted onto a film of MOF powder forming a 2D MOF patterned film. This straightforward method can be applied to most MOF materials, is versatile, cheap, and potentially useful for commercial applications such as lab-on-a-chip type devices.
Publisher: Wiley
Date: 20-07-2011
Publisher: Elsevier BV
Date: 2014
Publisher: American Chemical Society (ACS)
Date: 29-10-2018
Abstract: The ability to align porous metal-organic frameworks (MOFs) on substrate surfaces on a macroscopic scale is a vital step toward integrating MOFs into functional devices. But macroscale surface alignment of MOF crystals has only been demonstrated in a few cases. To accelerate the materials discovery process, we have developed a high-throughput computational screening algorithm to identify MOFs that are likely to undergo macroscale aligned heterepitaxial growth on a substrate. Screening of thousands of MOF structures by this process can be achieved in a few days on a desktop workstation. The algorithm filters MOFs based on surface chemical compatibility, lattice matching with the substrate, and interfacial bonding. Our method uses a simple new computationally efficient measure of the interfacial energy that considers both bond and defect formation at the interface. Furthermore, we show that this novel descriptor is a better predictor of aligned heteroepitaxial growth than other established interface descriptors, by testing our screening algorithm on a s le set of copper MOFs that have been grown heteroepitaxially on a copper hydroxide surface. Application of the screening process to several MOF databases reveals that the top candidates for aligned growth on copper hydroxide comprise mostly MOFs with rectangular lattice symmetry in the plane of the substrate. This result indicates a substrate-directing effect that could be exploited in targeted synthetic strategies. We also identify that MOFs likely to form aligned heterostructures have broad distributions of in-plane pore sizes and anisotropies. Accordingly, this suggests that aligned MOF thin films with a wide range of properties may be experimentally accessible.
Publisher: Elsevier BV
Date: 2006
Publisher: Elsevier
Date: 2019
Publisher: American Chemical Society (ACS)
Date: 06-2009
DOI: 10.1021/CM900288X
Publisher: American Chemical Society (ACS)
Date: 28-05-2020
DOI: 10.26434/CHEMRXIV.12369353.V1
Abstract: Here, we successfully prepared macroscopically oriented films of Cu-based pillar-layered MOFs (Cu 2 (Linker) 2 DABCO) having regularly ordered 1D nanochannels. The direction of 1D nanochannels was controllable by optimizing the crystal growth process 1D nanochannels either perpendicular or parallel to substrates, which offer molecular-scale pore arrays for a macroscopic alignment of functional guest molecules in the desired direction. We also showed the fabrication of oriented Cu 2 (Linker) 2 DABCO MOF patterns, where the direction of 1D nanochannels is controllable on in idual locations on the same substrate. These Cu 2 (Linker) 2 DABCO MOF films and patterns with controlled orientation are importante steps towards the development of MOF film-based applications such as sensors and electrical/optical devices because functionalities derived from the accommodated guest species in their 1D nanochannels are optimized for the rational direction on the desired substrate for the device fabrication.
Publisher: American Chemical Society (ACS)
Date: 07-11-2013
DOI: 10.1021/JP410025B
Location: Italy
No related grants have been discovered for Paolo Falcaro.