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      All-gas-phase synthesis of amino-functionalized UiO-66 thin films

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          Abstract

          Thin films of metal–organic frameworks (MOFs) prepared using all-gas-phase techniques such as atomic/molecular layer deposition (ALD/MLD) are emerging due to their potential for enabling suitable applications.

          Abstract

          Thin films of metal–organic frameworks (MOFs) prepared using all-gas-phase techniques such as atomic/molecular layer deposition (ALD/MLD) are emerging due to their potential for enabling suitable applications. Their high and specific porosity enables their use as membranes for separations and as a basis for sensors in microelectronics, provided that films can be made. The properties of such MOF materials can be tuned by choosing linker molecules that are functionalized with a variety of chemical groups. However, thin films of these functionalised MOFs have so far been prepared through wet based chemistries, which are difficult to combine with microelectronics and high aspect ratio structures. We here report on the thin film deposition of amino-functionalised UiO-66 through an all-gas-phase ALD/MLD process. By using amino-functionalised linkers, modulation by acetic acid to control the stoichiometry of the deposited film was no longer required, as opposed to the case in which unmodified terephthalic acid was used as a linker. The growth and properties of the films were characterised using an in situ quartz crystal microbalance (QCM), spectroscopic ellipsometry (SE), grazing incidence X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR) and other techniques to obtain information on their growth dynamics and physical properties.

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          Most cited references24

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          Postsynthetic modifications of iron-carboxylate nanoscale metal-organic frameworks for imaging and drug delivery.

          Fe(III)-carboxylate nanoscale metal-organic frameworks (NMOFs) with the MIL-101 structure were synthesized using a solvothermal technique with microwave heating. The approximately 200 nm particles were characterized using a variety of methods, including SEM, PXRD, nitrogen adsorption measurements, TGA, and EDX. By replacing a percentage of the bridging ligand (terephthalic acid) with 2-amino terephthalic acid, amine groups were incorporated into the framework to provide sites for covalent attachment of biologically relevant cargoes while still maintaining the MIL-101 structure. In proof-of-concept experiments, an optical contrast agent (a BODIPY dye) and an ethoxysuccinato-cisplatin anticancer prodrug were successfully incorporated into the Fe(III)-carboxylate NMOFs via postsynthetic modifications of the as-synthesized particles. These cargoes are released upon the degradation of the NMOF frameworks, and the rate of cargo release was controlled by coating the NMOF particles with a silica shell. Potential utility of the new NMOF-based nanodelivery vehicles for optical imaging and anticancer therapy was demonstrated in vitro using HT-29 human colon adenocarcinoma cells.
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            Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends

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              Destruction of chemical warfare agents using metal-organic frameworks.

              Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic Zr(IV) ions as the active sites and to their superb accessibility as a defining element of their efficacy.
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                Author and article information

                Journal
                ICHBD9
                Dalton Transactions
                Dalton Trans.
                Royal Society of Chemistry (RSC)
                1477-9226
                1477-9234
                2017
                2017
                : 46
                : 48
                : 16983-16992
                Affiliations
                [1 ]Department of Chemistry
                [2 ]University of Oslo
                [3 ]0315 OSLO
                [4 ]Norway
                [5 ]Centre for Materials Science and Nanotechnology
                Article
                10.1039/C7DT03518G
                7495f13c-10ee-4ab1-bb43-8ee886e02145
                © 2017

                http://creativecommons.org/licenses/by/3.0/

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