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      A new method to position and functionalize metal-organic framework crystals

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          Abstract

          With controlled nanometre-sized pores and surface areas of thousands of square metres per gram, metal-organic frameworks (MOFs) may have an integral role in future catalysis, filtration and sensing applications. In general, for MOF-based device fabrication, well-organized or patterned MOF growth is required, and thus conventional synthetic routes are not suitable. Moreover, to expand their applicability, the introduction of additional functionality into MOFs is desirable. Here, we explore the use of nanostructured poly-hydrate zinc phosphate (α-hopeite) microparticles as nucleation seeds for MOFs that simultaneously address all these issues. Affording spatial control of nucleation and significantly accelerating MOF growth, these α-hopeite microparticles are found to act as nucleation agents both in solution and on solid surfaces. In addition, the introduction of functional nanoparticles (metallic, semiconducting, polymeric) into these nucleating seeds translates directly to the fabrication of functional MOFs suitable for molecular size-selective applications.

          Abstract

          Metal-organic frameworks (MOFs) have potential catalysis, filtration and sensing applications, but device fabrication will require controlled MOF growth. Here, α-hopeite microparticles are used to achieve spatial control of MOF nucleation, and accelerate MOF growth.

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          Most cited references14

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          Thin films of metal-organic frameworks.

          The fabrication of thin film coatings of metal-organic frameworks (MOFs) on various substrates is discussed in this critical review. Interestingly, the relatively few studies on MOF films that have appeared in the literature are limited to the following cases: [Zn4O(bdc)3] (MOF-5; bdc=1,4-benzenedicarboxylate), [Cu3(btc)2] (HKUST-1; btc=1,3,5-benzenetricarboxylate), [Zn2(bdc)2(dabco)] (dabco=1,4-diazabicyclo[2.2.2]octane), [Mn(HCOO)], [Cu2(pzdc)2(pyz)] (CPL-1; pzdc=pyrazine-2,3-dicarboxylate, pyz=pyrazine), [Fe(OH)(bdc)] (MIL-53(Fe)) and [Fe3O(bdc)3(Ac)] (MIL-88B; Ac=CH3COO-). Various substrates and support materials have been used, including silica, porous alumina, graphite and organic surfaces, i.e. self-assembled monolayers (SAMs) on gold, as well as silica surfaces. Most of the MOF films were grown by immersion of the selected substrates into specifically pre-treated solvothermal mother liquors of the particular MOF material. This results in more or less densely packed films of intergrown primary crystallites of sizes ranging up to several microm, leading to corresponding film thicknesses. Alternatively, almost atomically flat and very homogenous films, with thicknesses of up to ca. 100 nm, were grown in a novel stepwise layer-by-layer method. The individual growth steps are separated by removing unreacted components via rinsing the substrate with the solvent. The layer-by-layer method offers the possibility to study the kinetics of film formation in more detail using surface plasmon resonance. In some cases, particularly on SAM-modified substrates, a highly oriented growth was observed, and in the case of the MIL-53/MIL-88B system, a phase selective deposition of MIL-88B, rather than MIL-53(Fe), was reported. The growth of MOF thin films is important for smart membranes, catalytic coatings, chemical sensors and related nanodevices (63 references).
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            Step-by-step route for the synthesis of metal-organic frameworks.

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              Nanoscale coordination polymers for platinum-based anticancer drug delivery.

              Pt-containing nanoscale coordination polymer (NCP) particles with the formula of Tb2(DSCP)3(H2O)12 (where DSCP represents disuccinatocisplatin), NCP-1, were precipitated from an aqueous solution of Tb3+ ions and DSCP bridging ligands via the addition of a poor solvent. SEM and TEM images showed that as-synthesized NCP-1 exhibited a spherical morphology with a DLS diameter of 58.3 +/- 11.3 nm. NCP-1 particles were stabilized against rapid dissolution in water by encapsulation in shells of amorphous silica. The resulting silica-coated particles NCP-1' exhibited significantly longer half-lives for DSCP release from the particles (a t1/2 of 9 h for NCP-1' with 7 nm silica coating vs t1/2 of 1 h for as-synthesized NCP-1). In vitro cancer cell cytotoxicity assays with the human colon carcinoma cell line (HT-29) showed that internalized NCP-1' particles readily released the DSCP moieties which were presumably reduced to cytotoxic Pt(II) species to give the Pt-containing NCPs anticancer efficacy superior to the cisplatin standard. The generality of this degradable nanoparticle formulation should allow for the design of NCPs as effective delivery vehicles for a variety of biologically and medically important cargoes such as therapeutic and imaging agents.
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                Author and article information

                Journal
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                15 March 2011
                : 2
                : 237
                Affiliations
                [1 ]simpleCSIRO, Division of Materials Science and Engineering , Private Bag 33, Clayton South MDC, Victoria 3169, Australia.
                [2 ]simpleAssociazione CIVEN, Via delle Industrie 5 , Venezia 30175, Italy.
                [3 ]simpleInstitute of Biophysics and Nanosystems Research, Austrian Academy of Sciences , Schmiedlstraße 6, Graz 8042, Austria.
                [4 ]simpleSchool of Earth and Environment, The University of Western Australia , 35 Stirling Highway, Crawley, Perth 6009, Western Australia .
                [5 ]simpleSchool of Mathematical Sciences, Faculty of Science, Monash University , Clayton, Victoria 3800, Australia.
                [6 ]simpleCentre for Micro-Photonics and CUDOS, Faculty of Engineering and Industrial Sciences, Swinburne University of Technology , Hawthorn, Victoria 3122, Australia.
                Author notes
                Article
                ncomms1234
                10.1038/ncomms1234
                3072101
                21407203
                bf1cc5bd-7554-4461-8925-5dfb72f91751
                Copyright © 2011, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-nd/3.0/

                History
                : 15 July 2010
                : 09 February 2011
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