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Xiao Wang, Le Yu, Bu Yuan Guan, Shuyan Song, Xiong Wen David Lou
Rational design of complex metal-organic framework (MOF) hybrid precursors offers a great opportunity to construct various functional nanostructures. Here, a novel MOF-hybrid-assisted strategy to synthesize Co3 O4 /Co-Fe oxide double-shelled nanoboxes is reported. In the first step, zeolitic imidazolate framework-67 (ZIF-67, a Co-based MOF)/Co-Fe Prussian blue analogue (PBA) yolk-shell nanocubes are formed via a facile anion-exchange reaction between ZIF-67 nanocube precursors and [Fe(CN)6 ]3- ions at room temperature...
May 21, 2018: Advanced Materials
Joshua Damron, Jialiu Ma, Ricardo Kurz, Kay Saalwaechter, Adam Matzger, Ayyalusamy Ramamoorthy
The robust synthetic flexibility of metal-organic frameworks (MOFs) offers a promising class of tailorable materials, for which, the ability to tune specific physicochemical properties is highly desired. This is achievable only through a thorough description of the consequences for chemical manipulations both in structure and dynamics. Magic angle spinning solid-state NMR spectroscopy offers many modalities in this pursuit, particularly for dynamic studies. Herein, we employ a separated-local-field NMR approach to show how specific intra-framework chemical modifications to MOF UiO66 heavily modulate the dynamic evolution of the organic ring moiety over several orders of magnitude...
May 21, 2018: Angewandte Chemie
Joseph M Palomba, Cy V Credille, Mark Kalaj, Jared B DeCoste, Gregory W Peterson, Trenton M Tovar, Seth M Cohen
A high-throughput screening (HTS) method was devised to increase the rate of discovery and evaluation of nerve agent degradation catalysts. Using this HTS method, >90 solid state materials, predominantly metal-organic frameworks (MOFs), were analyzed for their ability to hydrolyze the nerve agent simulant methyl paraoxon at two pH values (8.0 and 10.0).
May 21, 2018: Chemical Communications: Chem Comm
Natasha K Maddigan, Andrew Tarzia, David M Huang, Christopher J Sumby, Stephen G Bell, Paolo Falcaro, Christian J Doonan
The durability of enzymes in harsh conditions can be enhanced by encapsulation within metal-organic frameworks (MOFs) via a process called biomimetic mineralisation. Herein we show that the surface charge and chemistry of a protein determines its ability to seed MOF growth. We demonstrate that chemical modification of amino acids on the protein surface is an effective method for systematically controlling biomimetic mineralisation by zeolitic imidazolate framework-8 (ZIF-8). Reaction of surface lysine residues with succinic (or acetic) anhydride facilitates biomimetic mineralisation by increasing the surface negative charge, whereas reaction of surface carboxylate moieties with ethylenediamine affords a more positively charged protein and hinders the process...
May 14, 2018: Chemical Science
Yujia Li, Haiou Liu, Huanting Wang, Jieshan Qiu, Xiongfu Zhang
Highly oriented, ultrathin metal-organic framework (MOF) membranes are attractive for practical separation applications, but the scalable preparation of such membranes especially on standard tubular supports remains a huge challenge. Here we report a novel bottom-up strategy for directly growing a highly oriented Zn2 (bIm)4 (bIm = benzimidazole) ZIF nanosheet tubular membrane, based on graphene oxide (GO) guided self-conversion of ZnO nanoparticles (NPs). Through our approach, a thin layer of ZnO NPs confined between a substrate and a GO ultrathin layer self-converts into a highly oriented Zn2 (bIm)4 nanosheet membrane...
May 7, 2018: Chemical Science
Weibin Liang, Lin Li, Jingwei Hou, Nicholas D Shepherd, Thomas D Bennett, Deanna M D'Alessandro, Vicki Chen
Composite membranes with defective metal-organic frameworks (MOFs) connect the emerging fields of MOF topological modification, MOF-polymer interfacial engineering and composite material functionalization. Although defective MOFs can be fabricated via thermal or chemical treatment, the relationship between hierarchical MOF structure and their performance in a polymeric membrane matrix has so far not been investigated. Here we show how a modulator fumarate-based MIL-53(Al) microwave synthesis process results in defective MOFs...
April 14, 2018: Chemical Science
Zhenzhong Lu, Harry G W Godfrey, Ivan da Silva, Yongqiang Cheng, Mathew Savage, Pascal Manuel, Svemir Rudić, Anibal J Ramirez-Cuesta, Sihai Yang, Martin Schröder
Fine tuning of host-guest supramolecular interactions in porous systems enables direct control over the properties of functional materials. We report here a modification of hydrogen bonding and its effect on guest binding in a pair of redox-active metal-organic frameworks (MOFs). Oxidation of MFM-300(VIII ) {[VIII2(OH)2 (L)], LH4 = biphenyl-3,3',5,5'-tetracarboxylic acid} is accompanied by deprotonation of the bridging hydroxyl groups to afford isostructural MFM-300(VIV ), [VIV2O2 (L)]. The precise role of the hydroxyl groups, O -carboxylate centres and π-π interactions in the supramolecular binding of C2 hydrocarbons in these materials has been determined using neutron diffraction and inelastic neutron scattering, coupled with DFT modelling...
April 7, 2018: Chemical Science
Elena Caballero-Mancebo, Jose Maria Moreno, Avelino Corma, Urbano Díaz, Boiko Cohen, Abderrazzak Douhal
In this work, we unravel how the 2D-Al-ITQ-HB metal organic framework changes the interactions of Nile Red (NR) adsorbed on its surface. Time-resolved emission experiments indicate the occurrence of energy transfer between adsorbed NR molecules, in abnormally long time constant of 2-2.5 ns, getting shorter (~0.25 ns) when the concentration of the surface adsorbed NR increases. We identify the emission from local excited state of aggregates, and charge-transfer and energy transfer between adsorbed molecules...
May 21, 2018: ACS Applied Materials & Interfaces
Won-Tae Koo, Ji-Soo Jang, Shaopeng Qiao, Wontae Hwang, Gaurav Jha, Reginald M Penner, Il-Doo Kim
Here, we propose heterogeneous nucleation assisted hierarchical growth of metal-organic framework (MOF) for efficient particulate matter (PM) removal. The assembly of 2-dimensional (2D) Zn based zeolite imidazole framework (2D-ZIF-L) in deionized water over a period time produced hierarchical ZIF-L (H-ZIF-L) on hydrophilic substrates. During the assembly, the 2nd nucleation and growth of ZIF-L occurred on the surface of 1st ZIF-L, leading to the formation of flower-like H-ZIF-L on the substrate. The flower-like H-ZIF-L was easily synthesized on various substrates, including glass, polyurethane 3D foam, nylon microfibers, and non-woven fabrics...
May 21, 2018: ACS Applied Materials & Interfaces
Gabriela Wyszogrodzka, Przemysław Dorożyński, Barbara Gil, Wieslaw J Roth, Maciej Strzempek, Bartosz Marszałek, Władysław P Węglarz, Elżbieta Menaszek, Weronika Strzempek, Piotr Kulinowski
PURPOSE: The purpose of the study was initial evaluation of applicability of metal organic framework (MOF) Fe-MIL-101-NH2 as a theranostic carrier of antituberculous drug in terms of its functionality, i.e. drug loading, drug dissolution, magnetic resonance imaging (MRI) contrast and cytotoxic safety. METHODS: Fe-MIL-101-NH2 was characterized using X-ray powder diffraction, FTIR spectrometry and scanning electron microscopy. The particle size analysis was determined using laser diffraction...
May 18, 2018: Pharmaceutical Research
Hangzhen Lan, Leo D Salmi, Tuukka Rönkkö, Jevgeni Parshintsev, Matti Jussila, Kari Hartonen, Marianna Kemell, Marja-Liisa Riekkola
New chemical vapor reaction (CVR) and atomic layer deposition (ALD)-conversion methods were utilized for preparation of metal organic frameworks (MOFs) coatings of solid phase microextraction (SPME) Arrow for the first time. With simple, easy and convenient one-step reaction or conversion, four MOF coatings were made by suspend ALD iron oxide (Fe2 O3 ) film or aluminum oxide (Al2 O3 ) film above terephthalic acid (H2 BDC) or trimesic acid (H3 BTC) vapor. UIO-66 coating was made by zirconium (Zr)-BDC film in acetic acid vapor...
September 18, 2018: Analytica Chimica Acta
Yuanyuan Li, Xue Hu, Xiaodan Zhang, Haiyan Cao, Yuming Huang
Contrary to organic solvent-induced aggregation of Au nanoclusters (AuNCs), herein, we reported aggregation induced emission enhancement (AIEE) of AuNCs in an aqueous media through confinement of AuNCs by in situ formed Zn-MOF for detecting Zn2+ . Glutathione capped AuNCs (GSH-AuNCs) was synthesized through reduction of Au3+ by glutathione. Zn2+ could significantly enhance the fluorescence of GSH-AuNCs upon addition of 2-methylimidazole, which was attributed to the formation of Zn-MOF. XRD and TEM were used to characterize the in situ formed Zn-MOF...
September 18, 2018: Analytica Chimica Acta
Ning Huang, Hannah Drake, Jialuo Li, Jiangdong Pang, Ying Wang, Shuai Yuan, Qi Wang, Peiyu Cai, Junsheng Qin, Hong-Cai Zhou
The development of new types of porous composite materials is of great significance owing to their potentially improved performance over those of individual components and extensive applications in separation, energy storage, and heterogeneous catalysis. In this work, we integrated mesoporous metal-organic frameworks (MOFs) with macroporous melamine foam (MF) using a one-pot process, generating a series of MOF/MF composite materials with preserved crystallinity, hierarchical porosity, and increased stability over that of melamine foam...
May 18, 2018: Angewandte Chemie
Guo-Xia Jin, Jia Wang, Jing-Yi Liu, Jian-Ping Ma, Yu-Bin Dong
A CuI -MOF was found to be a highly selective visual sensor for recognizing C2 H2 . Gas chromatography studies indicated that it can be used to effectively remove minor amounts of C2 H2 from C2 H4 /C2 H2 mixtures (98:2) and produce highly pure C2 H4 (nearly 100%).
May 18, 2018: Inorganic Chemistry
Shao-Xian Liu, Guo-Jun Yuan, Lu Zhai, Lifeng Wang, Hong-Bin Luo, Xiao-Ming Ren
Two pairs of MOF-based hybrid enantiomorphs, [NH2(CH3)2]3[Pb2X3(BDC)2] (H2BDC = 1,4-benzenedicarboxylic acid, X = Br or I), have been synthesized using the solvothermal reaction and then manually separated, which are labeled as 1a/1b (X = Br) and 2a/2b (X = I). The isomorphic 1a and 2a crystallize in tetragonal space group P43212, and the isomorphic 1b and 2b in the enantiomorphic space group P41212. Twofold interpenetrated three-dimensional (3-D) networks were built from two sets of equivalent I1O2 type hybrid inorganic-organic frameworks in 1a/1b and 2a/2b...
May 18, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Xiaoli Huang, Qiyang Li, Xue Xiao, Shuping Jia, Yue Li, Zhigang Duan, Lei Bai, Ze Yuan, Lin Li, Zhihua Lin, Yonggang Zhao
We present here the synthesis of one enantiomeric pair of metal-organic framework materials comprised of a unique multioriented double-helix structure from an achiral spirocenter ligand. Our study clearly shows that the chiral MOF material encompasses concurrently multiple nonlinear-optical functions in the solid state: the noncentrosymmetric structural feature brings the chiral MOF high second-harmonic-generation efficiency; the incorporation of the spirocenter ligand can efficiently produce two-photon-excited photoluminescence with a larger-action cross-sectional value...
May 18, 2018: Inorganic Chemistry
Mohammad R Momeni, Christopher J Cramer
Recent experimental studies on ZrIV-based metal-organic frameworks (MOFs) have shown the extraordinary effective-ness of these porous materials for the detoxification of phos-phorus-based chemical warfare agents (CWAs). However, pressing challenges remain with respect to characterizing these catalytic processes both at the molecular and crystalline lev-els. We here use theory to compare the reactivity of different zirconium-based MOFs for the catalytic hydrolysis of the CWA sarin, using both periodic and cluster modeling...
May 18, 2018: ACS Applied Materials & Interfaces
Xiang Zhao, Edward T Nguyen, Anh N Hong, Pingyun Feng, Xianhui Bu
Homochiral metal-organic frameworks (MOFs) are an important class of chiral solids with potential applications in chiral recognition; however, relatively few are available. Of great importance is the availability of low-cost, racemization-resistant, and versatile enantiopure building blocks. Among chiral building blocks, d-camphoric acid is highly prolific, yet, its trans-isomer, l-isocamphoric acid, has remained unknown in the entire field of solid-state materials. Its rich yet totally untapped synthetic and structural chemistry has now been investigated through the synthesis of a large family of homochiral metal isocamphorates...
May 17, 2018: Angewandte Chemie
Alexey Pustovarenko, Maarten G Goesten, Sumit Sachdeva, Meixia Shan, Zakariae Amghouz, Youssef Belmabkhout, Alla Dikhtiarenko, Tania Rodenas, Damla Keskin, Ilja K Voets, Bert M Weckhuysen, Mohamed Eddaoudi, Louis C P M de Smet, Ernst J R Sudhölter, Freek Kapteijn, Beatriz Seoane, Jorge Gascon
During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application...
May 17, 2018: Advanced Materials
M Hoff, S Skurtveit, H E Meyer, A Langhammer, A J Søgaard, U Syversen, E Skovlund, B Abrahamsen, S Forsmo, B Schei
Use of anti-osteoporotic drugs (AODs) was examined in a Norwegian population 50-85 years. Among them with Fracture Risk Assessment Tool (FRAX) score for major osteoporotic fracture ≥ 20, 25% of the women and 17% of the men received AODs. The strongest predictors for AODs were high age in women and use of glucocorticoids among men. INTRODUCTION: To examine the use of anti-osteoporotic drugs (AODs) and to identify predictors for prescriptions. METHODS: Data were obtained from the Nord-Trøndelag Health Study (HUNT3) performed in 2006-2008 and the Norwegian Prescription Database, including 15,075 women and 13,386 men aged 50-85 years...
May 17, 2018: Osteoporosis International
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