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Metal–Organic Frameworks

Jonathan Cisterna, Catherine Araneda, Pilar Narea, Alejandro Cárdenas, Jaime Llanos, Iván Brito
To systematically investigate the influence of the positional isomeric effect on the structures of polymer complexes, we prepared two new polymers containing the two positional isomers ethyl 5-methyl-1-(pyridin-3-yl)-1 H -1,2,3-triazole-3-carboxylate ( L1 ) and ethyl-5-methyl-1-(pyridin-3-yl)-1 H -1,2,3-triazole-4-carboxylate ( L2 ), as well as Cd(II) ions. The structures of the metal⁻organic frameworks were determined by a single crystal XRD analysis. The compound [Cd(L1)₂·4H₂O] ( 1 ), is a hydrogen bond-induced coordination polymer, whereas the compound [Cd(L2)₄·5H₂O]n ( 2 ) is a three-dimensional (3-D) coordination polymer...
October 14, 2018: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
Yi Liu, Yue Zhao, Xiao-Hui Liu, Yan-Shang Kang, Peng Wang, Wei-Yin Sun
The stability and functionality of metal-organic frameworks (MOFs) are particularly important in considering their potential and/or practical use. Herein we report two novel aldehyde functional group-containing MOFs [Zn2(L)(BDC)2]·2DMF·MeOH·H2O (1) and [Co2(L)(BDC)2]·2DMF·2MeOH·H2O (2) (DMF = N,N-dimethylformamide, MeOH = methanol) achieved by reactions of mixed organic ligands of 2,4-bis[(pyridin-4-yl)methoxy]benzaldehyde (L) and 1,4-benzenedicarboxylic acid (H2BDC) with the corresponding metal salts under solvothermal conditions...
October 15, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
William Salomon, Anne Dolbecq, Catherine Roch-Marchal, Grégoire Paille, Rémi Dessapt, Pierre Mialane, Hélène Serier-Brault
The luminescent [EuW10 O36 ]9- polyoxometalate has been introduced into the cavities of the highly porous zirconium luminescent metal-organic framework UiO-67 via a direct synthesis approach, affording the EuW10 @UiO-67 hybrid. Using a combination of techniques (TGA, BET, elemental analysis, EDX mapping,…) this new material has been fully characterized, evidencing that it contains only 0.25% in europium and that the polyoxometalate units are located inside the octahedral cavities and not at the surface of the UiO-67 crystallites...
2018: Frontiers in Chemistry
Yuan Liu, Weijia Hou, Lian Xia, Cheng Cui, Shuo Wan, Ying Jiang, Yu Yang, Qiong Wu, Liping Qiu, Weihong Tan
Porphyrinic metal-organic framework (MOF) nanoparticles for photodynamic therapy solve the photosensitizer problems of poor solubility, self-quenching and aggregation. However, their low selectivity towards malignant tissues is an obstacle for bioimaging and a bottle-neck to cellular uptake for highly efficient photodynamic therapy of cancer. Here, ZrMOF nanoparticles as quenchers to conjugate DNA aptamers were developed for target-induced bioimaging and photodynamic therapy. A phosphate-terminal aptamer prepared by solid-phase DNA synthesis was anchored on the surface of ZrMOF nanoparticles through strong coordination between phosphate and zirconium...
October 14, 2018: Chemical Science
Da-Shuai Zhang, Qiang Gao, Ze Chang, Xiao-Ting Liu, Bei Zhao, Zhi-Hong Xuan, Tong-Liang Hu, Ying-Hui Zhang, Jian Zhu, Xian-He Bu
Organic donor-acceptor systems have attracted much attention due to their various potential applications. However, the rational construction and modulation of highly ordered donor-acceptor systems could be a challenge due to the complicated self-assembly process of donor and acceptor species. Considering the well-defined arrangement of species at the molecule level, a crystalline host-guest system could be an ideal platform for the rational construction of donor-acceptor systems. Herein, it is shown how the rational construction of highly tunable donor-acceptor materials can be achieved based on a crystalline host-guest platform...
October 15, 2018: Advanced Materials
Shanshan Ma, Meiyun Zhang, Jingyi Nie, Jiaojun Tan, Bin Yang, Shunxi Song
A biodegradable cellulose-based air filter (Ag-MOFs@CNF@ZIF-8) with multi-layer structure was fabricated by in situ generation of double-component metal-organic frameworks (MOFs) and reinforcement of cellulose nanofiber (CNF). It exhibits good filtration performance, gas adsorption, antibacterial activity and mechanical property. The presence of MOFs could enhance the interaction between the filter and particulate matter (PM) and significantly improve the specific surface area of the composite filter. Thus, the filtration efficiency of the composite filter could reach 94...
January 1, 2019: Carbohydrate Polymers
Lijuan Yang, Guancheng Xu, Jinjin Ban, Li Zhang, Gui Xu, Yan Lv, Dianzeng Jia
Nitrogen-doped carbon materials are promising oxygen reduction reaction (ORR) electrocatalysts owing to high performance and stability. Herein, a three-dimensional porous bio-MOF-1, Zn8 (Ad)4 (Bpdc)6 O·2Me2 NH2 (Ad = adeninate; Bpdc = biphenyldicarboxylate), was used as precursor to fabricate N-doped porous carbon materials (NPC-1000-ts, where 1000 stands for the carbonization temperature and t represents the carbonization time, t = 2, 3 and 4 h) by simple carbonization under Ar atmosphere. The porous carbon materials had different contents of graphitic N and graphitization degrees of carbon...
October 4, 2018: Journal of Colloid and Interface Science
Bernardo Monteiro, Ana R Nabais, Maria H Casimiro, Ana P S Martins, Rute O Francisco, Luísa A Neves, Cláudia C L Pereira
The efficient separation of gases has industrial, economic, and environmental importance. Here, we report the improvement in gas separation performance of a polyimide-based matrix (Matrimid® 5218) filled with a Cu-based metal organic framework [MOF, Cu₃(BTC)₂] with two different ionic liquids (ILs) confined within the pores. The chosen ILs are commonly used in gas solubilization, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF₄]) and 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][OTf]), and the incorporation of the [EMIM][BF₄]@Cu-BTC and [EMIM][OTf]@Cu-BTC composites in Matrimid® 5218 proved to be an efficient strategy to improve the permeability and selectivity toward CO₂/N₂ and CO₂/CH₄ mixtures...
October 11, 2018: Membranes
George Manos, Lawrence J Dunne
Currently, metal-organic frameworks (MOFs) are receiving significant attention as part of an international push to use their special properties in an extensive variety of energy applications. In particular, MOFs have exceptional potential for gas storage especially for methane and hydrogen for automobiles. However, using theoretical approaches to investigate this important problem presents various difficulties. Here we present the outcomes of a basic theoretical investigation into methane adsorption in large pore MOFs with the aim of capturing the unique features of this phenomenon...
October 11, 2018: Nanomaterials
Xiaokang Liu, Mengyao Hu, Minghua Wang, Yingpan Song, Nan Zhou, Linghao He, Zhihong Zhang
Owning to the misuse of the antibiotics in animal husbandry and agriculture, it is highly urgent to determine the quantification of antibiotics in biological systems by the simple, sensitive, and fast method. In this work, a novel nanoarchitecture of Co-based metal-organic frameworks (Co-MOF) and terephthalonitrile-based covalent organic framework (TPN-COF) was synthesized (represented by Co-MOF@TPN-COF), followed by the exploitation as the bioplatform of non-label aptasensor for detecting the most frequently used β-lactam antibiotics, ampicillin (AMP)...
September 27, 2018: Biosensors & Bioelectronics
Wenxiu Qin, Yue Gu, Guozhong Wang, Tianxing Wu, Haimin Zhang, Xiaoxian Tang, Yunxia Zhang, Huijun Zhao
In an effort to provide early warnings for the occurrence of eutrophication, it is highly desirable to develop an accurate and efficient technique to ensure continuous monitoring of dissolved reactive phosphorus (DRP) in the aquatic environment from the viewpoint of environmental management. Herein, a new diffusive gradient in thin film (DGT) technique was developed and evaluated for in situ measurement of DRP in waters, in which Zr-based metal organic frameworks (MOFs, UiO-66) were utilized as aqueous binding agent (abbreviated as UiO-66 DGT)...
October 5, 2018: Water Research
Chang Liu, Peng Wang, Xueke Liu, Xiaotong Yi, Donghui Liu, Zhiqiang Zhou
Heavy metals contaminated water has been identified as a significant threat to human health. To develop safe and rapid water treatment techniques is necessary. Herein, we synthesized an eco-friendly γ-cyclodextrin MOF-based nanoporous carbon (γ-CD MOF-NPC) material and conducted comprehensive characterization, and found its rapid and effective Cd(II) removal capacity. The γ-CD MOF-NPC could effectively sequester most of cadmium ions within 1 min, and it still demonstrated excellent adsorption ability under various conditions, including different pH, adsorbent dosage and coexisting ions...
October 12, 2018: Chemistry, An Asian Journal
Cole Grinnell, Alexander Samokhvalov
We investigated the electronic structure of a metal-organic framework (MOF), for the first time, by solid-state synchronous fluorescence spectroscopy in comparison with "conventional" fluorescence spectroscopy. The solid-state synchronous fluorescence spectra of aluminum MOF Basolite A100 in the UV-visible range at 25 °C are significantly narrower than the commonly used "conventional" fluorescence spectra. More importantly, the solid-state synchronous fluorescence spectra reveal major electronic transitions and fine molecular interactions in the MOF not available from the commonly used analysis...
October 12, 2018: Physical Chemistry Chemical Physics: PCCP
Daeok Kim, Kyung Seob Song, Onur Buyukcakir, Taner Yildirim, Ali Coskun
We demonstrated that the ratio and position of two different metal ions, Pd and Cu, can be precisely controlled within MOFs through predesigned metal clusters. These MOF structures incorporating Pd-Cu paddle wheel units were synthesised simply by reacting Pd-Cu acetate metal clusters and tritopic organic linkers at room temperature. Pd-Cu open metal sites were found to be uniformly distributed throughout the MOFs with a ca. 1 : 1 ratio. The incorporation of Pd into the MOF structure also led to enhanced affinity towards H2 with Qst values up to 8...
October 12, 2018: Chemical Communications: Chem Comm
Markus J Kalmutzki, Nikita Hanikel, Omar M Yaghi
The secondary building unit (SBU) approach was a turning point in the discovery of permanently porous metal-organic frameworks (MOFs) and in launching the field of reticular chemistry. In contrast to the single-metal nodes known in coordination networks, the polynuclear nature of SBUs allows these structures to serve as rigid, directional, and stable building units in the design of robust crystalline materials with predetermined structures and properties. This concept has also enabled the development of MOFs with ultra-high porosity and structural complexity...
October 2018: Science Advances
Neha Bhardwaj, Satish K Pandey, Jyotsana Mehta, Sanjeev K Bhardwaj, Ki-Hyun Kim, Akash Deep
More effective antibiotics are needed to overcome the problem of multidrug resistance. The antibacterial efficacies of three Zn-based nano metal-organic frameworks (nMOFs) - IRMOF-3, MOF-5, and Zn-BTC - were explored, both alone and as mixtures with ampicillin and kanamycin. When tested against Escherichia coli , Staphylococcus aureus , Staphylococcus lentus , and Listeria monocytogenes , the nMOF/drug mixtures demonstrated synergistic (IRMOF-3/kanamycin) or additive (other nMOF/drug combinations) effects compared with the nMOFs or antibiotics alone...
September 1, 2018: Toxicology Research
Ágnes Szécsényi, Guanna Li, Jorge Gascon, Evgeny A Pidko
Reaction paths underlying the catalytic oxidation of methane with H2 O2 over an Fe containing MIL-53(Al) metal-organic framework were studied by periodic DFT calculations. Not only the activation of methane, but the full reaction network was considered, which includes the formation of the active site, the overoxidation of methane to CO2 and the decomposition of H2 O2 to H2 O and O2 . Calculations indicate that the activation barrier for the initial activation of the Fe sites upon reaction with H2 O2 is comparable to that of the subsequent C-H activation and also of the reaction steps involved in the undesirable overoxidation processes...
September 7, 2018: Chemical Science
Tamoghna Mitra, Florian Moreau, Adam Nevin, Carlo U Perotto, Alex Summerfield, E Stephen Davies, Elizabeth A Gibson, Timothy L Easun, Martin Schröder
The application of metal-organic framework (MOF) materials in electrochemical and electrochromic devices remains rare. One of the main reasons for this is the inability to readily access their detailed electrochemistry. The inherent insolubility of these materials does not allow interrogation by traditional solution-based electrochemical or spectroscopic methods. In this study, we report a straightforward alternative approach to the spectroelectrochemical study of MOFs. We have used two systems as exemplars in this study, MFM-186 and MFM-180...
August 21, 2018: Chemical Science
Gavin A Craig, Patrick Larpent, Shinpei Kusaka, Ryotaro Matsuda, Susumu Kitagawa, Shuhei Furukawa
Gate-opening gas sorption is known for metal-organic frameworks, and is associated with structural flexibility and advantageous properties for sensing and gas uptake. Here, we show that gate-opening is also possible for metal-organic polyhedra (MOPs), and depends on the molecular organisation in the lattice. Thanks to the solubility of MOPs, several interchangeable solvatomorphs of a lantern-type MOP were synthesised via treatment with different solvents. One phase obtained through use of methanol induced a gate-opening effect in the lattice in response to carbon dioxide uptake...
August 21, 2018: Chemical Science
Nan Zhou, Fangfang Su, Chuanpan Guo, Linghao He, Zhankui Jia, Minghua Wang, Qiaojuan Jia, Zhihong Zhang, Siyu Lu
Fabricating novel bimetallic metal organic framework (MOF) architectures and exploiting them as aptasensor scaffolds for detecting diverse analytes, especially cancer markers, have aroused widespread research attention. Herein, we report a novel strategy for obtaining ZnZr bimetallic MOFs via the MOF-on-MOF method and exploit them as an aptasensor platform for detecting the cancer marker protein tyrosine kinase-7 (PTK7). Basic characterizations reveal that the chemical structure, crystalline properties, and surface functionality of bimetallic ZnZr-MOFs can be modulated by changing the order of addition of metal precursors and organic ligands...
September 22, 2018: Biosensors & Bioelectronics
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