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We use density functional theory, newly parameterized molecular dynamics simulations, and last generation 15 N dynamic nuclear polarization surface enhanced solid-state NMR spectroscopy (DNP SENS) to understand graft-host interactions and effects imposed by the metal-organic framework (MOF) host on peptide conformations in a peptide-functionalized MOF. Focusing on two grafts typified by MIL-68-proline (-Pro) and MIL-68-glycine-proline (-Gly-Pro), we identified the most likely peptide conformations adopted in the functionalized hybrid frameworks. We found that hydrogen bond interactions between the graft and the surface hydroxyl groups of the MOF are essential in determining the peptides conformation(s). DNP SENS methodology shows unprecedented signal enhancements when applied to these peptide-functionalized MOFs. The calculated chemical shifts of selected MIL-68-NH-Pro and MIL-68-NH-Gly-Pro conformations are in a good agreement with the experimentally obtained 15 N NMR signals. The study shows that the conformations of peptides when grafted in a MOF host are unlikely to be freely distributed, and conformational selection is directed by strong host-guest interactions., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Summary: Monoterpenes are the most prevalent compounds found in essential oils. They exhibit inhibitory actions against phytopathogenic postharvest fungi. Direct application limits their effectiveness due to their instability, high volatility, hydrophobicity and susceptibility to degradation. Encapsulation systems using metal–organic frameworks (MOFs) have been developed to maximise their use. In this study, four protocols were shown to encapsulate thymol and limonene in porous solids, such as ZIF‐8, UiO‐66‐(COOH)2 and zeolite 13X. Vapourisation and diffusion at 60 °C for 16 h was found to be the most efficient encapsulation process. A larger amount of thymol than limonene was loaded in the porous solids. Thymol released from MOFs slowed down the growth of Colletotrichum musae by up to 6 days at 25 °C. There was a sustained release of thymol even beyond the period of maximum fungal growth. This proof‐of‐concept study revealed the potential utility of MOFs as carriers of thymol against postharvest fungi. [ABSTRACT FROM AUTHOR]

Air purification of ammonia, a toxic industrial chemicals (TICs), by adsorption process on Metal-Organic Framework solids is attracting high scientific and commercial interests. While active carbon based adsorbents required high level of relative humidity for achieving proper performance ammonia capture, zeolite performance degrades in presence of humidity. For MOFs, the presence of humidity has been shown to be MOF dependent, either beneficial or detrimental. It appears that the role of humidity is of key importance and that different ammonia adsorption mechanisms co-exist depending on the material's physico-chemical features. Based on a screening of various microporous adsorbents including carbons, zeolites and MOFs, we show that in the presence of humidity, the ammonia uptake mostly follows the Henry law of ammonia solubilization in water. At the exception of Copper based MOF, the ammonia capture is mostly correlated with the amount of “condensed water” in the micropore. We also generally observe a systematic higher uptake than the Henry law which can be attributed to the effect of confinement i. e surface-condensed phase interaction. [ABSTRACT FROM AUTHOR]

Porous metal–organic frameworks (MOFs) are attracting great attention from industry, thanks to their myriad potential applications in areas such as catalysis and gas storage. Zr-MOFs (also known as UiO-type MOFs) are especially promising, owing to their large surface areas, high chemical versatility and remarkable hydrothermal, chemical and thermal stabilities. However, among the challenges currently precluding the industrial exploitation of MOFs is the lack of green methods for their synthesis. Herein we describe a continuous-flow spray-drying method for the simultaneous synthesis and shaping of spherical MOF microbeads in a mixture of water and acetic acid. We used this approach to build two archetypical Zr-MOFs: UiO-66-NH2 and Zr-fumarate. By tuning the concentration of acetic acid in water, we were able to produce, by a scalable process, UiO-66-NH2 and Zr-fumarate beads with SBET and water-sorption values comparable to the literature values obtained with other methods. [ABSTRACT FROM AUTHOR]

We use density functional theory, newly parameterized molecular dynamics simulations, and last generation 15N dynamic nuclear polarization surface enhanced solid-state NMR spectroscopy (DNP SENS) to understand graft-host interactions and effects imposed by the metal-organic framework (MOF) host on peptide conformations in a peptide-functionalized MOF. Focusing on two grafts typified by MIL-68-proline ( -Pro) and MIL-68-glycine-proline ( -Gly-Pro), we identified the most likely peptide conformations adopted in the functionalized hybrid frameworks. We found that hydrogen bond interactions between the graft and the surface hydroxyl groups of the MOF are essential in determining the peptides conformation(s). DNP SENS methodology shows unprecedented signal enhancements when applied to these peptide-functionalized MOFs. The calculated chemical shifts of selected MIL-68-NH- Pro and MIL-68-NH- Gly-Pro conformations are in a good agreement with the experimentally obtained 15N NMR signals. The study shows that the conformations of peptides when grafted in a MOF host are unlikely to be freely distributed, and conformational selection is directed by strong host-guest interactions. [ABSTRACT FROM AUTHOR]

Abstract: Metal–organic frameworks are appealing hybrid solids which attract continuously growing interest. Their advantageous application in sensing devices is demonstrated here. In particular, the use of a short‐pulse laser excitation of luminescent metal‐organic framework is reported for the first time to favor the ligand‐based emission. The designed MOF‐based system achieves in vitro H2S dosing by turn‐on fluorescence with unprecedented sensitivity. The Al‐MIL‐101‐based sensor detects sulfide produced by living cells and sulfide‐releasing molecules in physiological media with a constant accuracy at sub‐micromolar levels. The reported sensitivity is suitable for medical applications and opens new perspectives in the design of new point‐of‐care testing devices. The detailed relationship between photoluminescence mechanisms and chemical modification of the MOF upon sensing is also reported. [ABSTRACT FROM AUTHOR]

We report the supercell crystal structure of a ZIF-8 analog substituted imidazolate metal-organic framework (SIM-1) obtained by combining solid-state nuclear magnetic resonance and powder X-ray diffraction experiments with density functional theory calculations. [ABSTRACT FROM AUTHOR]

The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2-storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ~10% molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2. There is no precedent for a MOF catalyzing the latter reaction so far. [ABSTRACT FROM AUTHOR]

We report herein the upscaled synthesis and shaping of UiO66-COOH for NH3 air purification. The synthesis of the zirconium-based MOF was carried out in a batch reactor in an aqueous suspension with a yield of 89% and a space-time yield of 350 kg/day/m3. Neither toxic chemicals nor organic solvents were used, allowing this MOF to be employed in individual or collective air purification devices. Freeze-granulation and extrusion shaping techniques were investigated. The NH3 air purification performances of UiO66-COOH in bead, tablet and extrudate forms were compared to those of commercial carbon based materials (type K adsorbents from3M and Norit). Testing conditions were chosen to reflect current standards for ammonia concentration (600-1200 ppm) and velocity. In addition, the breakthrough measurements were carried out at three different relative humidity levels (0%, 40%, and 70%). Pellets and extrudates of UiO66-COOH outperformed commercial benchmark adsorbents in all conditions, especially in dry conditions, for which the commercial adsorbents suffered impaired ammonia uptake and shortened service life. Extrudates of UiO66-COOH also withstood attrition after intensive shaking. [ABSTRACT FROM AUTHOR]

We present herein the first example of metal-organic frameworks postfunctionalized with peptides. Our microwave-assisted postsynthetic modification method yields enantiopure peptides anchored inside MOF cavities. Al-MIL-101-NH2, In-MIL-68-NH2, and Zr-UiO-66-NH2 were chosen as starting platforms. A single amino acid and various oligopeptides are grafted with yields up to 60% after a 30 min microwave-assisted coupling-deprotection sequence. This allows efficient preparation of a library of functional hybrid solids for molecular recognition applications such as sensing, separation, or asymmetric catalysis, as demonstrated here for the chiral aldol reaction. [ABSTRACT FROM AUTHOR]

Two cobalt imidazolate metal-organic frameworks were evaluated as a bactericidal material against the growth of the Gram-negative bacteria Pseudomonas putida and Escherichia coli. Under the most unfavourable conditions, within the exponential growth phase and in the culture media for both microorganisms, the growth inhibition reached over 50% for concentrations of biocidal material in the 5-10mgL−1 range. The release of metal gives excellent durability with the antibacterial effect persisting after 3months. Both cobalt-based materials can be prepared with simple, cheap and easily accessible commercial ligands, leading to a more affordable possible future application as antimicrobial materials. [ABSTRACT FROM AUTHOR]