Shape Selectivity by Guest‐Driven Restructuring of a Porous Material

Warren, John E.; Perkins, Catherine; Jelfs, Kim E.; Boldrin, Paul; Chater, Philip A.; Miller, Gary J.; Manning, Troy D.; Briggs, Michael E.; Stylianou, Kyriakos C.; Claridge, John B.; Rosseinsky, Matthew J.

doi:10.1002/anie.201307656

Cited by 106 publications

(71 citation statements)

References 37 publications

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“…They all crystallized in the chiral P6 3 space group of the hexagonal system (Table S2) like precursor 1 (Figures 1, 2, and S3-S7). This striking feature of 1 is likely related to the intrinsic flexibility and structural adaptability [43][44][45][46][47] of its functional channels (Figure S6), which must be at the origin of the tunable structure/ conformation of the thioether chains that are reminiscent of the MR enzyme (Scheme S3). This striking feature of 1 is likely related to the intrinsic flexibility and structural adaptability [43][44][45][46][47] of its functional channels (Figure S6), which must be at the origin of the tunable structure/ conformation of the thioether chains that are reminiscent of the MR enzyme (Scheme S3).…”

Section: W Ere Obtained and Characterized By Icp Analyses (See The Exmentioning

confidence: 99%

“…[37] Thec rystal structures of the three adsorbates clearly confirmed the presence of HgCl 2 and CH 3 HgCl guest molecules hosted in the hexagonal nanopores of 1; [42] they are recognized by the thioether arms of the methionine residues and confined into the channels through S···Hg interactions.Y et, they showed different arrangements depending on the degree of loading or the nature of the guest molecule,l eading to either discrete mono-(3 HgCl 2 @1 and CH 3 HgCl@1)o r dinuclear species (5 HgCl 2 @1; Figures 2and S7). This striking feature of 1 is likely related to the intrinsic flexibility and structural adaptability [43][44][45][46][47] of its functional channels (Figure S6), which must be at the origin of the tunable structure/ conformation of the thioether chains that are reminiscent of the MR enzyme (Scheme S3). [34] TheH g 2+ ions from both the mononuclear HgCl 2 and CH 3 HgCl fragments in 3HgCl 2 @1 and CH 3 HgCl@1 (Figure 2a and c, respectively) and the chloride-bridged dinuclear [Hg 2 (m-Cl) 2 Cl 2 ]e ntities in 5HgCl 2 @1 (Figure 2b)a re tetracoordinated, being further grasped by two sulfur atoms from the thioether groups belonging to the amino acid residues of…”

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confidence: 99%

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Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF

et al. 2016

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A robust and water-stable metal-organic framework (MOF), featuring hexagonal channels decorated with methionine residues (1), selectively captures toxic species such as CH3 Hg(+) and Hg(2+) from water. 1 exhibits the largest Hg(2+) uptake capacity ever reported for a MOF, decreasing the [Hg(2+) ] and [CH3 Hg(+) ] concentrations in potable water from highly hazardous 10 ppm to the much safer values of 6 and 27 ppb, respectively. Just like with biological systems, the high-performance metal capture also involves a molecular recognition process. Both CH3 Hg(+) and Hg(2+) are efficiently immobilized by specific conformations adopted by the flexible thioether "claws" decorating the pores of 1. This leads to very stable structural conformations reminiscent of those responsible for the biological activity of the enzyme mercury reductase (MR).

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Section: W Ere Obtained and Characterized By Icp Analyses (See The Exmentioning

confidence: 99%

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confidence: 99%

Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF

et al. 2016

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“…The guest-driven restructuring of a flexible cerium tetradentate carboxylate MOF led to high selectivity by restructuring of the framework around p-and m-xylene, displaying molecular-level recognition, 28 and adding to the growing number of flexible MOFs having potential utility for separations. 6h,21,28 Here, we report the high selectivity of CD-MOFs (Figure 1) for the separation of aromatic hydrocarbons.…”

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confidence: 99%

Carbohydrate-Mediated Purification of Petrochemicals

et al. 2015

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Metal−organic frameworks (MOFs) are known to facilitate energy-efficient separations of important industrial chemical feedstocks. Here, we report how a class of green MOFsnamely CD-MOFsexhibits high shape selectivity toward aromatic hydrocarbons. CD-MOFs, which consist of an extended porous network of γ-cyclodextrins (γ-CDs) and alkali metal cations, can separate a wide range of benzenoid compounds as a result of their relative orientation and packing within the transverse channels formed from linking (γ-CD) 6 body-centered cuboids in three dimensions. Adsorption isotherms and liquid-phase chromatographic measurements indicate a retention order of ortho-> meta-> para-xylene. The persistence of this regioselectivity is also observed during the liquid-phase chromatography of the ethyltoluene and cymene regioisomers. In addition, molecular shape-sorting within CDMOFs facilitates the separation of the industrially relevant BTEX (benzene, toluene, ethylbenzene, and xylene isomers) mixture. The high resolution and large separation factors exhibited by CD-MOFs for benzene and these alkylaromatics provide an efficient, reliable, and green alternative to current isolation protocols. Furthermore, the isolation of the regioisomers of (i) ethyltoluene and (ii) cymene, together with the purification of (iii) cumene from its major impurities (benzene, n-propylbenzene, and diisopropylbenzene) highlight the specificity of the shape selectivity exhibited by CD-MOFs. Grand canonical Monte Carlo simulations and single component static vapor adsorption isotherms and kinetics reveal the origin of the shape selectivity and provide insight into the capability of CD-MOFs to serve as versatile separation platforms derived from renewable sources. ■ INTRODUCTIONWith the expanding global demand for petrochemical feedstocks, the development of novel, low-cost materials that reduce the impact of chemical processing on the environment is critically important. Improving the efficiency of the refinement and separation of aromatic hydrocarbons is of particular importance, given the large volumes on which these compounds are produced. The sustained interest in metal− organic frameworks 1 (MOFs) as adsorbents and sequestering agents for industrially important gases, 2−4 e.g., H 2 , CH 4 , CO 2 and N 2 , as well as for the liquid-phase separation of larger molecular compounds, which include (1) constitutional isomers, 5 (2) chiral compounds, 6 (3) aliphatic hydrocarbons, 3b,5b,7 and (4) pharmaceuticals, 8 is leading to MOFs being investigated as alternatives to zeolites 9 and activated carbon 10 as separation media. The improvements 5−7 in separation efficiencies using MOFs over traditional size-and shape-selective materials can be attributed primarily to (i) the physiochemical properties imbedded in their diverse building blocks, (ii) their higher surface areas, and (iii) their larger adsorption capacities, which reduce the amount of adsorbent required for industrial processes. 7a,11 Consequently, MOFs represent emergent materials f...

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“…Besides other applications like catalysis or sensing, their unlimited structural/chemical flexibility enables rational tailoring of the chemical function and pore dimensions for more efficient and selective separation of gases, 1 hydrocarbons 2,3 or aromatic compounds. 4 In this context, separation of chiral molecules with biological activity is also very relevant. A large number of drug compounds are often dosed as racemic mixtures.…”

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Peptide Metal–Organic Frameworks for Enantioselective Separation of Chiral Drugs

et al. 2017

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We report the use of a chiral Cu(II) 3D metal-organic framework (MOF) based on the tripeptide Gly-l-His-Gly (GHG) for the enantioselective separation of metamphetamine and ephedrine. Monte Carlo simulations suggest that chiral recognition is linked to preferential binding of one of the enantiomers as a result of either stronger or additional H-bonds with the framework that lead to energetically more stable diastereomeric adducts. Solid-phase extraction of a racemic mixture by using Cu(GHG) as the extractive phase permits isolating >50% of the (+)-ephedrine enantiomer as target compound in only 4 min. To our knowledge, this represents the first example of a MOF capable of separating chiral polar drugs.

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Shape Selectivity by Guest‐Driven Restructuring of a Porous Material

Cited by 106 publications

References 37 publications

Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF

Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF

Carbohydrate-Mediated Purification of Petrochemicals

Peptide Metal–Organic Frameworks for Enantioselective Separation of Chiral Drugs

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