title: Molecular Level Characterization of the Structure and Interactions in Peptide-Functionalized Metal-Organic Frameworks.
abstract: We use density functional theory, newly parameterized molecular dynamics simulations, and last generation15N 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 obtained15N 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.
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, UPMC Univ Paris 06, Collège de France, 11 Place Marcelin Berthelot, 75231, Paris Cedex 05, France.
authors.forename: Tanya K
authors.identifier: http://orcid.org/0000-0002-7731-6498
authors.initials: TK
authors.lastname: Todorova
authors.affiliation: Materials Design, S. A. R. L., 42 avenue Verdier, 92120, Montrouge, France.
authors.forename: Xavier
authors.identifier: http://orcid.org/0000-0001-9174-562X
authors.initials: X
authors.lastname: Rozanska
authors.affiliation: Sorbonne Universités - Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), UPMC Université Paris 06, UMR CNRS 7574, 4 place Jussieu, 75252, Paris cedex 05, France.
authors.forename: Christel
authors.identifier: http://orcid.org/0000-0001-7450-1738
authors.initials: C
authors.lastname: Gervais
authors.affiliation: IRCELYON, Université Lyon 1 - CNRS, UMR 5256, 2 Avenue Albert Einstein, 69626, Villeurbanne, France.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Legrand
authors.affiliation: IRCELYON, Université Lyon 1 - CNRS, UMR 5256, 2 Avenue Albert Einstein, 69626, Villeurbanne, France.
authors.forename: Linh N
authors.initials: LN
authors.lastname: Ho
authors.affiliation: Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Lyon 1, ENS Lyon-5, rue de la Doua, 69100, Villeurbanne, France.
authors.forename: Pierrick
authors.initials: P
authors.lastname: Berruyer
authors.affiliation: Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Lyon 1, ENS Lyon-5, rue de la Doua, 69100, Villeurbanne, France.
authors.forename: Anne
authors.identifier: http://orcid.org/0000-0003-1958-2840
authors.initials: A
authors.lastname: Lesage
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.
authors.forename: Lyndon
authors.identifier: http://orcid.org/0000-0003-1360-2572
authors.initials: L
authors.lastname: Emsley
authors.affiliation: IRCELYON, Université Lyon 1 - CNRS, UMR 5256, 2 Avenue Albert Einstein, 69626, Villeurbanne, France.
authors.forename: David
authors.identifier: http://orcid.org/0000-0002-9093-4143
authors.initials: D
authors.lastname: Farrusseng
authors.affiliation: IRCELYON, Université Lyon 1 - CNRS, UMR 5256, 2 Avenue Albert Einstein, 69626, Villeurbanne, France. jerome.canivet@ircelyon.univ-lyon1.fr.
authors.forename: Jérôme
authors.identifier: http://orcid.org/0000-0002-0458-3085
authors.initials: J
authors.lastname: Canivet
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, UPMC Univ Paris 06, Collège de France, 11 Place Marcelin Berthelot, 75231, Paris Cedex 05, France. caroline.mellot-draznieks@college-de-france.fr.
authors.forename: Caroline
authors.identifier: http://orcid.org/0000-0003-3670-4600
authors.initials: C
authors.lastname: Mellot-Draznieks
mesh_terms: D004151:Dipeptides / Q000737:chemistry*; D005998:Glycine / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D000073396:Metal-Organic Frameworks / Q000737:chemistry*; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D010455:Peptides / Q000737:chemistry*; D011392:Proline / Q000737:chemistry*
chemical_list: D004151:Dipeptides; D000073396:Metal-Organic Frameworks; D010455:Peptides; C015248:glycylproline; D011392:Proline; D005998:Glycine
keywords: NMR spectroscopy; density functional calculations; metal-organic frameworks; molecular dynamics; peptides