1. Molecular Level Characterization of the Structure and Interactions in Peptide-Functionalized Metal-Organic Frameworks
- Author
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Alexandre Legrand, Lyndon Emsley, David Farrusseng, Pierrick Berruyer, Jérôme Canivet, Caroline Mellot-Draznieks, Xavier Rozanska, Tanya K. Todorova, Linh Ngoc Ho, Christel Gervais, Anne Lesage, Laboratoire de Chimie des Processus Biologiques (LCPB), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SARL Mat Design, Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solid-State NMR Methods for Materials - Méthodes de RMN à l'état solide pour les matériaux, Institut des Sciences Analytiques (ISA), Institut des sciences et ingénierie chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), We acknowledge financial support from the French National Research Agency (ANR project: HOPFAME ANR-13-BS07-0002-01), the Fondation de l'Orangerie and the ERC Advanced Grant No. 320860. The calculations were performed by using the HPC resources from GENCI (CINES/TGCC/IDRIS) through Grants 2016-097343 and -097535., ANR-13-BS07-0002,HOPFAME,Matériaux poreux hybrides comme métalloenzymes artificielles(2013), European Project: 320860,EC:FP7:ERC,ERC-2012-ADG_20120216,HI-SENS(2013), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Magnetic Resonance Spectroscopy ,Proline ,Glycine ,Molecular Conformation ,Peptide ,02 engineering and technology ,Molecular Dynamics Simulation ,010402 general chemistry ,01 natural sciences ,Catalysis ,Molecular dynamics ,NMR spectroscopy ,Computational chemistry ,[CHIM.ANAL]Chemical Sciences/Analytical chemistry ,[CHIM]Chemical Sciences ,metal-organic frameworks ,chemistry.chemical_classification ,Hydrogen bond ,Chemical shift ,Organic Chemistry ,fungi ,Hydrogen Bonding ,General Chemistry ,Nuclear magnetic resonance spectroscopy ,Dipeptides ,021001 nanoscience & nanotechnology ,molecular dynamics ,0104 chemical sciences ,Characterization (materials science) ,chemistry ,density functional calculations ,peptides ,Metal-organic framework ,Density functional theory ,0210 nano-technology - Abstract
We thank Prof. Paul Tordo and Dr. Olivier Ouari for providing TEKPoL2.; International audience; 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.
- Published
- 2016