title: Self-Assembly of Silver Metal Clusters of Small Atomicity on Cyclic Peptide Nanotubes.
abstract: Subnanometric noble metal clusters, composed by only a few atoms, behave like molecular entities and display magnetic, luminescent and catalytic activities. However, noncovalent interactions of molecular metal clusters, lacking of any ligand or surfactant, have not been seen at work. Theoretically attractive and experimentally discernible, van der Waals forces and noncovalent interactions at the metal/organic interfaces will be crucial to understand and develop the next generation of hybrid nanomaterials. Here, we present experimental and theoretical evidence of noncovalent interactions between subnanometric metal (0) silver clusters and aromatic rings and their application in the preparation of 1D self-assembled hybrid architectures with ditopic peptide nanotubes. Atomic force microscopy, fluorescence experiments, circular dichroism and computational simulations verified the occurrence of these interactions in the clean and mild formation of a novel peptide nanotube and metal cluster hybrid material. The findings reported here confirmed the sensitivity of silver metal clusters of small atomicity toward noncovalent interactions, a concept that could find multiple applications in nanotechnology. We conclude that induced supramolecular forces are optimal candidates for the precise spatial positioning and properties modulation of molecular metal clusters. The reported results herein outline and generalize the possibilities that noncovalent interactions will have in this emerging field.
authors.affiliation: Technological Research Institute (IIT), Physical Chemistry Department, University of Santiago de Compostela (USC) , Santiago de Compostela 15782, Spain.
authors.forename: Miguel
authors.initials: M
authors.lastname: Cuerva
authors.affiliation: Center for Research in Biological Chemistry and Molecular Materials (CIQUS), Organic Chemistry Department, University of Santiago de Compostela (USC) , Santiago de Compostela 15782, Spain.
authors.forename: Rebeca
authors.initials: R
authors.lastname: García-Fandiño
authors.affiliation: Technological Research Institute (IIT), Physical Chemistry Department, University of Santiago de Compostela (USC) , Santiago de Compostela 15782, Spain.
authors.forename: Carlos
authors.initials: C
authors.lastname: Vázquez-Vázquez
authors.affiliation: Technological Research Institute (IIT), Physical Chemistry Department, University of Santiago de Compostela (USC) , Santiago de Compostela 15782, Spain.
authors.forename: M Arturo
authors.initials: MA
authors.lastname: López-Quintela
authors.affiliation: Center for Research in Biological Chemistry and Molecular Materials (CIQUS), Organic Chemistry Department, University of Santiago de Compostela (USC) , Santiago de Compostela 15782, Spain.
authors.forename: Javier
authors.initials: J
authors.lastname: Montenegro
authors.affiliation: Center for Research in Biological Chemistry and Molecular Materials (CIQUS), Organic Chemistry Department, University of Santiago de Compostela (USC) , Santiago de Compostela 15782, Spain.
authors.forename: Juan R
authors.initials: JR
authors.lastname: Granja
mesh_terms: D002942:Circular Dichroism; D018625:Microscopy, Atomic Force; D008958:Models, Molecular; D036103:Nanotechnology / Q000379:methods*; D045333:Nanotubes, Peptide / Q000737:chemistry* / Q000648:ultrastructure; D010456:Peptides, Cyclic / Q000737:chemistry*; D011721:Pyrenes / Q000737:chemistry; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D012996:Solutions; D013050:Spectrometry, Fluorescence
chemical_list: D045333:Nanotubes, Peptide; D010456:Peptides, Cyclic; D011721:Pyrenes; D012996:Solutions; D012834:Silver; C030984:pyrene
keywords: cyclic peptide; metal cluster; nanotubes; self-assembling