Probing Conformers and Adsorption Footprints at the Single-Molecule Level in a Highly Organized Amino Acid Assembly of (S)-Proline on Cu(110).

Establishing the nanoscale details of organized amino acid assemblies at surfaces is a major challenge in the field of organic-inorganic interfaces. Here, we show that the dense (4 x 2) overlayer of the amino acid, (S)-proline on a Cu(110) surface can be explored at the single-molecule level by scan...

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Publicado en:Journal of the American Chemical Society Vol. 131; no. 29; pp. 10173 - 10182
Autores principales: Forster, Matthew, Dyer, Matthew S., Persson, Mats, Raval, Rasmita
Formato: Artículo
Publicado: American Chemical Society 7/29/2009
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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      dt: 7/29/2009
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        atl: Probing Conformers and Adsorption Footprints at the Single-Molecule Level in a Highly Organized Amino Acid Assembly of (S)-Proline on Cu(110).
      aug:
        au:
          Forster, Matthew
          Dyer, Matthew S.
          Persson, Mats
          Raval, Rasmita
        affil:
          Surface Science Research Centre, Department of Chemistry, University of Liverpool, Liverpool, L69 3BX, U.K.
          Department of Applied Physics, Chalmers University of Technology, SE-412 96, Goteborg, Sweden
      su:
        Amino acids
        Proline
        Scanning tunneling microscopy
        Density functionals
        Pyrrolidine
        Amino group
        Adsorption (Chemistry)
        Infrared spectroscopy
      sug:
        subj:
          Amino acids
          Proline
          Scanning tunneling microscopy
          Density functionals
          Pyrrolidine
          Amino group
          Adsorption (Chemistry)
          Infrared spectroscopy
      ab: Establishing the nanoscale details of organized amino acid assemblies at surfaces is a major challenge in the field of organic-inorganic interfaces. Here, we show that the dense (4 x 2) overlayer of the amino acid, (S)-proline on a Cu(110) surface can be explored at the single-molecule level by scanning tunneling microscopy (STM), reflection absorption infrared spectroscopy (RAIRS), and periodic density functional theory (DFT) calculations. The combination of experiment and theory, allied with the unique structural rigidity of proline, enables the individual conformers and adsorption footprints adopted within the organized assembly to be determined. Periodic DFT calculations find two energetically favorable molecular conformations, projecting mirror-image chiral adsorption footprints at the surface. These two forms can be experimentally distinguished since the positioning of the amino group within the pyrrolidine ring leads each chiral footprint and associated conformer to adopt very different ring orientations, producing distinct contrasts in the STM images. DFT modeling shows that the two conformers can generate eight possible (4 x 2) overlayers with a variety of adsorption footprint arrangements. STM images simulated for each structural model enables a direct comparison to be made with the experiment and narrows the (4 x 2) overlayer to one specific structural model in which the juxtaposition of molecules leads to the formation of one-dimensional hydrogen bonded prolate chains directed along the [110] direction.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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