Helical Gold Nanorods as Chiral Recognition Nanostructures: A Relativistic Density Functional Theory Study.

We establish helical gold nanorods as the first examples of chiral recognition nanostructures by examining the simple chiral molecule CClHDT adsorbed on the helical Au nanorod. We calculate the vibrational circular dichroism (VCD) spectra of the R and S enantiomers of CClHDT adsorbed on the R (or S)...

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Published in:Journal of the American Chemical Society Vol. 136; no. 51; pp. 17757 - 17762
Main Authors: Xiaojing Liu, Hamilton, Ian P.
Format: Article
Published: American Chemical Society 12/24/2014
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Online Access:View this record in EBSCOhost
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      dt: 12/24/2014
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        10.1021/ja5084267
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        atl: Helical Gold Nanorods as Chiral Recognition Nanostructures: A Relativistic Density Functional Theory Study.
      aug:
        au:
          Xiaojing Liu
          Hamilton, Ian P.
        affil: Department of Chemistry, Wilfrid Laurier University, Waterloo, N2L 3C5 Ontario, Canada
      su:
        Gold nanoparticles
        Nanorods
        Chiral recognition
        Density functional theory
        Vibrational circular dichroism
        Adsorption (Chemistry)
        Chirality
        Enantiomers
      sug:
        subj:
          Gold nanoparticles
          Nanorods
          Chiral recognition
          Density functional theory
          Vibrational circular dichroism
          Adsorption (Chemistry)
          Chirality
          Enantiomers
      ab: We establish helical gold nanorods as the first examples of chiral recognition nanostructures by examining the simple chiral molecule CClHDT adsorbed on the helical Au nanorod. We calculate the vibrational circular dichroism (VCD) spectra of the R and S enantiomers of CClHDT adsorbed on the R (or S) enantiomer of Au using relativistic density functional theory. The highest adsorption energy is found when the Cl atom of CClHDT binds to a low-coordinated Au atom at the edge of Au. There are three adsorption modes (essentially identical in energy) corresponding to three orientations of the HDT moiety. We show that, for each adsorption mode, the VCD spectra are distinctly different for the Au(R)-ClHDT(R) and Au(R)-CClHDT(S) complexes, and we give a qualitative explanation for this based on the principle of chirality transfer. For comparison with the results for Au, we calculate the VCD spectra of the R and S enantiomers of CClHDT adsorbed on the achiral Au tetrahedral cluster. Again, there are three adsorption modes (essentially identical in energy) corresponding to three orientations of the HDT moiety. However, we show that, for each adsorption mode, the VCD spectra are mirror symmetric but otherwise essentially identical for the Au-CClHDT(R) and Au-CClHDT(S) complexes. Thus, the inherent chirality of the helical Au nanorod is essential for its chiral recognition functionality.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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