Switchable Amplification of Vibrational Circular Dichroism as a Probe of Local Chiral Structure

A new method to detect the vibrational circular dichroism (VCD) of a localized part of a chiral molecular system is reported. A local VCD amplifier was implemented, and the distance dependence of the amplification was investigated in a series of peptides. The results indicate a characteristic distan...

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Veröffentlicht in:Angewandte Chemie International Edition 2014-12, Vol.53 (51), p.14042-14045
Hauptverfasser: Domingos, Sérgio R., Sanders, Hans J., Hartl, František, Buma, Wybren J., Woutersen, Sander
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Sprache:eng
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Zusammenfassung:A new method to detect the vibrational circular dichroism (VCD) of a localized part of a chiral molecular system is reported. A local VCD amplifier was implemented, and the distance dependence of the amplification was investigated in a series of peptides. The results indicate a characteristic distance of 2.0±0.3 bonds, which suggests that the amplification is a localized phenomenon. The amplifier can be covalently coupled to a specific part of a molecule, and can be switched ON and OFF electrochemically. By subtracting the VCD spectra obtained when the amplifier is in the ON and OFF states, the VCD of the local environment of the amplifier can be separated from the total VCD spectrum. Switchable local VCD amplification thus makes it possible to “zoom in” on a specific part of a chiral molecule. Turn ON the amp: Vibrational circular dichroism (VCD) signals of a spatially restricted part of a molecule can be detected by employing a local VCD amplifier that can be turned ON and OFF electrochemically. The amplification is localized in the neighborhood of the amplifier and can thus be used to locally probe chiral molecular structure.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201407376