Optically Active Vibrational Spectroscopy of α‐Aminoisobutyric Acid Foldamers in Organic Solvents and Phospholipid Bilayers

Helical α‐aminoisobutyric acid (Aib) foldamers show great potential as devices for the communication of conformational information across phospholipid bilayers, but determining their conformation in bilayers remains a challenge. In the present study, Raman, Raman optical activity (ROA), infrared (IR...

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Bibliographic Details
Published in:Chemistry : a European journal 2018-07, Vol.24 (37), p.9399-9408
Main Authors: Lizio, Maria Giovanna, Andrushchenko, Valery, Pike, Sarah J., Peters, Anna D., Whitehead, George F. S., Vitórica‐Yrezábal, Iñigo J., Mutter, Shaun T., Clayden, Jonathan, Bouř, Petr, Blanch, Ewan W., Webb, Simon J.
Format: Article
Language:English
Subjects:
Acids
Aminoisobutyric Acids - chemistry
Biomimetics
Chemistry
chirality
Circular dichroism
Circular Dichroism - methods
Conformation
Conformational analysis
Dichroism
Electronic devices
foldamers
Helices
Infrared radiation
Lipid Bilayers - chemistry
membranes
Models, Molecular
Molecular chains
Molecular Conformation
Optical activity
Organic solvents
peptides
Phospholipids
Phospholipids - chemistry
Population distribution
Protein Structure, Secondary
Raman spectra
Raman spectroscopy
Signal transduction
Solvents
Solvents - chemistry
Spectrophotometry, Infrared - methods
Spectrum analysis
Spectrum Analysis, Raman - methods
Stereoisomerism
vibrational spectroscopy
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Summary:Helical α‐aminoisobutyric acid (Aib) foldamers show great potential as devices for the communication of conformational information across phospholipid bilayers, but determining their conformation in bilayers remains a challenge. In the present study, Raman, Raman optical activity (ROA), infrared (IR) and vibrational circular dichroism (VCD) spectroscopies have been used to analyze the conformational preferences of Aib foldamers in solution and when interacting with bilayers. A 310‐helix marker band at 1665–1668 cm−1 in Raman spectra was used to show that net helical content increased strongly with oligomer length. ROA and VCD spectra of chiral Aib foldamers provided the chiroptical signature for both left‐ and right‐handed 310‐helices in organic solvents, with VCD establishing that foldamer screw‐sense was preserved when the foldamers became embedded within bilayers. However, the population distribution between different secondary structures was perturbed by the chiral phospholipid. These studies indicate that ROA and VCD spectroscopies are valuable tools for the study of biomimetic structures, such as artificial signal transduction molecules, in phospholipid bilayers. The turn of the screw: Raman optical activity (ROA) and vibrational circular dichroism (VCD) spectroscopies of helical α‐aminoisobutyric acid foldamers have provided chiroptical signatures for both left‐ and right‐handed 310‐helices in organic solvents, with VCD indicating that foldamer screw‐sense is preserved when the foldamers are embedded in bilayers.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201801121