Organization of Carotenoid Aggregates in Membranes Studied Selectively using Resonance Raman Optical Activity

Small. 2024 Jun;20(26):e2306707. doi: 10.1002/smll.202306707. Epub 2024 Jan 21.

Abstract

In living organisms, carotenoids are incorporated in biomembranes, remarkably modulating their mechanical characteristics, fluidity, and permeability. Significant resonance enhancement of Raman optical activity (ROA) signals of carotenoid chiral aggregates makes resonance ROA (RROA), a highly selective tool to study exclusively carotenoid assemblies in model membranes. Hence, RROA is combined with electronic circular dichroism (ECD), dynamic light scattering (DLS), molecular dynamics, and quantum-chemical calculations to shed new light on the carotenoid aggregation in dipalmitoylphosphatidylcholine (DPPC) liposomes. Using representative members of the carotenoid family: apolar α-carotene and more polar fucoxanthin and zeaxanthin, the authors demonstrate that the stability of carotenoid aggregates is directly linked with their orientation in membranes and the monomer structures inside the assemblies. In particular, polyene chain distortion of α-carotene molecules is an important feature of J-aggregates that show increased orientational freedom and stability inside liposomes compared to H-assemblies of more polar xanthophylls. In light of these results, RROA emerges as a new tool to study active compounds and drugs embedded in membranes.

Keywords: Raman optical octivity; aggregates; carotenoids; chirality; membranes; supramolecules.

MeSH terms

  • 1,2-Dipalmitoylphosphatidylcholine / chemistry
  • Carotenoids* / chemistry
  • Circular Dichroism
  • Liposomes* / chemistry
  • Molecular Dynamics Simulation
  • Spectrum Analysis, Raman* / methods
  • Xanthophylls / chemistry

Substances

  • Carotenoids
  • Liposomes
  • 1,2-Dipalmitoylphosphatidylcholine
  • Xanthophylls