Conformation of self-assembled porphyrin dimers in liposome vesicles by phase-modulation 2D fluorescence spectroscopy

Proc Natl Acad Sci U S A. 2011 Oct 4;108(40):16521-6. doi: 10.1073/pnas.1017308108. Epub 2011 Sep 22.

Abstract

By applying a phase-modulation fluorescence approach to 2D electronic spectroscopy, we studied the conformation-dependent exciton coupling of a porphyrin dimer embedded in a phospholipid bilayer membrane. Our measurements specify the relative angle and separation between interacting electronic transition dipole moments and thus provide a detailed characterization of dimer conformation. Phase-modulation 2D fluorescence spectroscopy (PM-2D FS) produces 2D spectra with distinct optical features, similar to those obtained using 2D photon-echo spectroscopy. Specifically, we studied magnesium meso tetraphenylporphyrin dimers, which form in the amphiphilic regions of 1,2-distearoyl-sn-glycero-3-phosphocholine liposomes. Comparison between experimental and simulated spectra show that although a wide range of dimer conformations can be inferred by either the linear absorption spectrum or the 2D spectrum alone, consideration of both types of spectra constrain the possible structures to a "T-shaped" geometry. These experiments establish the PM-2D FS method as an effective approach to elucidate chromophore dimer conformation.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Computational Biology
  • Liposomes / metabolism*
  • Models, Biological*
  • Porphyrins / metabolism*
  • Protein Conformation*
  • Protein Multimerization / physiology*
  • Spectrometry, Fluorescence / methods*

Substances

  • Liposomes
  • Porphyrins