Lipid bilayer pre-transition as the beginning of the melting process.
We investigate the bilayer pre-transition exhibited by some lipids at temperatures below their main phase transition, and which is generally associated to the formation of periodic ripples in the membrane. Experimentally we focus on the anionic lipid dipalmytoylphosphatidylglycerol (DPPG) at different ionic strengths, and on the neutral lipid dipalmytoylphosphatidylcholine (DPPC). From the analysis of differential scanning calorimetry traces of the two lipids we find that both pre- and main transitions are part of the same melting process. Electron spin resonance of spin labels and excitation generalized polarization of Laurdan reveal the coexistence of gel and fluid domains at temperatures between the pre- and main transitions of both lipids, reinforcing the first finding. Also, the melting process of DPPG at low ionic strength is found to be less cooperative than that of DPPC. From the theoretical side, we introduce a statistical model in which a next-nearest-neighbor competing interaction is added to the usual two-state model. For the first time, modulated phases (ordered and disordered lipids periodically aligned) emerge between the gel and fluid phases as a natural consequence of the competition between lipid-lipid interactions.
Instituto de Física, Universidade de São Paulo, CP 66318, CEP 05315-970 São Paulo-SP, Brazil. kar@biofis.epm.br
Karin A
KA
Riske
Rafael P
RP
Barroso
Cíntia C
CC
Vequi-Suplicy
Renato
R
Germano
Vera B
VB
Henriques
M Teresa
MT
Lamy
D015060:1,2-Dipalmitoylphosphatidylcholine / Q000737:chemistry; D015081:2-Naphthylamine / Q000031:analogs & derivatives; D055592:Biophysical Phenomena; D002152:Calorimetry, Differential Scanning; D004578:Electron Spin Resonance Spectroscopy; D005456:Fluorescent Dyes; D005782:Gels; D007848:Laurates; D008051:Lipid Bilayers / Q000737:chemistry*; D008956:Models, Chemical; D015233:Models, Statistical; D009010:Monte Carlo Method; D009994:Osmolar Concentration; D010715:Phosphatidylglycerols / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013113:Spin Labels; D013816:Thermodynamics
D005456:Fluorescent Dyes; D005782:Gels; D007848:Laurates; D008051:Lipid Bilayers; D010715:Phosphatidylglycerols; D013113:Spin Labels; D015060:1,2-Dipalmitoylphosphatidylcholine; D015081:2-Naphthylamine; C030345:1,2-dipalmitoylphosphatidylglycerol; C065580:laurdan