Regional cooperativity in the phase transitions of dipalmitoylphosphatidylcholine bilayers: the lipid tail triggers the isothermal crystallization process.

We have a long-standing interest to explore the answer of the question: Which part of the amphiphilic molecule triggers the phase transition of the self-assembled aggregates consisting of these amphiphiles? This is an important issue regarding the phase transition kinetics of amphiphiles. To this end, we studied the phase transition behaviors of dipalmitoylphosphatidylcholine (DPPC) by differential scanning calorimetry, synchrotron X-ray scattering, Fourier transform infrared spectroscopy, and image analysis. We found that different parts (head, interface, and tail) of DPPC molecules all exhibit nonsynchronous changes during the sub-, pre-, and main transitions. Particular efforts have been devoted to studying the isothermal subgel (L(c')) formation process. It was found that only the lipid interface and tail regions change, and only when the rearrangement of the lipid hydrocarbon chain packing reaches a certain extent can the interfacial C═O groups be induced to undergo vibrational environment changes. The result means that the hydrocarbon tail is the part that triggers the gel (L(β')) to L(c') phase transition. The present work deepens our understanding on the phase transition mechanisms of DPPC and may shed light on those of other phospholipids and other types of amphiphiles.