Reversible Aggregation of Chlorophyll Derivative Induced by Phase Transition of Lipid.

Controlling the supramolecular organization of pigment molecules will provide innovative materials that exhibit variable optical properties. In nature, photosynthetic systems employ chlorophyllous supramolecules in which each pigment molecule is suitably organized in proteins, and their properties are adequately optimized by changing the structures of the surrounding amino acid residues. Here, we report a strategy for varying the aggregation behavior of a chlorophyll derivative by using a phase-transition phenomenon of lipid bilayers. Methyl pyropheophorbide a (MPP) was employed as a chlorophyllous pigment in our artificial system, and synthetic phosphatidylcholines with saturated acyl chain(s) were also used. The MPP molecules successfully accumulated within the lipid bilayer of liposomes without changing the vesicular structure. When the lipid bilayer was in a gel form (under the phase-transition temperature, T _m ), the embedded MPP aggregated to yield a dimeric form showing red-shifted absorption bands and circular dichroism signals. When the solutions of MPP-containing liposomes were heated to higher temperatures than their T _m , MPP disaggregated to monomeric form as the absorption spectrum changed into its original fashion in dichloromethane. The reversible thermochromic (dis)aggregation of the MPP molecules had good cyclability. Additional careful examination of the phase transition in the MPP-lipid co-assemblies clarified that the critical temperatures of the MPP (dis)aggregation were in good agreement with the phase-transition temperatures of the pigment-containing bilayers. The reversible MPP aggregation in the lipid bilayers occurred in a wide range of temperatures (around 10-55 °C) by changing the length of the diacyl side chains of phospholipids. The reversible thermochromism of the chlorophyllous system was established by varying the nature of the surrounding lipid bilayer. This study can provide a useful strategy for making variable tetrapyrrolic aggregate systems induced by mild extrinsic stimuli.