Phospholipids when dispersed in excess water generally form vesicular membr
ane structures. Cryo-transmission and freeze-fracture electron microscopy a
re combined here with calorimetry and viscometry to demonstrate the reversi
ble conversion of phosphatidylglycerol aqueous vesicle suspensions to a thr
ee-dimensional structure that consists of extended bilayer networks. Thermo
dynamic analysis indicates that the structural transitions arise from two e
ffects: (i) the enhanced membrane elasticity accompanying the lipid state f
luctuations on chain melting and (ii) solvent-associated interactions (incl
uding electrostatics) that favor a change in membrane curvature. The materi
al properties of the hydrogels and their reversible formation offer the pos
sibility of future applications, for example in drug delivery, the design o
f structural switches, or for understanding vesicle fusion or fission proce
sses.