Formation of nanopores in DiynePC-DPPC complex lipid bilayers triggered by on-demand photo-polymerizationElectronic supplementary information (ESI) available. See DOI: 10.1039/c8ra04908d

Vesicles have unique characteristics that enable the release of drugs as well as encapsulation while maintaining biocompatibility. A photo-polymerizable liposome composed of 1,2-bis(10,12-tricosadiynoyl)- sn-glycero -3-phosphocholine (23:2 DiynePC) has been investigated as vehicles for triggered delivery of drugs to cells. In this study, we confirmed for the first time that supported lipid bilayers (SLBs) prepared with a 1,2-dipalmitoyl- sn-glycero -3-phosphocholine (DPPC)/DiynePC mixture generated pores ca. 100-300 nm in size on the membrane after UV polymerization. This direct observation was done by analyzing the SLBs formed with the DPPC/DiynePC mixture by employing atomic force microscopy (AFM) in a liquid environment. However, photo-polymerization did not occur in the 1,2-dioleoyl- sn-glycero -3-phosphocholine (DOPC)/DiynePC mixed bilayer and pores were not formed. A theoretical study was performed to explore the phase behavior of the lipid mixtures. A coarse-grained model of DiynePC was developed that is comparable with the Martini force field; the parameters were validated against atomistic simulations. Transition from fluidic to gel phase was observed only when DiynePC was mixed with DPPC, whereas the DOPC mixture remained fluidic over the entire domain. This implies a correlation between the formation of DiynePC-rich gel phase domains and the generation of pores after polymerization. The size of the pores were found to be controlled by the amount of polymerizable lipid which results in higher release rate of encapsulated calcein from the vesicles with larger pores. Nanopores generated upon photo-polymerization of the lipid membrane containing DiynePC were identified and their size was controllable.