(558h) Membrane Surface-Enhanced Raman Spectroscopy for High-Sensitive Detection of Molecular Behavior of Lipid Assemblies

The dynamic properties of phospholipid (PL) membranes (phase state and phase transition) play crucial roles in biological systems. However, highly sensitive, direct analytical methods that shed light on the nature of lipids and their assemblies have not been developed to date. Here, we describe the analysis of PL-modified Au nanoparticles (Au@PL) using membrane surface-enhanced Raman spectroscopy (MSERS) and report the properties of the self-assembled PL membranes on the Au nanoparticle. The Raman intensity per PL concentration increased by 50−170 times with Au@PL, as compared to large unilamellar vesicles (LUVs) at the same PL concentration. The phase state and phase transition temperature of the PL membrane of Au@PL were investigated by analyzing the Raman peak ratio (R = I₂₈₈₂/I₂₉₃₀). The enhancement at 714 cm⁻¹ (EF₍₇₁₄₎) varied with the hydrocarbon chain length of the PLs and the assembled degree of Au@PLs. In calculation, the EF₍₇₁₄₎,assembled was estimated to be 111−142 when the distance between AuNPs was 7.0−7.5 nm, which was correlated to the speculative enhancement factor, suggesting that the assembly of the Au@PLs contributed to the MSERS.