Contribution of Temperature to Deformation of Adsorbed Vesicles Studied by Nanoplasmonic Biosensing

With increasing temperature, biological macromolecules and nanometer-sized aggregates typically undergo complex and poorly understood reconfigurations, especially in the adsorbed state. Herein, we demonstrate the strong potential of using localized surface plasmon resonance (LSPR) sensors to address challenging questions related to this topic. By employing an LSPR-based gold nanodisk array platform, we have studied the adsorption of sub-100-nm diameter 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) lipid vesicles on titanium oxide at two temperatures, 23 and 50 °C. Inside this temperature range, DPPC lipid vesicles undergo the gel-to-fluid phase transition accompanied by membrane area expansion, while DOPC lipid vesicles remain in the fluid-phase state. To interpret the corresponding measurement results, we have derived general equations describing the effect of deformation of adsorbed vesicles on the LSPR signal. At the two temperatures, the shape of adsorbed DPPC lipid vesicles on titanium oxide remains nearly equivalent, while DOPC lipid vesicles become less deformed at higher temperature. Adsorption and rupture of DPPC lipid vesicles on silicon oxide were also studied for comparison. In contrast to the results obtained on titanium oxide, adsorbed vesicles on silicon oxide become more deformed at higher temperature. Collectively, the findings demonstrate that increasing temperature may ultimately promote, hinder, or have negligible effect on the deformation of adsorbed vesicles. The physics behind these observations is discussed, and helps to clarify the interplay of various, often hidden, factors involved in adsorption of biological macromolecules at interfaces.