Comparison of Physicochemical Membrane Properties of Vesicles Modified with Guanidinium Derivatives.

Bilayer vesicles have garnered considerable research attention as molecular vehicles capable of noncovalent interaction with biomolecules via electrostatic and hydrophobic bonds and van der Waals interactions. Guanidinium strongly interacts with phosphate groups. Thus, guanidinium modification of vesicles helps intensify the interaction between lipid membranes and nucleic acids. Here, two kinds of guanidinium derivatives, stearylguanidinium (SG) and myristoylarginine (MA), were synthesized and incorporated into 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC) vesicles. Differences in their membrane properties were evaluated using Fourier transform infrared spectroscopy, Raman spectroscopy, and the fluorescent probes 1,6-diphenyl-1,3,5-hexatriene (DPH), 6-lauroyl-2-dimethylaminonaphthalene (Laurdan), and 2-p-toluidinylnaphthalene-6-sulfonate (TNS). The increased SG ratio increased overall hydrophobicity and lipid packing density compared to POPC vesicles, and SG-modified vesicles successfully attracted and then denatured negatively charged tRNAs (tRNAs). In contrast, MA-modified vesicles did not affect the stiffness of POPC membranes, wherein no conformational change in tRNAs was observed in the presence of POPC/MA vesicles. Analyses of the pH-dependent fluorescence emission of TNS suggested that SG and MA molecules render the membrane surfaces cationic and anionic, respectively, which was also revealed by zeta potential measurements. Our results enabled the construction of a model of the headgroup orientation of zwitterionic POPC molecules controlled by modification with guanidinium derivatives. The results also indicate the possibility to regulate the interaction and conformation of biological molecules, such as nucleic acid.