title: The impact of model peptides on structural and dynamic properties of egg yolk lecithin liposomes - experimental and DFT studies.
abstract: Electron spin resonance (ESR), (1) H-NMR, voltage and resistance experiments were performed to explore structural and dynamic changes of Egg Yolk Lecithin (EYL) bilayer upon addition of model peptides. Two of them are phenylalanine (Phe) derivatives, Ac-Phe-NHMe (1) and Ac-Phe-NMe2 (2), and the third one, Ac-(Z)-ΔPhe-NMe2 (3), is a derivative of (Z)-α,β-dehydrophenylalanine. The ESR results revealed that all compounds reduced the fluidity of liposome's membrane, and the highest activity was observed for compound 2 with N-methylated C-terminal amide bond (Ac-Phe-NMe2 ). This compound, being the most hydrophobic, penetrates easily through biological membranes. This was also observed in voltage and resistance studies. (1) H-NMR studies provided a sound evidence on H-bond interactions between the studied diamides and lecithin polar head. The most significant changes in H-atom chemical shifts and spin-lattice relaxation times T1 were observed for compound 1. Our experimental studies were supported by theoretical calculations. Complexes EYLAc-Phe-NMe2 and EYLAc-(Z)-ΔPhe-NMe2 , stabilized by NH⋅⋅⋅O or/and CH⋅⋅⋅O H-bonds were created and optimized at M06-2X/6-31G(d) level of theory in vacuo and in H2 O environment. According to our molecular-modeling studies, the most probable lecithin site of H-bond interaction with studied diamides is the negatively charged O-atom in phosphate group which acts as H-atom acceptor. Moreover, the highest binding energy to hydrocarbon chains were observed in the case of Ac-Phe-NMe2 (2).
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48 Str., PL-45-052 Opole, (phone: (+48) 77 452 7132; fax: (+48) 77 452 7101).
authors.forename: Roksana
authors.initials: R
authors.lastname: Wałęsa
authors.affiliation: Institute of Physics, University of Opole, Oleska 48 Str., PL-45-052 Opole.
authors.forename: Dariusz
authors.initials: D
authors.lastname: Man
authors.affiliation: Institute of Physics, University of Opole, Oleska 48 Str., PL-45-052 Opole.
authors.forename: Grzegorz
authors.initials: G
authors.lastname: Engel
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48 Str., PL-45-052 Opole, (phone: (+48) 77 452 7132; fax: (+48) 77 452 7101).
authors.forename: Dawid
authors.initials: D
authors.lastname: Siodłak
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48 Str., PL-45-052 Opole, (phone: (+48) 77 452 7132; fax: (+48) 77 452 7101).
authors.forename: Teobald
authors.initials: T
authors.lastname: Kupka
authors.affiliation: Department of Basic Medical Sciences, Wroclaw Medical University, Borowska 211 Str., PL-50-556 Wroclaw.
authors.forename: Tomasz
authors.initials: T
authors.lastname: Ptak
authors.affiliation: Faculty of Chemistry, University of Opole, Oleska 48 Str., PL-45-052 Opole, (phone: (+48) 77 452 7132; fax: (+48) 77 452 7101). Malgorzata.Broda@uni.opole.pl.
authors.forename: Małgorzata A
authors.initials: MA
authors.lastname: Broda
mesh_terms: D004530:Egg Yolk / Q000737:chemistry*; D054709:Lecithins / Q000737:chemistry*; D008081:Liposomes / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D054709:Lecithins; D008081:Liposomes; D010455:Peptides
keywords: Density-functional theory (DFT); ESR Spectroscopy; Egg Yolk Lecithin (EYL); Liposomes; NMR Spectroscopy; Peptides