The negative free energy previously reported is explained by the stabilization of a PC-Phe (phosphocholine-phenylalanine) complex in the presence of water shown by the decrease in the symmetric stretching frequency of the phosphate group of the lipid (PO2(-)). An entropic contribution due to the disruption of the water network around the phenyl and in the membrane defect may be invoked. The dipole potential decrease is explained by the orientation of the carboxylate opposing to the CO of the lipids with oxygen moiety toward the low hydrated hydrocarbon core. The symmetric bending frequency of NH3(+) group of Phe, decreases in 5.2 cm(-1) in relation to water congruent with zeta potential shift to positive values. The Phe to DPPC dissociation constant is Kd = 2.23 ± 0.09 mM, from which the free energy change is about -4.54 kcal/mol at 25 °C. This may be due to hydrophobic contributions and two hydrogen bonds.
Lipid membranes are one of the most important biological matrixes
in which biochemical processes take place. This particular lipid arrangement
is driven by different water disposition interacting with it, which
is related to different water states with different energy levels
at the interphase. In our work, we report changes in water content
and distinctive water states by Fourier transform infrared (FTIR)
spectroscopy of this self-assembled matrix at different water contents
and temperatures. To determine whether water properties at lipid interphases
depend on the group of the lipid molecule at which it is bound the
phase-transition temperature of 1,2-dimiristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-di-O-tetradecyl-sn-glycero-3-phosphocholine (14:0 diether PC) was followed
by the changes in frequency of the different groups of the lipids
by attenuated total reflection (ATR)-FTIR spectroscopy at different
humidities. A comparison of these two lipids enables us to put into
relevance the contribution of the CO groups as a hydration site. These
changes were compared with those occurring at the water band, and
a value of the enthalpic change was evaluated from them. The −OH
stretching in the liquid water IR spectrum is the principal region
used to understand its molecular organization (4000–3000 cm–1). The strength of hydrogen bonding depends on the
cooperative/anticooperative nature of the surrounding hydrogen bonds,
with the strongest hydrogen bonds giving the lowest vibrational frequencies.
Thus, we can use water as a mirror of the membrane state in this kind
of biological systems. Different phospholipids associate water at
particular modes according to their structures. This may produce modulation
of packing and hydration suitable for the incorporation of amino acids,
peptides, and enzymes.
The lack of carbonyl groups and the presence of ether bonds give the lipid interphase a different water organization around the phosphate groups that affects the compressibility and electrical properties of lipid membranes. Generalized polarization of 14:0 Diether PC in correlation with FTIR analysis indicates a higher level of polarizability of water molecules in the membrane phase around the phosphate groups both below and above T m . This reorganization of water promotes a different response in compressibility and dipole moment of the interphase which is related to different H-bonding of water molecules with PO and CO groups.
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