Biphenyl Bicelle Disks Align Perpendicular to Magnetic Fields on Large Temperature Scales: A Study Combining Synthesis, Solid-State NMR, TEM, and SAXS

A phosphatidylcholine lipid (PC) containing a biphenyl group in one of its acyl chains (1-tetradecanoyl-2-(4-(4-biphenyl)butanoyl)-sn-glycero-3-PC, TBBPC) was successfully synthesized with high yield. Water mixtures of TBBPC with a short-chain C6 lipid, dicaproyl-PC (DCPC), lead to bicelle systems formation. Freeze-fracture electron microscopy evidenced the presence of flat bilayered disks of 800 Å diameter for adequate composition, hydration, and temperature conditions. Because of the presence of the biphenyl group, which confers to the molecule a positive magnetic anisotropy Δχ, the disks align with their normal, n, parallel to the magnetic field B0, as directly detected by 31P, 14N, 2H solid-state NMR and also using small-angle x-ray scattering after annealing in the field. Temperature-composition and temperature-hydration diagrams were established. Domains where disks of TBBPC/DCPC align with their normal parallel to the field were compared to chain-saturated lipid bicelles made of DMPC(dimyristoylPC)/DCPC, which orient with their normal perpendicular to B0. TBBPC/DCPC bicelles exist on a narrow range of long- versus short-chain lipid ratios (3%) but over a large temperature span around room temperature (10–75°C), whereas DMPC/DCPC bicelles exhibit the reverse situation, i.e., large compositional range (22%) and narrow temperature span (25–45°C). The two types of bicelles present orienting properties up to 95% dilution but with the peculiarity that water trapped in biphenyl bicelles exhibits ordering properties twice as large as those observed in the saturated-chains analog, which offers very interesting properties for structural studies on hydrophilic or hydrophobic embedded biomolecules.