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 C(6) lipid, dicaproyl-PC (DCPC), lead to bicelle systems formation. Freeze-fracture electron microscopy evidenced the presence of flat bilayered disks of 800 A 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 Delta chi, the disks align with their normal, n, parallel to the magnetic field B(0), as directly detected by (31)P, (14)N, (2)H 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 B(0). 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 degrees C), whereas DMPC/DCPC bicelles exhibit the reverse situation, i.e., large compositional range (22%) and narrow temperature span (25-45 degrees 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.
Loudet
Cécile
C
UMR 5248 CBMN, CNRS-Université Bordeaux 1-ENITAB, Institut Européen de Chimie et Biologie, Pessac, France.
Manet
Sabine
S
Gineste
Stéphane
S
Oda
Reïko
R
Achard
Marie-France
MF
Dufourc
Erick J
EJ
D001713:Biphenyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D046529:Microscopy, Electron, Transmission; D010713:Phosphatidylcholines / Q000138:chemical synthesis / Q000737:chemistry*; D053838:Scattering, Small Angle; D013696:Temperature; D014961:X-Ray Diffraction
D001713:Biphenyl Compounds; D010713:Phosphatidylcholines