Magnetic resonance of perdeuterated potassium laurate in oriented soap-water multilayers

doi:10.1016/0009-2614(73)85094-8

Chemical Physics Letters

Volume 23, Issue 3, 1 December 1973, Pages 345-348

https://doi.org/10.1016/0009-2614(73)85094-8 Get rights and content

Abstract

The deuteron resonance of five of the eleven methylene and methyl groups of the paraffinic chains are distinctly resolved. The orientation of the monocrystalline lamellar mesophare is varied with respect to the external magnetic field. The evolution f the resonance positions with orientation confirms that the system has local uniaxial symmetry on time scale longer than a few 10⁻⁶ sec.

References (19)

J. Charvolin et al.
J. Chem. Phys.
(1973)
M. Bloom
Colloque Ampère
(1972)
E. Oldfield et al.
FEBS Letters
(1971)
E.A. Stenhagen et al.
Chem. Abstracts
(1967)
V. Iuzzati
H.M. McConnell et al.
Quart. Rev. Biophys.
(1970)
C.J. Scandella et al.
Proc. Natl. Acad. Sci. U.S.
(1972)
K.K. Lawson et al.
J. Phys. Chem.
(1968)
A.S. Waggoner et al.
Proc. Natl. Acad. Sci. U.S.
(1970)
J. Charvolin et al.
Chem. Phys. Letters
(1973)

There are more references available in the full text version of this article.

Cited by (88)

<sup>2</sup> H NMR of oriented phospholipid/cholesterol bilayers containing an amphiphilic peptide
2020, Biochimica et Biophysica Acta - Biomembranes
Citation Excerpt :
The orientation of these samples relative to the external magnetic field can be varied simply by rotating the stack of glass plates about an axis perpendicular to the magnetic field. In a fluid lipid bilayer the bilayer normal is an axis of symmetry for the molecular motions [31]. In the presence of rapid axial reorientation, aligning the bilayer normal parallel to the magnetic field maximizes the size of the residual quadrupolar splittings (for 2H NMR) or the dipolar splittings and anisotropic chemical shifts (for 31P, 1H, 19F, 15N or 13C NMR) and avoids the difficulties in alignment arising from the competition between the diamagnetic susceptibility of helical peptides and that of the phospholipids which are opposite in sign [14].
Lipid bilayers form the basis of cell membranes and the phase behaviour of the membrane has been linked to proper cell function. Model membranes composed of relatively simple mixtures of phospholipids and cholesterol can already exhibit complex phase behaviour. Specifically, liquid ordered–liquid disordered fluid phase coexistence occurs in mixtures which contain one saturated long chain phospholipid and one unsaturated long chain phospholipid and cholesterol. This fluid-fluid two phase region persists over a broad range of temperatures and sample compositions and can be observed experimentally in various sample preparations including multilamellar dispersions, bicelles, and multi-lamellae stacked on glass slides. In order to explore the practicality of using oriented samples with different concentrations of the peptide, we investigated the effect of the addition of a synthetic 22 residue amphiphilic peptide on the orientability and phase behaviour of the lipid mixtures, as well as the orientation and dynamics of the peptide itself via ²H NMR. Increasing the peptide concentration promoted the formation of the liquid ordered phase, suggesting a preferential interaction of the peptide with the thicker ordered phase. However, higher peptide content (> 4 mol%) had a significant negative effect on the alignment of bicelles with their bilayer normal perpendicular to the external magnetic field. In the stacked bilayer samples, 6 mol% peptide eliminated the two phase coexistence region altogether and a single liquid ordered phase was observed from 285 to 311 K. Even so, ²H spectra of the peptide itself did not reveal any preference for the peptide to partition into either the liquid disordered or liquid ordered phase and we found two populations of the peptide, one which undergoes rapid axial reorientation about the bilayer normal and a second (powder component) which does not.
Biphenyl bicelle disks align perpendicular to magnetic fields on large temperature scales: A study combining synthesis, solid-state NMR, TEM, and SAXS
2007, Biophysical Journal
Citation Excerpt :
We can also point out the case for X = 85.7% and a temperature below 35°C (Fig. 2), where the spectrum shape is quite odd. We performed spectral simulations (not shown) and could well account for the shape assuming a cylindrical symmetry (tubes) (40,41) or using a vesicle of prolate form oriented perpendicular to the field (42). Because we could not go further in assignment, and because more detailed studies (outside the scope of our study) clearly would have been needed to explore this domain of temperature and composition, we cannot comment further on such shapes.
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.
Surface charge response of the phosphatidylcholine head group in bilayered micelles from phosphorus and deuterium nuclear magnetic resonance
1999, Biochimica et Biophysica Acta - Biomembranes
Solid-state phosphorus (³¹P) and deuterium (²H) nuclear magnetic resonance (NMR) spectroscopy over the temperature range of 25–50°C were used to investigate bilayered micelles (bicelles) composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) in the presence of either the anionic lipid 1,2-dimyristoyl-sn-3-phosphoglycerol (DMPG) or the cationic lipid 1,2-dimyristoyl-3-trimethylammonium-propane (DMTAP). The ³¹P-NMR spectra demonstrate that bicellar structures form with DMPG/DMPC ratios ranging from 0 to 50/50 and with DMTAP/DMPC ratios from 0 to 40/60, while the overall concentration of DHPC remains constant. The formation of bicelles containing charged amphiphiles is contingent upon the presence of NaCl, with 50 mM NaCl being sufficient for bicelle formation at all concentrations of charged amphiphile investigated, while 150 mM NaCl affords better resolution of the various ³¹P-NMR resonance signals. The ²H-NMR spectra demonstrate that the quadrupolar splittings (Δν) of head group-deuterated DMPC change inversely as a function of the amount of negative versus positive charge present, and that the changes for deuterons on the α-carbon are opposite in sense to those for deuterons on the β-carbon. This indicates that head group-deuterated phosphatidylcholine functions as a molecular voltmeter in bicelles in much the same fashion as it does in spherical vesicles.
Determination of the sign of the order parameter from MAS spectra of oriented molecules
1990, Journal of Magnetic Resonance (1969)
The use of the intensities of the spinning sidebands in the magic-angle spinning spectra of oriented molecules is proposed for the determination of the signs of the order parameters. The method is demonstrated for benzene and chloroform oriented in nematic phases of liquid crystals. On the basis of the theoretical expressions derived for the various order sidebands, the applicability of the method for different experimental conditions is discussed.
An X-ray and NMR investigation of the lamellar liquid crystalline phase in the octylamine/octylammonium chloride/water system
1987, Journal of Colloid And Interface Science
The lamellar liquid crystalline phase in the system octylamine/octylammonium chloride/water has been investigated by X-ray low-angle diffraction and by²H NMR determinations of order parameter profiles from the quadrupolar splittings of deuterated surfactant. At a constant mole ratio water/surfactant 80/20, the lateral expansion of the surfactant bilayer starts when the mole fraction of charged surfactant exceeds 0.5. Accompanying conformational changes in the alkyl chains are reflected in the surfactant order parameter profile, and for most methylene segments there is a linear relationship between the area per headgroup and the measured order parameter. However, the order parameters, in particular for the α-methylene segment, show a deviation from this relationship in the amine-rich region. For high surface charge densities, the maximum in the order parameter profile occurs for the α-methylene segment, while for low surface charge densities the maximum occurs further down the chain. This is interpreted as an effect of different molecular orientations due to the interaction between the polar headgroup and the water molecules.
Lamellar liquid crystal and other phases in the system sodium dodecyl sulfate, hexylamine, water, and heptane
1987, Journal of Colloid And Interface Science
Phase equilibria have been studied for the system composed of sodium dodecyl sulfate, hexylamine, heptane, and water. Greatest emphasis has been placed on the lamellar liquid crystal region and X-ray diffraction measurements. Equations are developed or modified to allow determination of the degree of penetration of water into the amphiphilic double layer as a function of water or amphiphile concentration. It is found that the interfacial area occupied by the polar or ionic head groups of amphiphiles increases with increasing water content.

View all citing articles on Scopus

²: Laboratoire associé au C.N.R.S.

¹: Permanent address: D.Ph.G, SP.S.R.M., CEN Saclay, B.P. 2, 91190 Gif-sur-Yvette, France.

View full text

Magnetic resonance of perdeuterated potassium laurate in oriented soap-water multilayers

Abstract

J. Chem. Phys.

Colloque Ampère

FEBS Letters

Chem. Abstracts

Quart. Rev. Biophys.

Proc. Natl. Acad. Sci. U.S.

J. Phys. Chem.

Proc. Natl. Acad. Sci. U.S.

Chem. Phys. Letters