Citation
De. Cohen et al., LASER-LIGHT SCATTERING EVIDENCE FOR A COMMON WORMLIKE GROWTH-STRUCTURE OF MIXED MICELLES IN BILE SALT-PHOSPHATIDYLCHOLINE AND STRAIGHT-CHAIN DETERGENT-PHOSPHATIDYLCHOLINE AQUEOUS SYSTEMS - RELEVANCE TO THE MICELLAR STRUCTURE OF BILE, Biochemistry (Easton), 37(42), 1998, pp. 14798-14814
Abstract
We employed quasielastic and static light scattering to measure appare
nt values of the mean hydrodynamic radii (R-h)(app), molecular weights
(M-app), and radii of gyration (R-g)(app) in solutions containing mix
ed micelles composed of bile salts (cholate and taurochenodeoxycholate
, both cholanoyl derivatives) and the glycoacyl chain detergent, octyl
glucoside, with egg yolk phosphatidylcholine (EYPC) as functions of t
otal lipid concentration (0.1-10 g/dL), EYPC/detergent molar ratio (0-
1.2), and ionic strength (0.15-0.3 M NaCl) at 20 degrees C and 1 atm.
As the mixed micellar phase boundaries were approached by dilution, (R
-h)(app), M-app, and (R-g)(app) values increased markedly by up to 20-
fold. For each micellar system, the scaling ratios (R-h)(app)/M-app(1/
2) and (R-g)(app)/(R-h)(app) remained essentially constant at 0.018 nm
/(g/mol)(1/2) and 1.5 (dimensionless), respectively, despite large var
iations in total lipid concentration, detergent molecular species, and
ionic strength. Refined data analysis is inconsistent with a flat ''m
ixed-disc'' model for bile salt-EYPC micelles [Mazer, N. A,, Benedek,
G. B., and Carey, M. C. (1980) Biochemistry 19, 601] and octyl glucosi
de-EYPC micelles principally because the numerical value of (R-h)(app/
)M-app(1/2) corresponds to a hypothetical disk thickness of similar to
1 nm, which is 4-fold smaller than the bimolecular width of EYPC mole
cules, and for a disk, (R-g)(app)/(R-h)(app) ratios should be close to
1 at low total lipid concentrations. Assuming disc-shaped micelles, w
e show that intermicellar excluded volume interactions would have only
a minor effect on M-app, and cannot account for the unrealistic disk
thickness. instead, locally cylindrical, semiflexible wormlike micelle
s of diameter d = 4 nm and persistence length xi(p) = 17 nm in solutio
n are compatible with the observed (R-h)(app)/M-app(1/2) and (R-g)(app
)/(R-h)(app) values when intermicellar excluded-volume interactions ar
e considered. With EYPC/taurochenodeoxycholate = 0.6 and EYPC/cholate
= 1.0 in 0.15 M NaCl, independent micelles grow upon dilution and use
of the second virial coefficient [Egelhaaf, S. U., and Schurtenberger,
P. (1994) J. Phys. Chem. 98, 8560] is adequate for estimating micella
r weights. The systems EYPC/cholate = 1.0 in 0.4 M NaCl, EYPC/cholate
= 1.2 in 0.15 M NaCl, and EYPC/octyl glucoside = 0.13 in 0.15 M NaCl a
ll form highly overlapping, semidilute polymer solutions, which mimic
the observed scaling ratios. In such semidilute systems, use of the se
cond virial coefficient alone to account for intermicellar interaction
s is inadequate for estimating micellar weights. The results of the pr
esent study, in combination with locations of known phase boundaries o
f the ternary bile salt-EYPC-water phase diagram at high dilution, sug
gest that elongation, as well as entanglement of wormlike mixed micell
es may occur at concentrations approaching the micellar phase limit.