Laser light scattering evidence for a common wormlike growth structure of mixed micelles in bile salt- and straight-chain detergent-phosphatidylcholine aqueous systems: Relevance to the micellar structure of bile

摘要

We employed quasielastic and static light scattering to measure apparent values of the mean hydrodynamic radii (R-h)(app), molecular weights (M-app), and radii of gyration (R-g)(app) in solutions containing mixed 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 total 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 variations in total lipid concentration, detergent molecular species, and ionic strength. Refined data analysis is inconsistent with a flat "mixed-disc" model for bile salt-EYPC micelles [Mazer, N. A,, Benedek, G. B., and Carey, M. C. (1980) Biochemistry 19, 601] and octyl glucoside-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 molecules, 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, we 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 micelles of diameter d = 4 nm and persistence length xi(p) = 17 nm in solution 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 are 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 micellar 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 all form highly overlapping, semidilute polymer solutions, which mimic the observed scaling ratios. In such semidilute systems, use of the second virial coefficient alone to account for intermicellar interactions is inadequate for estimating micellar weights. The results of the present study, in combination with locations of known phase boundaries of the ternary bile salt-EYPC-water phase diagram at high dilution, suggest that elongation, as well as entanglement of wormlike mixed micelles may occur at concentrations approaching the micellar phase limit. [References: 99]