Micelle neutron scattering

Key words Sorbitol - cryoprotectant - phosphatidylcholine - micelle neutron scattering - contrast-variation method... 

The early Hartley model [2, 3] of a spherical micellar stmcture resulted, in later years, in some considerable debate. The self-consistency (inconsistency) of spherical symmetry witli molecular packing constraints was subsequently noted [4, 5 and 6]. There is now no serious question of tlie tenet tliat unswollen micelles may readily deviate from spherical geometry, and ellipsoidal geometries are now commonly reported. Many micelles are essentially spherical, however, as deduced from many light and neutron scattering studies. Even ellipsoidal objects will appear... 

M. Zulauf, K. Weckstrom, J. B. Hayter, V. Degiorgio, M. Corti. Neutron scattering study of micelle structure in isotopic aqueous solutions of poly(oxy-ethylene) amphiphiles. J Phys Chem 29 3411-3417, 1985. 

Cetyltrimethylammonium 4-vinylbenzoate (33) forms rod-like micelles that can be stabilized by radical polymerization. The resulting structure, was observed by small-angle neutron scattering to retain its original rod-like architecture and showed enhanced thermal stability and did not dissociate upon dilution. 

Time-resolved in situ Small Angle Neutron Scattering (SANS) investigations have provided direct experimental evidence for the initial steps in the formation of the SBA-15 mesoporous material, prepared using the non-ionic tri-block copolymer Pluronic 123 and TEOS as silica precursor. Upon time, three steps take place during the cooperative self-assembly of the Pluronic micelles and the silica species. First, the hydrolysis of TEOS is completed, without modifications of the Pluronic spherical micelles. Then, when silica species begin to interact with the micelles, a transformation from spherical to cylindrical micelles takes place before the precipitation of the ordered SBA-15 material. Lastly, the precipitation occurs and hybrid cylindrical micelles assemble into the two-dimensional hexagonal structure of SBA-15. 

Figure 2 Evolution of the neutron scattering intensities with time. Only spherical micelles of P123 block copolymer are present in the synthesis mixture within the first few minutes of the reaction (300 s), during the hydrolysis of the silica precursor. Then, hybrid organic-inorganic cylindrical micelles are detected (300-1400 s). The SBA-15 hexagonal phase is formed when the precipitation occurs, after 1400 s.

Finally, we have designed and synthesized a series of block copolymer surfactants for C02 applications. It was anticipated that these materials would self-assemble in a C02 continuous phase to form micelles with a C02-phobic core and a C02-philic corona. For example, fluorocarbon-hydrocarbon block copolymers of PFOA and PS were synthesized utilizing controlled free radical methods [104]. Small angle neutron scattering studies have demonstrated that block copolymers of this type do indeed self-assemble in solution to form multimolecular micelles [117]. Figure 5 depicts a schematic representation of the micelles formed by these amphiphilic diblock copolymers in C02. Another block copolymer which has proven useful in the stabilization of colloidal particles is the siloxane based stabilizer PS-fr-PDMS [118,119]. Chemical... 

Regioselective crosslinking of the core domain of cylindrically shaped, wormlike micelles composed of poly[(butadiene)45-b-(ethylene oxide)55] and assembled in aqueous solution at < 5% block copolymer concentrations, was performed using radical coupling of the double bonds throughout the poly(butadiene) phase [27] (Figure 6.3b). This resulted in a 13% reduction in the core diameter, from 14.2 to 12.4 nm, as measured by small-angle neutron scatter-... 

Holt, C., de Kruif C.G., Tuinier, R., Timmins, P.A. (2003). Substructure of bovine casein micelles by small-angle X-ray and neutron scattering. Colloids and Surfaces A Physicochemical and Engineering Aspects, 213, 275-284. 

Thurn, A., Burchard, W., Niki, R. (1987a). Structure of casein micelles. I. Small-angle neutron scattering and light scattering from p- and K-casein. Colloid and Polymer Science, 265, 653-666. 

Bewersdorff HW, Frings B, Lindner P, Oberthuer RC (1986) The conformation of drag reducing micelles from small-angle-neutron-scattering experiments Rheol Acta 25 642... 

Fig. 3.2 Small-angle neutron scattering intensity as a function of wave vector magnitude for a rfPS-PB diblock forming micelles in PB, c = 5x l(T2gcm 3. Symbols, experimental results line, theoretical scattering profile for a uniform sphere (Selb et al. 1983).

Fig. 4.1 Top schematic illustration of micellar phases formed by the Pluronic copolymer P85 (PE 026PP0i9 PEO,6) with increasing temperature. Bottom small-angle neutron scattering patterns from sheared solutions in D20 of this copolymer (25wt%). The three columns (left-right) correspond to a liquid spherical micelle phase at 25 °C, a cubic phase of spherical micelles at 27 °C and a hexagonal phase of rod-like micelles at 68 °C (Mortensen 1993a).

Fig. 4.8 Micelle volume fraction () versus polymer concentration at different temperatures for solutions of PEO26PPO39PEO26 in D20 (Mortensen 1993a). 4> was obtained from fits of the hard sphere Percus-Yevick model to neutron scattering profiles (see Fig. 3.9). At high concentration the asymptote = for hard sphere crystallization is reached.

Whitmore and Noolandi (1985b) developed the self-consistent field theory to examine micellization in AB diblocks in a blend of AB diblock and A homopolymer solvent . The model was applied specifically to the case of PS-PB diblocks in PB homopolymer for comparison with the results of small-angle neutron scattering (SANS) experiment by Selb et al. (1983). This model is discussed in more detail in Section 3.4.2. 

Figure 1. Guinier plot of SANS for casein sub-micelles in 0.07 M NaCl solution in D20. Protein concentration is 16.1 mg/ml. I is coherent neutron scattered intensity.

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