Online citations, reference lists, and bibliographies.
Referencing for people who value simplicity, privacy, and speed.
Get Citationsy
← Back to Search

Hydrophobically Modified Amphiphilic Block Copolymer Micelles In Non-Aqueous Polar Solvents. Fluorometric, Light Scattering And Computer-Based Monte Carlo Study

Pavel Matějíček, Filip Uhlík, Zuzana Limpouchová, Karel Procházka, Zdeněk Tuzar, Stephen E. Webber

Save to my Library
Download PDF
Analyze on Scholarcy Visualize in Litmaps
Share
Reduce the time it takes to create your bibliography by a factor of 10 by using the world’s favourite reference manager
Time to take this seriously.
Get Citationsy
The micellization behavior of a hydrophobically modified polystyrene-block-poly(methacrylic acid) diblock copolymer, PS-N-PMA-A, tagged with naphthalene between blocks and with anthracene at the end of the PMA block, was studied in 1,4-dioxane-methanol mixtures by light scattering and fluorescence techniques. The behavior of a single-tagged sample, PS-N-PMA, and low-molar-mass analogues was studied for comparison. Methanol-rich mixtures with 1,4-dioxane are strong selective precipitants for PS. Multimolecular micelles with compact PS cores and PMA shells may be prepared indirectly by dialysis from 1,4-dioxane-rich mixtures, or by a slow titration of copolymer solutions in 1,4-dioxane-rich solvents with methanol under vigorous stirring. In tagged micelles, the naphthalene tag is trapped in nonpolar and fairly viscous core/shell interfacial region. In hydrophobically modified PS-N-PMA-A micelles, the hydrophobic anthracene at the ends of PMA blocks tends to avoid the bulk polar solvent and buries in the shell. The distribution of anthracene tags in the shell is a result of the enthalpy-to-entropy interplay. The measurements of direct nonradiative excitation energy transfer were performed to estimate the distribution of anthracene-tagged PMA ends in the shell. The experimental fluorometric data show that anthracene tags penetrate into the inner shell in methanol-rich solvents. Monte Carlo simulations were performed on model systems to get reference data for analysis of time-resolved fluorescence decay curves. A comparison of experimental and simulated decays indicates that hydrophobic traps return significantly deep into the shell (although not as deep as in aqueous media). The combined light scattering, fluorometric and computer simulation study shows that the conformational behavior of shell-forming PMA blocks in non-aqueous media is less affected by the presence of nonpolar traps than that in aqueous media.