Pulsed laser-induced polymerization (PLP) in combination with analysis of formed polymer
by size exclusion chromatography (SEC) has been successfully applied in determining propagation rate
coefficient, k
p, of acrylic and methacrylic acid in organic solvents and water. For methacrylic acid solution
polymerization in methanol and in dimethyl sulfoxide (DMSO), minor but not negligible variations of k
p
with solvent have been observed. In contrast, k
p values for polymerizations in water are significantly
influenced by the solvent and furthermore by monomer concentration. The k
p values obtained from
polymerization experiments in water are significantly larger than the corresponding values obtained in
methanol or DMSO. Weighted nonlinear least-squares fitting (NLLS) has been applied to calculate
frequency factors, A, and activation energies, E
a, from the temperature dependence of k
p for methacrylic
acid in methanol, DMSO, and water in order to underline the reliability of the data. For acrylic acid it
turns out that optimized experimental conditions have to be chosen in order to determine reliable k
p
values at ambient temperature. Laser pulse repetition rates of at least 90 Hz are necessary to ensure
that “termination by the laser pulse” is the main chain stopping event. Smaller values of the laser pulse
repetition rate will not yield reliable k
p data. Furthermore, evidence of at least one first overtone inflection
point at L
2 ≈ 2L
1 is not only recommended, it is necessary to ensure a reliable measure of k
p. This is the
most important consistency criterion showing that experimental conditions are suitable.
Silica‐coated vesicles have been produced by the deposition of silica onto unilamellar vesicles from aqueous solution for the first time. The quaternary ammonium surface of the surfactant vesicles is receptive to silica and facilitates deposition of up to 5–10 nm of it. The “petrified” vesicles are stable to dehydration and can be visualized by conventional TEM (see Figure) without additional staining agents.
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