Kinetic model for Ostwald's rule of stages with applications to Boc-diphenylalanine self-assembly

A kinetic model which describes Ostwald's rule of stages, during the process of crystal growth from solution, is reported here. Reaction equations for stages are given where the stages convert from one to another. The final stage reacts to release a portion of solute back into solution, while the remainder converts to the final equilibrium form. Additionally, a remnant of the solute that was not consumed by any of the transitional stages, ultimately is converted into the final product. This particular model was motivated by a recent report for Boc-diphenylalanine self-assembly where the dissolved peptide was observed to go through two polymorphic stages before reaching the equilibrium supramolecular assembly [A. Levin et al., Nat. Commun. 5, 5219, (2014)]. Kinetic data for the concentration of solute present during the process are listed in the above-mentioned report. We show here how the model, for , describes the time-dependent behavior of the solute decay during the growth process. After comparing the model to the experimental data, we are able to report values for all of the rate constants and propose a rule whereby the relative magnitudes of these constants can be used to predict whether a supersaturated substance will noticeably pass through transitional stages or simply convert from solute to the equilibrium solid form.     

Temperature effect on the microstructure and viscoelastic properties of aqueous micellar systems of sodium <Emphasis Type="Italic">N</Emphasis>-methyl-<Emphasis Type="Italic">N</Emphasis>-oleyl taurate

The quantitative characteristics of the temperature effect on the rheological properties of aqueous solutions of the anionic surfactant sodium methyl oleyl taurate (SMOT) are presented. An increase in the intensity of thermal motion of surfactant molecules on heating from 25 to 45 °С was shown to decrease the average contour length of SMOT micelles from 2 μm to 700 nm. The decrease in the length of cylindrical micelles is probably one of the main reasons for a substantial decrease in the viscosity of micellar solutions of the surfactant with temperature.