Abstract
Using the ESR method in combination with the stop-flow technique the kinetics of crystal complex formation of hydrophobic nitroxide radicals with cyclodextrins has been studied upon mixing cyclodextrin aqueous solutions with nitroxides emulsified in aqueous milieu. The α β- and γ-cyclodextrins and the piperidine nitroxide radicals with a OC(O)CmH2m+i (m = 7, 10, and 17) substituent in a para-position were used. It was established that the complexation process in the system emulsion of probe–cyclodextrin solution consists of two mainstages. The first stage is the transfer of probes from drops into aqueous solution and the formation of complexes RCn, where R is the probe, C is cyclodextrin, n = 1, 2 and 3. The second stage is crystal complex formation and growth from solution of RCn complexes. The results obtained indicate that mainly RC3 complexes take part in crystallization. It was observed that the characteristic time of crystallization is approximately inversely proportional to the concentration of RC3 complexes.Equilibrium constants of the processes R + C ⇄ RC, RC + C ⇄ RC2 have been determined. It was found that complexation and further crystallization lead to the formation of monodispersed microcrystals.
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