By synthesizing unique nitroxide probes (α-substituted phenyl-2,4,6-trimethoxybenzyl(t-butyl)nitroxide), we have shown that p-sulfonatocalixarene (Calix-S8) and γ-cyclodextin (γ-CD) form electron spin resonance spectroscopically separable group-inclusion complexes (α-substituted phenyl-in (R-in) and t-butyl-in complexes) and determined the group-inclusion constants of Calix-S8 and γ-CD. Using nitroxide probes, we have examined the effects of substituent and external pressure on group-inclusion complexation with Calix-S8 and γ-CD. Experiments on pressure dependence enabled us to calculate the reaction volume (ΔV) for R-in and t-butyl-in complex formations. ΔV for group-in complexation with Calix-S8 had negative values. In contrast, ΔV values for γ-CD showed positive values, which is responsible for the repelled water molecules in the CD cavity. The characteristic pressure effects on group-in complexation suggest that group recognition by γ-CD is sensitive when compared with that by Calix-S8.
|Number of pages||8|
|Journal||High Pressure Research|
|Publication status||Published - Jul 5 2014|
- high pressure ESR
ASJC Scopus subject areas
- Condensed Matter Physics