TY - JOUR
T1 - Influence of temperature, pressure, and pH on the group-inclusion equilibrium in water soluble calixarenes
AU - Sueishi, Yoshimi
AU - Negi, Mieko
AU - Kotake, Yashige
PY - 2007/12/1
Y1 - 2007/12/1
N2 - Previously, we demonstrated, for the first time, that guest probes having more than one bulky group could produce a pair of bidirectional inclusion complexes with water soluble calixarene (Chem. Lett. 2006, 35, 772). The use of unique free radical probes and electron spin resonance has made this finding possible. In this report, we investigated thermodynamic and pH-dependent properties of the group-inclusion complex formation, i.e., the effects of temperature, pressure and the medium pH on group inclusion by p-sulfonatocalixarenes were determined. Temperature-dependence study indicated that enthalpy portions in ΔG play dominant roles in the group-in complexation. Pressure dependence experiments allowed us to calculate the reaction volumes, i.e., intrinsic volume changes related to inclusion into the calixarene cavity, which ranged from -5.1 to -16.3 cm3 mol -1. Data on pH dependence clarified the role of oxyanions in the entrant group of calixarenes. It should be emphasized that pressure-dependent study provided unique information on the structure of the group-inclusion complex.
AB - Previously, we demonstrated, for the first time, that guest probes having more than one bulky group could produce a pair of bidirectional inclusion complexes with water soluble calixarene (Chem. Lett. 2006, 35, 772). The use of unique free radical probes and electron spin resonance has made this finding possible. In this report, we investigated thermodynamic and pH-dependent properties of the group-inclusion complex formation, i.e., the effects of temperature, pressure and the medium pH on group inclusion by p-sulfonatocalixarenes were determined. Temperature-dependence study indicated that enthalpy portions in ΔG play dominant roles in the group-in complexation. Pressure dependence experiments allowed us to calculate the reaction volumes, i.e., intrinsic volume changes related to inclusion into the calixarene cavity, which ranged from -5.1 to -16.3 cm3 mol -1. Data on pH dependence clarified the role of oxyanions in the entrant group of calixarenes. It should be emphasized that pressure-dependent study provided unique information on the structure of the group-inclusion complex.
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U2 - 10.1246/bcsj.80.1932
DO - 10.1246/bcsj.80.1932
M3 - Article
AN - SCOPUS:58149287993
VL - 80
SP - 1932
EP - 1938
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 10
ER -