Suttinun Phongtamrug

A novel ion extraction material using host-guest properties of oligobenzoxazine local structure and benzoxazine monomer molecular assembly

Bisphenol-A based benzoxazine monomer (BA-m) and its oligomer are applied as an ionophore to study by Pedersens technique, the ion interaction with alkali and alkaline earth ions. Ion extraction efficiencies are significant when the solubility parameter of the organic phase is close to that of BA-m or the x-parameter is 0.34. Ionophore concentration controls the amount of metal ion extraction. Both BA-m and its oligomer show high entrapment efficiency over 70% extraction, for all types of ions.

Inclusion Compounds Formed from N,N-bis(2-hydroxybenzyl)alkylamine Derivatives and Transition Metal Ions via Molecular Assembly

A series of N,N-bis(2-hydroxybenzyl)alkylamine derivatives (1–5) have been found to form host–guest compounds with transition metal ions. The inclusion phenomena in solution are confirmed from the new peak at 415 nm observed by UV-Vis (ultraviolet-visible) spectroscopy and the aromatic and methylene peak shifts observed by 1H NMR (proton nuclear magnetic resonance) spectroscopy. Comparative studies on 1–5 by liquid–liquid extraction studies suggest that the bulky group at the aza position of the derivatives obstructs the ion interaction resulting in the decrease in ion extraction ability. Inclusion depends on the interaction of the transition metal ions with the compounds 1–5 at the aza and hydroxyl groups as identified by the two-dimensional nuclear Overhauser enhancement technique (1H–1H NOESY). The results from Jobs plot and electrospray ionization mass spectroscopy (ESIMS) imply molecular assembly of the host–guest system in a 2:1 ratio. Comparative studies among different ions, i.e., Cu2+, Zn2+ and Cd2+ suggest that the host–guest formation is effective when electron sharing is possible through the outer orbital of the transition metal ions. In the case of inclusion in the solid state, the FTIR (Fourier transform infrared) spectra show the changes in vibrational mode of the functional groups in host molecules whereas the X-ray diffraction (XRD) patterns suggest a change in the packing structure of the host molecules. After host–guest formation, the thermal stability of the host molecules decreases as a result of the change in the packing structure from a hydrogen-bonded network to one of ionic interaction with the guest.