TY - JOUR
T1 - Solution complexation behaviour of 1,3,5-trioxycyclohexane based ligands and their evaluation as ionophores for group IA/IIA metal cations
AU - Reany, Ofer
AU - Blair, Stephanie
AU - Kataky, Ritu
AU - Parker, David
PY - 2000/4
Y1 - 2000/4
N2 - A new series of cis,cis-cyclohexane-1,3,5-triol derivatives bearing one, two and three carbamoylalkyl substituents is reported. Ring interconversion promoted by intramolecular hydrogen bonding is observed for the mono- and di-alkylated derivatives 3 and 4 depending on solvent polarity. 1H NMR parameters obtained have allowed the calculation of the Gibbs free energy change (ΔG0) for the trioxa-equatorial ↔ trioxa-axial equilibrium, modelling the conformational changes promoted by ion binding. Selectivity coefficients have been assessed electrochemically using fixed interference methods for the detection of biologically relevant IA/IIA metal cations. Ionophore 4 displays a Nernstian response towards the detection of Ca2+ and logKCa,Mpot values are calculated. Solution NMR studies confirm the formation of 1:1 complexes for 4 with lithium, while 2:1 complexation is favoured with Ca2+. Detailed ES-MS studies performed under controlled conditions revealed similar trends in ion binding.
AB - A new series of cis,cis-cyclohexane-1,3,5-triol derivatives bearing one, two and three carbamoylalkyl substituents is reported. Ring interconversion promoted by intramolecular hydrogen bonding is observed for the mono- and di-alkylated derivatives 3 and 4 depending on solvent polarity. 1H NMR parameters obtained have allowed the calculation of the Gibbs free energy change (ΔG0) for the trioxa-equatorial ↔ trioxa-axial equilibrium, modelling the conformational changes promoted by ion binding. Selectivity coefficients have been assessed electrochemically using fixed interference methods for the detection of biologically relevant IA/IIA metal cations. Ionophore 4 displays a Nernstian response towards the detection of Ca2+ and logKCa,Mpot values are calculated. Solution NMR studies confirm the formation of 1:1 complexes for 4 with lithium, while 2:1 complexation is favoured with Ca2+. Detailed ES-MS studies performed under controlled conditions revealed similar trends in ion binding.
UR - https://www.scopus.com/pages/publications/0034175169
U2 - 10.1039/a909906i
DO - 10.1039/a909906i
M3 - Journal article
AN - SCOPUS:0034175169
SN - 0300-9580
SP - 623
EP - 630
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
IS - 4
ER -