Ferutinin as a Ca(2+) complexone: lipid bilayers, conductometry, FT-IR, NMR studies and DFT-B3LYP calculations.
Calcium ionophoretic properties of ferutinin were re-evaluated in solvent-containing bilayer lipid membranes. The slopes of conductance-concentration curves suggest that in the presence of a solvent in the membrane the majority of complexes appear to consist of a single terpenoid molecule bound to one Ca ion. By contrast, the stoichiometry of ferutinin-Ca(2+) complexes in acetone determined using the conductometric method was 2 : 1. While the cation-cation selectivity of ferutinin did not change, the cation-anion selectivity slightly decreased in solvent containing membranes. FT-IR and NMR data together with DFT calculations at the B3LYP/6-31G(d) level of theory indicate that in the absence of Ca ions ferutinin molecules are hydrogen-bonded at the phenol hydroxyl groups. The variations of absorption assigned to -OH and -C-O stretching mode suggest that ferutinin interacts strongly with Ca ions via the hydroxyl group of ferutinol and carboxyl oxygen of the complex ether bond. The coordination through the carbonyl group of ferutinin was demonstrated by theoretical calculations. Taken together, ferutinin molecules form H-bonded dimers, while complexation of Ca(2+) by ferutinin ruptures this hydrogen bond due to spatial re-orientation of the ferutinin molecules from parallel to antiparallel alignment.
Institute of Chemistry, University of Bialystok, Poland.
A
A
Dubis
M V
MV
Zamaraeva
L
L
Siergiejczyk
O
O
Charishnikova
V
V
Shlyonsky
D001565:Benzoates / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D002118:Calcium / Q000737:chemistry*; D003217:Conductometry; D056831:Coordination Complexes / Q000737:chemistry*; D003508:Cycloheptanes / Q000737:chemistry*; D006860:Hydrogen Bonding; D007477:Ions / Q000737:chemistry; D008051:Lipid Bilayers / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D012717:Sesquiterpenes / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
D001565:Benzoates; D001643:Bridged Bicyclo Compounds; D056831:Coordination Complexes; D003508:Cycloheptanes; D007477:Ions; D008051:Lipid Bilayers; D012717:Sesquiterpenes; C111068:4-oxy-6-(4-oxybezoyloxy)dauc-8,9-en; D002118:Calcium