Towards redox active liquid crystalline phases of lipids: a monoolein/water system with entrapped derivatives of ferrocene.
Chem Phys Lipids
; 123(1): 87-97, 2003 Mar.
Article
in En
| MEDLINE
| ID: mdl-12637167
ABSTRACT
The phase and electrochemical behavior of the aqueous mixtures of monoolein (MO) and synthetic ferrocene (Fc) derivatives containing long alkyl chains-(Z)-octadec-9-enoylferrocene (1), (Z)-octadecen-9-ylferrocene (2), and ferrocenylmethyl (Z)-octadec-9-enoate (3)-were studied. At low hydration, the reversed micelles (L(2) phase) and cubic Q(230) phase of MO can accommodate relatively high amounts (>6 wt.%) of the Fc-derivative 2, whereas at high hydration, the pseudoternary cubic phase Q(224) is destabilized even at about 2 wt.% of this Fc. Increasing the Fc-derivative content induces L(alpha)-->L(2) and L(alpha)-->reversed bicontinuous cubic phase (Q(II))-->H(II) transitions depending upon hydration. A rough study of the MO system containing compounds 1 and 3 indicates very similar phase behavior to that of the MO/2/H(2)O system. Compound 2 apparently has no effect on the lipid monolayer thickness in the pseudoternary L(alpha), H(II) and Q(II) liquid crystalline phases of MO. Within a 3D-structure of the Q(224) phase, derivatives 1-3 exhibit electrochemical activity on the gold electrode. The one-electron redox conversion processes are electrochemically quasi-reversible and controlled by diffusion. The values of apparent diffusion coefficient (D(app)) and heterogeneous electron-transfer rate constant (k(s)) of Fcs are significantly lower in the cubic phase matrix when compared to the acetonitrile solution. By contrast, the MO H(II) phase with entrapped Fc-derivatives does not exhibit electrochemical activity on the electrode surface. It is suggested that the diffusional anisotropy and/or localized aggregation of compounds 1-3 within a 2D-structure of the H(II) phase account(s) for the latter observation.
Search on Google
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Water
/
Ferrous Compounds
/
Crystallization
/
Crystallography
/
Glycerides
/
Micelles
Language:
En
Journal:
Chem Phys Lipids
Year:
2003
Type:
Article
Affiliation country:
Lithuania