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Towards redox active liquid crystalline phases of lipids: a monoolein/water system with entrapped derivatives of ferrocene

Barauskas, Justas LU ; Razumas, V ; Talaikyte, Z ; Bulovas, A ; Nylander, Tommy LU ; Tauraite, D and Butkus, E (2003) In Chemistry and Physics of Lipids 123(1). p.87-97
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... (More)
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 I and 3 indicates very similar phase behavior to that of the MO/2/H2O 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 Q224 phase, derivatives 1-3 exhibit electrochemical activity on the gold electrode. The one-electron redox conversion processes are electro-chemically 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 lo

er 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. (C) 2003 Elsevier Science Ireland Ltd. All rights reserved. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
1-Monooleoylglycerol, Ferrocene derivatives, Phase diagram, Swelling behavior, Electrochemical activity
in
Chemistry and Physics of Lipids
volume
123
issue
1
pages
87 - 97
publisher
Elsevier
external identifiers
  • wos:000182181900008
  • pmid:12637167
  • scopus:0037334840
ISSN
0009-3084
DOI
10.1016/S0009-3084(02)00170-6
language
English
LU publication?
yes
id
6cdd7287-d2fb-4ac2-bafa-c8c5845eb33c (old id 121930)
date added to LUP
2016-04-01 15:39:53
date last changed
2022-04-14 23:18:29
@article{6cdd7287-d2fb-4ac2-bafa-c8c5845eb33c,
  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)<br/><br>
and cubic Q(230) phase of MO can accommodate relatively high amounts ( &gt; 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 --&gt; reversed bicontinuous cubic phase (Q(II)) H-II transitions depending upon hydration. A rough study of the MO system containing compounds I and 3 indicates very similar phase behavior to that of the MO/2/H2O 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 Q224 phase, derivatives 1-3 exhibit electrochemical activity on the gold electrode. The one-electron redox conversion processes are electro-chemically 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 lo<br/><br>
er 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. (C) 2003 Elsevier Science Ireland Ltd. All rights reserved.}},
  author       = {{Barauskas, Justas and Razumas, V and Talaikyte, Z and Bulovas, A and Nylander, Tommy and Tauraite, D and Butkus, E}},
  issn         = {{0009-3084}},
  keywords     = {{1-Monooleoylglycerol; Ferrocene derivatives; Phase diagram; Swelling behavior; Electrochemical activity}},
  language     = {{eng}},
  number       = {{1}},
  pages        = {{87--97}},
  publisher    = {{Elsevier}},
  series       = {{Chemistry and Physics of Lipids}},
  title        = {{Towards redox active liquid crystalline phases of lipids: a monoolein/water system with entrapped derivatives of ferrocene}},
  url          = {{http://dx.doi.org/10.1016/S0009-3084(02)00170-6}},
  doi          = {{10.1016/S0009-3084(02)00170-6}},
  volume       = {{123}},
  year         = {{2003}},
}