Structure and electrochemistry of self-organized fullerene-lipid bilayer films.
The unique properties of C(60)-bearing artificial lipids with three C(16) (lipid 1), C(14) (lipid 2), or C(12) (lipid 3) alkyl chains have been characterized by a variety of techniques, including (13)C NMR, UV/Vis, and FT-IR spectroscopies, differential scanning calorimetry (DSC), X-ray diffraction, and electrochemistry. The (13)C NMR and UV/Vis spectra show that the lipids 1-3 have a closed aziridine structure at a 6/6-ring junction of C(60). The DSC data reveal that cast films of 1 exhibit two endothermic peaks at temperature ranges of 35-40 degrees C (main transition) and 47-49 degrees C (subtransition) in air, water, and 0.5 M aqueous tetraethylammonium chloride solution, while cast films of 2 and 3 each display one endothermic peak at 50-57 degrees C. The results of temperature-dependent FT-IR and UV/Vis studies of cast films of 1-3, together with the above data, reveal that the main peak in the DSC thermogram of a film of 1 can be attributed to a typical phase transition as seen in lipid bilayer membranes, while the sub-endothermic peak seen with 1 and the peaks for 2 and 3 stem from a change in the orientation of the C(60) moieties. X-ray diffraction patterns of each of the cast films of 1-3 show a diffraction peak corresponding to the (001) plane, suggesting the formation of molecular bilayer membrane structures. Cyclic voltammograms and Osteryoung square-wave voltammograms obtained from cast films of 1-3 on basal plane pyrolytic graphite (BPG) electrodes show strong temperature dependences. Finally, the thermodynamics of the binding of nine different alkylammonium ions and two alkylphosphonium ions to the electrogenerated radical monoanions and dianions of 1-3 cast on electrodes is described.
Nakanishi
Takashi
T
Department of Materials Science, Graduate School of Science and Technology, Nagasaki University, Bunkyo, Nagasaki 852-8521, Japan.
Morita
Makoto
M
Murakami
Hiroto
H
Sagara
Takamasa
T
Nakashima
Naotoshi
N
D002244:Carbon / Q000737:chemistry*; D004563:Electrochemistry; D037741:Fullerenes; D007477:Ions / Q000737:chemistry; D007700:Kinetics; D008051:Lipid Bilayers / Q000138:chemical synthesis / Q000737:chemistry*; D008563:Membrane Lipids / Q000737:chemistry; D008968:Molecular Conformation; D015394:Molecular Structure; D012995:Solubility; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D013696:Temperature
D037741:Fullerenes; D007477:Ions; D008051:Lipid Bilayers; D008563:Membrane Lipids; D002244:Carbon; C069837:fullerene C60