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ABSTRACT: Aqueous phase behavior of lipids with isoprenoid type hydrophobic chains (hereafter referred to as "isoprenoid-chained lipids") as functions of the chain length and the hydrophilic headgroup type has been examined over a chain length span from 12 to 16 carbon atoms long and a temperature range from -40 to 65 degrees C by using optical microscopy, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering) techniques. Characteristic phase behavior that arises from the unique "isoprenoid-chain" structure was discussed. This work together with previous studies (Prog. Colloid Polym. Sci. 2004, 123, 56-60 and J. Phys. Chem. B 2008, 112, 12286-12296) has clarified the molecular correlation of the aqueous phase behavior of "isoprenoid-chained lipids" over the chain lengths from 12 to 18 carbon atoms and introduced a new lipid library which can form a range of liquid crystals, such as an HII (an inverted hexagonal phase), a QII (an inverted cubic phase), and an Lalpha (a lamellar phase), that are stable over a wide temperature span from 0 degrees C.
The Journal of Physical Chemistry B 08/2009; 113(30):10196-209. · 3.70 Impact Factor
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ABSTRACT: With a view to discovering a new family of lipids that form inverted cubic phases, the aqueous phase behavior of a series of lipids with isoprenoid-type hydrophobic chains has been examined over a temperature range from -40 to 65 degrees C by using optical microscopy, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering) techniques. The lipids examined are those with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains linked to a series of headgroups, that is, erythritol, pentaerythritol, xylose, and glucose. All of the lipid/water systems displayed a "water + liquid crystalline phase" two-phase coexistence state when sufficiently diluted. The aqueous phase structures of the most diluted liquid crystalline phases in equilibrium with excess water depend both on the lipid molecular structure and on the temperature. Given an isoprenoid chain, the preferred phase consistently follows a phase sequence of an H II (an inverted hexagonal phase) to a Q II (an inverted bicontinuous cubic phase) to an L alpha (a lamellar phase) as A* (cross-section area of the headgroup) increases. For a given lipid/water system, the phase sequence observed as the temperature increases is L alpha to Q II to H II. The present study allowed us to find four cubic phase-forming lipid species, PEOC 18+4 [mono- O-(5,9,13,17-tetramethyloctadecyl)pentaerythritol], beta-XylOC 18+4 [1- O-(5,9,13,17-tetramethyloctadecyl)-beta- d-xylopyranoside], EROCOC 17+4 [1- O-(5,9,13,17-tetramethyloctadecanoyl)erythritol], and PEOCOC 17+4 [mono- O-(5,9,13,17-tetramethyloctadecanoyl)pentaerythritol]. The values of T K (hydrated solid-liquid crystalline phase transition temperature) of the cubic phase-forming lipids are all below 0 degrees C. Quantitative analyses of the lipid molecular structure-aqueous phase structure relationship in terms of the experimentally evaluated "surfactant parameter" allow us to rationally select an optimum combination of hydrophilic/hydrophobic part of a lipid molecule that will form a desired phase in a desired temperature range.
The Journal of Physical Chemistry B 10/2008; 112(39):12286-96. · 3.70 Impact Factor
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ABSTRACT: Mixtures of amphiphilic cholesteryl phosphate (CP), sitosteryl phosphate (SP), or cholesteryl phosphocholine (CPC) with the nonphosphoryl diacyl lipid dimyristoylglycerol (DMG) or with cholesterol give self-organized systems (giant vesicles) in a wide range of pH, as demonstrated by fluorescence microscopy, differential scanning calorimetry, and small-angle X-ray scattering. The water permeability of a 1 : 1 molar mixture of CPC and DMG was also measured by a stopped-flow/light-scattering method. The novel self-organized systems are akin to natural eukaryotic ones, the only difference being the site of the phosphate-containing head-group, located on cholesterol instead of DMG. They might be present in some organisms not yet studied for the composition of their membranes.
Chemistry & Biodiversity 03/2006; 3(2):198-209. · 1.80 Impact Factor
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ABSTRACT: Two alkyl glycosides with the same type of disaccharide headgroups (melibiose) and different methyl-branched alkyl chains, short chiral [(2R,4R,6R,8R)-2,4,6,8-tetramethyldecyl, extracted from an animal source] and long nonchiral (3,7,11,15-tetramethylhexadecyl, from a plant source), were synthesized. The supramolecular aggregate structure formed in dilute solutions was investigated by small-angle neutron scattering and surface tension measurements. The lyotropic phase diagram was studied by differential scanning calorimetry and water penetration scans. The thermotropic phase behavior was investigated by polarizing microscopy. The compounds showed unusual phase behavior: (i) The liquid-crystalline polymorphism is reduced to only form smectic A phases in the pure state; the formation of lyotropic phases such as hexagonal or lamellar phases was not observed. (ii) The compound with the longer nonchiral alkyl chain is more soluble in water than the one with the shorter chiral chain, most likely because of the different flexibilities of the chains. (iii) For the long-chain compound, the formation of micelles is observed, whereas the short-chain compound forms large disklike/bilayer aggregates. The method of methylation of the chain controls the self-assembly and can explain different biological functions for either plants (variable temperature) or animals (constant temperature).
The Journal of Physical Chemistry B 03/2005; 109(4):1599-608. · 3.70 Impact Factor
