Different phase behaviour of the sn-1 and sn-3 stereoisomers of the glycolipid di-tetradecyl-β-d-galactosylglycerol

Kuttenreich, H.; Hinz, Hans‐Jürgen; Koynova, Rumiana; Tenchov, Boris

doi:10.1016/0009-3084(93)90031-w

Cited by 21 publications

(1 citation statement)

References 23 publications

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“…Therefore, there is a demand for synthetic substitutes, such as GLs, which are cheap, renewable, biodegradable, nonionic, and environmentally friendly. The investigation of lyotropic mesophases formed by synthetic GLs is important not only for their technological relevance but also from a fundamental perspective because of their diverse functions in nature. ,− The effects of the sugar size, chirality, and subtle stereochemical changes of a single OH group in the pyranose ring have been widely studied, and these factors may significantly alter the stability of the phases and the nature of the phase transitions of these lipids. − …”

Section: Introductionmentioning

confidence: 99%

Investigation of the Effect of Sugar Stereochemistry on Biologically Relevant Lyotropic Phases from Branched-Chain Synthetic Glycolipids by Small-Angle X-ray Scattering

et al. 2013

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Synthetic branched-chain glycolipids are suitable as model systems in understanding biological cell membranes, particularly because certain natural lipids possess chain branching. Herein, four branched-chain glycopyranosides, namely, 2-hexyl-decyl-α-D-glucopyranoside (α-Glc-OC10C6), 2-hexyl-decyl-β-D-glucopyranoside (β-Glc-OC10C6), 2-hexyl-decyl-α-D-galactopyranoside (α-Gal-OC10C6), and 2-hexyl-decyl-β-D-galactopyranoside (β-Gal-OC10C6), with a total alkyl chain length of 16 carbon atoms have been synthesized, and their phase behavior has been studied. The partial binary phase diagrams of these nonionic surfactants in water were investigated by optical polarizing microscopy (OPM) and small-angle X-ray scattering (SAXS). The introduction of chain branching in the hydrocarbon chain region is shown to result in the formation of inverse structures such as inverse hexagonal and inverse bicontinuous cubic phases. A comparison of the four compounds showed that they exhibited different polymorphism, especially in the thermotropic state, as a result of contributions from anomeric and epimeric effects according to their stereochemistry. The neat α-Glc-OC10C6 compound exhibited a lamellar (Lα) phase whereas dry α-Gal-OC10C6 formed an inverse bicontinuous cubic Ia3d (QII(G)) phase. Both β-anomers of glucoside and galactoside adopted the inverse hexagonal phase (HII) in the dry state. Generally, in the presence of water, all four glycolipids formed inverse bicontinuous cubic Ia3d (QII(G)) and Pn3m (QII(D)) phases over wide temperature and concentration ranges. The formation of inverse nonlamellar phases by these Guerbet branched-chain glycosides confirms their potential as materials for novel biotechnological applications such as drug delivery and crystallization of membrane proteins.

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Section: Introductionmentioning

confidence: 99%

Investigation of the Effect of Sugar Stereochemistry on Biologically Relevant Lyotropic Phases from Branched-Chain Synthetic Glycolipids by Small-Angle X-ray Scattering

et al. 2013

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Lyotropic Phase Behaviour of Biological Amphiphiles

Seddon

1996

Ber Bunsenges Phys Chem

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Kinetics of glycolipid phase transitions: ms laser T‐jump synchrotron studies

Köberl

Hinz

Rappolt

et al. 1997

Ber Bunsenges Phys Chem

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The kinetics of the lamellar gel (Lp) to inverse hexagonal (Hll) phase transition as well as the L,+La phase change of aqueous suspensions of glycolipids were characterized using ms laser T-jump techniques in combination with synchrotron X-ray diffraction. The glycolipids employed were 1,2-di-O-alkyl-3-0-P-D-glucosyl-snglycerols with identical alkyl chains of 16 and 18 carbon atoms, respectively, and 1,2-di-O-alky1-3-O-P-D-galactosyl-sn-glycerol with C,, chains. The time course of the Lc-+La phase transition was probed using 1,2-di-O-hexadecyl-3-O-~-D-lactosyl-sn-glycerol, whose head group consists of the disaccharide P-D-galactopyranosyl-(1 -4)-P-D-glucopyranoside. Surprisingly the phase change from the lamellar to the inverse hexagonal topology is very fast despite the major structural changes involved in the lipid-water interface. The overall phase change of both glucolipids can be quantitatively described by a sequential mechanism of the type Lp A I A HIl.The intermediate I is thinner than both the Lp and the HI, phases. It has a relatively broad distribution of d-spacings and relaxes into the HI, phase with half times of approximately 125 ms (16-1,Z-Glc) and 244 ms (18-1,2-Glc), respectively. Both rate constants, k, and k,, are chain length dependent.The galactolipid transforms into the HI, phase following a sequential mechanism of the type Lg & I' % I & HII. The additional intermediate I' can be assigned to a lamellar phase bearing similarity to a thin La phase. The specific features of the galactose head group compared to glucose as head group that have been previously observed in equilibrium studies are also evident in the kinetic mechanism in that comparative structural changes in the intermediates are slower in the galactolipid than in the chain-homologous glucolipid.There is evidence from the X-ray data that the general transition mechanism is identical for gluco-and galactolipids. However, the first intermediate I' disappears too fast in the glucolipid phase change to be detectable with the present time resolution of the X-ray measurements.The kinetics of the phase change of the lactolipid is characterized within the resolution of the X-ray sequence (5ms) by a strict two-state mechanism L, --t La with transient coexistence of the initial and final phase during the kinetic phase transformation. The relaxation time has been found to be highly temperature dependent, being 57 ms at 79.1 "C and 14 ms at 81.1 "C.It is worth noting that there appears to be a principal difference in the phase change mechanism between glycolipids with mono-or disaccharide head groups in that the latter (16-1.2-Lac) shows no sign of any kinetic intermediate state. k k k k arrangements of the lipids, as seen in the HI, phase formed by a variety of lipids [8 -101. Prominent members of these lipids that form readily non-bilayer structures are glycolipids, both synthetic and natural, provided they have head groups that are small in surface area in comparison to the hydrophobic part of the molecule [l I]. Glycolipids show the most s...

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Different phase behaviour of the sn-1 and sn-3 stereoisomers of the glycolipid di-tetradecyl-β-d-galactosylglycerol

Cited by 21 publications

References 23 publications

Investigation of the Effect of Sugar Stereochemistry on Biologically Relevant Lyotropic Phases from Branched-Chain Synthetic Glycolipids by Small-Angle X-ray Scattering

Investigation of the Effect of Sugar Stereochemistry on Biologically Relevant Lyotropic Phases from Branched-Chain Synthetic Glycolipids by Small-Angle X-ray Scattering

Lyotropic Phase Behaviour of Biological Amphiphiles

Kinetics of glycolipid phase transitions: ms laser T‐jump synchrotron studies

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