Polymorphism of synthetic 1,2-O-β-dialkyl-3-O-β-D-galactosyl-sn-glycerols of different alkyl chain lengths

Kuttenreich, H.; Hinz, Hans‐Jürgen; Incźedy-Marcsek, M.; Koynova, Rumiana; Tenchov, Boris; Laggner, Peter

doi:10.1016/0009-3084(88)90048-5

Cited by 51 publications

(31 citation statements)

References 32 publications

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“…* *, and with the observed values of the basis vector length a (e.g., 5.62 nm ± 0.05 nm at 800C, seen for the 1,2-sn compound on cooling) is highly suggestive of a hexagonal lattice; the fact that the lattice spacing doesn't swell above certain full hydration limits Mannock [10,12,13,15] 65. strongly suggests that the lattice is of the inverse, HII type. This is supported by the DSC, the chemical structure of the lipid and diffraction studies of chemically similar lipids (33,(40)(41)(42)(43)(44)47).…”

Section: Methodsmentioning

confidence: 70%

“…3, Table 2). Likewise, changing the orientation ofthe OH4 ofthe sugar ring from equatorial to axial produces the corresponding f-GalDAGs with L,6/La Tm's similar to those of the fl-GlcDAGs (33,50) (Table 1). A comparison of the thermodynamic and x-ray diffraction data obtained for several phospholipid stereoisomers (Tables 1 and 2) shows that neither the chain-melting phase transition or the dimensions of the L,, and La phases depend significantly on the chirality of the glycerol backbone.…”

Section: Methodsmentioning

confidence: 96%

“…Thus, with glyceroglycolipids, which are known to form both lamellar and nonlamellar structures, the addition of a chiral center at C5 of each sugar molecule might be expected to produce differences in the physical properties of the 1,2-sn and 2,3-sn glycerol isomers. However, so far the biophysical studies of the dialkyl glycolipids have concentrated on a small number of 1,2-di-O-alkyl-3-0-(f-D-glucopyranosyl)- (28)(29)(30)(31)(32) and -(f-D-galactopyranosyl)-sn-glycerols ( 33) and a few impure diastereomeric mixtures (34,35), and have not investigated the properties ofthe naturally occurring 2,3-sn stereoisomers.…”

Section: Introductionmentioning

confidence: 99%

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Effect of the chirality of the glycerol backbone on the bilayer and nonbilayer phase transitions in the diastereomers of di-dodecyl-beta-D-glucopyranosyl glycerol

Mannock¹,

Lewis²,

McElhaney³

et al. 1992

Biophysical Journal

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We have studied the physical properties of aqueous dispersions of 1,2-sn- and 2,3-sn-didodecyl-beta-D-glucopyranosyl glycerols, as well as their diastereomeric mixture, using differential scanning calorimetry and low angle x-ray diffraction. Upon heating, both the chiral lipids and the diastereomeric mixture exhibit characteristically energetic L beta/L alpha phase transitions at 31.7-32.8 degrees C and two or three weakly energetic thermal events between 49 degrees C and 89 degrees C. In the diastereomeric mixture and the 1,2-sn glycerol derivative, these higher temperature endotherms correspond to the formation of, and interconversions between, several nonlamellar structures and have been assigned to L alpha/QIIa, QIIa/QIIb, and QIIb/HII phase transitions, respectively. The cubic phases QIIa and QIIb, whose cell lattice parameters are strongly temperature dependent, can be identified as belonging to space groups Ia3d and Pn3m/Pn3, respectively. In the equivalent 2,3-sn glucolipid, the QIIa phase is not observed and only two transitions are seen at 49 degrees C and 77 degrees C, which are identified as L alpha/QIIb and QIIb/HII phase transitions, respectively. These phase transitions temperatures are some 10 degrees C lower than those of the corresponding phase transitions observed in the diastereomeric mixture and the 1,2-sn glycerol derivative. On cooling, all three lipids exhibit a minor higher temperature exothermic event, which can be assigned to a HII/QIIb phase transition. An exothermic L alpha/L beta phase transition is observed at 30-31 degrees C. A shoulder is sometimes discernible on the high temperature side of the L alpha/L beta event, which may originate from a QIIb/L alpha phase transition prior to the freezing of the hydrocarbon chains. None of the lipids show evidence of a QIIa phase on cooling. No additional exothermic transitions are observed on further cooling to -3 degrees C. However, after nucleation at 0 degrees C followed by a short period of annealing at 22 degrees C, the 1,2-sn glucolipid forms an Lc phase that converts to an L alpha phase at 39.5 degrees C on heating. Neither the diastereomeric mixture nor the 2,3-sn glycerol derivative shows such behavior even after extended periods of annealing. Our results suggest that the differences in the phase behavior of these glycolipid isomers may not be attributable to headgroup size per se, but rather to differences in the stereochemistry of the lipid polar/apolar interfacial region, which consequently effects hydrogen-bonding, hydration, and the hydrophilic/hydrophobic balance.

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Section: Methodsmentioning

confidence: 70%

Section: Methodsmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

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Effect of the chirality of the glycerol backbone on the bilayer and nonbilayer phase transitions in the diastereomers of di-dodecyl-beta-D-glucopyranosyl glycerol

Mannock¹,

Lewis²,

McElhaney³

et al. 1992

Biophysical Journal

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“…Previous microcalorimetric, densimetric and X-ray equilibrium studies [19,22, 401 consistently revealed the significance of the stereochemistry of the sugar moieties for the stability and the nature of the phases adopted by the lipids in aqueous dispersion. Therefore we were anxious to investigate, whether also the kinetics of the phase changes, i.e.…”

Section: Kinetics Of the L*-'hii Phase Change Of 16-1z-galmentioning

confidence: 94%

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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“…Naturally occurring glyco-glycero-lipids normally have a Y-shaped structure (Fig. 1a) with a polar carbohydrate head group linked to a 1,2-or 1,3-di-O-acyl or alkyl-sn-glycerol (Ishizuka and Yamakawa, 1985;Minden et al, 2002a,b;Mannock et al, 1987Mannock et al, , 1990Mannock et al, , 2001Hinz et al, 1996;Six et al, 1983;Kuttenreich et al, 1988;Nagatsu et al, 1994;Minamikawa et al, 1994). But only a few compounds with an inverse structure ( Fig.…”

Section: Introductionmentioning

confidence: 96%