Thermotropic Behavior of Glycosphingolipids in Aqueous Dispersions

Bruno Maggio, Toshio Ariga, Julian M. Sturtevant, Robert K Yu

Research output: Contribution to journalArticle

101 Citations (Scopus)

Abstract

The thermotropic behavior of 20 chemically related glycosphingolipids (GSLs) of high purity, containing neutral and anionic carbohydrate residues in their oligosaccharide chains, was studied by high-sensitivity differential scanning calorimetry. In general, the polar head group of GSLs appears to be one of the major determinants of their phase behavior. Compared to phospholipids, the presence of the carbohydrate rather than the phosphorylcholine moiety in the polar head group and a sphingosine base in the hydrocarbon portion of GSLs reduces the effect on the transition temperature (Tm) brought about by increasing the number of methylene groups in the amide-linked fatty acyl chains. For simple neutral GSLs, the Tm's were 20-40 °C higher than those of phospholipids with comparable hydrocarbon chains. As the oligosaccharide chain of GSLs becomes more complex, the excess heat capacity, Tm, enthalpy (ΔHcal), and entropy of the transition decrease proportionally to the number of carbohydrate residues present in the polar head group. The Tm and ΔHCal for anionic GSLs were 16-25 °C and 1-3 kcal mol-1 lower than those of neutral GSLs with comparable oligosaccharide chains. A linear dependence of ΔHcal with Tm was found. However, the slopes of these plots were different for neutral and for anionic GSLs, suggesting different types of intermolecular organizations for the two. The Tm and ΔHcal were linearly dependent on the molecular area of both neutral and anionic GSLs; this indicated that the influence of the complexity of the polar head group in GSLs for establishing the thermodynamic behavior may be mediated by the intermolecular spacings.

Original languageEnglish (US)
Pages (from-to)1084-1092
Number of pages9
JournalBiochemistry
Volume24
Issue number5
DOIs
StatePublished - Feb 1 1985

Fingerprint

Glycosphingolipids
Neutral Glycosphingolipids
Dispersions
Oligosaccharides
Temperature
Carbohydrates
Hydrocarbons
Phospholipids
Sphingosine
Phosphorylcholine
Transition Temperature
Differential Scanning Calorimetry
Entropy
Thermodynamics
Amides
Phase behavior
Hot Temperature
Specific heat
Differential scanning calorimetry
Enthalpy

ASJC Scopus subject areas

  • Biochemistry

Cite this

Thermotropic Behavior of Glycosphingolipids in Aqueous Dispersions. / Maggio, Bruno; Ariga, Toshio; Sturtevant, Julian M.; Yu, Robert K.

In: Biochemistry, Vol. 24, No. 5, 01.02.1985, p. 1084-1092.

Research output: Contribution to journalArticle

Maggio, Bruno ; Ariga, Toshio ; Sturtevant, Julian M. ; Yu, Robert K. / Thermotropic Behavior of Glycosphingolipids in Aqueous Dispersions. In: Biochemistry. 1985 ; Vol. 24, No. 5. pp. 1084-1092.
@article{944471a4925643198dd1866c0edb76a6,
title = "Thermotropic Behavior of Glycosphingolipids in Aqueous Dispersions",
abstract = "The thermotropic behavior of 20 chemically related glycosphingolipids (GSLs) of high purity, containing neutral and anionic carbohydrate residues in their oligosaccharide chains, was studied by high-sensitivity differential scanning calorimetry. In general, the polar head group of GSLs appears to be one of the major determinants of their phase behavior. Compared to phospholipids, the presence of the carbohydrate rather than the phosphorylcholine moiety in the polar head group and a sphingosine base in the hydrocarbon portion of GSLs reduces the effect on the transition temperature (Tm) brought about by increasing the number of methylene groups in the amide-linked fatty acyl chains. For simple neutral GSLs, the Tm's were 20-40 °C higher than those of phospholipids with comparable hydrocarbon chains. As the oligosaccharide chain of GSLs becomes more complex, the excess heat capacity, Tm, enthalpy (ΔHcal), and entropy of the transition decrease proportionally to the number of carbohydrate residues present in the polar head group. The Tm and ΔHCal for anionic GSLs were 16-25 °C and 1-3 kcal mol-1 lower than those of neutral GSLs with comparable oligosaccharide chains. A linear dependence of ΔHcal with Tm was found. However, the slopes of these plots were different for neutral and for anionic GSLs, suggesting different types of intermolecular organizations for the two. The Tm and ΔHcal were linearly dependent on the molecular area of both neutral and anionic GSLs; this indicated that the influence of the complexity of the polar head group in GSLs for establishing the thermodynamic behavior may be mediated by the intermolecular spacings.",
author = "Bruno Maggio and Toshio Ariga and Sturtevant, {Julian M.} and Yu, {Robert K}",
year = "1985",
month = "2",
day = "1",
doi = "10.1021/bi00326a003",
language = "English (US)",
volume = "24",
pages = "1084--1092",
journal = "Biochemistry",
issn = "0006-2960",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Thermotropic Behavior of Glycosphingolipids in Aqueous Dispersions

AU - Maggio, Bruno

AU - Ariga, Toshio

AU - Sturtevant, Julian M.

AU - Yu, Robert K

PY - 1985/2/1

Y1 - 1985/2/1

N2 - The thermotropic behavior of 20 chemically related glycosphingolipids (GSLs) of high purity, containing neutral and anionic carbohydrate residues in their oligosaccharide chains, was studied by high-sensitivity differential scanning calorimetry. In general, the polar head group of GSLs appears to be one of the major determinants of their phase behavior. Compared to phospholipids, the presence of the carbohydrate rather than the phosphorylcholine moiety in the polar head group and a sphingosine base in the hydrocarbon portion of GSLs reduces the effect on the transition temperature (Tm) brought about by increasing the number of methylene groups in the amide-linked fatty acyl chains. For simple neutral GSLs, the Tm's were 20-40 °C higher than those of phospholipids with comparable hydrocarbon chains. As the oligosaccharide chain of GSLs becomes more complex, the excess heat capacity, Tm, enthalpy (ΔHcal), and entropy of the transition decrease proportionally to the number of carbohydrate residues present in the polar head group. The Tm and ΔHCal for anionic GSLs were 16-25 °C and 1-3 kcal mol-1 lower than those of neutral GSLs with comparable oligosaccharide chains. A linear dependence of ΔHcal with Tm was found. However, the slopes of these plots were different for neutral and for anionic GSLs, suggesting different types of intermolecular organizations for the two. The Tm and ΔHcal were linearly dependent on the molecular area of both neutral and anionic GSLs; this indicated that the influence of the complexity of the polar head group in GSLs for establishing the thermodynamic behavior may be mediated by the intermolecular spacings.

AB - The thermotropic behavior of 20 chemically related glycosphingolipids (GSLs) of high purity, containing neutral and anionic carbohydrate residues in their oligosaccharide chains, was studied by high-sensitivity differential scanning calorimetry. In general, the polar head group of GSLs appears to be one of the major determinants of their phase behavior. Compared to phospholipids, the presence of the carbohydrate rather than the phosphorylcholine moiety in the polar head group and a sphingosine base in the hydrocarbon portion of GSLs reduces the effect on the transition temperature (Tm) brought about by increasing the number of methylene groups in the amide-linked fatty acyl chains. For simple neutral GSLs, the Tm's were 20-40 °C higher than those of phospholipids with comparable hydrocarbon chains. As the oligosaccharide chain of GSLs becomes more complex, the excess heat capacity, Tm, enthalpy (ΔHcal), and entropy of the transition decrease proportionally to the number of carbohydrate residues present in the polar head group. The Tm and ΔHCal for anionic GSLs were 16-25 °C and 1-3 kcal mol-1 lower than those of neutral GSLs with comparable oligosaccharide chains. A linear dependence of ΔHcal with Tm was found. However, the slopes of these plots were different for neutral and for anionic GSLs, suggesting different types of intermolecular organizations for the two. The Tm and ΔHcal were linearly dependent on the molecular area of both neutral and anionic GSLs; this indicated that the influence of the complexity of the polar head group in GSLs for establishing the thermodynamic behavior may be mediated by the intermolecular spacings.

UR - http://www.scopus.com/inward/record.url?scp=0022432688&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0022432688&partnerID=8YFLogxK

U2 - 10.1021/bi00326a003

DO - 10.1021/bi00326a003

M3 - Article

C2 - 4096890

AN - SCOPUS:0022432688

VL - 24

SP - 1084

EP - 1092

JO - Biochemistry

JF - Biochemistry

SN - 0006-2960

IS - 5

ER -