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. 2004 Sep;87(3):1722-31.
doi: 10.1529/biophysj.104.044529.

The 4,5-double bond of ceramide regulates its dipole potential, elastic properties, and packing behavior

Howard L Brockman  1 , Maureen M Momsen, Rhoderick E Brown, Linli He, Jiong Chun, Hoe-Sup Byun, Robert Bittman
Affiliations

The 4,5-double bond of ceramide regulates its dipole potential, elastic properties, and packing behavior

Howard L Brockman et al. Biophys J. 2004 Sep.

Abstract

The biological activities of ceramides show a large variation with small changes in molecular structure. To help understand how the structure regulates the activity of this important lipid second messenger, we investigated the interfacial features of a series of synthetic ceramide analogs in monomolecular films at the argon-buffer interface. To minimize differences arising from the N-acyl moiety, each analog had either a N-hexadecanoyl or a N-cis-4-hexadecenoyl moiety amide linked to the nitrogen of the sphingosine backbone. We found that the trans 4,5-unsaturation in the sphingosine backbone promoted closer packing and lower compressibilities of ceramide analogs in interfaces relative to comparable saturated species. Moreover, structures with this feature exhibited dipole potentials as much as 150-250 mV higher than comparable compounds lacking 4,5-unsaturation. The results support the hypothesis by M.C. Yappert and co-workers that trans unsaturation in the vicinity of C4 of the sphingoid backbone augments intramolecular hydration/hydrogen bonding in the polar region. This intramolecular hydration may allow the close packing of the ceramide molecules and engender their high dipole potentials. These properties of ceramides and their analogs may be important determinants of biological function.

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Figures

FIGURE 1
FIGURE 1
The structures and codes of d-erythro-ceramide and its analogs used in this study.
FIGURE 2
FIGURE 2
Role of C4 unsaturation in regulating the surface behavior of ceramide analogs. (A) Surface pressure-molecular isotherms and (B) dipole potential-molecular area isotherms for Δ4t(2N)16:0 (▪), ΔΔ4(2N)16:0 (•), [DE](2N)16:0 (▴), [LT](2N)16:0 (▾), and Δ4Δ5(2N)16:0 (♦).
FIGURE 3
FIGURE 3
Role of trans double bond position in the sphingoid base in regulating surface behavior of ceramide analogs. (A) Surface pressure-molecular area isotherms and (B) surface potential-molecular area isotherms for Δ15t(2N)16:0 (▪), Δ7t(2N)16:0 (•), Δ5t(2N)16:0 (▴), and Δ4t(2N)16:0 (▾).
FIGURE 4
FIGURE 4
Comparison of the surface behavior of N-4-cis-hexadecenoyl- and N-hexadecanoylceramide analogs. (A–C) Surface pressure-molecular area isotherms and (D–F) surface potential-molecular area isotherms for (A and D) Δ4t(2N)16:1 and Δ4t(2N)16:0; (B and E) Δ5t(2N)16:0 and Δ5t(2N)16:1; and (C and F) Δ15t (2N)16:0 and Δ15t(2N)16:1. Lines without symbols denote the N-hexadecanoyl species.
FIGURE 5
FIGURE 5
Role of polar headgroup structure in regulating surface behavior of ceramide analogs. (A) Surface pressure-molecular isotherms and (B) surface potential-molecular area isotherms for ΔΔ4(3N)16:0 (▪), Δ4c(3N)16:0 (•), 4OH(2N)16:0 (▴), and Δ3t5OH(2N)16:0 (▾).
FIGURE 6
FIGURE 6
Dominance of the sphingoid base double bond position in determining the dipole potential at 35 mN/m N-acyl saturated and unsaturated ceramide analogs; N-hexadecanoylceramides (▪), N-4-cis-hexadecenoylceramides (▴), and dihydroceramide (·······).
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