Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR

Nobuaki Matsumori, Toshiyuki Yamaguchi, Yoshiko Maeta, Michio Murata

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Sphingomyelin (SM) and cholesterol (Chol) are considered essential for the formation of lipid rafts; however, the types of molecular interactions involved in this process, such as intermolecular hydrogen bonding, are not well understood. Since, unlike other phospholipids, SM is characterized by the presence of an amide group, it is essential to determine the orientation of the amide and its order in the lipid bilayers to understand the nature of the hydrogen bonds in lipid rafts. For this study, 1′-13C-2-15N-labeled and 2′-13C-2-15N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on 13C and 15N chemical-shift anisotropies and intramolecular 13C-15N dipole coupling constants. Results revealed that the amide orientation was minimally affected by Chol, whereas the order was enhanced significantly in its presence. Thus, Chol likely promotes the formation of an intermolecular hydrogen-bond network involving the SM amide without significantly changing its orientation, providing a higher order to the SM amide. To our knowledge, this study offers new insight into the significance of the SM amide orientation with regard to molecular recognition in lipid rafts, and therefore provides a deeper understanding of the mechanism of their formation.

Original languageEnglish
Pages (from-to)2816-2824
Number of pages9
JournalBiophysical Journal
Volume108
Issue number12
DOIs
Publication statusPublished - Jun 18 2015

Fingerprint

Sphingomyelins
Amides
Cholesterol
Lipids
Hydrogen
Anisotropy
Lipid Bilayers
Hydrogen Bonding
Phospholipids

All Science Journal Classification (ASJC) codes

  • Biophysics

Cite this

Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR. / Matsumori, Nobuaki; Yamaguchi, Toshiyuki; Maeta, Yoshiko; Murata, Michio.

In: Biophysical Journal, Vol. 108, No. 12, 18.06.2015, p. 2816-2824.

Research output: Contribution to journalArticle

Matsumori, Nobuaki ; Yamaguchi, Toshiyuki ; Maeta, Yoshiko ; Murata, Michio. / Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR. In: Biophysical Journal. 2015 ; Vol. 108, No. 12. pp. 2816-2824.
@article{b1c282be900a4afda3ef173f3bfd328b,
title = "Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR",
abstract = "Sphingomyelin (SM) and cholesterol (Chol) are considered essential for the formation of lipid rafts; however, the types of molecular interactions involved in this process, such as intermolecular hydrogen bonding, are not well understood. Since, unlike other phospholipids, SM is characterized by the presence of an amide group, it is essential to determine the orientation of the amide and its order in the lipid bilayers to understand the nature of the hydrogen bonds in lipid rafts. For this study, 1′-13C-2-15N-labeled and 2′-13C-2-15N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on 13C and 15N chemical-shift anisotropies and intramolecular 13C-15N dipole coupling constants. Results revealed that the amide orientation was minimally affected by Chol, whereas the order was enhanced significantly in its presence. Thus, Chol likely promotes the formation of an intermolecular hydrogen-bond network involving the SM amide without significantly changing its orientation, providing a higher order to the SM amide. To our knowledge, this study offers new insight into the significance of the SM amide orientation with regard to molecular recognition in lipid rafts, and therefore provides a deeper understanding of the mechanism of their formation.",
author = "Nobuaki Matsumori and Toshiyuki Yamaguchi and Yoshiko Maeta and Michio Murata",
year = "2015",
month = "6",
day = "18",
doi = "10.1016/j.bpj.2015.05.011",
language = "English",
volume = "108",
pages = "2816--2824",
journal = "Biophysical Journal",
issn = "0006-3495",
publisher = "Biophysical Society",
number = "12",

}

TY - JOUR

T1 - Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR

AU - Matsumori, Nobuaki

AU - Yamaguchi, Toshiyuki

AU - Maeta, Yoshiko

AU - Murata, Michio

PY - 2015/6/18

Y1 - 2015/6/18

N2 - Sphingomyelin (SM) and cholesterol (Chol) are considered essential for the formation of lipid rafts; however, the types of molecular interactions involved in this process, such as intermolecular hydrogen bonding, are not well understood. Since, unlike other phospholipids, SM is characterized by the presence of an amide group, it is essential to determine the orientation of the amide and its order in the lipid bilayers to understand the nature of the hydrogen bonds in lipid rafts. For this study, 1′-13C-2-15N-labeled and 2′-13C-2-15N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on 13C and 15N chemical-shift anisotropies and intramolecular 13C-15N dipole coupling constants. Results revealed that the amide orientation was minimally affected by Chol, whereas the order was enhanced significantly in its presence. Thus, Chol likely promotes the formation of an intermolecular hydrogen-bond network involving the SM amide without significantly changing its orientation, providing a higher order to the SM amide. To our knowledge, this study offers new insight into the significance of the SM amide orientation with regard to molecular recognition in lipid rafts, and therefore provides a deeper understanding of the mechanism of their formation.

AB - Sphingomyelin (SM) and cholesterol (Chol) are considered essential for the formation of lipid rafts; however, the types of molecular interactions involved in this process, such as intermolecular hydrogen bonding, are not well understood. Since, unlike other phospholipids, SM is characterized by the presence of an amide group, it is essential to determine the orientation of the amide and its order in the lipid bilayers to understand the nature of the hydrogen bonds in lipid rafts. For this study, 1′-13C-2-15N-labeled and 2′-13C-2-15N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on 13C and 15N chemical-shift anisotropies and intramolecular 13C-15N dipole coupling constants. Results revealed that the amide orientation was minimally affected by Chol, whereas the order was enhanced significantly in its presence. Thus, Chol likely promotes the formation of an intermolecular hydrogen-bond network involving the SM amide without significantly changing its orientation, providing a higher order to the SM amide. To our knowledge, this study offers new insight into the significance of the SM amide orientation with regard to molecular recognition in lipid rafts, and therefore provides a deeper understanding of the mechanism of their formation.

UR - http://www.scopus.com/inward/record.url?scp=84931259631&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84931259631&partnerID=8YFLogxK

U2 - 10.1016/j.bpj.2015.05.011

DO - 10.1016/j.bpj.2015.05.011

M3 - Article

C2 - 26083921

AN - SCOPUS:84931259631

VL - 108

SP - 2816

EP - 2824

JO - Biophysical Journal

JF - Biophysical Journal

SN - 0006-3495

IS - 12

ER -