Nanoclusters of Guest Molecules in Lipid Rafts of a Model Membrane Revealed by Pulsed Dipolar EPR Spectroscopy

Plasma membranes are known to segregate into liquid disordered and ordered nanoscale phases, the latter being called lipid rafts. The structure, lipid composition, and function of lipid rafts have been the subject of numerous studies using a variety of experimental and computational methods. Double...

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Published inThe journal of physical chemistry. B Vol. 129; no. 2; pp. 650 - 658
Main Authors Golysheva, Elena A., Kashnik, Anna S., Baranov, Denis S., Dzuba, Sergei A.
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 16.01.2025
Subjects
1,2-Dipalmitoylphosphatidylcholine - chemistry
adsorption
B: Biomaterials and Membranes
cholesterol
Cholesterol - chemistry
electron paramagnetic resonance spectroscopy
Electron Spin Resonance Spectroscopy
family
ibuprofen
Ibuprofen - chemistry
Lipid Bilayers - chemistry
lipid composition
liquids
Membrane Microdomains - chemistry
nanoparticles
Phosphatidylcholines - chemistry
phospholipids
Spin Labels
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Abstract Plasma membranes are known to segregate into liquid disordered and ordered nanoscale phases, the latter being called lipid rafts. The structure, lipid composition, and function of lipid rafts have been the subject of numerous studies using a variety of experimental and computational methods. Double electron–electron resonance (DEER, also known as PELDOR) is a member of the pulsed dipole EPR spectroscopy (PDS) family of techniques, allowing the study of nanoscale distances between spin-labeled molecules. To extend the possibilities of DEER in the study of molecule clusters, its joint application with the simple two-pulse electron spin echo (2p ESE) method is carried out here. We studied spin-labeled ibuprofen (ibuprofen-SL) diluted in bilayers composed of equimolar mixtures of dioleoyl-glycero-phosphocholine (DOPC) and dipalmitoyl-glycero-phosphocholine (DPPC) phospholipids, with added cholesterol, a system known as a raft-mimicking. The data obtained show that ibuprofen-SL molecules in this system form isolated clusters of about 4 nm in size, containing 6–8 molecules spaced at least 1.3 nm apart. These results indicate the interaction of ibuprofen-SL molecules with lipid rafts, for which the existence of nanoscale substructures at the boundaries of which adsorption of these molecules occurs is suggested.
AbstractList Plasma membranes are known to segregate into liquid disordered and ordered nanoscale phases, the latter being called lipid rafts. The structure, lipid composition, and function of lipid rafts have been the subject of numerous studies using a variety of experimental and computational methods. Double electron-electron resonance (DEER, also known as PELDOR) is a member of the pulsed dipole EPR spectroscopy (PDS) family of techniques, allowing the study of nanoscale distances between spin-labeled molecules. To extend the possibilities of DEER in the study of molecule clusters, its joint application with the simple two-pulse electron spin echo (2p ESE) method is carried out here. We studied spin-labeled ibuprofen (ibuprofen-SL) diluted in bilayers composed of equimolar mixtures of dioleoyl-glycero-phosphocholine (DOPC) and dipalmitoyl-glycero-phosphocholine (DPPC) phospholipids, with added cholesterol, a system known as a raft-mimicking. The data obtained show that ibuprofen-SL molecules in this system form isolated clusters of about 4 nm in size, containing 6-8 molecules spaced at least 1.3 nm apart. These results indicate the interaction of ibuprofen-SL molecules with lipid rafts, for which the existence of nanoscale substructures at the boundaries of which adsorption of these molecules occurs is suggested.Plasma membranes are known to segregate into liquid disordered and ordered nanoscale phases, the latter being called lipid rafts. The structure, lipid composition, and function of lipid rafts have been the subject of numerous studies using a variety of experimental and computational methods. Double electron-electron resonance (DEER, also known as PELDOR) is a member of the pulsed dipole EPR spectroscopy (PDS) family of techniques, allowing the study of nanoscale distances between spin-labeled molecules. To extend the possibilities of DEER in the study of molecule clusters, its joint application with the simple two-pulse electron spin echo (2p ESE) method is carried out here. We studied spin-labeled ibuprofen (ibuprofen-SL) diluted in bilayers composed of equimolar mixtures of dioleoyl-glycero-phosphocholine (DOPC) and dipalmitoyl-glycero-phosphocholine (DPPC) phospholipids, with added cholesterol, a system known as a raft-mimicking. The data obtained show that ibuprofen-SL molecules in this system form isolated clusters of about 4 nm in size, containing 6-8 molecules spaced at least 1.3 nm apart. These results indicate the interaction of ibuprofen-SL molecules with lipid rafts, for which the existence of nanoscale substructures at the boundaries of which adsorption of these molecules occurs is suggested.
Plasma membranes are known to segregate into liquid disordered and ordered nanoscale phases, the latter being called lipid rafts. The structure, lipid composition, and function of lipid rafts have been the subject of numerous studies using a variety of experimental and computational methods. Double electron–electron resonance (DEER, also known as PELDOR) is a member of the pulsed dipole EPR spectroscopy (PDS) family of techniques, allowing the study of nanoscale distances between spin-labeled molecules. To extend the possibilities of DEER in the study of molecule clusters, its joint application with the simple two-pulse electron spin echo (2p ESE) method is carried out here. We studied spin-labeled ibuprofen (ibuprofen-SL) diluted in bilayers composed of equimolar mixtures of dioleoyl-glycero-phosphocholine (DOPC) and dipalmitoyl-glycero-phosphocholine (DPPC) phospholipids, with added cholesterol, a system known as a raft-mimicking. The data obtained show that ibuprofen-SL molecules in this system form isolated clusters of about 4 nm in size, containing 6–8 molecules spaced at least 1.3 nm apart. These results indicate the interaction of ibuprofen-SL molecules with lipid rafts, for which the existence of nanoscale substructures at the boundaries of which adsorption of these molecules occurs is suggested.
Author Golysheva, Elena A.
Dzuba, Sergei A.
Baranov, Denis S.
Kashnik, Anna S.
AuthorAffiliation Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences
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  givenname: Elena A.
  surname: Golysheva
  fullname: Golysheva, Elena A.
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  givenname: Anna S.
  surname: Kashnik
  fullname: Kashnik, Anna S.
– sequence: 3
  givenname: Denis S.
  orcidid: 0000-0002-0225-0455
  surname: Baranov
  fullname: Baranov, Denis S.
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  givenname: Sergei A.
  orcidid: 0000-0001-8880-6559
  surname: Dzuba
  fullname: Dzuba, Sergei A.
  email: dzuba@kinetics.nsc.ru
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SubjectTerms 1,2-Dipalmitoylphosphatidylcholine - chemistry
adsorption
B: Biomaterials and Membranes
cholesterol
Cholesterol - chemistry
electron paramagnetic resonance spectroscopy
Electron Spin Resonance Spectroscopy
family
ibuprofen
Ibuprofen - chemistry
Lipid Bilayers - chemistry
lipid composition
liquids
Membrane Microdomains - chemistry
nanoparticles
Phosphatidylcholines - chemistry
phospholipids
Spin Labels
Title Nanoclusters of Guest Molecules in Lipid Rafts of a Model Membrane Revealed by Pulsed Dipolar EPR Spectroscopy
URI http://dx.doi.org/10.1021/acs.jpcb.4c05217
https://www.ncbi.nlm.nih.gov/pubmed/39772603
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Volume 129
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