Raman study of temperature-induced hydrocarbon chain disorder in saturated phosphatidylcholines

Zaytseva, Yu.V.; Adichtchev, S. V.; Surovtsev, N. V.

doi:10.1016/j.chemphyslip.2020.104926

Cited by 12 publications

(6 citation statements)

References 29 publications

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“…For example, in the ordered conformational state, I(ν as CH 2 ) increases with the length of the hydrocarbon chain. [ 41,42 ] I(ν as CH 2 )/I(ν s CH 2 ) demonstrates the sharp change at the main transition and increases towards temperature lowering (Figure 3f). The latter temperature dependence relates, at least partly, to the temperature dependence of the ordered conformational states population.…”

Section: Resultsmentioning

confidence: 96%

Raman spectra of deuterated hydrocarbons for labeling applications

Okotrub

Shamaeva

Surovtsev

2021

J Raman Spectroscopy

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Raman spectroscopy is used for studying the composition of cell lipidome. However, the Raman approach suffers from limited distinguish power for different lipids. In recent years, isotopically labeled molecules are increasingly used to enhance the Raman resolution of similar compounds in biological samples. Here, we present Raman study of fully deuterated stearic acid (stearic‐d35), semi‐deuterated oleic acid (oleic d‐9), arachidonic acid with deuterated methine groups (arachidonic‐d8), and their hydrogenated analogs. Polarization properties and temperature dependences of CD stretching modes were investigated to reveal the capability of the isotopically shifted Raman peaks in molecular characterization. Sensitivity of Raman peaks to order–disorder transition corresponding was demonstrated for deuterated methine, methylene, and methyl groups. It was found that the isotopically shifted Raman peaks provide information about the orientation of deuterated Raman tags and their surroundings.

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Section: Resultsmentioning

confidence: 96%

Raman spectra of deuterated hydrocarbons for labeling applications

Okotrub

Shamaeva

Surovtsev

2021

J Raman Spectroscopy

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“…The degeneracy g m and the excitation energy U m correspond to the disordered state of the lipid molecule. The Raman experiment provided g k = 2.5, U k / k B = 650 K, g m = 10 8 , and U m / k B = 5550 K in the case of DMPC Figure provides the direct comparison of the temperature dependences of the Brillouin acoustic velocity and the fraction of hydrocarbon chains in the all-trans conformational state.…”

Section: Resultsmentioning

confidence: 99%

“…Temperature dependences for the sound velocity of the hydrated planar DMPC scaled to the lowest temperature value (open circles) and the chain fraction in the all-trans conformation f ( T ) (solid circles, data from ref ). Line corresponds to eq .…”

Section: Resultsmentioning

confidence: 99%

“…Equation implies different storage moduli for the all-trans conformational state of chains ( M LT ′ ( T )) and other conformational states ( M HT ′ ( T )). The prediction of eq with f ( T ) described by eq and the DMPC parameters in the gel phase [ f ( T ) = 0 for the fluid phase] is shown in Figure . Equation captures the main trend of M ′( T ) and describes it up to ∼260 K. Different reasons for the deviation of eq from the experimental data can be considered.…”

Section: Resultsmentioning

confidence: 99%

“…The Raman experiment provided g k = 2.5, U k /k B = 650 K, g m = 10 8 , and U m /k B = 5550 K in the case of DMPC. 17 It can be assumed that the longitudinal modulus relevant for Brillouin scattering consists of contributions from the effective modulus of the all-trans conformational state and others…”

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confidence: 99%

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Effect of the Hydrocarbon Chain Disorder in Phosphatidylcholine Bilayers on Gigahertz Sound Velocity

2020

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Suspensions of multilamellar vesicles of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and hydrated and dehydrated aligned multilamellar samples of DMPC were studied by Brillouin spectroscopy in the temperature range from 90 to 333 K. The sound velocity of the longitudinal acoustic wave was evaluated from the Brillouin spectra. It was found that phase transition, hydration state, and planar or vesicular form of bilayers affect the gigahertz sound velocity. Usually, the temperature dependence of the sound velocity is weak in solid substances. Amazingly, the sound velocity of hydrated DMPC samples showed significant temperature-induced changes of up to 1.8 times, even within the solid-like gel phase. We explained this effect by temperature-induced excitations of the disordered conformational states of the hydrocarbon chains as well as anharmonic effects. In addition, the relevance of the gigahertz sound velocity to the description of subterahertz Raman features was demonstrated.

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Sensitivity of the C–H Stretching Band in Raman Spectra to Phospholipid Order

Zaytseva,

Okotrub,

Surovtsev

2024

J Raman Spectroscopy

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Phospholipid bilayers, which are a major component of cellular membranes and some drug delivery vehicles, can be in different states of order depending on the conformations of the hydrocarbon tails and their mutual arrangement. The important task of experimental characterization of phospholipid order is often addressed using Raman spectra of the C–H stretching bands. Such characterization uses some empirical relationships for apparent maxima in the spectra, although the origin of the sensitivity of the C–H band to phospholipid order and its model description remain unclear. Surely, a correct description of the sensitivity of the C–H band to phospholipid order is critical for its proper application. Here, we provide a description of the ordering sensitivity of the C–H stretching band using a polarized Raman experiment with hydrated aligned multibilayers of a saturated phospholipid. By this way, Raman contributions from symmetric and antisymmetric vibrations of CH2 were obtained in a model‐free manner. Experiments in a wide temperature range and the use of isotopic isolation helped us to consider separately the effects of conformational and lateral order of chains. The conformational sensitivity of the spectrum of antisymmetric vibrations was confirmed by DFT modeling. The outcomes of the study allowed us to provide recommendations for the use of the Raman spectrum of the C–H stretching band to characterize the conformational and lateral order of phospholipid‐containing materials.

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Raman study of temperature-induced hydrocarbon chain disorder in saturated phosphatidylcholines

Cited by 12 publications

References 29 publications

Raman spectra of deuterated hydrocarbons for labeling applications

Raman spectra of deuterated hydrocarbons for labeling applications

Effect of the Hydrocarbon Chain Disorder in Phosphatidylcholine Bilayers on Gigahertz Sound Velocity

Sensitivity of the C–H Stretching Band in Raman Spectra to Phospholipid Order

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