Stretch Vibrations of CH2 as a Measure of Conformational and Lateral Orders in Fatty Acid and Phospholipid Layers
- 4 Downloads
Abstract
The intensity of the line of antisymmetric vibrations of CH2 in the Raman spectrum of molecular layers of fatty acids and phospholipids is sensitive both to the molecular order in the layer (lateral order) and to the conformational order of the hydrocarbon chain of the molecule. Though the intensity of this line is widely used as an indicator of order in molecular layers containing hydrocarbon tails, the nature of sensitivity of the line of antisymmetric vibrations to the order is still disputable. This issue has been experimentally studied, and it has been demonstrated that disordering leads to redistribution of vibrational modes and to changes in polarizability of antisymmetric vibrations. A hypothesis is proposed that the intensity of the line of the Raman scattering of antisymmetric vibrations of CH2 is determined to a large extent by their interaction with electron excitation of the hydrocarbon chain.
Keywords
Raman scattering order indicator hydrocarbon chainPreview
Unable to display preview. Download preview PDF.
References
- 1.N. V. Surovtsev, N. V. Ivanisenko, K. Y. Kirillov, and S. A. Dzuba, “Low-Temperature Dynamical and Structural Properties of Saturated and Monounsaturated Phospholipids Bilayers Revealed by Raman and Spin-Label EPR Spectroscopy,” J. Phys. Chem. B 116 (28), 8139–8144 (2012).CrossRefGoogle Scholar
- 2.B. P. Gaber and W. L. Peticolas, “On the Quantitative Interpretation of Biomembrane Structure by Raman Spectroscopy,” Biochim. Biophys. Acta 2 (465), 260–274 (1977).CrossRefGoogle Scholar
- 3.N. Yellin and I. W. Levin, “Hydrocarbon Chain Disorder in Lipid Bilayers: Temperature Dependence Raman Spectra of 1,2-Diacyl Phosphatidylcholine-Water Gels,” Biochim. Biophys. Acta 2 (489), 177–190 (1977).CrossRefGoogle Scholar
- 4.R. Gharib, L. Auezova, C. Charcosset, and H. Greige-Gerges, “Effect of a Series of Essential Oil Molecules on DPPC Membrane Fluidity: A Biophysical Study,” J. Iran. Chem. Soc. 15 (1), 75–84 (2018).CrossRefGoogle Scholar
- 5.D. A. Bryce, J. P. Kitt, and J. M. Harris, “Confocal-Raman Microscopy Characterization of Supported Phospholipids Bilayers Deposited on the Interior Surfaces of Chromatographic Silica,” J. Am. Chem. Soc. 140 (11), 4071–4078 (2018).CrossRefGoogle Scholar
- 6.J. M. Arias, M. E. Tuttolomondo, S. B. Diaz, and A. B. Altabef, “Molecular View of the Structural Reorganization ofWater in DPPC Multilamellar Membranes Induced by L-Cysteine Methyl Ester,” J. Mol. Struct. 1156, 360–368 (2018).ADSCrossRefGoogle Scholar
- 7.P. Chatzigeorgiou, A. Mourelatou, E. Pollatos, et al., “Comparison of the Thermal Behavior and Conformational Changes in Partially and Fully Hydrated Dipalmitoylphosphatidylcholine Systems,” J. Therm. Anal. Calorimetry 131 (2), 887–898 (2018).CrossRefGoogle Scholar
- 8.R. G. Snyder, S. L. Hsu, and S. Krimm, “Vibrational Spectra in the C—H Stretching Region and the Structure of the Polymethylene Chain,” Spectrochim. Acta A 34 (4), 395–406 (1978).ADSCrossRefGoogle Scholar
- 9.R. G. Snyder and J. R. Scherer, “Band Structure in the C—H Stretching Region of the Raman Spectrum of the Extended Polymethylene Chain: Influence of Fermi Resonance,” J. Chem. Phys. 71 (8), 3221–3228 (1979).ADSCrossRefGoogle Scholar
- 10.B. P. Gaber, P. Yager, and W. I. Peticolas, “Deuterated Phospholipids as Nonperturbing Components for Raman Studies of Biomembranes,” Biophys. J. 22 (2), 191–207 (1978).ADSCrossRefGoogle Scholar
- 11.L. Ricard, S. Abbate, and G. Zerbi, “Conformationally Dependent Fermi Resonances and Long-Range Interaction between σ Bonds in Polymethylene Systems Derived from their Raman Spectra,” J. Phys. Chem. 89 (22), 4793–4799 (1985).CrossRefGoogle Scholar
- 12.L. Collard, D. Perez-Guaita, B. H. Faraj, et al., “Light Scattering by Optically-Trapped Vesicles Affords Unprecedented Temporal Resolution of Lipid-Raft Dynamics,” Sci. Rep. 7, 8589 (2017)ADSCrossRefGoogle Scholar
- 13.A. A. Dmitriev and N. V. Surovtsev, “Temperature-Dependent Hydrocarbon Chain Disorder in Phosphatidylcholine Bilayers Studied by Raman Spectroscopy,” J. Phys. Chem. B 119 (51), 15613–15622 (2015).CrossRefGoogle Scholar
- 14.N. V. Surovtsev, “Suppression of Spurious Background in Low-Frequency Raman Spectroscopy,” Avtometriya 53 (3), 58–63 (2017) [Optoelectron., Instrum. Data Process. 53 (3), 250–254 (2017)].Google Scholar
- 15.N. V. Surovtsev and S. A. Dzuba, “Conformational Changes of Lipids in Bilayers at the Dynamical Transition near 200 K Seen by Raman Scattering,” J. Phys. Chem. B 113 (47), 15558–15562 (2009).CrossRefGoogle Scholar