Raman Spectroscopic Study of Phase Coexistence in Binary Phospholipid Bilayers

2020 ◽  
Vol 75 (1) ◽  
pp. 87-93 ◽  
Author(s):  
Sergey V. Adichtchev ◽  
Konstantin A. Okotrub ◽  
Alexey M. Pugachev ◽  
Irina V. Zaytseva ◽  
Nikolay V. Surovtsev
Keyword(s):  
Raman Line ◽  
Low Frequency ◽  
Phospholipid Bilayers ◽  
Phase Coexistence ◽  
Lipid Phase ◽  
Label Free ◽  
Scanning Calorimetry ◽  
Two Phase ◽  
Raman Spectroscopic ◽  
Raman Scattering Spectra

Binary phospholipid bilayers composed of 1,2-dioleoyl-sn-glycero-3-phosphocholine and 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC) were studied by Raman spectroscopy and differential scanning calorimetry (DSC). We examined features in Raman scattering spectra that are sensitive to the lipid phase and, therefore, could indicate the phase coexistence. It was found that the low-frequency half-width of half-maximum (LHWHM) of the 2850 cm−1 Raman line, corresponding to the symmetric CH2 stretching vibrations, unequivocally reveals the coexisting phospholipids in ordered and disordered conformational states, which correspond to ordered and disordered phases coexistence, in the DPPC mole concentration range from 0.4 to 0.9. The phase coexistence in this concentration range was supported by the particular concentration behavior of the ratio between the intensities of the 2880 cm−1 antisymmetric CH2 vibration line and the 2850 cm−1 symmetric one. It was also shown that the spectral shape of the 1300 cm−1 Raman line, corresponding to the CH2 twisting vibrations, is a good indicator for the phase state and phase coexistence in the phospholipid bilayers. Comparison with the DSC curves confirmed that in the DPPC mole concentration range from 0.4 to 0.9, the two phase transition peaks are observed in DSC curve, those positions are independent of the DPPC concentration. The outcome of the study is the robust label-free contactless approach for the detection of the lipid phase separation, which can be realized with the micrometer resolution.

scholarly journals Effects of nicotine on the thermodynamics of the DPPC phase coexistence region

2019 ◽  
Author(s):  
Ernanni D. Vieira ◽  
A. J. Costa-Filho ◽  
Luis. G. M. Basso
Keyword(s):  
Heat Capacity ◽  
Electrostatic Interactions ◽  
Lipid Membrane ◽  
Phase Coexistence ◽  
Thermodynamic Quantities ◽  
Scanning Calorimetry ◽  
Two Phase ◽  
Membrane Function ◽  
Non Linear ◽  
Entropically Driven

ABSTRACTPhase separation plays critical roles in several membrane functions, and reduction or disappearance of phase coexistence by action of membrane-interacting molecules have been implicated in membrane function impairment. Here, we applied differential scanning calorimetry, electron paramagnetic resonance (EPR), and non-linear least-squares (NLLS) spectral simulations to study the effects of nicotine, a parasympathomimetic drug, on the two-phase coexistence of dipalmitoyl phosphatidylcholine (DPPC) lipid membrane. The thermodynamic quantities describing the DPPC phase coexistence are temperature dependent, giving rise to non-linear van’t Hoff behavior. Our results showed that nicotine preferentially binds to the fluid phase and modifies the enthalpy and entropy changes of the DPPC heat capacity profile, while marginally perturbing the homogeneous gel and fluid phases. An EPR/NLLS/van’t Hoff analysis of the DPPC phase coexistence revealed that nicotine significantly modified the temperature dependence of the free energy change of the two-phase equilibrium from a cubic to a parabolic behavior, resulting in an alteration of the thermodynamical driving force and the balance of the non-covalent interactions of the lipids in equilibrium. The thermotropic behavior of the enthalpy, entropy, and heat capacity changes, as determined by EPR, indicated that nicotine modified the relative contributions of hydrogen-bonding, electrostatic interactions, and conformational entropy of the lipids to the thermodynamics of the phase coexistence. The predominantly entropically-driven gel-fluid transition in nicotine-free DPPC changes to a temperature-triggered entropically-driven or enthalpically-driven process in nicotine-bound DPPC. Further applications of this thermodynamic EPR/NLLS/van’t Hoff analysis are discussed.

GDC - Y 2 O 3 Oxide Based Two Phase Nanocomposite Electrolyte

2011 ◽  
Vol 8 (4) ◽  
Author(s):  
Rizwan Raza ◽  
Ghazanfar Abbas ◽  
S. Khalid Imran ◽  
Imran Patel ◽  
Bin Zhu
Keyword(s):  
Fuel Cell ◽  
Ionic Conductivities ◽  
Morphological Properties ◽  
Scanning Calorimetry ◽  
Two Phase ◽  
Composite Electrolyte ◽  
Significant Performance ◽  
Advanced Fuel ◽  
Nanocomposite Electrolyte ◽  
Scherrer Formula

Oxide based two phase composite electrolyte (Ce0.9Gd0.1O2–Y2O3) was synthesized by coprecipitation method. The nanocomposite electrolyte showed the significant performance of power density 785 mW cm−2 and higher conductivities at relatively low temperature 550°C. Ionic conductivities were measured with ac impedance spectroscopy and four-probe dc method. The structural and morphological properties of the prepared electrolyte were investigated by scanning electron microscope (SEM). The thermal stability was determined with differential scanning calorimetry. The particle size that was calculated with Scherrer formula, 15–20 nm, is in a good agreement with the SEM and X- ray diffraction results. The purpose of this study is to introduce the functional nanocomposite materials for advanced fuel cell technology to meet the challenges of solid oxide fuel cell.

Films in narrow tubes

2014 ◽  
Vol 762 ◽  
pp. 68-109 ◽  
Author(s):  
Georg F. Dietze ◽  
Christian Ruyer-Quil
Keyword(s):  
Liquid Film ◽  
Silicone Oil ◽  
Low Frequency ◽  
Cylindrical Tube ◽  
Film Coating ◽  
Two Phase ◽  
Integral Boundary ◽  
Tube Cross Section ◽  
Free Liquid Film ◽  
Low Dimensional

AbstractWe consider the axisymmetric arrangement of an annular liquid film, coating the inner surface of a narrow cylindrical tube, in interaction with an active core fluid. We introduce a low-dimensional model based on the two-phase weighted residual integral boundary layer (WRIBL) formalism (Dietze & Ruyer-Quil, J. Fluid Mech., vol. 722, 2013, pp. 348–393) which is able to capture the long-wave instabilities characterizing such flows. Our model improves upon existing works by fully representing interfacial coupling and accounting for inertia as well as streamwise viscous diffusion in both phases. We apply this model to gravity-free liquid-film/core-fluid arrangements in narrow capillaries with specific attention to the dynamics leading to flooding, i.e. when the liquid film drains into large-amplitude collars that occlude the tube cross-section. We do this against the background of linear stability calculations and nonlinear two-phase direct numerical simulations (DNS). Due to the improvements of our model, we have found a number of novel/salient physical features of these flows. First, we show that it is essential to account for inertia and full interphase coupling to capture the temporal evolution of flooding for fluid combinations that are not dominated by viscosity, e.g. water/air and water/silicone oil. Second, we elucidate a viscous-blocking mechanism which drastically delays flooding in thin films that are too thick to form unduloids. This mechanism involves buckling of the residual film between two liquid collars, generating two very pronounced film troughs where viscous dissipation is drastically increased and growth effectively arrested. Only at very long times does breaking of symmetry in this region (due to small perturbations) initiate a sliding motion of the liquid film similar to observations by Lister et al. (J. Fluid Mech., vol. 552, 2006, pp. 311–343) in thin non-flooding films. This kickstarts the growth of liquid collars anew and ultimately leads to flooding. We show that streamwise viscous diffusion is essential to this mechanism. Low-frequency core-flow oscillations, such as occur in human pulmonary capillaries, are found to set off this sliding-induced flooding mechanism much earlier.

The thermodynamic properties of mixed phospholipid bilayers: a theoretical analysis

1984 ◽  
Vol 62 (8) ◽  
pp. 796-802 ◽  
Author(s):  
Maryse Mondat ◽  
A. Georgallas ◽  
D. A. Pink ◽  
M. J. Zuckermann
Keyword(s):  
Experimental Data ◽  
Thermodynamic Properties ◽  
Reasonable Agreement ◽  
Phospholipid Bilayers ◽  
Scanning Calorimetry ◽  
Phase Separations ◽  
Lipid Mixtures ◽  
Wide Range ◽  
Acyl Chains ◽  
Gel Phase

A theoretical model is presented with the intention of describing lateral phase separations in binary lipid mixtures in which the acyl chains of the components differ in their length. The model includes explicitly interactions between the acyl chains and between polar heads of the lipid molecules. Phase diagrams and thermodynamic properties of binary lipid mixtures were calculated using a wide range of interaction parameters. It is shown that the occurrence of immiscibility in the gel phase is related to the interactions between the polar heads of the lipid molecules. The calculated results for binary lipid mixtures are compared with the available experimental data. In particular, the calculated specific heat for dilauroyl phosphatidylcholine – distearoyl phosphatidylcholine is in reasonable agreement with experimental results obtained from differential scanning calorimetry measurements.

Experimental Study of the Liquid-Glass Transition in an Inorganic Polymer Li0.5Na0.5PO3

1995 ◽  
Vol 407 ◽  
Author(s):  
B. Rufflé ◽  
S. Beaufils ◽  
Y. Délugeard ◽  
G. Coddens ◽  
J. Etrillard ◽  
...  
Keyword(s):  
Experimental Study ◽  
Glass Transition ◽  
Raman Scattering ◽  
Viscous Flow ◽  
Liquid Glass ◽  
Low Frequency ◽  
Glass Forming ◽  
Scattering Spectra ◽  
Temperature Ranges ◽  
Raman Scattering Spectra

ABSTRACTNew experimental results obtained with various techniques on a less-studied glass-forming system are presented. At low frequency, a secondary βslow-process, decoupled from the viscous flow, is observed by 3 1P NMR. Raman scattering spectra and coherent neutron scattering spectra has been obtained in wide frequency and temperature ranges showing the same qualitative features for the Boson peak while the quasielastic contribution seems to differ markedly.

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