Prodan fluorescence detects the bilayer packing of asymmetric phospholipids

Goto, Masaki; Matsui, Takayuki; Tamai, Naoto; Matsuki, Hitoshi; Kaneshina, Shoji

doi:10.1016/j.colsurfb.2010.12.015

Cited by 22 publications

(10 citation statements)

References 29 publications

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“…DSC is highly sensitive to energetic thermotropic events like conformational changes of the acyl chains of phospholipid molecules. Prodan is known as a polarity-sensitive membrane probe, and its emission spectrum varies sensitively in response to the change in polarity of the microenvironment around it [26][27][28][29][30]. Therefore, the combination of the two complementary techniques allows us to examine the phase behavior of those binary bilayers from different aspects.…”

Section: Introductionmentioning

confidence: 98%

How does acyl chain length affect thermotropic phase behavior of saturated diacylphosphatidylcholine–cholesterol binary bilayers?

Tamai¹,

Izumikawa²,

Fukui³

et al. 2013

Biochimica et Biophysica Acta (BBA) - Biomembranes

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Thermotropic phase behavior of diacylphosphatidylcholine (CnPC)-cholesterol binary bilayers (n=14-16) was examined by fluorescence spectroscopy using 6-propionyl-2-(dimethylamino)naphthalene (Prodan) and differential scanning calorimetry. The former technique can detect structural changes of the bilayer in response to the changes in polarity around Prodan molecules partitioned in a relatively hydrophilic region of the bilayer, while the latter is sensitive to the conformational changes of the acyl chains. On the basis of the data from both techniques, we propose possible temperature T-cholesterol composition Xch phase diagrams for these binary bilayers. A notable feature of our phase diagrams, including our previous results for diheptadecanoylphosphatidylcholine (C17PC) and distearoylphosphatidylcholine (C18PC), is that there is a peritectic-like point around Xch=0.15, which can be interpreted as indicating the formation of a 1:6-complex of cholesterol and CnPCs within the binary bilayer irrespective of the acyl chain length. We could give a reasonable explanation for such complex formation using the modified superlattice view. Our results also showed that the Xch value of the abolition of the main transition is almost constant for n=14-17 (ca. 0.33), while it increases to ca. 0.50 for n=18. By contrast, a biphasic n-dependence of Xch was observed for the abolition of the pretransition, suggesting that there are at least two antagonistic n-dependent factors. We speculate that this could be explained by the enhancement of the van der Waals interaction with increases in n and the weakening of the repulsion between the neighboring headgroups with decreases in n.

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Section: Introductionmentioning

confidence: 98%

How does acyl chain length affect thermotropic phase behavior of saturated diacylphosphatidylcholine–cholesterol binary bilayers?

Tamai¹,

Izumikawa²,

Fukui³

et al. 2013

Biochimica et Biophysica Acta (BBA) - Biomembranes

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“…Moreover, there is a two-phase coexistence region (gray-colored area in the figure) of the L β ′ and L β I phases in the SPPC bilayer. We elucidated from the high-pressure fluorometry [34,39] that the region results from a less polar “pocket” in the membrane, which is formed from the chain asymmetry in the terminal parts of acyl chains of SPPC.…”

Section: Effect Of Acyl Chain Structure On the Phase Behavior Of Pmentioning

confidence: 99%

Thermotropic and Barotropic Phase Behavior of Phosphatidylcholine Bilayers

Matsuki

Goto

Tada

et al. 2013

IJMS

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Bilayers formed by phospholipids are frequently used as model biological membranes in various life science studies. A characteristic feature of phospholipid bilayers is to undergo a structural change called a phase transition in response to environmental changes of their surroundings. In this review, we focus our attention on phase transitions of some major phospholipids contained in biological membranes, phosphatidylcholines (PCs), depending on temperature and pressure. Bilayers of dipalmitoylphosphatidylcholine (DPPC), which is the most representative lipid in model membrane studies, will first be explained. Then, the bilayer phase behavior of various kinds of PCs with different molecular structures is revealed from the temperature–pressure phase diagrams, and the difference in phase stability among these PC bilayers is discussed in connection with the molecular structure of the PC molecules. Furthermore, the solvent effect on the phase behavior is also described briefly.

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“…Since the D -spacings for the L β ′, P β ′, L α , and L β I phase are 6.3, 7.2, 6.7, and 4.8 nm, respectively, in the case of the DPPC bilayer, , it can also be said that the Prodan molecules can change the location in response to the change in the membrane structure. Furthermore, we have developed a novel analysis method by using second derivatives of the fluorescence spectra, which enables us to investigate the precise location of the Prodan molecules in the PC bilayer. ,,,,− It is advantageous to use the second-derivative spectra to separate overlapping multiple peaks because multiple peaks including main and shoulder components in the original spectrum can be converted to individual valleys (λ″ min ) in its second-derivative spectrum. From temperature dependence of the second derivative spectra, ,, we constructed a three-dimensional image plot (hereafter abbreviated to image plot) of the second-derivative spectra for the Prodan fluorescence of the PC bilayer membranes under atmospheric and high pressures.…”

Section: Resultsmentioning

confidence: 99%

“…Fluorescence measurements under atmospheric and high pressures were carried out using an F-2500 spectrophotometer (Hitachi High-Technology Corp., Tokyo, Japan) equipped with a high-pressure cell assembly (PCI-400; Syn Corp., Ltd., Kyoto, Japan). Fluorescence spectra of Prodan in the MPPC bilayer of various phases were observed by isothermal barotropic and isobaric thermotropic phase transition measurements described previously. ,,, The excitation wavelength was 361 nm, and the emission spectra were recorded in the wavelength range from 400 to 600 nm. The pressurizing rate was 2 MPa min –1 , and the heating rate was 0.5 °C min –1 .…”

Section: Methodsmentioning

confidence: 99%

Study on the Subgel-Phase Formation Using an Asymmetric Phospholipid Bilayer Membrane by High-Pressure Fluorometry

et al. 2012

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The myristoylpalmitoylphosphatidylcholine (MPPC) bilayer membrane shows a complicated temperature-pressure phase diagram. The large portion of the lamellar gel (L(β)'), ripple gel (P(β)'), and pressure-induced gel (L(β)I) phases exist as metastable phases due to the extremely stable subgel (L(c)) phase. The stable L(c) phase enables us to examine the properties of the L(c) phase. The phases of the MPPC bilayers under atmospheric and high pressures were studied by small-angle neutron scattering (SANS) and fluorescence spectroscopy using a polarity-sensitive fluorescent probe Prodan. The SANS measurements clearly demonstrated the existence of the metastable L(β)I phase with the smallest lamellar repeat distance. From a second-derivative analysis of the fluorescence data, the line shape for the L(c) phase under high pressure was characterized by a broad peak with a minimum of ca. 460 nm. The line shapes and the minimum intensity wavelength (λ″(min)) values changed with pressure, indicating that the L(c) phase has highly pressure-sensible structure. The λ″(min) values of the L(c) phase spectra were split into ca. 430 and 500 nm in the L(β)I phase region, which corresponds to the formation of a interdigitated subgel L(c) (L(c)I) phase. Moreover, the phase transitions related to the L(c) phase were reversible transitions under high pressure. Taking into account the fluorescence behavior of Prodan for the L(c) phase, we concluded that the structure of the L(c) phase is highly probably a staggered structure, which can transform into the L(c)I phase easily.

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Prodan fluorescence detects the bilayer packing of asymmetric phospholipids

Cited by 22 publications

References 29 publications

How does acyl chain length affect thermotropic phase behavior of saturated diacylphosphatidylcholine–cholesterol binary bilayers?

How does acyl chain length affect thermotropic phase behavior of saturated diacylphosphatidylcholine–cholesterol binary bilayers?

Thermotropic and Barotropic Phase Behavior of Phosphatidylcholine Bilayers

Study on the Subgel-Phase Formation Using an Asymmetric Phospholipid Bilayer Membrane by High-Pressure Fluorometry

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