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ABSTRACT: 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.
International Journal of Molecular Sciences 01/2013; 14(2):2282-302. · 2.60 Impact Factor
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ABSTRACT: 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.
Langmuir 07/2012; 28(33):12191-8. · 4.19 Impact Factor
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ABSTRACT: Interaction modes of halothane and palmitic acid with bovine serum albumin (BSA) were studied from the thermal and volumetric
viewpoints. The thermal stability of BSA was increased by increasing both ligand concentrations. However, the stronger effect
of palmitic acid than halothane on BSA was observed at lower concentrations irrespective of the pH-dependent BSA structure.
On the other hand, the volume of BSA in the solution shrunk by adding halothane independent of its structure while it expanded
by adding palmitic acid. The molar ratio of halothane to BSA at the effective concentration was not consistent with the binding
numbers on human serum albumin determined from the X-ray analysis, whereas that of palmitic acid was in good agreement with
the numbers. We judged from these facts that halothane is a nonspecific binder to BSA; by contrast, palmitic acid is a specific
binder. The stabilization mechanisms of the BSA structure were also revealed.
Colloid and Polymer Science 04/2012; 287(8):979-989. · 2.33 Impact Factor
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ABSTRACT: We investigated the thermotropic volume behavior of dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC) and dihexadecylphosphatidylcholine (DHPC) membranes using pressure perturbation calorimetry (PPC) and densitometry. The ln φ(2) vs temperature curves (φ(2): apparent molar volume of phospholipid) obtained from the PPC data using an analysis method that we developed agreed with the results from the density measurements for these lipids within the relative difference of about 0.62%. From those curves, the volume changes with the main transition were estimated at 18.0±0.49, 23.5±2.33 and 23.0±0.33 cm(3) mol(-1) for DMPC, DPPC and DHPC, respectively. For DPPC and DMPC, the average volume per methylene group of the hydrocarbon chains v(CH2) calculated by referring to the procedure by Nagle and Wilkinson was consistent with the previous result, which indicates that the DPPC bilayer in the gel state has denser hydrophobic bilayer core than the DMPC bilayer. For DHPC, the volume of the headgroup region v(H) was calculated to be 244 Å(3) by assuming that v(CH2) of DHPC equals that of DPPC above 45°C. This value was comparable to that of DPPC when the volume of the carbonyl groups was considered, which may signify that there is no significant conformational difference in the polar headgroups of both phospholipids. However, it was suggested from the consideration on v(H) of DHPC at 20°C that expansion of the headgroup region should occur as the interdigitated structure is formed, which means some conformational change of the headgroup region is induced by the interdigitation.
Colloids and surfaces. B, Biointerfaces 04/2012; 92:232-9. · 2.60 Impact Factor
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ABSTRACT: The bilayer phase transitions of dialkyldimethylammonium bromides (2C(n)Br; n = 12, 14, 16) were observed by differential scanning calorimetry and high-pressure light-transmittance measurements. Under atmospheric pressure, the 2C(12)Br bilayer membrane underwent the stable transition from the lamellar crystal (L(c)) phase to the liquid crystalline (L(α)) phase. The 2C(14)Br bilayer underwent the main transition from the metastable lamellar gel (L(β)) phase to the metastable L(α) phase in addition to the stable L(c)/L(α) transition. For the 2C(16)Br bilayer, moreover, three kinds of phase transitions were observed: the metastable main transition, the metastable transition from the metastable lamellar crystal (L(c(2))) phase to the metastable L(α) phase, and the stable lamellar crystal (L(c(1)))/L(α) transition. The temperatures of all the phase transitions elevated almost linearly with increasing pressure. The temperature (T)-pressure (p) phase diagrams of the 2C(12)Br and 2C(14)Br bilayers were simple, but that of the 2C(16)Br bilayer was complex; that is, the T-p curves for the metastable main transition and the L(c(2))/L(α) transition intersect at ca. 25 MPa, which means the inversion of the relative phase stability between the metastable phases of L(β) and L(c(2)) above and below the pressure. Moreover, the T-p curve of the L(c(2))/L(α) transition was separated into two curves under high pressure, and as a result, the pressure-induced L(c(2P)) phase appeared in between. Thermodynamic quantities for phase transitions of the 2C(n)Br bilayers increased with an increase in alkyl-chain length. The chain-length dependence of the phase-transition temperature for all kinds of transitions observed suggests that the stable L(c(1))/L(α) transition incorporates the metastable L(c(2))/L(α) transition in the bilayers of 2C(n)Br with shorter alkyl chains, and the main-transition of the 2C(12)Br bilayer would occur at a temperature below 0 °C.
Langmuir 05/2011; 27(10):5824-31. · 4.19 Impact Factor
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ABSTRACT: The phase transitions of dibehenoylphosphatidylcholine (C22PC) bilayer membrane were observed by differential scanning calorimetry under atmospheric pressure and light-transmittance measurements under high pressure. The constructed temperature-pressure phase diagram suggests that the gel phase at low temperatures is the interdigitated gel phase. To confirm the phase state, we performed small-angle neutron scattering and fluorescence measurements using a polarity-sensitive probe Prodan for the C22PC bilayer membrane under atmospheric pressure. The peaks obtained in both measurements clearly showed the characteristic patterns of the fully interdigitated gel phase. Taking into account of previous studies on the gel phase for long-chain PC bilayers under atmospheric pressure and our studies on the pressure-induced bilayer interdigitaion of diacyl-PCs, it turned out that the interdigitation of diacyl-PC bilayer membranes occurs when the carbon number of acyl chain reaches at least 22. The present study revealed that the interdigitation of PC bilayer membranes occurs not only by weakening the attractive force of polar head groups but also by strengthening the cohesive force of acyl chains. When dominating the force of acyl chains, the interdigitation can be induced even in a diacyl-PC bilayer membrane by only hydration under atmospheric pressure.
Colloids and surfaces. B, Biointerfaces 05/2011; 84(1):44-8. · 2.60 Impact Factor
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ABSTRACT: The bilayer phase behavior of asymmetric phospholipids, palmitoylstearoylphosphatidylcholine (PSPC) and stearoylpalmitoylphosphatidylcholine (SPPC), with different vesicle sizes (large multilamellar vesicle (LMV) and giant multilamellar vesicle (GMV)) was investigated by fluorescence spectroscopy using a polarity-sensitive fluorescent probe Prodan under high pressure. The results were compared with those of a symmetric phospholipid, diheptadecanoyl PC (C17PC). The difference in phase transitions of the PSPC and SPPC bilayers and in thermodynamic quantities of the transitions was hardly observed between LMV and GMV as the case of the C17PC bilayer. On the other hand, the Prodan fluorescence showed clear differences between LMV and GMV of the asymmetric PC bilayers. From the second derivative of Prodan fluorescence spectra, the three dimensional image plots in which we can clearly see the location of Prodan in the bilayer membrane as blue valleys were constructed for LMV and GMV under high pressure. We revealed from the plots that the bilayer packing is significantly dependent on not only the vesicle size but also the acyl-chain asymmetry of PC molecule in addition to the phase states. It was found that the packing of the gel phases of the asymmetric PC bilayers is weaker than that of the symmetric PC bilayer, and the size of vesicle affects the packing of the interdigitated gel phase the most markedly among three gel phases. This study suggests that the Prodan molecules can detect the effect of vesicle size on the phase states for the asymmetric PC bilayers, and they become a useful indicator for various membrane properties, especially bilayer interdigitation.
Colloids and surfaces. B, Biointerfaces 05/2011; 84(1):55-62. · 2.60 Impact Factor
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ABSTRACT: Bilayer phase transitions of dioctadecyldimethylammonium bromide (2C(18)Br) and chloride (2C(18)Cl) were observed by differential scanning calorimetry and high-pressure light-transmittance measurements. The 2C(18)Br bilayer membrane showed different kinds of transitions depending on preparation methods of samples under atmospheric pressure. Under certain conditions, the 2C(18)Br bilayer underwent three kinds of transitions, the metastable transition from the metastable lamellar crystal (L(c(2))) phase to the metastable lamellar gel (L(β)) phase at 35.4 °C, the metastable main transition from the metastable L(β) phase to the metastable liquid crystalline (L(α)) phase at 44.5 °C, and the stable transition from the stable lamellar crystal (L(c(1))) phase to the stable L(α) phase at 52.8 °C. On the contrary, the 2C(18)Cl bilayer underwent two kinds of transitions, the stable transition from the stable L(c) phase to the stable L(β) phase at 19.7 °C and the stable main transition from the stable L(β) phase to the stable L(α) phase at 39.9 °C. The temperatures of the phase transitions of the 2C(18)Br and 2C(18)Cl bilayers were almost linearly elevated by applying pressure. It was found from the temperature (T)-pressure (p) phase diagram of the 2C(18)Br bilayer that the T-p curves for the main transition and the L(c(1))/L(α) transition intersect at ca. 130 MPa because of the larger slope of the former transition curve. On the other hand, the T-p phase diagram of the 2C(18)Cl bilayer took a simple shape. The thermodynamic properties for the main transition of the 2C(18)Br and 2C(18)Cl bilayers were comparable to each other, whereas those for the L(c(1))/L(α) transition of the 2C(18)Br bilayer showed considerably high values, signifying that the L(c(1)) phase of the 2C(18)Br bilayer is extremely stable. These differences observed in both bilayers are attributable to the difference in interaction between a surfactant and its counterion.
Langmuir 03/2011; 27(5):1592-8. · 4.19 Impact Factor
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ABSTRACT: Pressure perturbation calorimetry (PPC) is a relatively new technique which provides the thermal expansion coefficient α2 of a solute. We give a detailed description on the theoretical background of this technique for a binary solution and a theoretical explanation for the method to estimate the volume change Δ v app, 2 with a phase transition. In this theory, a reversible isothermal pressure change is assumed, although an irreversible pressure change is applied in the PPC experiment. In order to verify the effect of this inconsistency, we carried out the PPC measurements for the dimyristoylphosphatidylcholine bilayer membrane. The Δ v app, 2 value with the gel-to-liquid-crystalline transition was estimated at 18.3 ml mol−1, which is in agreement with the literature values obtained by other techniques. This indicates that the irreversibility has virtually no effect on the Δ v app, 2 value and also supports the validity of the method for estimating the Δ v app, 2 value that we adopted.
High Pressure Research 12/2010; 30(4):490-498. · 0.78 Impact Factor
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ABSTRACT: The bilayer phase behavior of diheptadecanoylphosphatidylcholine (C17PC) with different vesicle sizes (large multilamellar vesicle (LMV) and giant multilamellar vesicle (GMV)) was investigated by fluorescence spectroscopy using a polarity-sensitive fluorescent probe Prodan under atmospheric and high pressures. The difference in phase transitions and thermodynamic quantities of the transition was hardly observed between LMV and GMV used here. On the contrary, the Prodan fluorescence in the bilayer membranes changed depending on the size of vesicles as well as on the phase states. From the second derivative of fluorescence spectra, the three-dimensional image plots in which we can see the location of Prodan in the bilayer membrane as blue valleys were constructed for LMV and GMV under atmospheric pressure. The following characteristic behavior was found: (1) the Prodan molecules in GMV can be distributed to not only adjacent glycerol backbone region, but also near bulk-water region in the lamellar gel or ripple gel phase; (2) the blue valleys of GMV became deeper than those of LMV because of the greater surface density of the Prodan molecules per unit area of GMV than LMV; (3) the liquid crystalline phase of the bilayer excludes the Prodan molecules to a more hydrophilic region at the membrane surface with an increase in vesicle size; (4) the accurate information as to the phase transitions is gradually lost with increasing vesicle size. Under the high-pressure condition, the difference in Prodan fluorescence between LMV and GMV was essentially the same as the difference under atmospheric pressure except for the existence of the pressure-induced interdigitated gel phase. Further, we found that Prodan fluorescence spectra in the interdigitated gel phase were especially affected by the size of vesicles. This study revealed that the Prodan molecules can move around the headgroup region by responding not only to the phase state but also to the vesicle size, and they become a useful membrane probe, detecting important membrane properties such as the packing stress.
Langmuir 08/2010; 26(16):13377-84. · 4.19 Impact Factor
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ABSTRACT: Effects of a short-chain phospholipid, dihexanoylphosphatidylcholine (DHPC), on the structure and morphology of membrane assemblies of a long-chain phospholipid, dimyristoylphosphatidylcholine (DMPC), were examined by fluorescence spectroscopy, differential scanning calorimetry (DSC), and cryogenic transmission electron microscopy (cryo-TEM). It was found by fluorescence measurements that DHPC affects on the gel and liquid crystalline state of DMPC vesicle membranes in different ways. Further, the result of DSC suggested that, along the transition process from DMPC vesicle to DMPC-DHPC mixed micelle, there are at least three different concentration regions which are characterized by the individual variation pattern of the transition temperature and enthalpy change. The cryo-TEM micrographs demonstrated the formation of thread-like assemblies in the second region and the coexistence of the assemblies and spherical micelles in the third region. Thus, it was concluded that the structural transition from DMPC vesicle to DMPC-DHPC mixed micelle could occur in a stepwise manner through the formation of the thread-like assembly, which cannot be described by the three-stage model of vesicle to micelle transition.
Colloids and surfaces. B, Biointerfaces 04/2010; 76(2):571-6. · 2.60 Impact Factor
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ABSTRACT: The recovery of Nicotiana tabacum L. cv. Bright Yellow 2 (BY-2) cells in Linsmaire and Skoog medium after treatment at high hydrostatic pressure was investigated using an Evans Blue staining method to discriminate live from dead cells. The survival of BY-2 cells just after the high-pressure treatment at 5 degrees C and 25 degrees C decreased abruptly at pressures higher than 50 MPa and 100 MPa, respectively. Furthermore, almost all of the BY-2 cells treated at 5 degrees C and 25 degrees C recovered pressures below 25 MPa and 75 MPa, respectively. However, no BY-2 cells recovered at pressures above 100 MPa at either temperature.
Annals of the New York Academy of Sciences 02/2010; 1189:139-42. · 3.15 Impact Factor
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ABSTRACT: The bilayer phase behavior of symmetric and asymmetric phosphatidylcholines (PCs), 1,2-diheptadecanoyl-PC (C17PC), 1-palmitoyl-2-stearoyl-PC (PSPC), and 1-stearoyl-2-palmitoyl-PC (SPPC), with different vesicle sizes were investigated by a high-pressure fluorescence method using the polarity-sensitive fluorescent probe Prodan. The second derivative of fluorescence spectra for all the PCs of small-sized vesicle showed four minima characteristic of four membrane states on the spectra irrespective of the acyl-chain symmetry, whereas those of large-sized vesicle had one more minimum originating from the most hydrophilic site at the membrane surface. These findings indicate that Prodan molecules can distribute into multiple sites in the bilayer and move around the head-group region depending on the vesicle size. The behavior of the spectra in the SPPC bilayer suggested that the interdigitated gel phase had a less polar "pocket" formed by a space between uneven terminal methyl ends of the sn-1 and sn-2 chains. It turned out that the curvature of vesicles affects the distribution of the Prodan molecules in all phases, more particularly in the interdigitated gel phase.
Annals of the New York Academy of Sciences 02/2010; 1189:68-76. · 3.15 Impact Factor
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ABSTRACT: The bilayer phase transitions of mixed-chain lipids with monounsaturated acyl chain in the sn-2 position, 1-myristoyl-2-oleoyl-sn-glycero-3-phosphocholine (MOPC), 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC), and with a polyunsaturated acyl chain in the sn-2 position, 1-stearoyl-2-linoleoyl-sn-glycero-3-phosphocholine (SLPC), 1-stearoyl-2-arachidonoyl-sn-glycero-3-phosphocholine (SAPC), and 1-stearoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine (SDPC), were observed by differential scanning calorimetry (DSC) under ambient pressure and by light-transmittance measurements under high pressure. The DSC thermogram for each lipid bilayer showed only one transition between the lamellar gel and liquid crystalline phases. The introduction of one or two cis double bonds into the sn-2 acyl chain caused the significant depression of the main-transition temperature and an obvious decrease of enthalpy and volume changes associated with the transition. These features are attributable to loose packing of saturated and unsaturated acyl chains in the bilayer gel phase. The existence of four or six double bonds in the sn-2 chain produced no further decrease in the transition temperature, and in fact six double bonds caused a slight increase in the transition temperature. Thermodynamic properties associated with the bilayer phase transition were discussed.
Annals of the New York Academy of Sciences 02/2010; 1189:77-85. · 3.15 Impact Factor
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ABSTRACT: Oligopeptidase B from Trypanosoma brucei (Tb OPB) is a virulence factor and therapeutic target in African sleeping sickness. Three glutamic acid residues at positions 607, 609 and 610 of the catalytic domain are highly conserved in the OPB subfamily. In this study, the roles of Glu(607), Glu(609) and Glu(610) in Tb OPB were investigated by site-directed mutagenesis. A striking effect on k(cat)/K(m) was obtained following mutation of Glu(607) to glutamine. In contrast, the heat stability of Tb OPB decreased markedly following the single mutation of Glu(610) to glutamine, although this mutation had significantly less effect on catalytic properties compared with the Glu(607) mutation. Although no differences were found in the tertiary and secondary structures between wild-type (WT) OPB and the E610Q mutant prior to heat treatment, the E610Q mutant is inactivated more rapidly than WT OPB following heat treatment in a manner correlating with its attendant structural changes. Trypsin digestion showed that the boundary regions between the beta-propeller and catalytic domain of the E610Q mutant are unfolded with heat treatment. It is concluded that Glu(607) is essential for the catalytic activity of Tb OPB and that Glu(610) plays a critical role in stabilization rather than catalytic activity despite their close proximity.
Journal of biochemistry 10/2009; 147(2):201-11. · 1.95 Impact Factor
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ABSTRACT: The bilayer phase transition of plasmalogen, monounsaturated plasmenylcholine 1-O-1'-(Z)-octadecenyl-2-oleoyl-sn-glycero-3-phosphocholine (Plg-SOPC), was examined by differential scanning calorimetry, high-pressure transmittance, and fluorescence techniques. The bilayer properties of Plg-SOPC such as the temperature-pressure phase diagram, the thermodynamic quantities of the transition, and the location of a fluorescent membrane probe in the bilayer, were compared with those of a similar phospholipid 1-stearoyl-2-oleoyl-phosphatidylcholine (SOPC). It turned out that a vinyl-ether bond in the sn-1 position of the glycerol backbone in the Plg-SOPC molecule produces a peculiar phase transition under high pressure and significantly affects the membrane properties.
Langmuir 09/2009; 25(19):11265-8. · 4.19 Impact Factor
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ABSTRACT: Inhibitions of amphiphiles with a long chain (alcohols with carbon number of 10, 12, 14, 16 and the corresponding fatty acids) on the antigen-antibody reaction between fluorescent probe (fluorescein (FL)) and anti-fluorescent probe monoclonal antibody (immunoglobulin G (IgG)-49) were investigated by fluorescence spectroscopy. The resulting inhibition modes were compared with those of specific inhibitors, 5- and 6-aminofluoresceins (5- and 6-FLNH(2)). In the presence of all inhibitors, the fluorescence quenching of FL as the result of inhibitor binding to IgG-49 was hindered in an inhibitor concentration-dependent manner. The values of IC(50) and Hill number for the inhibitors were determined from dose-response curves of the quenching inhibition. The IC(50) values of the alcohols were much more dependent on the chain length than those of the fatty acids although all the values were in orders of microM. The Hill numbers of both kinds of inhibitors became larger values than 1, but they had different values for a series of alcohols and fatty acids, respectively. By contrast, the IC(50) values of 5- and 6-FLNH(2) were in orders of nM and the Hill numbers became smaller values than 1. Since the Lineweaver-Burk plots produced an intersection point on the intercept of the X-axis for the long-chain inhibitors with carbon number of 14 while did that on the intercept of the Y-axis for 6-FLNH(2), respectively, we judged the inhibition modes of the former as non-competitive ones and those of the latter as a competitive one. Further, the effect of pressure on the inhibition by C(14)OH, C(13)COOH and 5-FLNH(2) was examined, and the standard volume changes of IgG-49 for the inhibitor binding were calculated from the Johnson-Eyring plots. The volume change for 5-FLNH(2) was smaller than those for C(14)OH and C(13)COOH although they became all negative. This suggests that the volume of IgG-49 shrinks by the addition of these inhibitors, and IgG-49 is not relevant to a model protein for the molecular mechanism of anesthesia.
Colloids and surfaces. B, Biointerfaces 09/2009; 75(1):80-7. · 2.60 Impact Factor
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ABSTRACT: The alignment of the sn-1 and sn-2 acyl chains at the terminal methyl ends generally produces significant influence on the thermodynamic properties of the bilayer phase transitions. We investigated the bilayer phase behavior of asymmetric phospholipids, myristoylpalmitoylphosphatidylcholine and palmitoylmyristoylphosphatidylcholine, by high-pressure light-transmittance and Prodan-fluorescence techniques and differential scanning calorimetry. Constructed temperature-pressure phase diagrams revealed that no stable Lbeta' phase can exist in the whole pressure range because of the formation of the most stable Lc phase. Nevertheless, the pretransition, the detection of which is severely hampered by the exceptionally prompt formation of the Lc phase, was successfully observed. Moreover, the effect of the total and difference of the sn-1 and sn-2 acyl chain lengths on minimal interdigitation pressure (MIP) was summarized in a MIP vs. chain-length inequivalence parameter plot, where the effect was proved to be classified in three zones depending on the alignment of both terminal methyl ends.
Chemistry and physics of lipids 08/2009; 161(2):65-76. · 2.15 Impact Factor
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ABSTRACT: The phase transitions of distearoyl- (DSPC), dipalmitoyl- (DPPC) and dimyristoyl-phosphatidylcholine (DMPC) bilayer membranes were observed by means of differential scanning calorimetry as a function of the concentration of a local anesthetic tetracaine hydrochloride (TC.HCl). The depression of both temperatures of the main- and pre-transition, which is accompanied by a decrease in enthalpy changes for both transitions, was observed initially by the addition of TC.HCl. Bilayer interdigitation, which is accompanied by an increase in enthalpy change for the main transition from the interdigitated gel phase to the liquid crystalline phase, was followed by disappearance of the pretransition. The TC.HCl concentration necessary for the bilayer interdigitation was found to be 10, 21 and 6 mmol kg(-1) for DSPC, DPPC and DMPC bilayers, respectively, which was not consistent with the order of acyl-chain length of lipids. Biphasic interactions for the interdigitation, that is, repulsive interaction between polar head groups and van der Waals attractive interaction between hydrophobic chains of lipids, were discussed. On the other hand, vesicle-to-micelle transformation, which is accompanied by a cooperative decrease in enthalpy change for the main transition, was observed at higher concentration of TC.HCl and was confirmed by the vesicle size determined by the dynamic light scattering. The longer the acyl-chain length of lipids, the higher the TC.HCl concentration necessary for the vesicle-to-micelle transformation.
Colloids and surfaces. B, Biointerfaces 05/2009; 72(1):135-40. · 2.60 Impact Factor
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ABSTRACT: The effects of long-chain fatty acids (four saturated and two unsaturated fatty acids, one derivative) on phase transitions of dipalmitoylphosphatidylcholine (DPPC) bilayer membranes were examined in the low concentration region, and the results were compared with those for an inhalation anesthetic. The effects of all fatty acids on the pre- and main-transition temperatures of the DPPC bilayer membrane appeared in the concentration range of microM order while that of the anesthetic appeared in the mM order. The appearance modes of these ligand actions were significantly different from one another. The three differential partition coefficients of the ligands between two phases of the DPPC bilayer membrane were evaluated by applying the thermodynamic equation to the variation of the phase-transition temperatures. The DPPC bilayer membranes showed the different receptivity for the ligands; the saturated fatty acids had an affinity for gel phase whereas unsaturated fatty acids and an anesthetic had an affinity for liquid-crystalline phase to the contrary. In particular, the receptivity for the ligands in the gel phase markedly changed depending on kinds of ligands. The interaction modes between the DPPC and fatty acid molecules in the gel phase were considered from the hexagonal lattice model. The disappearance compositions of the pretransition by the fatty acids coincided with the compositions at which the membrane is all covered by the units in each of which two fatty acids molecules are regularly distributed in the hexagonal lattice in a different way, and the distribution depended on the chain length and existence of a double bond for the fatty acids. The interpretation did not hold for the case of the anesthetic at all, which proved that a number of anesthetic molecules act the surface region of the bilayer membrane nonspecifically. The present study clearly implies that DPPC bilayer membranes have high ability to recognize kinds of ligand molecules and can discriminate among them with specific interaction by the membrane states.
Chemistry and physics of lipids 05/2009; 158(2):71-80. · 2.15 Impact Factor
