Biophysical Chemistry, Colloid and Surface Chemistry, Molecular Theory of Anesthesia, High Pressure Science
Subject of Study
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High Pressure Adaptation of Living Organisms, Solution and Surface Properties of Amphiphilic Drugs, Local Anesthetic Sensor, Pressure Denaturation of Proteins (Phospholipids, Local Anesthetics, Surfactants, High Pressure, Bilayer Membranes)
Hitoshi Matsuki and Shoji Kaneshina : Encyclopedia of Surface and Colloid Science, --- Molecular Interactions between Local Anesthetics and Model Biomembranes ---, Marcel Dekker.Inc, New York, May 2002.
Shoji Kaneshina, Katsuhiro Tamura, Takayoshi Isaka and Hitoshi Matsuki : High Pressure Liquids and Solutions, --- Pressure Studies on the Phase-Transition Behavior in Phospholipid/Anesthetic Suspensions ---, Elsevier, Amsterdam, Sep. 1994.
Nobutake Tamai, Maiko Uemura, Takuya Izumikawa, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : Phase Behavior of Cholesterol-Containing Binary Membrane of an Ether-Linked Phospholipid, Dihexadecylphosphatidylcholine, Colloid and Polymer Science, Vol.296, No.4, 697-711, 2018.
(Summary)
The thermotropic phase behavior of the cholesterol (Chol)-containing binary membrane of dihexadecylphosphatidylcholine (DHPC) was investigated as a function of the mole fraction of Chol Xch by DSC and fluoresce spectroscopy using 6-propionyl-2-(N,N-dimethylamino)naphthalene (Prodan). The main-transition enthalpy Hm was almost constant at Xch < ca. 0.05, but it decreased almost linearly with increasing Xch above 0.05 until it reached 0 at Xch = ca. 0.50, suggesting that the interaction between DHPC and Chol is relatively weaker than that between dipalmitoylphosphatidylcholine (DPPC) and Chol. The Prodan fluorescence spectra changed depending on the phase state, which was characterized by the wavelength at the emission maximum. Particularly, the two-phase state of the interdigitated (LβI) and non-interdigitated gel (Lβ) was sensitively detected as the superposition of the two elementary spectra corresponding to each phase state, allowing us to explain the Xch dependent non-linear behavior of the Chol-induced Lβ phase by introducing a proportionality factor ξ(Xch) and by assuming a simple probabilistic process. By comparing the phase diagram constructed for the DHPC Chol binary membrane with that for the DPPC Chol binary bilayer, a difference was observed in the minimum Xch value for the entire formation of the liquid ordered (Lo) phase. This difference could be explained in terms of the hydrophobic mismatch at the bilayer midplane by taking into account the difference in the capability of hydrogen bonding with the 3β-OH group of Chol due to the presence or absence of the carbonyl oxygens at the glycerol backbone.
Hitoshi Matsuki, Kentaro Kato, Hirotsugu Okamoto, Shuntaro Yoshida, Masaki GOTO, Nobutake Tamai and Shoji Kaneshina : Ligand partitioning into lipid bilayer membranes under high pressure: implication of variation in phase-transition temperatures, Chemistry and Physics of Lipids, Vol.209, 9-18, 2017.
(Summary)
The variation in phase-transition temperatures of dipalmitoylphosphatidylcholine (DPPC) bilayer membrane by adding two membrane-active ligands, a long-chain fatty acid (palmitic acid (PA)) and an inhalation anesthetic (halothane (HAL)), was investigated by light-transmittance measurements and fluorometry. By assuming the thermodynamic colligative property for the bilayer membrane at low ligand concentrations, the partitioning behavior of these ligands into the DPPC bilayer membrane was considered. It was proved from the differential partition coefficients between two phases that PA has strong affinity with the gel (lamellar gel) phase in a micro-molal concentration range and makes the bilayer membrane more ordered while HAL has strong affinity with the liquid crystalline phase in a milli-molal concentration range and does the bilayer membrane more disordered. The transfer volumes of both ligands from the aqueous solution to each phase of the DPPC bilayer membrane showed that the preferential partitioning of the PA molecule into the gel (lamellar gel) produces about 20% decrease in transfer volume as compared with the liquid crystalline phase, whereas that of the HAL molecule into the liquid crystalline phase does about twice increase in transfer volume as compared with the gel (ripple gel) phase. Furthermore, changes in thermotropic and barotropic phase behavior of the DPPC bilayer membrane by adding the ligand was discussed from the viewpoint of the ligand partitioning. Reflecting the contrastive partitioning of PA and HAL into the pressure-induced interdigitated gel phase among the gel phases, it was revealed that PA suppresses the formation of the interdigitated gel phase under high pressure while HAL promotes it. These results clearly indicate that each phase of the DPPC bilayer membrane has a potential to recognize various ligand molecules.
Hitoshi Matsuki, Shigeru Endo, Ryosuke Sueyoshi, Masaki GOTO, Nobutake Tamai and Shoji Kaneshina : Thermotropic and barotropic phase transitions on diacylphosphatidylethanolamine bilayer membranes, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.1859, No.7, 1222-1232, 2017.
(Summary)
The bilayer phase transitions of four diacylphosphatidylethanolamines (PEs) with identical two saturated acyl chains (Cn = 12, 14, 16 and 18) and two PEs with identical two unsaturated acyl chains containing a different kind of double bonds were observed by differential scanning calorimetry under atmospheric pressure and light-transmittance measurements under high pressure. The temperature-pressure phase diagrams for these PE bilayer membranes were constructed from the obtained phase-transition data. The saturated PE bilayer membranes underwent two different phase transitions related to the liquid crystalline (Lα) phase, the transition from the hydrated crystalline (Lc) phase and the chain melting (main) transition, depending on the thermal history. Pressure induced the change in the gel-phase stability of the bilayer membranes of PEs with longer chains at a low pressure. Comparing the thermodynamic quantities of the saturated PE bilayer membranes with those of diacylphosphatidylcholines (PC) bilayer membranes, the PE bilayer membranes showed higher phase-transition temperatures and formed more stable Lc phase, which originates from the strong interaction between polar head groups of PE molecules. On the other hand, the unsaturated PE bilayer membranes underwent the transition from the Lα phase to the inverted hexagonal (HII) phase at a high temperature and this transition showed small thermodynamic quantities but high-pressure responsivity. It turned out that the kind of double bonds markedly affects both bilayer-bilayer and bilayer-nonbilayer transitions and the Lα/HII transition is a volume driven transition for the reconstruction of molecular packing. Further, the phase-transition behavior was explained by chemical potential profiles of bilayer phases.
Nobutake Tamai, Takuya Izumikawa, Suguru Fukui, Maiko Uemura, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : How Does Acyl-chain Length Affect Thermotropic Phase Behavior of Saturated Diacylphosphatidylcholine-chloresterol Binary Bilayers?, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.1828, No.11, 2513-2523, 2013.
(Summary)
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 C17PC and 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.
Nobutake Tamai, Yuko Nambu, Saeko Tanaka, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : Volumetric characterization of ester- and ether-linked lipid bilayers by pressure perturbation calorimetry and densitometry, Colloids and Surfaces B:Biointerfaces, Vol.92, No.1, 232-239, 2012.
(Summary)
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.
Saeko Tanaka, Nobutake Tamai, Masaki GOTO, Shoji Kaneshina and Hitoshi Matsuki : Morphological Change of Vesicle Particle can Produce a Peculir Stepwise Transition in Dipalmitoylphosphatidylglycerol Bilayer at High NaCl Concentration, Chemistry Letters, Vol.41, No.3, 304-306, 2012.
Makoto Nishimoto, Ukyo Komatsu, Nobutake Tamai, Michio Yamanaka, Shoji Kaneshina, Kenji Ogli and Hitoshi Matsuki : Intrinsic interaction mode of an inhalation anesthetic with globular proteins: a comparative study on ligand recognition, Colloid and Polymer Science, Vol.289, No.17-18, 1785-1797, 2011.
Masaki GOTO, Shunsuke Ishida, Yuka Ito, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Thermotropic and Barotropic Phase Transitions of Dialkyldimethylammonium Bromide Bilayer Membranes: Effect of Chain Length, Langmuir, Vol.27, No.10, 5824-5831, 2011.
(Summary)
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.
Masaki GOTO, Takayuki Matsui, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Prodan fluorescence detects the bilayer packing of asymmetric phospholipids, Colloids and Surfaces B:Biointerfaces, Vol.84, No.1, 55-62, 2011.
(Summary)
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.
Masaki GOTO, Yuka Ito, Shunsuke Ishida, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Hydrostatic Pressure Reveals Bilayer Phase Behavior of Dioctadecyldimethylammonium Bromide and Chloride, Langmuir, Vol.27, No.5, 1592-1598, 2011.
(Summary)
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.
Nobutake Tamai, Yuko Nambu, Maiko Tsutsui, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : Application of pressure perturbation calorimetry to the aqueous system of phospholipid vesicle dispersion, High Pressure Research, Vol.30, No.4, 490-498, 2010.
Hitoshi Matsuki, Makoto Nishimoto, Kaori Tada, Masaki GOTO, Nobutake Tamai and Shoji Kaneshina : Packing state in bilayer membranes of diacylphosphatidylcholines with varying acyl chain lengths under high pressure, High Pressure Research, Vol.30, No.4, 475-482, 2010.
Masaki GOTO, Hiroshi Sawaguchi, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Effect of Vesicle Size on the Prodan Fluorescence in Diheptadecanoylphosphatidylcholine Bilayer Membrane under Atmospheric and High Pressures, Langmuir, Vol.26, No.16, 13377-13384, 2010.
(Summary)
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.
Masaki GOTO, Masataka Kusube, Makoto Nisimoto, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Pressure Study on Symmetric and Asymmetric Phospholipid Bilayers: Effect of Vesicle Size on Prodan Fluorescence, Annals of the New York Academy of Sciences, Vol.1189, 68-76, 2010.
(Summary)
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.
Kaori Tada, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Pressure Effect on the Bilayer Phase Transition of Asymmetric Lipids with an Unsaturated Acyl Chain, Annals of the New York Academy of Sciences, Vol.1189, 77-85, 2010.
(Summary)
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.
Makoto Nishimoto, Tohru Morimitsu, Nobutake Tamai, Shoji Kaneshina, Hideaki Nagamune and Hitoshi Matsuki : Inhibition of anti-fluorescent probe monoclonal antibody by long-chain amphiphiles, Colloids and Surfaces B:Biointerfaces, Vol.75, No.1, 80-87, 2010.
(Summary)
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.
Masaki GOTO, Shunsuke Ishida, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Chain asymmetry alters thermotropic and barotropic properties of phospholipid bilayer membranes, Chemistry and Physics of Lipids, Vol.161, No.2, 65-76, 2009.
(Summary)
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.
Makoto Nishimoto, Ukyo Komatsu, Nobutake Tamai, Michio Yamanaka, Shoji Kaneshina, Kenji Ogli and Hitoshi Matsuki : A comparative study on specific and nonspecific interactions in bovine serum albumin: thermal and volume effects of halothane and palmitic acid, Colloid and Polymer Science, Vol.287, No.8, 979-989, 2009.
Koichi Takeda, Hiroko Okuno, Takashi Hata, Makoto Nishimoto, Hitoshi Matsuki and Shoji Kaneshina : Interdigitation and vesicle-to-micelle transformation induced by a local anesthetic tetracaine in phospholipids bilayers, Colloids and Surfaces B:Biointerfaces, Vol.72, No.1, 135-140, 2009.
(Summary)
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.
Koichi Takeda, You Sano, Sosaku Ichikawa, Yuuki Hirata, Hitoshi Matsuki and Shoji Kaneshina : Effect of a Local Anesthetic Lidocaine Hydrochloride on the Bilayer Structure of Phospholipids, Journal of Oleo Science, Vol.58, No.7, 369-377, 2009.
(Summary)
The effect of a local anesthetic, lidocaine hydrochloride (LC x HCl), on the bilayer systems of purified egg phosphatidylcholine (EPC), dipalmitoylphosphatidylcholine (DPPC) and dioleoylphosphatidylcholine (DOPC) was studied by means of small-angle X-ray scattering (SAXS), Prodan fluorescence and electrophoretic light scattering. In the liquid crystalline phase of EPC and DOPC bilayers, the contraction of lamellar distance by ca. 0.8-1.0 nm and the decrease of average vesicle size were observed in the presence of LC x HCl. The adsorption of LC x HCl on the vesicle interface brought about the lateral expansion of bilayers and the decrease in the radius of curvature of vesicles. The contraction in the lamellar distance of EPC bilayer caused by high concentration of LC x HCl is attributable to the chain folding in the liquid crystalline state. In the gel phase of DPPC bilayer, the contraction of the lamellar distance in the presence of 0.37 M LC x HCl amounts to 1.6 nm, and the emission maximum of Prodan fluorescence was red-shifted from 440 nm to 518 nm. These phenomena are attributed to the formation of LC x HCl-induced interdigitated gel phase.
Kaori Tada, Eri Miyazaki, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Barotropic and thermotropic bilayer phase behavior of positional isomers of unsaturated mixed-chain phosphatidylcholines, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.1788, No.5, 1056-1063, 2009.
(Summary)
The bilayer phase transitions of six kinds of mixed-chain phosphatidylcholines (PCs) with an unsaturated acyl chain in the sn-1 or sn-2 position, 1-oleoyl-2-stearoyl- (OSPC), 1-stearoyl-2-oleoyl- (SOPC), 1-oleoyl-2-palmitoyl- (OPPC), 1-palmitoyl-2-oleoyl- (POPC), 1-oleoyl-2-myristoyl- (OMPC) and 1-myristoyl-2-oleoyl-sn-glycero-3-phosphocholine (MOPC), were observed by means of differential scanning calorimetry (DSC) and high-pressure light transmittance measurements. Bilayer membranes of SOPC, POPC and MOPC with an unsaturated acyl chain in the sn-2 position exhibited only one phase transition, which was identified as the main transition between the lamellar gel (L(beta)) and liquid crystalline (L(alpha)) phases. On the other hand, the bilayer membranes of OSPC, OPPC and OMPC with an unsaturated acyl chain in the sn-1 position exhibited not only the main transition but also a transition from the lamellar crystal (L(c)) to the L(beta) (or L(alpha)) phase. The stability of their gel phases was markedly affected by pressure and chain length of the saturated acyl chain in the sn-2 position. Considering the effective chain lengths of unsaturated mixed-chain PCs, the difference in the effective chain length between the sn-1 and sn-2 acyl chains was proven to be closely related to the temperature difference of the main transition. That is, a mismatch of the effective chain length promotes a temperature difference of the main transition between the positional isomers. Anomalously small volume changes of the L(c)/L(alpha) transition for the OPPC and OMPC bilayers were found despite their large enthalpy changes. This behavior is attributable to the existence of a cis double bond and to significant inequivalence between the sn-1 and sn-2 acyl chains, which brings about a small volume change for chain melting due to loose chain packing, corresponding to a large partial molar volume, even in the L(c) phase. Further, the bilayer behavior of unsaturated mixed-chain PCs containing an unsaturated acyl chain in the sn-1 or sn-2 position was well explained by the chemical-potential diagram of a lipid in each phase.
Makoto Nishimoto, Takashi Hata, Masaki GOTO, Nobutake Tamai, Shoji Kaneshina, Hitoshi Matsuki and Issaku Ueda : Interaction modes of long-chain fatty acids in dipalmitoylphosphatidylcholine bilayer membrane: contrast to mode of inhalation anesthetics, Chemistry and Physics of Lipids, Vol.158, No.2, 71-80, 2009.
(Summary)
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.
Kaori Tada, Kensuke Saito, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : High-pressure study on bilayer phase behavior of oleoylmyristoyl- and myristoyloleoyl-phosphatidylcholines, Biophysical Chemistry, Vol.138, No.1-2, 36-41, 2008.
(Summary)
We investigated the thermotropic and barotropic bilayer phase behavior of 1-myristoyl-2-oleoyl-sn-glycero-3-phosphocholine (MOPC) and 1-oleoyl-2-myristoyl-sn-glycero-3-phosphocholine (OMPC) by means of the differential scanning calorimetry (DSC) and high-pressure light-transmittance technique. Water could be used as a solvent for measurements at high pressures because of the elevation of the transition temperatures above 0 degrees C by pressurization, whereas aqueous 50 wt.% ethylene glycol solution was used mainly for those at low pressures. Only one phase transition was observed in the DSC thermogram of the MOPC bilayer membrane as an endothermic peak, and also observed at high pressures as an abrupt change of the light-transmittance. The transition was assigned as a main transition between the lamellar gel (L(beta)) and liquid-crystalline (L(alpha)) phases on the basis of the values of enthalpy change (DeltaH) and slope of the transition temperature with respect to pressure (dT/dP). The DSC thermogram of the OMPC bilayer membrane similarly showed a single endothermic peak but two kinds of phase transitions were observed at different temperatures in the light-transmittance profile at high pressures. The extrapolation of the lower-temperature transition in the high-pressure range to an ambient pressure coincided with the transition observed in the DSC thermogram. This transition was identified as a transition between the lamellar crystal (L(c)) and L(alpha) (or L(beta)) phases from the DeltaH and dT/dP values. The higher-temperature transition, appearing only at high pressures, was identified as the L(beta)/L(alpha) transition considering the topological resemblance of its temperature-pressure phase diagram as that of the dioleoylphosphatidylcholine bilayer membrane. The phase diagram of the OMPC bilayer membrane demonstrated that the L(beta) phase cannot exist at pressures below ca. 190 MPa while it can exist stably in a finite temperature range at pressures above the pressure.
Nobutake Tamai, Maiko Uemura, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : Lateral phase separation in cholesterol/diheptadecanoylphosphatidylcholine binary bilayer membrane, Colloids and Surfaces B:Biointerfaces, Vol.65, No.2, 213-219, 2008.
(Summary)
We investigated the phase behavior of cholesterol/diheptadecanoylphosphatidylcholine (C17:0-PC) binary bilayer membrane as a function of the cholesterol composition (X(ch)) by fluorescence spectroscopy using 6-propionyl-2-(dimethylamino)naphthalene (Prodan) and differential scanning calorimetry (DSC). The fluorescence spectra showed that the wavelength at the maximum intensity (lambda(max)) changed depending on the bilayer state: ca. 440 nm for the lamellar gel (L'(beta) or L(beta)) and the liquid ordered (L(o)) phases and ca. 490 nm for the liquid-crystalline (L(alpha)) phase. The transition temperatures were determined from the temperature dependence of lambda(max) and endothermic peaks of the DSC thermograms. Both measurements showed that the pre- and main transition disappear around X(ch)=0.05 and 0.30, respectively. The constructed temperature-X(ch) phase diagram resembled a typical phase diagram for a eutectic binary mixture containing a peritectic point. The presence of a peritectic point at X(ch)=0.15 suggested that a complex of cholesterol and C17:0-PC is stoichiometrically formed in the gel phase. Consideration based on the hexagonal lattice model revealed that the compositions of 0.05 and 0.15 correspond to the bilayer states where cholesterol molecules are regularly distributed in different ways. The former is nearly equal to the composition for the membrane occupied entirely with Units (1:18), composed of a cholesterol and 18 surrounding C17:0-PC molecules within the next-next nearest neighbor sites. The latter is represented by a Unit (1:6), including a cholesterol and 6 surrounding C17:0-PC molecules. Further, the disappearance of the main transition at X(ch)=0.30 indicates that the pure L(o) phase can exist in X(ch)>0.30. The eutectic behavior observed in the phase diagram was explainable in terms of phase separation between two different types of regions with different types of regular distributions of cholesterol.
Nobutake Tamai, Maiko Uemura, Tetsuya Takeichi, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : A new interpretation of eutectic behavior for distearoylphosphatidylcholine-cholesterol binary bilayer membrane, Biophysical Chemistry, Vol.135, No.1-3, 95-101, 2008.
(Summary)
We investigated the thermotropic phase behavior of the distearoylphosphatidylcholine (DSPC)-cholesterol binary bilayer membrane as a function of the cholesterol composition (X(ch)) by fluorescence spectroscopy using 6-propionyl-2-(dimethylamino)naphthalene (Prodan) and differential scanning calorimetry (DSC). The fluorescence spectra, each of which has a single maximum, showed that the wavelength at the maximum intensity (lambda(max)) changed depending on the bilayer state: ca. 440 nm for the lamellar gel (L(beta)' or L(beta)) and the liquid ordered (L(o)) phases, ca. 470 nm for the ripple gel (P(beta)') phase and ca. 490 nm for the liquid crystalline (L(alpha)) phase, respectively. The transition temperatures were determined from the temperature dependences of the lambda(max) and endothermic peaks of the DSC thermograms. Both measurements showed that the pretransition disappears around X(ch)=0.035. The constructed temperature-X(ch) phase diagram indicated that the phase behavior of the binary bilayer membrane at X(ch)< or =0.15 is similar to that of general liquid-solid equilibrium for a binary system where both components are completely miscible in the liquid phase and completely immiscible in the solid phase. It was also revealed that the diagram has two characteristic points: a congruent melting point at X(ch)=0.08 and a peritectic-like point at X(ch)=0.15. The hexagonal lattice model was used for the interpretation of the phase behavior of the binary bilayer membrane. These characteristic compositions well correspond to the bilayer states in each of which cholesterol molecules are regularly distributed in the hexagonal lattice in a different way. That is, each composition of 0.035, 0.08 and 0.15 is nearly equal to that for the binary bilayer membrane which is entirely occupied with units, each composed of a cholesterol and 30 surrounding DSPC molecules within the next-next-next nearest neighbor sites (Unit (1:30): L(beta)(1:30)), with units, each of a cholesterol and 12 surrounding DSPC molecules within the next nearest sites (Unit (1:12): L(beta)(1:12)) or with units, each of a cholesterol and 6 surrounding DSPC molecules at the nearest neighbor sites (Unit (1:6): L(beta)(1:6)), respectively. Therefore, the eutectic behavior observed in the phase diagram was fully explainable in terms of a kind of phase separation between two different types of regions with different types of regular distributions of cholesterol. Further, the L(o) phase was found in the higher X(ch)-region (X(ch)>0.15). No endothermic peak over the temperature range from 10 to 80 degrees C at X(ch)=0.50 suggested that the single L(o) phase can exist at X(ch)>0.50.
Kaori Tada, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Thermotropic and barotropic phase transitions of dilauroylphosphatidylcholine bilayer, Chemistry and Physics of Lipids, Vol.153, No.2, 138-143, 2008.
(Summary)
The bilayer phase transitions of dilauroylphosphatidylcholine (DLPC), containing two linear acyl chains with 12 carbon atoms, were observed by means of differential scanning calorimetry (DSC) under ambient pressure and light transmittance under high pressure. When the heating scan for the DLPC bilayer in 50 wt.% aqueous ethylene glycol (EG) solution began at -30 degrees C after cold storage, the DSC thermogram showed two endothermic peaks at 1.7 and 4.5 degrees C, which correspond to the transition from the lamellar crystalline (Lc) phase to the intermediate liquid crystalline (Lx) phase and the transition from the Lx phase to the liquid crystalline (L) phase, respectively. Extremely large enthalpy change (32.9 kJ mol(-1)) is characteristic of the Lc/Lx phase transition. The DSC thermogram for the heating scan beginning from -10 degrees C showed a single endothermic peak with 9.2 kJ mol(-1) at -0.4 degrees C, which was assigned as the so-called main transition between the metastable ripple gel (P'(beta)) and metastable Lalpha phases. The DLPC bilayer under high pressure underwent three kinds of transitions in EG solution, whereas only one transition was observed in water under high pressure. The middle-temperature transition in EG solution could be assigned to the main transition because of its consistency with the main transition in water. The lower-temperature transition is probably assigned as transition from the Lc phase to the P'(beta) phase. Since the slope (dT/dp) of the Lc/P'(beta) phase boundary is smaller than that for the main transition, the Lc/P'(beta) phase boundary and the main transition curves crossed each other at 40 MPa on the temperature-pressure phase diagram. The higher-temperature transition in EG solution refers to the transition from the Lx phase to the Lalpha phase. The Lx phase disappeared at about 180 MPa, and the direct transition from the P'(beta) phase to the Lalpha phase was observed at high pressures above 180 MPa.
Masaki GOTO, Masataka Kusube, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Effect of hydrostatic pressure on the bilayer phase behavior of symmetric and asymmetric phospholipids with the same total chain length, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.1778, No.4, 1067-1078, 2008.
(Summary)
The bilayer phase transitions of palmitoylstearoyl-phosphatidylcholine (PSPC), diheptadecanoyl-PC (C17PC) and stearoylpalmitoyl-PC (SPPC) which have the same total carbon numbers in the two acyl chains were observed by differential scanning calorimetry and high-pressure optical method. As the temperature increased, these bilayers exhibited four phases of the subgel (Lc), lamellar gel (L beta'), ripple gel (P beta') and liquid crystal (L alpha), in turn. The Lc phase was observed only in the first heating scan after cold storage. The temperatures of the phase transitions were almost linearly elevated by applying pressure. The temperature-pressure phase diagrams and the thermodynamic quantities associated with the phase transitions were compared among the lipid bilayers. For all the bilayers studied, the pressure-induced interdigitated gel (L beta I) phase appeared above the critical interdigitation pressure (CIP) between the L beta' and P beta' phases. The CIPs for the PSPC, C17PC and SPPC bilayers were found to be 50.6, 79.1 and 93.0 MPa, respectively. Contribution of two acyl chains to thermodynamic properties for the phase transitions of asymmetric PSPC and SPPC bilayers was not even. The sn-2 acyl chain lengths of asymmetric PCs governed primarily the bilayer properties. The fluorescence spectra of Prodan in lipid bilayers showed the emission maxima characteristic of bilayer phases, which were dependent on the location of Prodan in the bilayers. Second derivative of fluorescent spectrum exhibited the original emission spectrum of Prodan to be composed of the distribution of Prodan into multiple locations in the lipid bilayer. The F''497/F''430 value, a ratio of second derivative of fluorescence intensity at 497 nm to that at 430 nm, is decisive evidence whether bilayer interdigitation will occur. With respect to the L beta'/L beta I phase transition in the SPPC bilayer, the emission maximum of Prodan exhibited the narrow-range red-shift from 441 to 449 nm, indicating that the L beta I phase in the SPPC bilayer has a less polar "pocket" formed by a space between uneven terminal methyl ends of the sn-1 and sn-2 chains, in which the Prodan molecule remains stably.
Yuichi Takajo, Hitoshi Matsuki, Shoji Kaneshina, Makoto Aratono and Michio Yamanaka : Miscibility and interaction between 1-alkanol and short-chain phosphocholine in the adsorbed film and micelles, Colloids and Surfaces B:Biointerfaces, Vol.59, No.1, 52-58, 2007.
(Summary)
The miscibility and interaction of 1-hexanol (C6OH) and 1-heptanol (C7OH) with 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) in the adsorbed films and micelles were investigated by measuring the surface tension of aqueous C6OH-DHPC and aqueous C7OH-DHPC solutions. The surface density, the mean molecular area, the composition of the adsorbed film, and the excess Gibbs energy of adsorption g(H,E), were estimated. Further, the critical micelle concentration of the mixtures was determined from the surface tension versus molality curves; the micellar composition was calculated. The miscibility of the 1-alkanols and DHPC molecules in the adsorbed film and micelles was examined using the phase diagram of adsorption (PDA) and that of micellization (PDM). The PDA and the composition dependence of g(H,E) indicated the non-ideal mixing of the 1-alkanols and DHPC molecules due to the attractive interaction between the molecules in the adsorbed film, while the PDM indicated that the 1-alkanol molecules were not incorporated in the micelles within DHPC rich region. The dependence of the mean molecular area of the mixtures on the surface composition suggested that the packing property of the adsorbed film depends on the chain length of 1-alkanol: C6OH expands the DHPC adsorbed film more than C7OH.
Michio Yamanaka, Yuichi Takajo, Shinji Ono, Hitoshi Matsuki and Shoji Kaneshina : Volume study on the exclusion of lithium naphthylsulfonate from lithium decylsulfonate micelles, Colloid and Polymer Science, Vol.285, No.7, 761-769, 2007.
Hitoshi Matsuki, Michio Yamanaka, Yuji Yamashita and Shoji Kaneshina : Adsorption-Equilibrium Surface Tension of Surfactant Solutions -Examination by the Drop Volume Method-, Bulletin of the Chemical Society of Japan, Vol.79, No.11, 1704-1710, 2006.
Masataka Kusube, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Bilayer Phase Transitions of N-methylated Dioleoylphosphatidylethanolamines under High Pressure, Chemistry and Physics of Lipids, Vol.142, No.1-2, 94-102, 2006.
(Summary)
The bilayer phase transitions of four kinds of unsaturated phospholipids with different-sized polar head groups, dioleoylphosphatidylethanolamine (DOPE), dioleoylphosphatidyl-N-methylethanolamine (DOMePE), dioleoylphosphatidyl-N,N-dimethylethanolamine (DOMe2PE) and dioleoylphosphatidylcholine (DOPC), were observed by means of differential scanning calorimetry (DSC) and high-pressure light-transmittance. DSC thermogram and light-transmittance curve for each phospholipid vesicle solution exhibited only one phase transition under ambient pressure, respectively. The light-transmittance of DOPC solution at pressure higher than 234 MPa abruptly increased stepwise at two temperatures, which corresponds to the appearance of stable subgel and lamellar gel phases under high pressure in addition to the liquid crystal phase. The constructed temperature (T)-pressure (p) phase diagrams were compared among these phospholipids. The phase-transition temperatures of the phospholipids decreased stepwise by N-methylation of the head group. The slops of the T-p phase boundary (dT/dp) of DOPE, DOMePE and DOMe2PE bilayers (0.127-0.145 K MPa-1) were found to be close to that of the transition from the lamellar crystal (or subgel; Lc) phase to the liquid crystal (Lalpha) phase for DOPC bilayer (0.131 K MPa-1). On the other hand, the dT/dp value of the main transition from the lamellar gel (Lbeta) phase to the Lalpha phase for DOPC bilayer (0.233 K MPa-1) was significantly different from that of the Lc/Lalpha transition, hence both curves intersected with each other at 234 MPa. The thermodynamic quantities associated with the phase transition of DOPE, DOMePE and DOMe2PE bilayers had also similar values to those for the Lc/Lalpha transition of DOPC bilayer. Taking into account of the values of transition temperature, dT/dp and thermodynamic quantities compared with the corresponding results of saturated phospholipids, we identified the phase transitions observed in the DOPE, DOMePE and DOMe2PE bilayers as the transition from the Lc phase to the Lalpha phase although they have been regarded as the main transition in the previous studies. The Lbeta phase is probably unstable for DOPE, DOMePE and DOMe2PE bilayers at all pressures, it exists as a metastable phase at pressures below 234 MPa while as a stable phase at pressures above 234 MPa in DOPC bilayer. The difference in phase stability among the phospholipid bilayers is originated from that in hydration structure of the polar head groups.
Ryosuke Sueyoshi, Kaori Tada, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Barotropic phase transition between the lamellar liquid crystal phase and the inverted hexagonal phase of dioleoylphosphatidylethanolamine, Colloids and Surfaces B:Biointerfaces, Vol.50, No.1, 85-88, 2006.
(Summary)
The phase transition between the lamellar liquid crystal (Lalpha) phase and the inverted hexagonal (H(II)) phase of dioleoylphosphatidylethanolamine (DOPE) in aqueous NaCl solutions was observed by means of differential scanning calorimetry (DSC) under ambient pressure and light-transmittance technique under high pressure. The pressure dependence of the transition temperature (dT/dp) and the thermodynamic quantities for the Lalpha/H(II) transition were compared with those of another phase transition found in the DOPE bilayer membrane, which is the transition from the lamellar crystal (Lc) phase to the Lalpha phase. The dT/dp value of the Lalpha/H(II) transition was about 3.5 times as large as that of the Lc/Lalpha transition while the thermodynamic quantities were significantly smaller than those of the latter to the contrary. Comparing the enthalpy and volume behavior of the Lalpha/H(II) transition with that of the Lc/Lalpha transition, we concluded that the Lalpha/H(II) transition can be regarded as the volume-controlled transition for the reconstruction of molecular packing.
Naho Yamasaki, Kazuhiko Matsuoka, Kazuhito Nagayama, Takashi Hata, Hitoshi Matsuki, Hiromu Satake and Shoji Kaneshina : Observation of the lipid bilayer phase transition using the ion sensor, Bunseki Kagaku, Vol.54, No.10, 975-978, 2005.
(Summary)
Some aromatic amine local anesthetics are a kind of amphiphilic ion. Binding of local anesthetics, dibucaine (DC), bupivacaine (BC), and lidocaine (LC) to a dipalmitoylphosphatidylcholine (DPPC) bilayer membrane was studied by potentiometry with ion-selective electrodes sensitive to DC, BC and LC cations, respectively. The DPPC membrane-buffer partition coefficient was directly determined as a function of the anesthetic concentration and the temperature. The DPPC bilayer underwent a thermotropic pretransition from the lamellar gel phase to the ripple gel phase as well as a main transition from the ripple gel phase to the liquid crystal phase. The partition coefficients of anesthetics at pH 5.5 varied with the temperature, namely the bilayer phases. Potentiometry using an ion-selective electrode sensitive to amphiphilic ions is effective for the detection of a bilayer phase transition through partition coefficients.
(Keyword)
ion sensor / local anesthetic / lipid bilayer membrane / phase transition / partition coefficient
Masataka Kusube, Hitoshi Matsuki and Shoji Kaneshina : Effect of Pressure on the Prodan Fluorescence in Bilayer Membranes of Phospholipids with Varying Acyl Chain Lengths, Colloids and Surfaces B:Biointerfaces, Vol.42, No.1, 79-88, 2005.
Kazuhiko Matsuoka, Yasuhiro Tanioka, Takashi Hata, Hiromu Satake, Hitoshi Matsuki and Shoji Kaneshina : Effect of cholesterol on partition coefficients of local anesthetic into bilayer membranes of dimyristoylphosphatidylcholine, Anesthesia and Resuscitation, Vol.41, No.1, 17-20, 2005.
Kenji Ogli, Ukyo Komatsu, Hitoshi Matsuki and Shoji Kaneshina : Effect of halothane on the viscosity of aqueous bovine serum albumin solutions, Anesthesia and Resuscitation, Vol.41, No.1, 39-42, 2005.
Hitoshi Matsuki, Hideaki Nagamune, Shoji Kaneshina and Issaku Ueda : Inhibition modes of amphiphilic ligands with a long chain on the anti-fluorescent probe monoclonal antibody, Anesthesia and Resuscitation, Vol.41, No.1, 35-38, 2005.
Hitoshi Matsuki, Michio Yamanaka, Hiroshi Kamaya, Shoji Kaneshina and Issaku Ueda : Dissociation Equilibrium between Uncharged and Charged Local Anesthetic Lidocaine in a Surface-Adsorbed Film, Colloid and Polymer Science, Vol.283, No.5, 512-520, 2005.
Akihiro Shirai, Takuya Maeda, Hideaki Nagamune, Hitoshi Matsuki, Shoji Kaneshina and Hiroki Kourai : Biological and physicochemical properties of gemini quaternary ammonium compounds in which the positions of a cross-linking sulfur in the spacer differ, European Journal of Medicinal Chemistry, Vol.40, No.1, 113-123, 2005.
Hitoshi Matsuki, Michio Yamanaka, Hiroshi Kamaya, Shoji Kaneshina and Issaku Ueda : Preferential partitioning of uncharged local anesthetics into the surface-adsorbed film, Colloids and Surfaces B:Biointerfaces, Vol.38, No.1-2, 91-99, 2004.
Makoto Nishimoto, Kazuhiko Matsuoka, Kazuhito Nagayama, Takashi Hata, Hitoshi Matsuki, Hiromu Satake and Shoji Kaneshina : Partition coefficients of the local anesthetic dibucaine into a lipid bilayer membrane determined with a dibucaine cation sensor, Bunseki Kagaku, Vol.52, No.9, 781-785, 2003.
Masumi Michelle Villeneuve, Shoji Kaneshina and Makoto Aratono : Effect of Equimolar Salt to Decyltrimethylammonium Decyl Sulfate on Vesicle Formation and Surface Adsorption, Journal of Colloid and Interface Science, Vol.262, No.1, 227-234, 2003.
Takashi Hata, Takako Sakamoto, Hitoshi Matsuki and Shoji Kaneshina : Partition coefficients of charged and uncharged local anesthetics into dipalmitoylphosphatidylcholine bilayer membrane: estimation from pH dependence on the depression of phase transition temperatures, Colloids and Surfaces B:Biointerfaces, Vol.22, No.1, 77-84, 2001.
(Summary)
Effects of the local anesthetics, dibucaine, bupivacaine and lidocaine on the phase transition temperatures of dipalmitoylphosphatidylcholine (DPPC) bilayer membrane were studied by the optical method. We focus our attention on pH dependence of the depression of main transition and pretransition temperatures. The temperatures of both transitions of DPPC bilayer membrane were depressed by the addition of anesthetics; the higher the value of pH, the larger the depression of main transition temperature and/or pretransition temperature by anesthetics. By extending the colligative thermodynamic framework to the depression of main transition temperature by an anesthetic, we can estimate the differential partition coefficient, which is defined by the difference in partition coefficients of an anesthetic into the ripple gel and liquid crystal phases. The difference in partition coefficient between the lamellar and ripple gel phases can also be estimated from the depression of pretransition temperature. Since the differential partition coefficients include both contributions of the charged and uncharged anesthetics, we could estimate the partition coefficients of the charged and uncharged anesthetic into the membranes from the pH dependence of differential partition coefficients. The liquid crystalline membrane of DPPC bilayer was more receptive to the uncharged local anesthetics than the charged species. The partition coefficients of the charged and uncharged anesthetics into the liquid crystalline phase of DPPC bilayer membrane were 3540 and 249000 (for dibucaine), 1120 and 83900 (for bupivacaine), 256 and 11700 (for lidocaine), respectively. The transfer free energy of uncharged anesthetics from the aqueous phase to the liquid crystalline membrane was well correlated to the local anesthetic potency.
Hitoshi Matsuki, Takashi Hata, Michio Yamanaka and Shoji Kaneshina : Partitioning of uncharged local anesthetic benzocaine into model biomembranes, Colloids and Surfaces B:Biointerfaces, Vol.22, No.1, 69-76, 2001.
(Summary)
The partitioning of uncharged local anesthetic benzocaine (BzC) into molecular aggregates formed by cationic surfactant decylammonium chloride (DeAC) and phospholipid dipalmitoylphosphatidylcholine (DPPC) was studied from the surface tension and light transmittance measurements. The quantities concerning the partitioning of BzC, the compositions of BzC in the surface-adsorbed film and micelle and three kinds of differential partition coefficients corresponding to phase transitions of the DPPC bilayer membrane were evaluated from thermodynamic analysis of the experimental data. The surface-adsorbed film and micelle were more abundant in BzC than the aqueous solution and significantly large differential partition coefficients for the DPPC membranes were observed. The results clearly showed that the BzC molecules greatly partitioned into hydrophobic environments produced by surfactant-monolayer and phospholipid-bilayer membranes. The partitioning behavior of BzC was also compared with that of charged local anesthetic procaine hydrochloride (PC.HCl). It was shown that the PC.HCl molecule did not or hardly partition into such hydrophobic environments. The contrasting results of the partitioning between BzC and PC.HCl are attributable to the drastic decrease of hydrophilicity of BzC due to the lacking of ionic polar head group in comparison with PC.HCl.
Michio Yamanaka, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Volumetric Study on the Protein-Anesthetic Binding, Colloids and Surfaces B:Biointerfaces, Vol.22, No.1, 23-29, 2001.
(Summary)
Thermodynamic equations describing the volume behavior of protein-ligand mixtures in water were derived. In order to estimate the volume and binding parameters, the equations were combined with a Langmuir-type binding isotherm. Densities of aqueous solutions of mixtures of bovine serum albumin (BSA) and octanol (C8OH) were measured as a function of total BSA molality, m(M)(T), at constant total C8OH molalities, m(X)(T). The data were analyzed by the equations. The partial molar volumes at infinite dilution of BSA and C8OH, V(M)(T,0) and V(X)(T,0), respectively, were estimated. It was seen that V(M)(T,0) decreases by the addition of C8OH to the solution and that V(X)(T,0) decreases gradually with increasing m(M)(T) and approaches asymptotically to a certain value at high m(M)(T). From the concentration dependence of V(M)(T,0) and V(X)(T,0), the values of the association constant K=392 kg mol(-1), the maximum binding number b(max)=1.9, and the volume change DeltaV=-109 cm(3) mol(-1) were obtained for BSA-C8OH interaction in water. The negative value of DeltaV indicates that the hydrophobic interaction reduces the protein volume and elevation of pressure promotes BSA-C8OH binding. These results is inconsistent with the pressure reversal of anesthesia.
Shoji Kaneshina, Takahiro Miyata, Hitoshi Matsuki, Hiromu Satake and Motohiko Kuroki : Solubilization Study of Local Anesthetics into Sodium Dodecyl Sulfate Micelle Using Anesthetic Cation Selective Electrodes, Colloids and Surfaces B:Biointerfaces, Vol.22, No.1, 55-62, 2001.
(Summary)
The free concentrations of local anesthetic cations in equilibrium with sodium dodecyl sulfate (SDS) micelle which solubilized the anesthetic were determined by using ion-selective electrodes sensitive to local anesthetics, procaine (PC), lidocaine (LC), and mepivacaine (MC). Solubilizate distribution between water and SDS micelle was analyzed by means of the stepwise mass-action model. Association constant, K(1), was found to depend upon the anesthetic concentration, which decreased exponentially as the concentration of free anesthetic increased. Therefore, K(1) should include the interaction function φ(A) as K(1)=K(int)exp{-φ(A)} where K(int) is an intrinsic association constant. φ(A) is an increasing function of the anesthetic concentration, which means that occupation of a solubilization site by a local anesthetic cation makes sequential solubilization more difficult. The binding affinity of an anesthetic with SDS micelle increased in the following order PC<LC<MC.The critical micelle concentration (CMC) of mixed micelle was determined as a function of the concentration of free anesthetic. The CMC decreased with an increasing amount of anesthetics solubilized. All the anesthetic compositions in the micelle calculated thermodynamically from the CMC data were larger than the corresponding ones in the aqueous phase. Although the local anesthetics used here do not form micelles by themselves, the CMC vs composition curve can be regarded as a part of a micellar phase diagram showing the negative azeotropic behavior, which reflects the attractive interaction between the anionic surfactant micelle and the local anesthetic cation.
Masumi Michelle Villeneuve, Shoji Kaneshina and Makoto Aratono : Thermodynamic Study on Vesicle Formation and Adsorption of Decyltrimethylammonium Decyl Sulfate, Journal of Colloid and Interface Science, Vol.239, No.1, 254-263, 2001.
(Summary)
The surface tension of an aqueous solution of decyltrimethylammonium decyl sulfate (DeTADeS) was measured as a function of temperature T at various molalities &mcirc; under atmospheric pressure. DeTADeS has been found to form equilibrium multilamellar vesicles (MLV) spontaneously. The surface density, the entropies of adsorption, and the entropy of vesicle formation are evaluated. The mechanism of formation of equilibrium vesicles is investigated from the standpoint of thermodynamics and from the comparison of the results with those of the micelle-forming systems. From the relatively small change of the surface density Gamma;(H) on T at a given &mcirc;, the adsorbed film is implied to be tightly packed due to the strong electrostatic attraction between the polar headgroups. The energy change associated with adsorption from the vesicular state per mole of surfactant Delta(V)(H)u is positive in the entire temperature range; thus, the curved bilayer in MLV is energetically more favorable than the planar adsorbed film. From the negative values of the entropy of vesicle formation Delta(W)(V)s, it is concluded that vesicle formation is driven by enthalpy whereas micelle formation is mostly entropy driven. Copyright 2001 Academic Press.
Hitoshi Matsuki, Yuji Yamashita and Shoji Kaneshina : Surface Tension Measurements with High Accuracy: Investigation of Accuracy for Automatic Measurements by the Drop Volume Method, Journal of Oleo Science, Vol.50, No.3, 31-41, 2001.
Masumi Michelle Villeneuve, Teruko Nomura, Hitoshi Matsuki, Shoji Kaneshina and Makoto Aratono : Miscibility of Hydrocarbon and Fluorocarbon Surfactants in Adsorbed Film and Micelle, Journal of Colloid and Interface Science, Vol.234, No.1, 127-136, 2001.
(Summary)
We investigated the miscibility of nonionic hydrocarbon and fluorocarbon surfactants in the adsorbed film and the micelle by surface tension measurements of the aqueous solution. The combination of tetraethyleneglycol monodecyl ether (C10E4) and tetraethyleneglycol mono-1,1,7-trihydrododecafluoroheptyl ether (FC7E4) was chosen because they have the same hydrophilic groups and about the same surface activity. The extent of nonideal mixing was estimated quantitatively in terms of the excess Gibbs energy in the adsorbed film g(H,E) and that in the micelle g(M,E). The excess area per adsorbed molecule, A(H,E), was also evaluated and discussed. The ionic hydrocarbon and fluorocarbon mixed surfactant systems, lithium dodecyl sulfate (LiDS)/lithium perfluorooctane sulfonate (LiFOS) and lithium tetradecyl sulfate (LiTS)/LiFOS systems are also investigated from the standpoint of excess Gibbs energy and excess area. It is also clearly shown that the regular solution approach does not fit in the systems that contain ionic species. Copyright 2001 Academic Press.
Takashi Hata, Hitoshi Matsuki, Hiromu Satake and Shoji Kaneshina : Interdigitation of Phospholipid Bilayer Membrane and Vesicle-Micelle Transition Induced by Local Anesthetic, Anesthesia and Resuscitation, Vol.36, No.4, 175-178, 2000.
Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Effect of Local Anesthetics on the Bilayer Membranes of Dipalmitoylphosphatidylcholine: Interdigitation of Lipid Bilayer and Vesicle-Micelle Transition, Biophysical Chemistry, Vol.87, No.1, 25-36, 2000.
(Summary)
The phase transitions of dipalmitoylphosphatidylcholine (DPPC) bilayer membrane were observed by means of differential scanning calorimetry (DSC) as a function of the concentration of local anesthetics, dibucaine (DC x HCl), tetracaine (TC x HCl), lidocaine (LC x HCl) and procaine hydrochlorides (PC x HCl). LC x HCl and PC x HCl depressed monotonously the temperatures of the main- and pre-transition of DPPC bilayer membrane. The enthalpy changes of both transitions decreased slightly with an increase in anesthetic concentration up to 160 mmol kg(-1). In contrast, the addition of TC x HCl or DC x HCl, having the ability to form a micelle by itself, induced the complex phase behavior of DPPC bilayer membrane including the vesicle-to-micelle transition. The depression of both temperatures of the main- and pre-transition, which is accompanied with a decrease in enthalpy, was observed by the addition of TC x HCl up to 21 mmol kg(-1) or DC x HCl up to 11 mmol kg(-1). The pretransition disappeared when these concentrations of anesthetic were added, and the interdigitated gel phase appeared above these concentrations. The appearance of the interdigitated gel phase, instead of the ripple gel phase, brings about the stabilization of the gel phase by 1.8-2.4 kcal mol(-1). In the concentration range of 70-120 mmol kg(-1) TC x HCl (or 40-60 mmol kg(-1) DC x HCl), the enthalpy of the main transition exhibited a drastic decrease, resulting in the virtual disappearance of the main transition. This process includes the decrease in vesicle size with increasing anesthetic concentration, resulting in the mixed micelle of DPPC and anesthetics. Therefore, in this range of anesthetic concentration, the DPPC vesicle solubilized an anesthetic which coexists with the DPPC-anesthetic mixed micelle. Above the concentration of 120 mmol kg(-1) TC x HCl (or 60 mmol kg(-1) DC x HCl), there exists the DPPC-anesthetic mixed micelle. Two types of new transitions concerned with the mixed micelle of DPPC and micelle-forming anesthetics were observed by DSC.
Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Effect of Local Anesthetics on the Phase Transition Temperatures of Ether- and Ester-Linked Phospholipid Bilayer Membranes, Colloids and Surfaces B:Biointerfaces, Vol.18, No.1, 41-50, 2000.
Hayato Ichimori, Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Effect of Unsaturated Acyl Chains on the Thermotropic and Barotropic Phase Transitions of Phospholipid Bilayer Membranes, Chemistry and Physics of Lipids, Vol.100, No.1-2, 151-164, 1999.
Hitoshi Matsuki, Kensaku Shimada, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Difference in Surface Activities between Charged and Uncharged Local Anesthetics: Correlation with Their Anesthetic Potencies, Colloids and Surfaces B:Biointerfaces, Vol.11, No.6, 287-295, 1998.
Hiromu Satake, Takuo Kageyama, Hitoshi Matsuki and Shoji Kaneshina : Membrane-Buffer Partition Coefficients of a Local Anesthetic Tetracaine Monitored by an Anesthetic Sensor, Toxicology Letters, Vol.100-101, 441-445, 1998.
Hayato Ichimori, Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Barotropic phase transitions and pressure-induced interdigitation on bilayer membranes of phospholipids with varying acyl chain-lengths, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.1414, No.2, 165-174, 1998.
(Summary)
The bilayer phase diagrams of a series of 1, 2-diacylphosphatidylcholines containing linear saturated acyl chain (C=13, 14, 15, 16, 17 and 18) were constructed by two kinds of high-pressure optical methods. One is the observation of isothermal barotropic phase transition and the other is the isobaric thermotropic phase transition. The temperature of the main transition from the ripple gel (Pbeta') phase to the liquid crystal (Lalpha) phase for each lipid was elevated by pressure. The slope of the temperature-pressure diagram, dT/dP, was in the range of 0.21-0. 23 K MPa-1 depending on the acyl chain length. The temperature of the pretransition from the lamellar gel (Lbeta') phase to the Pbeta' phase for each lipid was also elevated by pressure. The slope of phase boundary, dT/dP, for the pretransition was in the range of 0. 12-0.14 K MPa-1. Both temperatures of the main and pretransition under ambient pressure increased with an increase in acyl chain length. The chain length dependences of the pretransition and main transition temperatures describe smooth curves with no evidence of odd/even discontinuities. Pressure-induced interdigitated gel (LbetaI) phase was observed beyond 300 MPa for 14:0-PC, 175 MPa for 15:0-PC, 100 MPa for 16:0-PC, 80 MPa for 17:0-PC and 70 MPa for 18:0-PC, respectively. The minimum pressure for the interdigitation of lipid bilayer membranes decreased with an increase in acyl chain length in a manner of non-linear relation. The slopes of phase boundary between Lbeta' and LbetaI phases transformed from the negative slope to the positive slope as the pressure increases.
Shoji Kaneshina, Hayato Ichimori, Takashi Hata and Hitoshi Matsuki : Barotropic phase transitions of dioleoylphosphatidylcholine and stearoyl-oleoylphosphatidylcholine bilayer membranes, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.1374, No.1-2, 1-8, 1998.
(Summary)
In order to understand the effect of cis unsaturation on the thermotropic and barotropic phase behavior of phospholipid bilayer membranes, the phase transitions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC), 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) bilayer membranes were observed by high-pressure optical method. With respect to DOPC bilayer membrane, the so-called main transition between the liquid crystalline (Lalpha) and the lamellar gel (Lbeta) phases was observed in water at above 0 degrees C under high pressure, in addition to the transition between the Lalpha and the lamellar crystalline (L(C)) phases in 50% aqueous ethylene glycol. The pressure of main transition increased linearly with an increase in temperature. Extrapolation of temperature (T)-pressure (P) phase boundary to ambient pressure suggests the temperature of the main transition to be -40.3 degrees C, which has never been found by the DSC method. On the other hand, the temperature of L(C)/Lalpha phase transition in 50% aqueous ethylene glycol was found to be -12.0 degrees C at ambient pressure. The main transition temperatures for DSPC, SOPC and DOPC are 55.6, 6.7 and -40.3 degrees C, respectively, at ambient pressure. The substitution of cis unsaturated chain for saturated chains of DSPC brings about the depression of the main transition temperature by about 48 (+/-1) degrees C for each chain. The volume changes (deltaV) associated with the transitions were calculated from the transition enthalpy (deltaH) and the slope of T-P diagram (dT/dP) by means of the Clapeyron-Clausius equation. The value of deltaV for the main transition of SOPC bilayer membranes was reduced to half the volume change for DSPC bilayers, which means the introduction of the cis double bond in the acyl chain of lipids brings about the reduction of deltaV because of the disordered packing of unsaturated chains in the gel phase of lipid bilayer membranes.
Hitoshi Matsuki, Hiroshi Kamaya, Issaku Ueda, Michio Yamanaka and Shoji Kaneshina : Volume Properties of Decylammonium Chloride and Micelle-Forming Local Anesthetic Mixtures in the Micelle, Langmuir, Vol.14, No.15, 4030-4035, 1998.
Hitoshi Matsuki, Michio Yamanaka, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Surface Tension Study on the Molecular-Aggregate Formation of Local Anesthetic Dibucaine Hydrochloride, Colloids and Surfaces B:Biointerfaces, Vol.11, No.1-2, 87-94, 1998.
Hitoshi Matsuki, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Partitioning of Charged Local Anesthetics into Model Membranes Formed by Cationic Surfactant: Effect of Hydrophobicity of Local Anesthetic Molecules, The Journal of Physical Chemistry B, Vol.102, No.17, 3295-3304, 1998.
Hitoshi Matsuki, Kensaku Shimada, Shoji Kaneshina, Michio Yamanaka, Hiroshi Kamaya and Issaku Ueda : Exclusion of the Local Anesthetic Procaine Hydrochloride from a Surface-Adsorbed Film and Micelle of Decylammonium Chloride, Langmuir, Vol.13, No.23, 6115-6119, 1997.
Shoji Kaneshina, Hiromu Satake, Tetsuya Yamamoto, Yasuhiro Kume and Hitoshi Matsuki : Partitioning of Local Anesthetic Dibucaine into Bilayer Membranes of Dimyristoylphosphatidylcholine, Colloids and Surfaces B:Biointerfaces, Vol.10, No.1, 51-57, 1997.
Hayato Ichimori, Takashi Hata, Toshiharu Yoshioka, Hitoshi Matsuki and Shoji Kaneshina : Thermotropic and Barotropic Phase Transition on Bilayer Membranes of Phospholipids with Varying Acyl Chain-Lengths, Chemistry and Physics of Lipids, Vol.89, No.1, 97-105, 1997.
Hitoshi Matsuki, Shinichiro Hashimoto, Shoji Kaneshina and Michio Yamanaka : Incorporation of Micelle-Forming Local Anesthetics into Surface Adsorbed Films and Micelles of Decylammonium Chloride, Langmuir, Vol.13, No.10, 2687-2693, 1997.
Shoji Maruyama, Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Effects of Pressure and Local Anesthetic Tetracaine on Dipalmitoylphosphatidylcholine Bilayers, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.1325, No.2, 272-280, 1997.
(Summary)
The temperature-pressure phase diagram of dipalmitoylphosphatidylcholine (DPPC) multilamellar vesicles was constructed in the presence of a local anesthetic tetracaine hydrochloride (TC-HCl). The phase-transition temperatures under various pressures were determined by the method of high-pressure light transmission. The temperature of the main transition from the ripple gel (P'(beta)) to the liquid crystal (L(alpha)) phase was depressed by the addition of TC-HCl and elevated by application of pressure up to 150 MPa. The temperature of the pretransition from the lamellar gel (L'(beta)) to the P'(beta) phase was also depressed by the addition of TC-HCl below ca. 10.0 mmol kg(-1) and elevated by the pressure below ca. 50 MPa. Therefore, pressure-anesthetic antagonism for both phase-transitions was confirmed. The pressure-induced interdigitated gel (L(beta)I) phase has been observed under high pressure above 100 MPa in the absence of TC-HCl. The L(beta)I phase is known to be induced also by a variety of small amphiphilic molecules such as ethanol, benzyl alcohol and TC-HCl. In the presence of TC-HCl ranging in concentration up to 20.0 mmol kg(-1), the L(beta)I phase instead of the P'(beta) phase appeared at higher pressure. Present results revealed that pressure facilitates, rather than antagonizes, the effect of TC-HCl on the occurrence of interdigitated gel phase. Furthermore, two regions of two phase coexistence were observed under high pressure in the presence of TC-HCl. One is probably a region of coexisting L(beta)I and L(alpha) phase, which was found between L(beta)I and L(alpha) phases under various pressures. The other is probably a region of coexisting L'(beta) and L(beta)I phase, which was observed in the presence of TC-HCl up to 10.0 mmol kg(-1) at the pressure above 40 MPa and at the temperature below ca. 35 degrees C.
(Keyword)
1,2-Dipalmitoylphosphatidylcholine / Anesthetics, Local / Calorimetry, Differential Scanning / Lipid Bilayers / Pressure / Temperature / Tetracaine
Shoji Maruyama, Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Effects of Pressure and Local Anesthetic Tetracaine on Dihexadecylphosphatidylcholine Bilayer Membrane, Colloids and Surfaces B:Biointerfaces, Vol.8, No.2, 261-266, 1997.
Hitoshi Matsuki, Ryoichi Ichikawa, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Differential Scanning Calorimetric Study on the Krafft Phenomenon of Local Anesthetics, Journal of Colloid and Interface Science, Vol.181, No.2, 362-369, 1996.
Michio Yamanaka, Hitoshi Matsuki and Shoji Kaneshina : Volume Study on the Micelle Formation of Local Anesthetic Dibucaine Hydrochloride and Dodecyltrimethylammonium Chloride Mixtures, Bulletin of the Chemical Society of Japan, Vol.68, No.8, 2159-2164, 1995.
Hitoshi Matsuki, Michio Yamanaka and Shoji Kaneshina : Effect of Counterion on the Surface Adsorption and Volume Behavior of Micelle-Forming Local Anesthetics, Bulletin of the Chemical Society of Japan, Vol.68, No.7, 1833-1838, 1995.
Hitoshi Matsuki, Shoji Maruyama and Shoji Kaneshina : Effect of Pressure on the Colloidal Solution Behavior of Aqueous Local Anesthetic Tetracaine Solutions, Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol.97, No.1, 21-26, 1995.
Shoji Kaneshina, Hitoshi Matsuki and Katsuhiro Tamura : Thermodynamics of Anesthetic Effect on the Phase Transitions of Lipid Membranes, Progress in Anesthetic Mechanism, Vol.2, 1-10, 1994.
Hitoshi Matsuki, Norihiro Ikeda, Makoto Aratono, Shoji Kaneshina and Kinsi Motomura : Study on the Miscibility of Lithium Tetradecyl Sulfate and Lithium Perfluorooctane Sulfonate in the Adsorbed Film and Micelle, Journal of Colloid and Interface Science, Vol.154, No.2, 454-460, 1992.
Shoji Kaneshina, Katsuhiro Tamura, Hitoshi Kawakami and Hitoshi Matsuki : Effects of Pressure and Ethanol on the Phase Behavior of Dipalmitoylphosphatidylcholine Multilamellar Vesicles, Chemistry Letters, Vol.21, No.10, 1963-1966, 1992.
Hitoshi Matsuki, Norihiro Ikeda, Makoto Aratono, Shoji Kaneshina and Kinsi Motomura : Study on the Miscibility of Lithium Dodecyl Sulfate and Lithium Perfluorooctane Sulfonate in the Adsorbed Film and Micelle, Journal of Colloid and Interface Science, Vol.150, No.2, 331-337, 1992.
Michio Yamanaka and Shoji Kaneshina : Volume Behavior of Mixed Micelles of Dodecyltrimethylammonium Chloride and Bromide, Journal of Solution Chemistry, Vol.20, No.12, 1159-1167, 1991.
Hiromu Satake, Takahiro Miyata and Shoji Kaneshina : Coated Wire Electrode Sensitive to Local Anesthetic Cations and Their Application to Potentiometric Determination, Bulletin of the Chemical Society of Japan, Vol.64, No.10, 3029-3034, 1991.
Hiromu Satake, Hitoshi Hori and Shoji Kaneshina : A Coated Wire Electrode Sensitive to Tetraphenylphosphonium Ion for Measurement of the Mitochondrial Membrane Potential, Analytical Letters, Vol.24, No.2, 295-304, 1991.
Shoji Kaneshina and Michio Yamanaka : Effect of Pressure on the Thermotropic Phase Behavior of Surfactant Assemblies in Water, Journal of Colloid and Interface Science, Vol.140, No.2, 474-480, 1990.
Shoji Kaneshina and Michio Yamanaka : A Differential Scanning Calorimetric Study of the Thermotropic Phase Behavior of Surfactants Assemblies in Water, Journal of Colloid and Interface Science, Vol.131, No.2, 493-497, 1989.
Kozue Kaibara, Keiko Ito, Hideo Kimizuka, Kenji Miyagawa and Shoji Kaneshina : Ion Transport Mediated by Inverted Micellar Aggeregates across a Phosphatidylcholine - Octanol Liquid Membrane, Journal of Membrane Science, Vol.41, 187-196, 1989.
Osamu Shibata, Shoji Kaneshina and Ryohei Matuura : Monolayers of Triple Long - Chain Salts on the Concentrated NaCl Solution, Bulletin of the Chemical Society of Japan, Vol.61, No.9, 3077-3082, 1988.
Yukio Suezaki, Shoji Kaneshina, Keishiro Shirahama, Issaku Ueda and Hiroshi Kamaya : A Simple Statistical Mechanical Theory for the Mutual Solubility of Fluid Mixtures of Water and Organic Solvents under High Pressure, Journal of Solution Chemistry, Vol.17, No.7, 637-651, 1988.
Tadayoshi Yoshida, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Enhancement of Counterion Binding to Micelles by Inhalation Anesthetics, Journal of Colloid and Interface Science, Vol.116, No.2, 458-462, 1987.
Shoji Kaneshina : The Effect of Pressure on the Micelle/Water Partition of 1-Heptanol. An Interpretation for the CMC Decrease by Solubilization under High Pressure, Colloids and Surfaces, Vol.13, No.2-3, 249-256, 1985.
Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Benzyl Alcohol Penetration into Micelles, Dielectric Constants of the Binding Site, Partition Coefficient and High - Pressure Squeeze - Out, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.777, No.1, 75-83, 1984.
(Summary)
The absorbance maximum, lambda max, of a local anesthetic, benzyl alcohol, is shifted to longer wavelengths when solvent polarity is decreased. The shift was approximately a linear function of the dielectric constant of the solvent. This transition in electronic spectra according to the microenvironmental polarity is used to analyze benzyl alcohol binding to surfactant micelles. A facile method is devised to estimate the micelle/water partition coefficient from the dependence of lambda max of benzyl alcohol on surfactant concentrations. The effective dielectric constants of the sodium decyl sulfate, dodecyl sulfate and tetradecyl sulfate micelles were 29, 31 and 33, respectively. The partition coefficient of benzyl alcohol between the micelles and the aqueous phase was 417, 610 and 1089, respectively, in the mole fraction unit. The pressure dependence of the partition coefficient was estimated from the depression of the critical micelle concentration of sodium dodecyl sulfate by benzyl alcohol under high pressure up to 200 MPa. High pressure squeezed out benzyl alcohol molecules from the micelle until about 120 MPa, then started to squeeze in when the pressure was further increased. The volume change of benzyl alcohol by transfer from the aqueous to the micellar phase was calculated from the pressure dependence of the partition coefficient. The volume change, estimated from the thermodynamic argument, was 3.5 +/- 1.1 cm3.mol-1 at 298.15 K, which was in reasonable agreement with the partial molal volume change determined directly from the solution density measurements, 3.1 +/- 0.2 cm3.mol-1. Benzyl alcohol apparently solvates into the micelles close to surface without losing contact with the aqueous phase.
Osamu Shibata, Shoji Kaneshina, Makoto Nakamura and Ryohei Matuura : Monolayers of Alkylammonium Alkanoates on the Concentrated NaCl Solution, Journal of Colloid and Interface Science, Vol.95, No.1, 87-96, 1983.
Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Thermodynamics of Pressure-Anesthetic Antagonism on the Phase Transition of Lipid Membranes: Displacement of Anesthetic Molecules, Journal of Colloid and Interface Science, Vol.93, No.1, 215-224, 1983.
Yukio Suezaki, Shoji Kaneshina and Issaku Ueda : Statistical Mechanics of Pressure-Anesthetic Antagonism on the Phase Transition of Phospholipid Membranes: Interfacial Water Hypothesis, Journal of Colloid and Interface Science, Vol.93, No.1, 225-234, 1983.
Shoji Kaneshina, Osamu Shibata, Makoto Nakamura and Mitsuru Tanaka : The Effect of Pressure on the Micelle Formation of Octyltrimethylammonium Octylsulfate and its Homologous Surfactants, Colloids and Surfaces, Vol.6, 73-82, 1983.
Osamu Shibata, Shoji Kaneshina, Makoto Nakamura and Ryohei Matuura : Monolayers of Alkylammonium Alkanesulfonates, Bulletin of the Chemical Society of Japan, Vol.55, No.7, 2243-2247, 1982.
Yoshio Murata, Kousi Isomura, Kosuke Fukushima, Nagamune Nishikido, Gohsuke Sugihara, Shoji Kaneshina and Mitsuru Tanaka : A High - Pressure Study on the Sol - Gel Transition in Aqueous Solutions of Alkali Metal Salts of Deoxycholic acid, Fukuoka Daigaku Rigaku Shuho, Vol.12, No.1, 33-40, 1982.
Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Interfacial Adsorption of an Inhalation Anesthetic onto Ionic Surfactant Micelles and its Desorption by High Pressure, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.685, No.3, 307-314, 1982.
(Summary)
The effects of pressure and temperature on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS) wer measured in the presence of various concentrations of an inhalation anesthetic, methoxyflurane. The change in the partial molal volume of SDS on micellization delta Vm, increased with the increase in the concentration of methoxyflurane. The CMC-decreasing power, which is defined as the slope of the linear plot between In(CMC) vs. mole fraction of anesthetic, was determined as a function of pressure and temperature. Since the CMC-decreasing power is correlated to the micelle/water partition coefficient of anesthetic, the volume change of the transfer (delta Vop) of methoxyflurane from water to the micelle can be determined from the pressure dependence of the CMC-decreasing power. The value of delta Vop amounts 6.5 +/- 1.8 cm3.mol-1, which is in reasonable agreement with the volume change determined directly from the density data, 5.5+/-0.6 cm3.mol-1. Under the convention of thermodynamics, this indicates that the application of pressure squeezes out anesthetic molecules from the micelle. The transfer enthalpy of anesthetic from water to the micelle is slightly endothermic. The partial molal volume of methoxyflurane in the micelle (112.0 cm3.mol-1) is smaller than that in decane (120.5 cm3.mol-1) and is larger than that in water (108.0 cm3. mol-1. This indicates that the anesthetic molecules are incorporated into the micellar surfaces region, i.e., the palisade layer of the micelle in contact with water molecules, rather than into the micelle core.
Shoji Kaneshina, Osamu Shibata and Makoto Nakamura : The Effect of Pressure on the Mutual Solubility of a Nonionic Surfactant - Water System, Bulletin of the Chemical Society of Japan, Vol.55, No.3, 951-952, 1982.
Shoji Kaneshina, Hao-Chou Lin and Issaku Ueda : Anisotropic Solubilization of an Inhalation Anesthetic Methoxyflurane into the Interfacial Region of Cationic Surfactant Micelles, Biochimica et Biophysica Acta, Vol.647, No.2, 223-226, 1981.
Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Transfer of Anesthetics and Alcohols into Ionic Surfactant Micelles in Relation to Depression of Krafft Point and CMC, and Interfacial Action of Anesthetics, Journal of Colloid and Interface Science, Vol.83, No.2, 589-598, 1981.
Shao-Mu Ma, Henry Eyring, Issaku Ueda and Shoji Kaneshina : Modeling of Biological Reactions, International Journal of Chemical Kinetics, Vol.13, No.9, 913-923, 1981.
Hiroshi Kamaya, Shoji Kaneshina and Issaku Ueda : Patition Equlibrium of Inhalation Anesthetics and Alcohols between Water and Membranes of Phospholipids with Varying Acyl - Chain Lengths, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.646, No.1, 135-142, 1981.
(Summary)
From the depression of the phase-transition temperature of phospholipid membranes, the partition coefficients of inhalation anesthetics (methoxyflurane, halothane, enflurane, chloroform and diethyl ether) and alcohols (benzyl alcohol and homologous n-alcohols up to C = 7) between phospholipid vesicle membranes and water were determined. The phospholipids used were dimyristoyl-, dipalmitoyl- and distearoylphosphatidylcholines. It was found that the difference in the acyl chain length of the three phospholipids did not affect the partition coefficients of the inhalation anesthetics and benzyl alcohol. The actions of these drugs are apparently directed mainly to the interfacial region. In contrast, n-alcohols tend to bind more tightly to the phospholipid vesicles with longer acyl chains. The absolute values of the transfer free energies of n-alcohols increased with the increase of the length of the alkyl chain of the alcohols. The increment was 3.43 kJ per each carbon atom. The numerical values of the partition coefficients are not identical when different expressions for solute concentrations (mole fraction, molality and molarity) are employed. The conversion factors among these values were estimated from the molecular weights and the partial molal volumes of the phospholipids in aqueous solution determined by oscillation densimetry.
Nagamune Nishikido, Nobuyoshi Yoshimura, Mitsuru Tanaka and Shoji Kaneshina : Effect of Pressure on the Solution Behavior of Nonionic Surfactants in Water, Journal of Colloid and Interface Science, Vol.78, No.2, 338-346, 1980.
Shoji Kaneshina, Issaku Ueda, Hiroshi Kamaya and Henry Eyring : Pressure - Anesthetic Antagonism on the Phase Separation of Nonionic Surfactant Micelles, Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol.603, No.2, 237-244, 1980.
(Summary)
An aqueous solution of non-ionic surfactants becomes suddenly turbid when heated to a critical temperature, known as the cloud point, and concomitantly expands the volume. The volume expansion is caused by release of structured water molecules from the hydrophilic polyoxyethyelene moieties. Inhalation anesthetics decreased the cloud-point temperature of hexaoxyethylene dodecyl ether micelles. The concentrations of methoxyflurane, halothane and enflurane causing a 1 degree C depression of the cloud-point temperature were 0.51, 0.71 and 0.78 mmolal, respectively. Hydrostatic pressure increased the cloud-point temperature in the absence and presence of the anesthetics. The change of the apparent molal volume at the cloud point was estimated to be 2.2 cm3/mol in the absence of anesthetics. This value decreased in the presence of the anesthetics, dose dependently. The results indicate that the anesthetics favor dehydration of the hydrophilic surface of the non-ionic surfactant micelles.
Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Destruction of Interfacial Water Structure as a Cause of Volume Expansion by Anesthetics, Anesthesiology, Vol.53, No.3, 20, 1980.
Hao-Chou Lin, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Anesthetics Do Not Fluidize the Lipid Core of Surfactant Micelle, Anesthesiology, Vol.53, No.3, 21, 1980.
Nagamune Nishikido, Masanobu Shinozaki, Gohsuke Sugihara, Mitsuru Tanaka and Shoji Kaneshina : A Study on the Micelle Formation of Surfactants in Aqueous Solutions under High Pressure by Laser Light - Scattering Technique, Journal of Colloid and Interface Science, Vol.74, No.2, 474-482, 1980.
Shoji Kaneshina, Osamu Shibata and Makoto Nakamura : Effects of Pressure on the Cloud Point of Nonionic Surfactant Solutions and on the Solubilization of Hydrocarbons, Bulletin of the Chemical Society of Japan, Vol.52, No.1, 42-44, 1979.
Gohsuke Sugihara, Toshiaki Ueda, Shoji Kaneshina and Mitsuru Tanaka : The Sol - Gel Transition of Sodium Deoxycholate Solutions under High Pressure, Bulletin of the Chemical Society of Japan, Vol.50, No.3, 604-607, 1977.
Norihiro Matubayasi, Kinsi Motomura, Shoji Kaneshina, Makoto Nakamura and Ryohei Matuura : Effect of Pressure on Interfacial Tension between Oil and Water, Bulletin of the Chemical Society of Japan, Vol.50, No.2, 523-524, 1977.
Mitsuru Tanaka, Shoji Kaneshina and Gohsuke Sugihara : The Effect of Pressure on the Micellization and Solution Behavior of Surfactants in Water, Poc. 7th Int. Cong. Surf. Act. Substances, 757-764, 1976.
Shoji Kaneshina, Masahiro Manabe, Gohsuke Sugihara and Mitsuru Tanaka : Partial Molal Volumes of Surfactants in Methanol - Water Mixtures, Bulletin of the Chemical Society of Japan, Vol.49, No.4, 876-879, 1976.
Takashi Moriyoshi, Shoji Kaneshina, Kikuo Aihara and Keizo Yabumoto : Mutual Solubilities of 2-Butanol + Water under High Pressure, The Journal of Chemical Thermodynamics, Vol.7, 537-545, 1975.
Mitsuru Tanaka, Shoji Kaneshina, Seiji Kuramoto and Ryohei Matuura : The Effect of Pressure on the Micellization of Surfactant in Aqueous Urea Solutions, Bulletin of the Chemical Society of Japan, Vol.48, No.2, 432-434, 1975.
Shoji Kaneshina, Mitsuru Tanaka, Tahei Tomida and Ryohei Matuura : Micelle Formation of Sodium Alkylsulfates under High Pressure, Journal of Colloid and Interface Science, Vol.48, No.3, 450-460, 1974.
Shoji Kaneshina, Mitsuru Tanaka and Ryohei Matuura : The Effect of Temperature and Pressure on the Micelle Formation of Surfactants in Water-Organic Solvent Mixtures, Mem. Fac. Sci. Kyushu Univ., Vol.9, No.1, 71-84, 1974.
Mitsuru Tanaka, Shoji Kaneshina, Kaoru Shinno, Takayoshi Okajima and Tahei Tomida : Partial Molal Volumes of Surfactant and its Homologous Salts under High Pressure, Journal of Colloid and Interface Science, Vol.46, No.1, 132-138, 1974.
Shoji Kaneshina, Mitsuru Tanaka, Tatsuhiko Kondo, Tomoaki Mizuno and Koichiro Aoki : Interaction of Bovine Serum Albumin with Detergent Cations, Bulletin of the Chemical Society of Japan, Vol.46, No.9, 2735-2738, 1973.
Mitsuru Tanaka, Shoji Kaneshina, Tahei Tomida, Kazutaka Noda and Koichiro Aoki : The Effect of Pressure on Solubilities of Ionic Surfactants in Water, Journal of Colloid and Interface Science, Vol.44, No.3, 525-531, 1973.
Mitsuru Tanaka, Shoji Kaneshina, Wataru Nishimoto and Hiroyuki Takabatake : The Viscosities of Aqueous Sodium Alkylsulfate and Alkyltrimethylammonium Bromide Solutions, Bulletin of the Chemical Society of Japan, Vol.46, No.2, 364-368, 1973.
Koichiro Aoki, Koichi Hiramatsu, Kunio Kimura, Shoji Kaneshina, Yoshitoyo Nakamura and Kenji Sato : Heat Denaturation of Bovine Serum Albumin. I. Analysis by Acrylamide Gel Electrophoresis, Bulletin of the Institute for Chemical Research, Kyoto University, Vol.47, No.4, 274-282, 1969.
Koichiro Aoki, Koichi Hiramatsu, Mitsuru Tanaka and Shoji Kaneshina : Bovine Serum Albumin Exposed to High Pressure, Biochimica et Biophysica Acta, Vol.160, No.3, 368-377, 1968.
Koichiro Aoki, Mitsuru Tanaka, Koichi Hiramatsu and Shoji Kaneshina : Aggregation of Bovine Serum Albumin under High Pressure, Review of Physical Chemistry of Japan, Vol.36, No.2, 111-113, 1967.
Koichiro Aoki and Shoji Kaneshina : Electrophoretic Study on the Egg White of Loggerhead Turtle, Bulletin of Faculty of Engineering, The University of Tokushima, Vol.3, No.2, 95-99, 1966.
Shoji Kaneshina, Hitoshi Matsuki and Nobutake Tamai : 高圧力下における脂質膜の構造転移と相挙動, Journal of the Society of Materials Science, Japan, Vol.58, No.6, 456-464, Jun. 2009.
Shoji Kaneshina, Hitoshi Matsuki and Nobutake Tamai : Pressure-induced Interdigitation in Phospholipid Bilayer Membranes, The Review of High Pressure Science and Technology, Vol.18, No.2, 110-118, May 2008.
(Summary)
Pressure studies on the bilayer phase transitions of ester-linked diacylphosphatidylcholines (diacyl-PCs) and ether-linked dialkyl-PCs are reviewed. Comparing the bilayer phase diagrams and the thermodynamic quantities of phase transitions for diacyl-PCs with those for dialkyl-PCs, the difference in lateral interaction between polar head groups of diacyl-PC and dialkyl-PC was elucidated. The mechanism of bilayer interdigitation induced by high-pressure, which is characteristic of phospholipids with a choline head group, is discussed on the basis of molecular interaction in lipid bilayer membranes.
Shoji Kaneshina and Hitoshi Matsuki : Thermotropic and Barotropic Structural Transitions in Phospholipid Bilayer Membranes, The Review of High Pressure Science and Technology, Vol.17, No.2, 106-112, May 2007.
(Summary)
Pressure studies on the bilayer phase transitions of phospholipids with different polar head groups (i.e., phosphatidylcholine and phosphatidylethanolamine) and different types of acyl chains (i.e., saturated and unsaturated acyl chains) are reviewed. Phase behavior of these lipid bilayers is elucidated thermodynamically by the temperature-pressure phase diagrams and the results of DSC measurements. The phase stability of bilayers is also discussed in connection with molecular structure of lipids.
Shoji Kaneshina, Hitoshi Matsuki and Hayato Ichimori : 高圧力下におけるリン脂質二重膜, The Review of High Pressure Science and Technology, Vol.9, No.3, 213-220, Aug. 1999.
Hitoshi Matsuki, Hiromu Satake, Shoji Kaneshina, P. R. Krishna and Issaku Ueda : Surface and Colloidal Properties of Local Anesthetic Solutions, Current Topics in Colloid & Interface Science, Vol.2, 69-82, Nov. 1997.
Nobutake Tamai, Sanae Inazawa, Daiki Fijiwara, Masaki GOTO, Shoji Kaneshina and Hitoshi Matsuki : Effect of Stigmasterol and Ergosterol on the Thermotropic Bilayer Phase Behavior of Dipalmitoylphosphatidylcholine, 14th International Association of Colloid and Interface Scientists, Conference (IACIS2012), Sendai, May 2012.
2.
Sanae Inazawa, Takuya Izumikawa, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Comparison between effects of cholesterol and stigmasterol on bilayer phase behavior of dipalmitoylphosphatidylcholine, The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem2010), Honolulu, Dec. 2010.
3.
Maiko Tsutsui, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Themotropic volume behavior of bilayer membranes of saturated and unsaturated phosphatidylcholines, The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem2010), Honolulu, Dec. 2010.
4.
Nobutake Tamai, Takuya Izumikawa, Maiko Uemura, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : Thermotropic phase behavior of binary bilayer membranes of cholesterol and a homologous series of saturated diasylphosphatidylcholines of different chain lengths, The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem2010), Honolulu, Dec. 2010.
5.
Hitoshi Matsuki, Makoto Nishimoto, Nobutake Tamai, Michio Yamanaka and Shoji Kaneshina : Anesthetic interactions with model proteins:intrinsic binding modes and validity as the model, The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem2010), Honolulu, Dec. 2010.
6.
Hitoshi Matsuki, Agnieszka Broniek, Masaki GOTO, Nobutake Tamai and Shoji Kaneshina : Phase behavior of plasmalogen bilayer membrane under high pressure, The 3rd International Kyushu Colloid Colloquium, Fukuoka, Sep. 2010.
7.
Hitoshi Matsuki, Hiroshi Sawaguchi, Masaki GOTO, Nobutake Tamai and Shoji Kaneshina : Subgel Phase Formation on Bilayer Membranes of Diacyl- and Dialkylphosphatidylcholines with Varying Acyl Chain Lengths, International Conference on Nanoscopic Colloid and Surface Science (NCSS2010), Chiba, Sep. 2010.
8.
Saeko Tanaka, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Phase Behavior of Dipalmitoylphosphatidylglycerol Bilayer under High Pressure, International Conference on Nanoscopic Colloid and Surface Science (NCSS2010), Chiba, Sep. 2010.
9.
Ryo Kishizoe, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Anomalous Phase Behavior of Ditridecanoylphosphatidylcholine Bilayer under High Pressure, International Conference on Nanoscopic Colloid and Surface Science (NCSS2010), Chiba, Sep. 2010.
10.
Sanae Inazawa, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Comparative Study on Effects of Stigmasterol and Cholesterol on Bilayer Phase Behavior of Dipalmitoylphosphatidylcholine, International Conference on Nanoscopic Colloid and Surface Science (NCSS2010), Chiba, Sep. 2010.
11.
Nobutake Tamai, Takuya Izumikawa, Maiko Uemura, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : Acyl-chain Length Dependent and Independent Effects of Chlolesterol on Bilayer Phase Behavior of Diacylphosphatidylcholines, International Conference on Nanoscopic Colloid and Surface Science (NCSS2010), Chiba, Sep. 2010.
12.
Nobutake Tamai, Yuko Nambu, Maiko Tsutsui, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : Volume properties of diacylphosphatidylcholine bilayer membranes revealed by pressure perturbation calorimetry and densitometry, 6th Internationl Conference on High Pressure Bioscience and Biotechnology (HPBB2010), Freising, Germany, Aug. 2010.
13.
Hitoshi Matsuki, Masaki GOTO, Nobutake Tamai and Shoji Kaneshina : Packing state in bilayer membranes of diacylphosphatidylcholines with varying acyl chain lengths under high pressure, 6th Internationl Conference on High Pressure Bioscience and Biotechnology (HPBB2010), Freising, Germany, Aug. 2010.
14.
Nobutake Tamai, Masaki GOTO, Hitoshi Matsuki and Shoji Kaneshina : A mechanism of pressure-induced interdigitation of lipid bilayers, Journal of Physics: Conference Series, Vol.215, No.1, 12161, Bristol, Mar. 2010.
Kaori Tada, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Effect of pressure on the bilayer phase transitions of asymmetric lipids with an unsaturated acyl chain in sn-1 position, Journal of Physics: Conference Series, Vol.215, No.1, 12162, Bristol, Mar. 2010.
Makoto Nishimoto, Masaki GOTO, Nobutake Tamai, Hideaki Nagamune, Shoji Kaneshina and Hitoshi Matsuki : Effect of pressure on interactions of anti-fluorescent probe monoclonal antibody with a ligand and inhibitors, Journal of Physics: Conference Series, Vol.215, No.1, 12157, Bristol, Mar. 2010.
Nobutake Tamai, Kazuyo Fujishige, Masafumi Sakamoto, Masataka Kusube, Hitoshi Matsuki and Shoji Kaneshina : Volumetric Study on Barotropic and Thermotropic Phase Transitions of Dimyristoylphosphatidylcholine Bilayer, The Proceedings of 4th Internationl Conference on High Pressure Bioscience and Biotechnology, Vol.1, 79-85, Tsukuba, Aug. 2007.
20.
Masaki GOTO, Masataka Kusube, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Bilayer Phase Behavior of an Asymmetric Lipid, 1-Stearoyl-2-palmitoylphosphatidylcholine, under High Pressure, The Proceedings of 4th Internationl Conference on High Pressure Bioscience and Biotechnology, Vol.1, 73-78, Tsukuba, Aug. 2007.
21.
Kaori Tada, Masaki GOTO, Masataka Kusube, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Barotropic Phase Transitions of Dilauroylphosphatidylcholine Bilayer Membrane, The Proceedings of 4th Internationl Conference on High Pressure Bioscience and Biotechnology, Vol.1, 68-72, Tsukuba, Aug. 2007.
22.
Masataka Kusube, Masaki GOTO, Nobutake Tamai, Hitoshi Matsuki and Shoji Kaneshina : Effect of Pressure on the Prodan Fluorescence in Bilayer Membrane of Ether-linked Lipid, Dihexadecylphosphatidylcholine, The Proceedings of 4th Internationl Conference on High Pressure Bioscience and Biotechnology, Vol.1, 61-67, Tsukuba, Aug. 2007.
23.
Kazuhiko Matsuoka, Kazuhito Nagayama, Takashi Hata, Hiromu Satake, Hitoshi Matsuki and Shoji Kaneshina : Partition coefficients of local anesthetic into phospholipid-cholesterol mixed bilayer membranes, International Congress Series, Vol.1283, 328-329, Nara, Dec. 2005.
24.
Naho Yamazaki, Kazuhiko Matsuoka, Makoto Nishimoto, Takashi Hata, Hiromu Satake, Hitoshi Matsuki and Shoji Kaneshina : Distribution of charged and uncharged local anesthetics into phospholipid bilayer membrane: correlation between partition coefficients and anesthetic potency, International Congress Series, Vol.1283, 330-331, Nara, Dec. 2005.
25.
Ukyo Komatsu, Hitoshi Matsuki, Shoji Kaneshina and Ogli Kenji : Effect of an inhalation anesthetic on the viscosity of aqueous bovine serum albumin solutions, International Congress Series, Vol.1283, 322-323, Nara, Dec. 2005.
26.
Makoto Nishimoto, Hitoshi Matsuki, Shoji Kaneshina and Ogli Kenji : Study on the interaction between bovine serum albumin and inhalation anesthetic halothane by differential scanning calorimetry, International Congress Series, Vol.1283, 326-327, Takamatsu, Dec. 2005.
27.
Hitoshi Matsuki, Masataka Kusube, Nobutake Tamai, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Recognition for long-chain saturated fatty acids, by dipalmitoylphosphatidylcholine bilayer membranes, International Congress Series, Vol.1283, 324-325, Nara, Dec. 2005.
28.
Shoji Kaneshina, Hitoshi Matsuki, Takashi Hata, Hiroko Okuno, Masataka Kusube and Nobutake Tamai : Local anesthetic tetracaine induces the interdigitation of lipid bilayers, International Congress Series, Vol.1283, 320-321, Nara, Dec. 2005.
29.
Hitoshi Matsuki, Ukyo Komatsu, Makoto Nishimoto, Shoji Kaneshina and Ogli Kenji : Comparative study of specific and non-specific interactions between bio-macromolecules and ligands, International Congress Series, Vol.1283, 207-210, Nara, Dec. 2005.
30.
Hitoshi Matsuki, Masataka Kusube, Takashi Hata and Shoji Kaneshina : Barotropic and Thermotropic Phase Behavior of Bilayer Membranes Composed of Phospholipids Containing Cis Double Bond in the Sn-2 Acyl Chain, Advances in High Pressure Bioscience and Biotechnology II, 199-202, Dortmund, Jun. 2003.
Shoji Kaneshina, Hitoshi Matsuki, Masataka Kusube and Hayato Ichimori : Effects of Cis and Trans Unsaturation on the Barotropic and Thermotropic Phase Behavior of Phospholipid Bilayers, Advances in High Pressure Bioscience and Biotechnology II, 195-198, Dortmund, Jun. 2003.
Hitoshi Matsuki, Masataka Kusube, Hayato Ichimori and Shoji Kaneshina : Effect of Pressure on the Bilayer Phase Transition of N-Methylated Dipalmitoylphosphatidylethanolamines, Trends in High Pressure Bioscience and Biotechnology, 153-158, Kyoto, Jan. 2002.
Hayato Ichimori, Fumihiko Sakano, Hitoshi Matsuki and Shoji Kaneshina : Effect of Deuterium Oxide on the Phase Transitions of Phospholipid Bilayer Membranes under High Pressure, Trends in High Pressure Bioscience and Biotechnology, 147-152, Kyoto, Jan. 2002.
Shoji Kaneshina, Shigeru Endo, Hitoshi Matsuki and Hayato Ichimori : Effect of pressure on the bilayer phase transition of diacylphosphatidylethanolamine, Trends in High Pressure Bioscience and Biotechnology, 139-146, Kyoto, Jan. 2002.
Hitoshi Matsuki, Takahiro Miyata, Toshiharu Yoshioka, Hiromu Satake and Shoji Kaneshina : Pre-Micelle and Micelle Formation of Local Anesthetic Dibucaine Hydrochloride, Studies in Surface Science and Catalysis, Vol.132, 113-116, Tokyo, Mar. 2001.
Shoji Kaneshina, Hitoshi Matsuki, Ryoichi Ichikawa and Toshiharu Kuwahara : Thermotropic Phase Behavior of Binary Cationic Surfactant Mixtures in Water, Studies in Surface Science and Catalysis, Vol.132, 45-48, Tokyo, Mar. 2001.
Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Effect of Local Anesthetics on the Main- and Pre-transition Temperatures of Ether-Linked Phospholipid Bilayer Membranes, Progress in Anesthetic Mechanism, Vol.6, 536-541, Takamatsu, Mar. 2000.
Hiromu Satake, Takuo Kageyama, Shoji Kaneshina, Takaaki Ohkawa, Satoshi Yokono, Masaru Sano and Kenji Ogli : The Effect of Intracelluar pH on the Blocking Action of a Local Anesthetic Lidocaine in Internally Perfused Squid Giant Axons, Progress in Anesthetic Mechanism, Vol.6, 434-441, Takamatsu, Mar. 2000.
Issaku Ueda, Hitoshi Matsuki, Yoshiro Kaminoh, Shoji Kaneshina and Hiroshi Kamaya : The Meyer-Overton Rule Does Not Imply Lipid Membranes. Does Low Temperature Increase Anesthetic Potency ?, Progress in Anesthetic Mechanism, Vol.6, 207-212, Takamatsu, Mar. 2000.
Hitoshi Matsuki, Shoji Kaneshina, Hiroshi Kamaya and Issaku Ueda : Preferential Partitioning of Uncharged Local Anesthetics into Suface-Adsorbed Film, Progress in Anesthetic Mechanism, Vol.6, 186-191, Takamatsu, Mar. 2000.
Shoji Kaneshina, Takashi Hata, Takako Sakamoto and Hitoshi Matsuki : Partitioning of Charged and Uncharged Local Anesthetics into DPPC Bilayer Membranes in Relation to pH Dependence on the Transition-Tempearture Depression of the Bilayer Membranes, Progress in Anesthetic Mechanism, Vol.6, 103-108, Takamatsu, Mar. 2000.
Shoji Kaneshina, Hiroya Endo, Takashi Hata and Hitoshi Matsuki : Effects of Pressure and Local Anesthetics on the Phase Transitions of Ether-Linked Dihexadecylphosphatidylcholine Bilayer Membrane, Advances in High Pressure Bioscience and Biotechnology, 165-168, Heidelberg, Jun. 1999.
Hayato Ichimori, Hitoshi Matsuki, Takashi Hata and Shoji Kaneshina : Thermotropic and Barotropic Phase Behavior of 1-Hexadecyl-2-palmitoylphosphatidylcholine Bilayer Membrane, Advances in High Pressure Bioscience and Biotechnology, 161-164, Heidelberg, Jun. 1999.
Hayato Ichimori, Shigeru Endo, Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Effects of Pressure on the Phase Transitions of Dimyristoylphosphatidylethanolamine and Dimyristoylphosphatidylcholine Bilayers, Advances in High Pressure Bioscience and Biotechnology, 149-152, Heidelberg, Jun. 1999.
Shoji Kaneshina, Hayato Ichimori, Takashi Hata and Hitoshi Matsuki : New Transition of Dioleoylphosphatidylcholine Bilayer Membrane under High Pressure, Advances in High Pressure Bioscience and Biotechnology, 145-148, Heidelberg, Jun. 1999.
Shoji Kaneshina, Hayato Ichimori, Takashi Hata and Hitoshi Matsuki : Effect of Pressure on the Phase Behavior of DiheptadecanoylphosphatidylcholineBilayer Membrane, The Review of High Pressure Science and Technology, Vol.7, 1277-1279, Kyoto, Mar. 1998.
Hayato Ichimori, Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Pressure-Induced Interdigitation on Bilayer Membranes of Diacylphosphatidylcholine, Workshop on Structural and Thermodynamic Approaches to Study Functional Mechanisms in Lipid Membranes, 33-36, Kyoto, Nov. 1997.
51.
Shoji Kaneshina, Hayato Ichimori, Takashi Hata and Hitoshi Matsuki : Thermotropic and Barotropic Phase Transitions of Phospholipid Bilayer Membranes, Workshop on Structural and Thermodynamic Approaches to Study Functional Mechanisms in Lipid Membranes, 37-40, Kyoto, Nov. 1997.
52.
Hayato Ichimori, Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Pressure-Induced Interdigitation on Bilayer Membranes of Diacylphosphatidylcholine, Workshop on Structural and Thermodynamic Approaches to Study Functional Mechanisms in Lipid Membranes, 33-36, Kyoto, Nov. 1997.
53.
Takashi Hata, Hitoshi Matsuki and Shoji Kaneshina : Differential Scanning Calorimetric Study on the Interaction of a Local Anesthetic Tetracaine with DPPC Bilayer Membrane, Workshop on Structural and Thermodynamic Approaches to Study Functional Mechanisms in Lipid Membranes, 29-32, Kyoto, Nov. 1997.
54.
Shoji Kaneshina, Shoji Maruyama and Hitoshi Matsuki : Effect of Pressure on the Phase Behavior of Ester- and Ether-Linked Phospholipid Bilayer Membranes, High Pressure Bioscience and Biotechnology, 175-180, Kyoto, Jun. 1996.
Shoji Kaneshina, Hitoshi Matsuki and Katsuhiro Tamura : The Effects of Pressure and Inhalation Anesthetics on the Phase Transitions of Lipid Bilayer Membranes, Progress in Anesthetic Mechanism, Vol.3, 471-478, Takamatsu, Dec. 1995.
Shoji Maruyama, Hitoshi Matsuki and Shoji Kaneshina : Effects of Pressure and Local Anesthetic Tetracaine on the Phase Behavior of Dipalmitoylphosphatidylcholine Multilamellar Vesicles, Progress in Anesthetic Mechanism, Vol.3, 404-409, Takamatsu, Dec. 1995.
Hitoshi Matsuki, Shinichiro Hashimoto and Shoji Kaneshina : Correlation between Anesthetic Potency and Surface Activities of Local Anesthetics, Progress in Anesthetic Mechanism, Vol.3, 385-391, Takamatsu, Dec. 1995.
Hiromu Satake, Tetsuya Yamamoto, Hitoshi Matsuki and Shoji Kaneshina : Bilayer Membrane-Buffer Partition Coefficient of a Local Anesthetic Dibucaine by a Method of Anesthetic Sensor, Progress in Anesthetic Mechanism, Vol.3, 241-246, Takamatsu, Dec. 1995.
Shoji Kaneshina, Hitoshi Matsuki and Katsuhiro Tamura : The effects of pressure and inhalation anesthetics on the phase transitions of lipid bilayer membranes, International Workshop on Anesthetic Mechanisms, Takamatsu, Dec. 1994.
Shoji Kaneshina and Katsuhiro Tamura : Effects of pressure and inhalation anesthetics on the phase transition of DPPC vesicles, 7th International Conference of Surface and Colloid Science, Compiegne, Jul. 1991.