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PubMed2002

Determination of L(alpha)-H(II) phase transition temperature for 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine.

The thermodynamic properties of fully-hydrated lipids provide important information about the stability of membranes and the energetic interactions of lipid bilayers with membrane proteins (Nagle and Scott, Physics Today, 2:39, 1978). The lamellar/inverse hexagonal (L(alpha)-H(II)) phase transition of 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE) water mixtures is a first-order transition and, therefore, at constant pressure, must have a thermodynamically well-defined equilibrium transition temperature. The observed transition temperature is known to be dependent upon the rate at which the temperature is changed, which accounts for the many different values in the literature. X-ray diffraction was used to study the phase transition of fully-hydrated DOPE to determine the rate-independent transition temperature, T(LH). Samples were heated or cooled for a range of rates, 0.212 < r < 225 degrees C/hr, and the rate-dependent apparent phase transition temperatures, T(A)(r) were determined from the x-ray data. By use of a model-free extrapolation method, the transition temperature was found to be T(LH) = 3.33 +/- 0.16 degrees C. The hysteresis, /T(A)(r) - T(LH)/, was identical for heating and cooling rates, +/-r, and varied as /r/beta for beta approximately 1/4. This unexpected power-law relationship is consistent with a previous study (Tate et al., Biochemistry, 31:1081-1092, 1992) but differs markedly from the exponential behavior of activation barrier kinetics. The methods used in this study are general and provide a simple way to determine the true mesomorphic phase transition temperatures of other lipid and lyotropic systems.

Hot Temperature↗
PubMed1986

Dose-dependent nonlinear response of the main phase-transition temperature of phospholipid membranes to alcohols.

The effect of 1-alkanols upon the main phase-transition temperature of phospholipid vesicle membranes between gel and liquid-crystalline phases was not a simple monotonic function of alkanol concentration. For instance, 1-decanol decreased the transition temperature at low concentrations, but increased it at high concentrations, displaying a minimal temperature. This concentration-induced biphasic effect cannot be explained by the van't Hoff model on the effect of impurities upon the freezing point. To explain this nonlinear response, a theory is presented which treats the effect of 1-alkanols (or any additives) on the transition temperature of phospholipid membranes in a three-component mixture. By fitting the experimental data to the theory, the enthalpy of the phase transition delta H* and the interaction energy, epsilon*AB between the additive and phospholipid molecules may be estimated. The theory predicts that when epsilon*AB greater than 2 (where epsilon*AB = epsilon AB/RT0, T0 being the transition temperature of phospholipid), both minimum and maximum transition temperatures should exist. When epsilon*AB = 2, only one inflection point exists. When epsilon*AB less than 2, neither maximum nor minimum exists. The alkanol concentration at which the transition temperature is minimum (Xmin) depends on the epsilon*AB value: the larger the epsilon*AB values, the smaller the Xmin. When epsilon*AB is large enough, Xmin values become so small that the plot delta T vs. X shows positive delta T in almost all alkanol concentrations. The interaction energy between 1-alkanols and phospholipid molecules increased with the increase in the carbon chain-length of 1-alkanols. In the case of the dipalmitoylphosphatidylcholine vesicle membrane, the carbon chain-length of 1-alkanols that caused predominantly positive delta T was about 12.

Alcohols↗
PubMed1988

Depression of phase-transition temperature by anesthetics: nonzero solid membrane binding.

The anesthetic-induced depression of the main phase-transition temperature of phospholipid membranes is often analyzed according to the van't Hoff model on the freezing point depression. In this procedure, zero interaction between anesthetics and solid-gel membranes is assumed. Nevertheless, anesthetics bind to solid-gel membranes to a significant degree. It is necessary to analyze the difference in the anesthetic binding between the liquid-crystal and solid-gel membranes to probe the anesthetic action on the lipid membranes. This article describes a theory to estimate the anesthetic binding to each state at the phase-transition temperature. The equations derived here reveal the relation between the partition coefficients of anesthetics and the anesthetic effects on the transition characters: the change in the transition temperature, and the broadening of transition. The theory revealed that the width of transition temperature is determined primarily by the membrane/buffer partition coefficients of anesthetics. Our previous data on the local anesthetic action on the transition temperature of the dipalmitoylphosphatidylcholine vesicle membrane (Ueda, I., Tashiro, C. and Arakawa, K. (1977) Anesthesiology 46, 327-332) are analyzed by this method. The numerical values for the partition of local anesthetics into the liquid-crystal and solid-gel dipalmitoyl-phosphatidylcholine vesicle membranes at the phase-transition temperature are: procaine 8.0 x 10(3) and 4.7 x 10(3), lidocaine, 3.7 x 10(3) and 2.3 x 10(3), bupivacaine 4.1 x 10(4), and 2.6 x 10(4), and tetracaine 7.3 x 10(4) and 4.7 x 10(4), respectively.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1990

Evaluation of analytical techniques for measurement of denture-base acrylic resin glass-transition temperature.

The glass-transition temperature of a range of acrylic resin materials used in prosthetic dentistry was determined. The techniques used to make the measurement included: thermal mechanical analysis, dynamic mechanical thermal analysis, and differential scanning calorimetry. It was found that the measuring techniques used yielded very similar results, and as a consequence it was concluded that: familiarity and easy availability of thermal mechanical analysis lead to the recommendation that this technique should be employed as the standard glass-transition evaluation technique for denture-base acrylic resins.

Acrylic Resins↗
PubMed1978

A transition temperature for acetylcholine channel conductance in chick myoballs.

1. The temperature dependence of ACh channel conductance (gamma) and channel open time (tau) was determined by analysing ACh induced membrane current fluctuations in voltage clamped chick myoballs. 2. gamma decreased from 25-30 pmho at 37 degrees C to less than 5 phmo at 10 degrees C. An Arrhenius plot of gamma vs. temperature exhibited a clear break or 'transition temperature' at 20 degrees C. 3. tau increased from 2 msec at 37 degrees C to 16 msec at 10 degrees C. The Arrhenius plot of tau vs. temperature was linear. No transition temperature was detected. 4. Submicellar concentrations of the non-ionic detergent, Triton X-100 reversibly blocked ACh respnses. The effect was all-or-none at the molecular level. 5. These results are consistent with the possibility that the fluidity of membrane lipids in the ACh receptor micro-environment may influence the degree to which the channel can open.

Acetylcholine↗
PubMed1991

Analysis of the chainlength dependence of lipid phase transition temperatures: main and pretransitions of phosphatidylcholines; main and non-lamellar transitions of phosphatidylethanolamines.

The dependence on chainlength, n, of the temperatures at which the various thermotropic phase transitions in phospholipid bilayers take place can be fitted to high accuracy with an expression of the form: Tt = Tt infinity (1-A/(n-d)) where Tt infinity, A and d are the constants to be fitted. This expression works well with literature values for the main and pretransitions of saturated straight-chain phosphatidylcholines, for the main transition of isobranched- and anteisobranched-chain phosphatidylcholines, and for the main and non-lamellar phase transitions of saturated straight-chain phosphatidylethanolamines, and also for diacylglycerol glycolipids. The parameters in the fit can be related thermodynamically to the calorimetric properties of the phase transition. The constants A and d are related to the end effects in the chainlength dependence of the transition enthalpy and transition entropy, respectively, and the transition temperature extrapolated to infinite chainlength, Tt infinity, is determined by the ratio of the incremental transition enthalpy and transition entropy per methylene group. A reasonable correspondence is found between the chainlength dependence of the transition temperature and of the transition enthalpy and transition entropy for saturated straight-chain diacylphosphatidylcholines. It is likely, however, that the expression for the chainlength dependence of the transition temperature may be of more general applicability, because, on the one hand of the greater inherent precision of the transition temperature measurements, and on the other hand because the expression for the transition temperature is of more general validity, provided that the chainlength dependence of the incremental transition enthalpy and entropy are the same.

Gels↗
PubMed1988

Entropic elastic processes in protein mechanisms. I. Elastic structure due to an inverse temperature transition and elasticity due to internal chain dynamics.

Numerous physical characterizations clearly demonstrate that the polypentapeptide of elastin (Val1-Pro2-Gly3-Val4-Gly5)n in water undergoes an inverse temperature transition. Increase in order occurs both intermolecularly and intramolecularly on raising the temperature from 20 to 40 degrees C. The physical characterizations used to demonstrate the inverse temperature transition include microscopy, light scattering, circular dichroism, the nuclear Overhauser effect, temperature dependence of composition, nuclear magnetic resonance (NMR) relaxation, dielectric relaxation, and temperature dependence of elastomer length. At fixed extension of the cross-linked polypentapeptide elastomer, the development of elastomeric force is seen to correlate with increase in intramolecular order, that is, with the inverse temperature transition. Reversible thermal denaturation of the ordered polypentapeptide is observed with composition and circular dichroism studies, and thermal denaturation of the crosslinked elastomer is also observed with loss of elastomeric force and elastic modulus. Thus, elastomeric force is lost when the polypeptide chains are randomized due to heating at high temperature. Clearly, elastomeric force is due to nonrandom polypeptide structure. In spite of this, elastomeric force is demonstrated to be dominantly entropic in origin. The source of the entropic elastomeric force is demonstrated to be the result of internal chain dynamics, and the mechanism is called the librational entropy mechanism of elasticity. There is significant application to the finding that elastomeric force develops due to an inverse temperature transition. By changing the hydrophobicity of the polypeptide, the temperature range for the inverse temperature transition can be changed in a predictable way, and the temperature range for the development of elastomeric force follows. Thus, elastomers have been prepared where the development of elastomeric force is shifted over a 40 degrees C temperature range from a midpoint temperature of 30 degrees C for the polypentapeptide to 10 degrees C by increasing hydrophobicity with addition of a single CH2 moiety per pentamer and to 50 degrees C by decreasing hydrophobicity.(ABSTRACT TRUNCATED AT 400 WORDS)

Chemical Phenomena↗
PubMed1983

An X-ray diffraction study on phase transition temperatures of various membranes isolated from Tetrahymena pyriformis cells grown at different temperatures.

Mitochondrial, microsomal and pellicular membranes were isolated from Tetrahymena cells grown at 39 degrees C or 15 degrees C, and phospholipids, in turn, were separated from total lipids extracted from these membranes. The effect of growth temperature on their solid-to-fluid phase transition temperature was examined by wide-angle X-ray diffraction. The transition temperatures of phospholipids from mitochondria, microsomes and pellicles were 21, 19 and 26 degrees C for cells grown at 39 degrees C and -8, -3 and 6 degrees C for cells grown at 15 degrees C, respectively. All phospholipids were found in a completely fluid state at these growth temperatures. From a comparison between the phospholipids and total lipids from pellicles of cells grown at 39 degrees C, a triterpenoid alcohol, tetrahymanol, caused the transition temperature to increase. The alignment of tetrahymanol in membranes was examined with pellicle'a total lipid oriented in a sample holder.

Cholesterol↗
PubMed2005

Glass transition-related changes in molecular mobility below glass transition temperature of freeze-dried formulations, as measured by dielectric spectroscopy and solid state nuclear magnetic resonance.

The purpose of this study was to explore why changes in the molecular mobility associated with glass transition, the timescale of which is on the order of 100 s, can be detected by measuring the nuclear magnetic resonance relaxation times that reflect molecular motions on the order of 10 kHz and 1 MHz. The molecular motions in freeze-dried dextran 40k, dextran 1k, isomaltotriose (IMT), and alpha-glucose comprising a common unit but with different glass transition temperatures, were investigated by dielectric spectroscopy (DES) in the frequency range of 0.01 Hz to 100 kHz and in the temperature range of -20 degrees to 200 degrees C, in order to compare with the molecular motions reflected in nuclear magnetic resonance relaxation times. The alpha-relaxation process for freeze-dried alpha-glucose was visualized by DES, whereas those for freeze-dried dextran 40k, dextran 1k, and IMT were too slow to be visualized by DES. The latter freeze-dried cakes exhibited quasi-dc polarization because of proton-hopping-like motion rather than alpha-relaxation process. The correlation time (tau(c)) for the backbone carbon of dextran 40k and IMT, calculated from the measured value of spin-lattice relaxation time in the rotating frame, was found to be close to the relaxation time of proton-hopping-like motion determined by DES (tau(DES)) at temperatures around glass transition temperature. The timescales of molecular motions reflected in the tau(c) and tau(DES) were significantly smaller than that of motions leading to molecular rearrangement (molecular rearrangement motions), which correspond to alpha-relaxation. However, the shapes of temperature dependence for the tau(c) and tau(DES) were similar to that of the calorimetrically determined relaxation time of molecular rearrangement motions. Results suggest that the molecular motions reflected in the tau(c) and tau(DES) are linked to molecular rearrangement motions, such that enhancement of molecular rearrangement motions enhances the molecular motions reflected in the tau(c) and tau(DES). Thus, the tau(DES) and tau(c) can reflect changes in molecular mobility leading to unwanted changes in amorphous formulations, and are thought to be a useful measure for evaluating the stability of formulations.

Dextrans↗
PubMed1981

Gel to liquid-crystalline transition temperatures of water dispersions of two pairs of positional isomers of unsaturated mixed-acid phosphatidylcholines.

The gel to liquid-crystalline phase transition temperatures of dispersions of mixed-acid sn-1,2-lecithins which contain one unsaturated and one saturated fatty acid have been studied by differential scanning calorimetry. The temperature for 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (containing no reversed isomer) was -9.3 degrees C while that for 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphocholine (containing 8% of the reversed isomer) was -2.6 degrees C. The temperature for 2-oleoyl-1-stearoyl-sn-glycero-3-phosphocholine (containing 6% of the reversed isomer) was 6.3 degrees C while that for 1-oleoyl-2-stearoyl-sn-glycero-3-phosphocholine (containing 18% of the reversed isomer) was 8.6 degrees C. The differences in transition temperatures for the isomers of a pair containing the same two acids were consistent with those observed for positional isomers of saturated mixed-acid lecithins in that the isomer of the pair which had the longer fatty acid in the sn-1 position had the lower temperature. The phase transition temperatures of pairs of isomers containing palmitate and oleate at the sn-1 and -2 positions were different by at least 6.7 degrees C, while those containing stearate and oleate were different by at least 2.3 degrees C. Differences in the chain lengths of the fatty acids at the two positions of the glycerol appear to predominate over differences in the depths of the double bonds in the bilayer in determining the transition temperatures.

Gels↗
PubMed1985

Taurine effects on the transition temperature in Arrhenius plots of ATP-dependent calcium ion uptake in rat retinal membrane preparations.

The transition temperatures calculated from Arrhenius plots of ATP-dependent calcium ion uptake in rat retinal membrane preparations differed depending upon the presence or absence of exogenous taurine. At a constant calcium ion concentration of 10 microM and in the absence of taurine the transition temperature was 17.9 +/- 4.9 degrees, whereas in the presence of 20 mM taurine the transition temperature was raised to 25.4 +/- 0.8 degrees. Arrhenius plots of maximum velocities of calcium ion uptake (calculated from six calcium ion concentrations which varied from 5 to 300 microM) also demonstrated a taurine effect on the transition temperatures (13.5 degrees vs 25.5 degrees). In addition, taurine lowered the apparent activation energy for calcium ion uptake.

Adenosine Triphosphate↗
PubMed1994

The relationship between the glass transition temperature and the water content of amorphous pharmaceutical solids.

The glass transition temperature of an amorphous pharmaceutical solid is a critical physical property which can dramatically influence its chemical stability, physical stability, and viscoelastic properties. Water frequently acts as a potent plasticizer for such materials, and since many amorphous solids spontaneously absorb water from their surroundings the relationship between the glass transition temperature and the water content of these materials is important. For a wide range of amorphous and partially amorphous pharmaceutical solids, it was found that there is a rapid initial reduction in the glass transition temperature from the dry state as water is absorbed, followed by a gradual leveling off of the response at higher water contents. This plasticization effect could generally be described using a simplified form of the Gordon-Taylor/Kelley-Bueche relationships derived from polymer free volume theory. Most of the systems considered showed a nearly ideal volume additivity and negligible tendency to interact. This is consistent with the hypothesis that such mixtures behave as concentrated polymer solutions and indicates that water acts as a plasticizer in a way similar to that of other small molecules and not through any specific or stoichiometric interaction process(es).

Chemistry, Pharmaceutical↗
PubMed2003

Shifts in chain-melting transition temperature of liposomal membranes by polymer-grafted lipids.

The chain-melting transition temperature of dipalmitoyl phosphatidylcholine (DPPC) bilayer membranes containing poly(ethylene glycol)-grafted dipalmitoyl phosphatidylethanolamine (PEG-DPPE) was determined by optical turbidity measurements. The dependence on content, Xp, of PEG-DPPE lipid was studied for different polar headgroup sizes, np, of the polymer lipid, throughout the lamellar phase of the mixtures with DPPC. Mean-field theory for the polymer brush regime predicts that the downward shift in transition temperature should vary with polymer size and content as npXp(5/3) (approximately npXp(11/6) for scaling theory). Any shift induced by the charge on PEG-lipids is independent of polymer size. These predictions are reasonably borne out for the longer polymer lipids (PEG molecular masses 750, 2000 and 5000 Da). Transition temperature shifts in the lamellar phase, before the onset of micellisation, are in the region of -1 to -2 degrees C (+/-0.1-0.2 degrees C) in reasonable accord with theoretical estimates of the lateral pressure exerted by the polymer brush. Shifts of this size are significant to the design of liposomes for controlled release of contents by mild hyperthermia.

1,2-Dipalmitoylphosphatidylcholine↗
PubMedDate not supplied

The effect of excipients on glass transition temperatures for FK906 in the frozen and lyophilized states.

FK906, a tripeptide, has been used as a model compound to study the effect of excipients on the glass transition temperature for peptides and related compounds in the frozen solution and lyophilized states. Three kinds of excipients were chosen for study, low molecular weight sugars, high molecular weight polymers and salts. Our results indicate that the Gordon-Taylor equation can be used to predict the glass transition temperature of FK906 in the presence of sucrose, lactose, trehalose and maltose in the frozen solutions and in lyophilized products. Dextrans having different molecular weights can have different effects on the glass transition temperature of FK906 in the frozen state. Cooling rate can also have an effect on the glass transition temperature for FK906 frozen solutions in the presence of dextran. Finally, salts have a significant effect on the glass transition temperature of FK906 in the frozen state but not in lyophilized FK906.

Antihypertensive Agents↗
PubMed1985

Molecular origin of biphasic response of main phase-transition temperature of phospholipid membranes to long-chain alcohols.

A statistical mechanical theory is proposed which explains the molecular mechanism of the nonlinear response of the phase-transition temperature of phospholipid vesicle membranes to added 1-alkanols. By assuming that the free energy of transfer of 1-alkanols from the aqueous phase to the membrane and the interaction energy between 1-alkanol molecules are linear functions of alkanol alkyl chain-length, the nonlinear behavior is explained in the Bragg-Williams approximation. For dipalmitoylphosphatidylcholine vesicle membranes, the theory reveals a larger free energy of transfer of 1-alkanols from the aqueous phase to the solid-gel membrane than to the liquid-crystalline membrane when the number of carbon atoms of 1-alkanol exceeds 12. When the intermolecular interaction force between 1-alkanol molecules residing in the gel phase is stronger than the interaction force between those residing in the liquid-crystalline phase, the ligand effect is to tighten the lipid matrix structure, causing the transition temperature to rise. The interaction force is a quadratic function of 1-alkanol concentration; hence, the response of the transition temperature to the 1-alkanol concentration is nonlinear. At low concentrations of the long-chain 1-alkanols that predominantly elevate the transition temperature, this intermolecular interaction force is negligible. In this case, the entropic effect of the incorporated ligand molecules, which loosens the lipid matrix, predominates, and the transition temperature decreases. The biphasic action of long-chain 1-alkanols originates from the balance of these two opposing effects: entropy and intermolecular interaction.

Alcohols↗
PubMed2001

Partition coefficients of charged and uncharged local anesthetics into dipalmitoylphosphatidylcholine bilayer membrane: estimation from pH dependence on the depression of phase transition temperatures.

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.

Journal Article↗
PubMed1991

High pressure antagonism of alcohol effects on the main phase-transition temperature of phospholipid membranes: biphasic response.

The combined effects of high pressure (up to 300 bar) and a homologous series of 1-alkanols (ethanol C2 to 1-tridecanol C13) were studied on the main phase-transition temperature of dipalmitoylphosphatidylcholine (DPPC) vesicle membranes. It is known that short-chain alkanols depress and long-chain alkanols elevate the main transition temperature. The crossover from depression to elevation occurs at the carbon-chain length about C10-C12 in DPPC vesicle membranes coinciding with the cutoff chain-length where anesthetic potency suddenly disappears. Alkanols shorter than C8 linearly decreased the transition temperature and high pressure antagonized the temperature depression. Alkanols longer than C10 showed biphasic dose-response curves. High pressure enhanced the biphasic response. In addition, alkanols longer than the cutoff length depressed the transition temperature under high pressure at the low concentration range. These non-anesthetic alkanols may manifest anesthetic potency under high pressure. At higher concentrations, the temperature elevatory effect was accentuated by pressure. This biphasic effect of long-chain alkanols is not related to the 'interdigitation' associated with short-chain alkanols. The increment of the transition temperature by pressure was 0.0242 K bar-1 in the absence of alkanols. The volume change of the transition was estimated to be 27.7 cm3 mol-1. This value stayed constant to the limit of the present study of 300 bar.

1,2-Dipalmitoylphosphatidylcholine↗