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At least 145 records · Page 8Linked to original sources
PubMed2005

Morphological behavior of lipid bilayers induced by melittin near the phase transition temperature.

Morphological changes of DMPC, DLPC, and DPPC bilayers containing melittin (lecithin/melittin molar ratio of 10:1) around the gel-to-liquid crystalline phase transition temperatures (Tc) were examined by a variety of biophysical methods. First, giant vesicles with the diameters of approximately 20 microm were observed by optical microscopy for melittin-DMPC bilayers at 27.9 degrees C. When the temperature was lowered to 24.9 degrees C (Tc = 23 degrees C for the neat DMPC bilayers), the surface of vesicles became blurred and dynamic pore formation was visible in the microscopic picture taken at different exposure times. Phase separation and association of melittin molecules in the bilayers were further detected by fluorescent microscopy and mass spectrometry, respectively. These vesicles disappeared completely at 22.9 degrees C. It was thus found that the melittin-lecithin bilayers reversibly undergo their fusion and disruption near the respective Tcs. The fluctuation of lipids is, therefore, responsible for the membrane fusion above the Tc, and the association of melittin molecules causes membrane fragmentation below the Tc. Subsequent magnetic alignments were observed by solid-state (31)P NMR spectra for the melittin-lecithin vesicles at a temperature above the respective Tcs. On the other hand, additional large amplitude motion induced by melittin at a temperature near the Tc breaks down the magnetic alignment.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1999

Effects of pH and the gel state on the mechanical properties, moisture contents, and glass transition temperatures of whey protein films.

The mechanical properties, moisture contents (MC), and glass transition temperature (T(g)) of whey protein isolate (WPI) films were studied at various pH values using sorbitol (S) as a plasticizer. The films were cast from heated aqueous solutions and dried in a climate chamber at 23 degrees C and 50% relative humidity (RH) for 16 h. The critical gel concentrations (c(g)) for the cooled aqueous solutions were found to be 11.7, 12.1, and 11.3% (w/w) WPI for pH 7, 8, and 9, respectively. The cooling rate influenced the c(g), in that a lower amount of WPI was needed for gelation when a slower cooling rate was applied. Both cooling rates used in this study showed a maximum in the c(g) at pH 8. The influence of the polymer network on the film properties was elucidated by varying the concentration of WPI over and under the c(g). Strain at break (epsilon(b)) showed a maximum at the c(g) for all pH values, thus implying that the most favorable structure regarding the ability of the films to stretch is formed at this concentration. Young's modulus (E) and stress at break (sigma(b)) showed a maximum at c(g) for pH 7 and 8. The MC and epsilon(b) increased when pH increased from 7 to 9, whereas T(g) decreased. Hence, T(g) values were -17, -18, and -21 degrees C for pH 7, 8, and 9, respectively. E and sigma(b) decreased and epsilon(b) and thickness increased when the surrounding RH increased. The thickness of the WPI films also increased with the concentration of WPI.

Animals↗
PubMed2005

The glass transition temperature of polymer melts.

We develop an analytic theory to estimate the glass transition temperature T(g) of polymer melts as a function of the relative rigidities of the chain backbone and side groups, the monomer structure, pressure, and polymer mass. Our computations are based on an extension of the semiempirical Lindemann criterion of melting to locate T(g) and on the use of the advanced mean field lattice cluster theory (LCT) for treating the thermodynamics of systems containing structured monomer, semiflexible polymer chains. The Lindemann criterion is translated into a condition for T(g) by expressing this relation in terms of the specific volume, and this free volume condition is used to calculate T(g) from our thermodynamic theory. The mass dependence of T(g) is compared to that of other characteristic temperatures of glass-formation. These additional characteristic temperatures are determined from the temperature variation of the LCT configurational entropy, in conjunction with the Adam-Gibbs model for long wavelength structural relaxation. Our theory explains generally observed trends in the variation of T(g) with polymer microstructure, and we find that T(g) can be tuned either upward or downward by increasing the length of the side chains, depending on the relative rigidities of the side groups and the chain backbone. The elucidation of the molecular origins of T(g) in polymer liquids should be useful in designing and processing new synthetic materials and for understanding the dynamics and controlling the preservation of biological substances.

Journal Article↗
PubMed2003

Free surfaces cause reductions in the glass transition temperature of thin polystyrene films.

The effect of free surfaces on the glass transition temperature (T(g)) of thin polystyrene films was studied. Measurements were performed on films (8 nm<h<290 nm) with one free surface and on films capped with a 5 nm thick metal layer (no free surfaces). Potential problems with evaporative deposition were eliminated by studying samples made of two supported films placed with their free surfaces in contact and annealed. Uncapped films displayed reduced T(g) values for h less, similar 40 nm while all "properly" capped films exhibited a T(g) value the same as that of the bulk polymer (370+/-1 K). When the free surface was restored, the measured T(g) values the same as those of uncapped films of the same thickness. These results show that free surfaces are crucial for observing T(g) reductions in thin polymer films and address the role of the sample preparation history.

Journal Article↗
PubMed2003

Effect of triphenyl bismuth on glass transition temperature and residual monomer content of acrylic bone cements.

Self-curing acrylic bone cements are widely used in the fixation of prosthetic implants in orthopaedic surgery. Commercial bone cements are rendered radiopaque by the addition of heavy metal salts of barium and zirconia. The addition of barium sulphate adversely affects the mechanical strength and fracture toughness of bone cement and despite the fact that it has low solubility in water; its slow release and subsequent toxicity have caused concern. In an earlier study triphenyl bismuth (TPB) was found to be a viable alternative as a radiopaque agent in acrylic bone cements, which provided enhanced homogeneity. In this study we report the effect of the inclusion of TPB on the thermal properties of PMMA-based bone cements using both conventional DSC and Modulated Temperature DSC. Furthermore, analysis of the residual monomer contents is reported analysed by NMR spectroscopy in order to ascertain the influence of TPB on the polymerisation reaction. The glass transition temperature (Tg) determined by DSC showed that the values decreased with the addition of increasing amounts of TPB through both blending and dissolution methods; however, the method of incorporating TPB did not influence Tg. The magnitude of reduction was dependent of the amount of TPB and was greatest in the case of highest concentration of TPB used. A TPB melting peak was observed in the 25 wt% TPBBC, suggesting a limit to the solubility of TPB. The residual monomer analysis showed that at 10 and 15% by weight of TPB in the cement caused no significant changes in the residual monomer content but 25 wt% of TPB exhibited a significantly higher residual monomer content.

Calorimetry, Differential Scanning↗
PubMed1996

Is vitrification involved in depression of the phase transition temperature in dry phospholipids?

Recent literature has suggested that the depression of the phase transition temperature (Tm) in dry phospholipids by sugars may be ascribed to vitrification of the stabilizing solute, rather than by the direct interaction between sugar and phospholipid we have proposed. Koster et al. ((1994) Biochim. Biophys. Acta 1193, 143-150) claim that the only necessity is that the glass transition (Tg) for the sugar exceed Tm for the lipid. Evidence is presented in the present paper that this is not sufficient. Based on the vitrification hypothesis of Koster et al., the predicted order of effectiveness in depressing Tm in dry dipalmitoylphosphatidylcholine (DPPC) is dextran > or = hydroxyethyl starch > stachyose > raffinose > trehalose > sucrose > glucose. In fact, the opposite order was seen. The effect of raffinose, sucrose, or trehalose on Tm in dry DPPC depends on the thermal history of the sample, as we have reported previously. When DPPC dried with trehalose is heated for the first time, Tm is about 55 degrees C, but on the second and subsequent heating scans Tm falls to about 25 degrees C. Koster et al. suggest that this effect is due to heating the sample above Tg rather than to melting the hydrocarbon chains. We present evidence here that all that is required is for the chains to be melted. Further, we show that retention of residual water by DPPC dried with trehalose depends on the drying temperature, but is independent of drying temperature with glucose, a finding that is consistent with direct interaction. We conclude that vitrification is not in itself sufficient to depress Tm in dry phospholipids.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2006

Determination of lipid phase transition temperatures in hybrid bilayer membranes.

The main gel-to-liquid-crystal (LC) phase transition temperature, T(m), of the lipid monolayer in hybrid bilayer membranes (HBMs) was investigated using vibrational sum frequency spectroscopy (VSFS). In the gel phase, the acyl chains of the lipid molecules assume an ordered, all-trans configuration, whereas in the LC phase, the acyl chains exhibit a significant number of disordered gauche conformers. VSFS has unique sensitivity to the order/disorder transitions in the acyl chains and was used to determine T(m) for a series of saturated phosphatidylcholine lipids on octadecanethiolate self-assembled monolayers (SAMs). The values obtained for T(m) for all lipids studied are significantly higher than for the corresponding lipids in vesicles in solution. Additionally, the transition widths are broader for the lipids in HBMs. The underlying SAM clearly influences the phase behavior of the overlying lipid monolayer.

Journal Article↗
PubMed1995

Pressure dependence of the helix-coil transition temperature of poly[d(G-C)].

The pressure dependence of the helix-coil transition temperature (Tm) of poly[d(G-C)] was studied as a function of sodium ion concentration in phosphate buffer. The molar volume change of the transition (delta V) was calculated using the Clapeyron equation and calorimetrically determined enthalpies. The delta V of the transition increased from +4.80 (+/- 0.56) to +6.03 (+/- 0.76) mL mol-1 as the sodium ion concentration changed from 0.052 to 1.0M. The van't Hoff enthalpy of the transition calculated from the half-width of the differentiated transition displayed negligible pressure dependence; however, the value of this parameter decreased with increasing sodium ion concentration, indicating a decrease in the size of the cooperative unit. The volume change of the transition exhibits the largest magnitude of any double-stranded DNA polymer measured using this technique. For poly[d(G-C)] the magnitude of the change in delta V with sodium ion concentration (0.94 +/- 0.05 mL mol-1) is approximately one-half that observed for either poly[d(A-T)] or poly(dA).poly(dT). The delta V values are interpreted as arising from changes in the hydration of the polymer due to the release of counterions and changes in the stacking of the bases of the coil form. As a consequence of solvent electrostriction, the release of counterions makes a net negative contribution to the total delta V, implying that disruption of the stacking interactions contributes a positive volume change to the total delta V.(ABSTRACT TRUNCATED AT 250 WORDS)

Hydrostatic Pressure↗
PubMed1999

Electro-optic response of surface-induced nematic order above the nematic-isotropic phase transition temperature.

The optical retardation of a liquid crystal above the nematic-isotropic phase transition temperature T(NI) and subjected to planar alignment conditions at the substrate was investigated in the presence of an electric field applied normal to the substrates. The response was found to exhibit "S"-shaped behavior with electric field, and was larger near T(NI) than well above T(NI). The results were examined in the context of a model that permits both biaxiality and a field-induced tilt of the molecular director. The results suggest that the primary effect of the electric field is to induce biaxiality, and in consequence suppress the order induced by the surface. No clear indication of a Freedericksz-like transition, either experimental or theoretical, was observed.

Journal Article↗
PubMed1977

Effect of primidone concentration on glass transition temperature and dissolution of solid dispersion systems containing primidone and citric acid.

The glass transition temperatures of glasses containing various concentrations of primidone in citric acid were measured and found to increase as the primidone concentration increased. Dissolution studies of these systems and particle-size measurements of primidone precipitated during dissolution of devitrified glasses suggest that the increase in the dissolution rate of the devitrified systems is due to both the small size of the precipitated crystals and the excellent wettability of these systems.

Chemistry, Pharmaceutical↗
PubMed1996

On the bilayer phase transition temperatures for monoenoic phosphatidylcholines and phosphatidylethanolamines and the interconversion between them.

The dependence of the phase transition temperature, Tm, on the structural parameters of the lipid molecule has been firmly established for lipid bilayers composed of saturated phosphatidylcholines (PC) or phosphatidylethanolamines (PE). It is from such a dependence that conversions of Tm values from saturated PC to PE and vice versa have been successfully demonstrated. In this communication, similar chain-melting-structure relationships are sought for monoenoic PC and PE in which the long hydrocarbons linked at the sn-1 and sn-2 positions are saturated and cis-mono-unsaturated chains, respectively. Specifically, various molecular species of monoenoic PC and PE were first semisynthesized and their Tm values were subsequently determined by high-resolution differential scanning calorimetry. Based on the crankshaft-like kink motif model, the synthesized monoenoic PC and PE can each be divided into two groups, each group being characterized by three structural parameters. For each group of monoenoic PC or PE, a specific equation correlating the changes in Tm with variations in the structural parameters was derived using the multiple regression analysis. Furthermore, within each group of lipids including both PC and PE, an explicit equation describing the interconversion of Tm values between PC and PE with the same fatty acyl chain composition was established. The present work not only extends the earlier work relating the chain-melting temperature of saturated PC and PE to their structural parameters, but also indicates that the basic topology of the sn-2 mono-unsaturated acyl chain of PC and PE in the gel-state bilayer can be approximated by the crankshaft-like kink motif with the longer segment being packed much more orderly than the shorter segment.

Calorimetry, Differential Scanning↗
PubMed2005

Anomalous pressure dependence of the superconducting transition temperature of beta-pyrochlore AOs2O6 oxides.

High-pressure effects on the superconducting transitions of beta-pyrochlore oxide superconductors AOs(2)O(6) (A = Cs,Rb,K) are studied by measuring resistivity under high pressures up to 10 GPa. The superconducting transition temperature T(c) first increases with increasing pressure in every compound and then exhibits a broad maximum at 7.6 K (6 GPa), 8.2 K (2 GPa), and 10 K (0.6 GPa) for A = Cs, Rb, and K, respectively. Finally, the superconductivity is suppressed completely at a critical pressure near 7 GPa and 6 GPa for A = Rb and K and probably above 10 GPa for A = Cs. Characteristic changes in the coefficient A of the T(2) term in resistivity and residual resistivity are observed, both of which are synchronized with the corresponding change in T(c).

Journal Article↗
PubMed2006

Inverse temperature transition of a biomimetic elastin model: reactive flux analysis of folding/unfolding and its coupling to solvent dielectric relaxation.

The inverse temperature transition (ITT) of a biomimetic model for elastin, capped GVG(VPGVG) in liquid water, is investigated by a comprehensive classical molecular dynamics study. The temperature dependence of the solvation structure and dynamics of the octapeptide are compared using three common force fields, CHARMM, GROMOS, and OPLS. While these force fields differ in quantitative detail, they all predict this octapeptide to undergo a "folding transition" to closed conformations upon heating and a subsequent "unfolding transition" to open conformations at still higher temperatures, thus reproducing the ITT scenario. The peptide kinetics is analyzed within the reactive flux formalism applied to the largest-amplitude mode extracted from principal component analysis, and the solvent's dielectric fluctuations are obtained from the total water dipole autocorrelations. Most importantly, preliminary evidence for an intimate coupling of peptide folding/unfolding dynamics, and thus the ITT, and dielectric relaxation of bulk water is given, possibly being consistent with a "slave mode" picture.

Biomimetic Materials↗
PubMed1997

[Determination of liquid-crystalline transition temperature of temperature-sensitive liposomes of futraful by 1HNMR].

1HNMR was employed to determine the liquid-crystalline transition temperature (TC) of the temperature-sensitive liposomes of futraful. It is a method with high sensitivity, high accuracy and furnishing more information. The 1HNMR spectra were made and studied. The rate of peak height increase of phospholipid correlates to the thermotropic phase transition of liposomes. The study shows that the TC of DPPC-liposomes and DSPC-liposomes is 36 degrees C and 48 degrees C, respectively. The TC of DPPC-DSPC-liposomes correlates with the proportion of the amount of DPPC and DSPC. The TC is not affected by futraful. The temperature-sensitive liposomes of futraful with TC of 41 degrees C were prepared which consisted of 60% DPPC and 40% DSPC.

Crystallins↗
PubMed1996

Effects of alcohols on the phase transition temperatures of mixed-chain phosphatidylcholines.

The biphasic effect of ethanol on the main phase transition temperature (Tm) of identical-chain phosphatidyl-cholines (PCs) in excess H2O is now well known. This biphasic effect can be attributed to the transformation of the lipid bilayer, induced by high concentrations of ethanol, from the partially interdigitated L beta, phase to the fully interdigitated L beta I phase at T < Tm. The basic packing unit of the L beta I phase has been identified recently as a binary mixture of PC/ethanol at the molar ratio of 1:2. The ethanol effect on mixed-chain PCs, however, is not known. We have thus in this study investigated the alcohol effects on the Tm of mixed-chain PCs with different delta C values, where delta C is the effective acyl chain length difference between the sn-1 and sn-2 acyl chains. Initially, molecular mechanics (MM) simulations are employed to calculate the steric energies associated with a homologous series of mixed-chain PCs packed in the partially and the fully interdigitated L beta I motifs. Based on the energetics, the preference of each mixed-chain PC for packing between these two different motifs can be estimated. Guided by MM results, high-resolution differential scanning calorimetry is subsequently employed to determine the Tm values for aqueous lipid dispersions prepared individually from a series of mixed-chain PCs (delta C = 0.5-6.5 C-C bond lengths) in the presence of various concentrations of ethanol. Results indicate that aqueous dispersions prepared from mixed-chain PCs with a delta C value of less than 4 exhibit a biphasic profile in the plot of Tm versus ethanol concentration. In contrast, highly asymmetric PCs (delta C > 4) do not exhibit such biphasic behavior. In the presence of a longer chain n-alcohol, however, aqueous dispersions of highly asymmetric C(12):C(20)PC (delta C = 6.5) do show such biphasic behavior against ethanol. Our results suggest that the delta C region in a highly asymmetric PC packed in the L beta I phase is most likely the binding site for n-alcohol.

Alcohols↗
PubMed1999

Determination of the glass transition temperatures of some new methyl methacrylate copolymers using modulated temperature differential scanning calorimetry (MTDSC).

PURPOSE: The purpose of this study was to determine the glass transition temperatures of new graft copolymers using Modulated Temperature Differential Scanning Calorimetry (MTDSC), and to assess the differences between starch and cellulosic derivatives of methyl methacrylate and between two different drying methods used in their preparation. METHODS: Graft copolymers of methyl methacrylate were synthesized and dried by oven or freeze-drying. Surface area measurements and different thermal analysis techniques (Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TGA) and MTDSC) were used to characterize these copolymers. Results. DSC was not sensitive enough to identify the T(g)s of the copolymers, however they were clearly identifiable by MTDSC. T(g) values obtained may depend on the method of preparation that also altered their physical characteristics e.g. specific surface area. Cellulose derivatives showed lower T(g)s than starch derivatives. The results also depended on the drying method used, thus, freeze dried products had slightly lower T(g)s than oven dried products. CONCLUSIONS: MTDSC represents a useful thermal technique that allows the identification of glass transitions in these new copolymers with higher sensitivity and resolution than conventional DSC, separating the transition from overlapping phenomena such as decomposition or dehydration. The Tg of this new class of copolymers appeared to be dependent on polymer composition and drying method used.

Calorimetry, Differential Scanning↗