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Diffusion of short chain alcohols from amorphous maltose-water mixtures above and below their glass transition temperature.

The apparent diffusion coefficient for short chain alcohols in undercooled maltose-water mixtures close to the calorimetric glass transition temperature, Tg, was measured by following desorption using headspace gas chromatography. The plasticising effect of the alcohols on Tg was characterised using differential scanning calorimetry. The initial appearance of alcohol in the headspace showed a linear dependence on the square root of time, allowing it to be modelled as a Fickian diffusive process. The diffusion coefficient decreased with increasing molecular size of alcohol and proximity to Tg. Close to the glass transition the variation of diffusion coefficient with temperature and composition does not follow that of viscosity and, for ethanol, divergence was observed at Tg/T> 0.88.

Alcohols↗

Effect of 1-anilinonaphthalene-8-sulphonate on phase transition temperature of dipalmitoylphosphatidylcholine liposomes.

The effect of 1-anilinonaphthalene-8-sulfonate (ANS) on the thermotropic phase transition of dipalmitoylphosphatidylcholine (DPPC) bilayers was examined by differential scanning calorimetry. The main phase transition temperature was found to be shifted to lower values in the presence of the probe. The shift strongly depends on pH and the presence of salts. This indicates that the penetration of the probe of the hydrocarbon moiety of the bilayer is influenced by coulombic interactions. Pretransition phenomena are also affected. The implications for the interpretation of experimental data of biomembrane studies are discussed.

Anilino Naphthalenesulfonates↗

An explanation for a universality of transition temperatures in families of copper oxide superconductors.

A remarkable mystery of the copper oxide high-transition-temperature (T(c)) superconductors is the dependence of T(c) on the number of CuO2 layers, n, in the unit cell of a crystal. In a given family of these superconductors, T(c) rises with the number of layers, reaching a peak at n = 3, and then declines: the result is a bell-shaped curve. Despite the ubiquity of this phenomenon, it is still poorly understood and attention has instead been mainly focused on the properties of a single CuO2 plane. Here we show that the quantum tunnelling of Cooper pairs between the layers simply and naturally explains the experimental results, when combined with the recently quantified charge imbalance of the layers and the latest notion of a competing order nucleated by this charge imbalance that suppresses superconductivity. We calculate the bell-shaped curve and show that, if materials can be engineered so as to minimize the charge imbalance as n increases, T(c) can be raised further.

Journal Article↗

Changes in phase transition temperature of phospholipids induced by endotoxin.

The effects of endotoxin (lipopolysaccharide from Salmonella minnesota Re 595) on the phase transition temperature (Tm) of various phospholipids were studied. Endotoxin had no effect on the Tm and the width of the phase transition of dipalmitoyl-sn-3-phosphatidylcholine. Endotoxin at 100 micrograms/ml increased the Tm of dipalmitoyl-sn-3-phosphatidylethanolamine by 1.1 degrees C (P less than 0.01) and narrowed the range of transition from 4.5 to 2.6 degrees C; the endotoxin-induced changes in the Tm and the transition range were abolished by the presence of 0.25 mM CaCl2. Endotoxin increased the Tm of dipalmitoyl-sn-3-phosphatidic acid by 1.1 (P less than 0.01), 1.2 (P less than 0.01), and 3.1 (P less than 0.01) degrees C at 25, 50 and 100 micrograms/ml, respectively. Furthermore, the width of phase transition of phosphatidic acid was narrowed from 6.5 to 4.0 degrees C by endotoxin at 100 micrograms/ml. The endotoxin-induced changes in the Tm and the transition range of phosphatidic acid were not affected by the presence of EDTA (1 mM) or CaCl2 (0.05-0.1 mM). These results suggest that endotoxin decreases the fluidity of negatively charged phospholipids such as phosphatidic acid and phosphatidylethanolamine. A change in the physical properties of membrane lipid bilayers induced by endotoxin may have an adverse effect on the function of biological membranes.

Endotoxins↗

Simulation study of the glass transition temperature in poly(methyl methacrylate).

The glass transition in syndiotactic poly (methyl methacrylate) has been studied through atomistic molecular dynamics simulations performed at temperatures in the range from 297 K to 684 K. The mean squared deviations of atoms, monomers, and molecules from their initial positions were analyzed by means of a technique that separates the effects of diffusive motion from the underlying vibrational motion. The diffusive motion shows a novel power-law variation with time, with an exponent that varies continuously from 0.5 below the glass transition temperature T(g) to 1 at high temperatures. The self part of the van Hove correlation functions for both hydrogen atoms and monomers shows structural arrest at the lowest temperature studied. A second peak in the atomic van Hove correlation is attributed to rotation of the CH3 group.

Journal Article↗

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: novel fluorescence measurements.

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T(g), the relative strength of the glass transition, and the relative rate of physical aging below T(g) in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T(g). Positive deviations from bulk T(g) are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T(g) are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm.

Journal Article↗

Nonanalytic dependence of the transition temperature of the homogeneous dilute Bose gas on scattering length.

We show that the shift in the transition temperature of the dilute homogeneous Bose gas is nonanalytic in the scattering amplitude a. The first correction beyond the positive linear shift in a is negative and of order a(2)lna. This nonuniversal nonanalytic structure indicates how the discrepancies between numerical calculations at finite a can be reconciled with calculations of the limit a-->0, since the linearity is apparent only for anomalously small a.

Journal Article↗

Measurement of glass transition temperatures in freeze concentrated solutions of non-electrolytes by electrical thermal analysis.

The electrical resistance (R) of frozen aqueous solutions was measured as a function of temperature in order to determine whether this technique can be applied for determination of glass transition temperatures of maximally freeze concentrated solutions (Tg') of non-electrolytes which do not crystallize during freezing. Electrical thermal analysis (ETA) thermograms of frozen solutions containing the solute alone show a gradual change in slope over the temperature range of interest, with no inflection point which corresponds to Tg'. However, addition of low levels (about 0.1%) of electrolyte changes the shape of the thermogram into a biexponential function where the intersection of the two linear portions of the log (R) vs. T plot corresponds to the glass transition region. The total change in log (R) over the temperature range studied increases as the ionic radius of the reporter ion increases. The sharpest inflection points in the log (R) vs T curves, and the best correlation with DSC results, were obtained with ammonium salts. Tg' values measured by ETA were compared with values measured by DSC. DSC thermograms of solutes with and without electrolyte (0.1%) show that the electrolyte decreases Tg' by about 0.5 to 1.0 degrees C. However, Tg' values measured by ETA are somewhat higher than those measured by DSC, and difference between the two methods seems to increase as Tg' decreases. Tg' as measured by ETA is less heating rate dependent than DSC analysis, and ETA is a more sensitive method than DSC at low solute concentrations and at low heating rates.(ABSTRACT TRUNCATED AT 250 WORDS)

Calorimetry, Differential Scanning↗

Glass transition temperatures and fermentative activity of heat-treated commercial active dry yeasts.

Differential scanning calorimetry thermograms of various samples of commercial instant active dry yeasts revealed a clear glass transition typical of amorphous carbohydrates and sugars. The resulting glass transition temperatures were found to decrease with increasing moisture content. The observed glass curve was similar to that of pure trehalose, which is known to accumulate in large amounts in baker's yeast. The effect of heat treatment at various temperatures on the fermentative activity (as measured by the metabolic production of CO(2)) of dry yeast was studied. First-order plots were obtained representing the loss of fermentative activity as a function of heating time at the various temperatures assayed. Significant losses of fermentative activity were observed in vitrified yeast samples. The dependence of rate constants with temperature was found to follow Arrhenius behavior. The relationship between the loss of fermentative activity and glass transition was not verified, and the glass transition was not reflected on the temperature dependence of fermentative activity loss.

Biotechnology↗

Reductions of the glass transition temperature in thin polymer films: probing the length scale of cooperative dynamics

We report measurements of the glass transition temperature, T(g), in free standing polymer films in a low M(n) limit where chain confinement effects are not observed. The measured T(g) values are accurately described by a layer model incorporating a mobile surface layer with a size determined by the length scale of cooperative dynamics. The analysis leads to a surface T(g) value and length scale of cooperative motion near bulk T(g) which quantitatively agree with independently determined values. The model and parameters provide a framework within which all previous measurements of T(g) values in thin supported films may be understood and provides values for the length scale of cooperative motion over an extended range of temperatures below the bulk T(g) value.

Journal Article↗

Influence of various cationic amphiphilic drugs on the phase-transition temperature of phosphatidylcholine liposomes.

The influence of 16 cationic amphiphilic compounds from various pharmacological groups on the phase-transition temperature (Tt) of dipalmitoyl-phosphatidylcholine (DPPC) liposomes was investigated using the method of differential scanning calorimetry. All drugs, the hydrophobicity of which varied in a wide range, depressed Tt. Biphasic dose-effect curves were obtained when the reduction of Tt (delta Tt) was plotted vs the molar ratio of drug/DPPC; beyond a plateau, Tt could again be reduced markedly by increasing the molar ratio. Concomitantly with the depression of Tt, the width of the transition peak changed in a characteristic way: it broadened during the (first) steep part of the dose-effect curves and became narrow like a control transition when the plateau of the dose-effect curves was reached. At still higher ratios the peak broadened again and eventually vanished, probably due to a detergent-like effect of the drug. Increasing hydrophobicity of the compounds shifted the dose-effect curves to lower molar ratios and enhanced the delta Tt attained at the plateau phase. It is proposed that the different potencies of the drugs to depress Tt result from different binding equilibria between the compounds and DPPC membranes, the individual equilibrium being determined by hydrophobic attraction and electrostatic repulsion.

Anions↗

Degradation rate of lyophilized insulin, exhibiting an apparent Arrhenius behavior around glass transition temperature regardless of significant contribution of molecular mobility.

The relative influences of chemical activation energy and molecular mobility in determining chemical reactivity were evaluated for insulin lyophilized with alpha,beta-poly(N-hydroxyethyl)-L-aspartamide (PHEA), and compared with that for insulin lyophilized with trehalose, which had been found to have the ability to decrease the molecular mobility of insulin at low humidity. The ratio of the observed rate constant k(obs) to the chemical activation energy-controlled rate constant k(act) (k(obs)/k(act)) at glass transition temperature (T(g)) was estimated to be approximately 0.6 and 0.8 at 6% RH and 12% RH, respectively, indicating that the degradation rate is significantly affected by molecular mobility at lower humidity conditions. However, these k(obs)/k(act) values at T(g) were larger than those for the insulin-trehalose system, and changes in the temperature-dependent slope around T(g) were less obvious than those for the insulin-trehalose system. Thus, the contribution of molecular mobility to the degradation rate in the insulin-PHEA system appeared to be less intense than that in the insulin-trehalose system. The subtle change in the temperature-dependent slope around T(g) observed in the insulin-PHEA system brought about a significant bias in shelf-life estimation when the reaction rate was extrapolated from temperatures above T(g) according to the Arrhenius equation.

Calorimetry, Differential Scanning↗

Electrolyte-induced changes in glass transition temperatures of freeze-concentrated solutes.

Addition of electrolytes to solutions of non-crystallizing solutes can cause a significant decrease in the glass transition temperature (Tg') of the maximally freeze-concentrated solution. For example, addition of 2% sodium chloride to 10% solutions of dextran, PVP, lactose, and sucrose causes a decrease in Tg' of 14 degrees to 18 degrees C. Sodium phosphate has a smaller effect on Tg' and is unusual in that 1% to 2% sodium phosphate in 10% PVP causes a second glass transition to be observed in the low-temperature thermogram, indicating a phase separation in the freeze concentrate. Comparison of DSC thermograms of fast-frozen solutions of sucrose with and without added sodium chloride shows that electrolyte-induced reduction of Tg' is not caused by a direct plasticizing effect of the electrolyte on the freeze concentrate. Measurement of unfrozen water content as a function of temperature by a pulsed nmr method shows that the most likely mechanism for electrolyte-induced changes in Tg' is by increasing the quantity of unfrozen water in the freeze concentrate, where the unfrozen water acts as a plasticizer and decreases Tg'. The correlation time (tau c) of water in the freeze concentrate is in the range of 10(-7) to 10(-8) seconds. The results underscore the importance of minimizing the amount of added salts to formulations intended for freeze drying.

Calorimetry, Differential Scanning↗

Gap-modulation infrared spectroscopy of high transition temperature superconductors.

Conventional methods of determining the coupling factor alpha(2)(omega)F(omega) for the newly discovered high transition temperature (T(c)) cuprate superconductors by using tunneling and infrared measurements have thus far failed to show the cause of the very high T(c) of these compounds. This is due in part to difficulties in sample preparation for tunneling studies and to difficulties in obtaining good data at relatively high tunneling voltages. Also, in IR (infrared) measurements, small differences in absorptivity between the normal and superconducting state can be masked by changes in the phonon occupation at high and low temperatures. Here we propose a technique for determing the coupling constant, which should be less dependent on the surface quality of the sample than with tunneling and should allow measurements at higher energies with greater precision than do tunneling or simple IR observations. This should make possible a definitive determination of any possible exciton contribution to this coupling term, which would appear at energies well above the range where conventional IR or tunneling measurements are effective.

Journal Article↗

Glass transition temperature of freely-standing films of atactic poly(methyl methacrylate).

We have used ellipsometry to measure the glass transition temperature T(g) of high molecular weight (M(w)=790 x 10(3)), freely-standing films of atactic poly(methyl methacrylate) (a-PMMA), as well as films of the same polymer supported on two different substrates: the native oxide layer of silicon (Si) and gold-covered Si. We observe linear reductions in T(g) with decreasing film thickness h for the freely-standing PMMA films with 30 nm < h<100 nm, which is qualitatively similar to previous results obtained for freely-standing polystyrene (PS) films. However the magnitude of the T(g) reductions for PMMA is much less than for freely-standing films of PS of comparable molecular weight and thickness. We also find that for films supported on either substrate, with thicknesses as small as 30 nm, the T(g) values do not deviate substantially from the value measured for thick films.

Journal Article↗

Molecular weight dependence of reductions in the glass transition temperature of thin, freely standing polymer films.

We have used transmission ellipsometry to perform a comprehensive study of the glass transition temperature T(g) of freely standing polystyrene films. Six molecular weights M(w), ranging from 575 x 10(3) to 9100 x 10(3), were used in the study. For each M(w) value, large reductions in T(g) (as much as 80 degrees C below the bulk value) were observed as the film thickness h was decreased. We have studied in detail the dependence of the T(g) reductions on M(w) in a regime dominated by chain confinement effects. The empirical analysis presented is highly suggestive of the existence of a mechanism of mobility in thin freely standing films that is inhibited in the bulk and distinct from the usual cooperative motion associated with the glass transition.

Journal Article↗

Low amounts of sucrose are sufficient to depress the phase transition temperature of dry phosphatidylcholine, but not for lyoprotection of liposomes.

Disaccharides such as sucrose and trehalose play an important role in stabilizing cellular structures during dehydration. In fact, most organisms that are able to survive desiccation accumulate high concentrations of sugars in their cells. The mechanisms involved in the stabilization of cellular membranes in the dry state have been investigated using model membranes, such as phosphatidylcholine liposomes. It has been proposed that the lyoprotection of liposomes depends on the depression of the gel to liquid-crystalline phase transition temperature (T(m)) of the dry membranes below ambient and on the prevention of membrane fusion by sugar glass formation, because both lead to leakage of soluble content from the liposomes. Since fusion is prevented at lower sugar/lipid mass ratios than leakage, it has been assumed that more sugar is needed to depress T(m) than to prevent fusion. Here, we show that this is not the case. In air-dried egg phosphatidylcholine liposomes, T(m) is depressed by >60 degrees C at sucrose/lipid mass ratios 10-fold lower than those needed to depress fusion to below 20%. In fact, T(m) is significantly reduced at mass ratios where no bulk sugar glass phase is detectable by Fourier transform infrared spectroscopy or differential scanning calorimetry. A detailed analysis of the interactions of sucrose with the P=O, C=O, and choline groups of the lipid and a comparison to published data on water binding to phospholipids suggests that T(m) is reduced by sucrose through a "water replacement" mechanism. However, the sucrose/lipid mass ratios necessary to prevent leakage exceed those necessary to prevent both phase transitions and membrane fusion. We hypothesize that kinetic phenomena during dehydration and rehydration may be responsible for this discrepancy.

Calorimetry, Differential Scanning↗

The distribution of glass-transition temperatures in nanoscopically confined glass formers.

Despite the decade-long study of the effect of nanoconfinement on the glass-transition temperature (T(g)) of amorphous materials, the quest to probe the distribution of T(g)s in nanoconfined glass formers has remained unfulfilled. Here the distribution of T(g)s across polystyrene films has been obtained by a fluorescence/multilayer method, revealing that the enhancement of dynamics at a surface affects T(g) several tens of nanometres into the film. The extent to which dynamics smoothly transition from enhanced to bulk states depends strongly on nanoconfinement. When polymer films are sufficiently thin that a reduction in thickness leads to a reduction in overall T(g), the surface-layer T(g) actually increases with a reduction in overall thickness, whereas the substrate-layer T(g) decreases. These results indicate that the gradient in T(g) dynamics is not abrupt, and that the size of a cooperatively rearranging region is much smaller than the distance over which interfacial effects propagate.

Journal Article↗