Metastable crystalline lamella of cetylpyridinium chloride in the Krafft transition

The metastable crystalline lamella was found in the Krafft transition of aqueous cetylpyridinium chloride (CPC) solutions. Temperature-dependent profiles of small-angle X-ray scattering (SAXS) for the CPC solution incubated for 10 min at 5 degrees C exhibited the metastable lamella structure with a lattice spacing of dL = 3.19 nm at temperatures below 12 degrees C and the stable lamella structure with a lattice spacing of dL = 2.85 nm at temperatures between 12 and 19 degrees C. The former lamella structure, however, was not observed in the temperature scanning SAXS profiles of the CPC solution incubated for 24 h at 5 degrees C. The latter lamella structure observed in the SAXS profile mentioned above started melting at 18 degrees C. The electric conductance change of the CPC solution with a time elapsed after dropping the temperature showed the existence of the temperature-dependent induction period in the Krafft transition, indicating high activation energies for the transition. In the differential scanning calorimetry measurements over temperatures ranging from 5 to 30 degrees C, a single endothermic enthalpy peak at 19 degrees C observed for the CPC solution incubated at 5 degrees C for a longer period than 6 h was split into double peaks at 14 and 19 degrees C when the same solution was incubated at 5 degrees C for a shorter period than 6 h. The observed calorimetric behavior is explained by the existence of the metastable crystalline state that grows faster and melts at a lower melting temperature than the stable crystalline state.     

Thermal transitions in the bilayer assembly of dimyristoylphosphatidylglycerol sodium salt dispersion in water: a new phase transition through an intermediate state

The thermal properties of the dispersion of sodium salt of dimyristoylphosphatidylglycerol (NaDMPG) in water have been investigated as functions of incubation temperature and aging time by DSC, XRD, sodium ion activity, pH, zeta-potential, and IR measurements. The DSC charts for NaDMPG dispersions incubated below 30 degrees C showed an endothermic peak at 31.7 degrees C with a small shoulder peak at Tm (gel-liquid crystal transition temperature: 23.5 degrees C). The temperature of 31.7 degrees C coincides with the T* temperature at which a high-order transition in the NaDMPG bilayer assembly has been found to occur in our previous studies. However, no peak was observed for the dispersions incubated above 32 degrees C. These results indicate that thermal properties of NaDMPG bilayers definitely differ below and above the T* temperature. The dispersion which had been once incubated at 40 degrees C for 24 h never showed the endothermic peak at T* even after the further aging at 3 degrees C for 12-day. Namely, the NaDMPG bilayer assembly exhibits an intensive thermohysteresis. The XRD charts for the NaDMPG dispersions incubated at 25 degrees C showed a sharp X-ray diffraction pattern corresponding to the repeat distance of d = 4.75 nm regardless of their aging time, while the dispersions incubated at 40 degrees C had no diffraction peak until 9-day elapsed. After 10-day aging at 40 degrees C, however, a diffraction peak corresponding to d = 5.55 nm clearly appeared. In the DSC measurements for the dispersion incubated at 40 degrees C, a few endothermic peaks began to appear between Tm and T* after approximately 7-day aging. Then, they shifted toward higher temperatures and finally converged into a single peak at 40-42 degrees C after 14-day aging. These XRD and DSC peaks observed after a long period of aging time above T* suggest that conformations of the hydrophilic groups and the hydrocarbon chains in the NaDMPG bilayers take a more tight and closer arrangement very slowly via an intermediate state above T*, and a new gel phase of the bilayers is consequently formed, the transition temperature (T(I) temperature) of which is 40-42 degrees C. A molecular interpretation for such transition processes in the bilayer assembly of NaDMPG dispersions has been proposed on the basis of pH, sodium ion activity, zeta-potential, IR data, etc.     

Microsecond melting of a folding intermediate in a coiled-coil peptide, monitored by T-jump/UV Raman spectroscopy

A truncated version of the GCN4 coiled-coil peptide has been studied by ultraviolet resonance Raman (UVRR) spectroscopy with 197 nm excitation, where amide modes are optimally enhanced. Although the CD melting curve could be satisfactorily described with a two-state transition having Tm = 30 degrees C, singular value decomposition of the UVRR data yielded three principal components, whose temperature dependence implicates an intermediate form between the folded and unfolded forms, with formation and melting temperatures of 10 and 40 degrees C. Two alpha-helical amide III bands, at 1340 and 1300 cm(-1), melted out selectively at 10 and 40 degrees C, respectively, and are assigned to hydrated and unhydrated helical regions. The hydrated regions are proposed to be melted in the intermediate form, while the unhydrated regions are intact. Time-resolved UVRR spectra following laser-induced temperature jumps revealed two relaxations, with time constants of 0.2 and 15 mus. These are suggested to reflect the melting times of hydrated and unhydrated helices. The unhydrated helical region may be associated with a 14-residue "trigger" sequence that has been identified in the C-terminal half of GCN4. Dehydration of helices may be a key step in the folding of coiled-coils.     

Laser-induced shape transformation of gold nanoparticles below the melting point: the effect of surface melting

Relatively large gold nanoparticles (mean diameter of major axis 38.2 nm, mean aspect ratio 1.29) in aqueous solution were found to undergo shape transformations from ellipsoids to spheres at ca. 940 degrees C, which is much lower than their melting point, ca. 1060 degrees C. The shape transformation of gold nanoparticles induced by a single pulse of a Nd:YAG laser (lambda = 355 nm, pulse width = 30 ps) was directly observed by a transmission electron microscope (TEM). Analysis of the experimental data showed that the threshold energy for photothermally induced shape transformation was on the order of 40 fJ for a particle, which is smaller than the energy, 67 fJ, required for its complete melting. Estimations based on the heat balance and surface melting model revealed that the temperature which particles reach after a single laser pulse was about 940 degrees C, with the thickness of the liquid layer on the surface of the solid core being 1.4 nm. We also examined thermally induced shape transformation of gold nanoparticles on Si substrates; above 950 degrees C they changed their shapes to spheres, which supported our estimation. Due to the surface melting of particles, their shape transformation occurs at a temperature much lower than their melting point.     

Composition dependence and the nature of endothermic freezing and exothermic melting

The heat capacity, C(p), and enthalpy and entropy change of alpha-cyclodextrin, H(2)O, and 4-methylpyridine solutions have been studied during their freezing on heating, isothermal freezing, and the solid's melting on cooling. Freezing occurs in several endothermic steps on heating to 383 K and alpha-cyclodextrin rich solutions freeze in four steps. The melting rate becomes slower with decrease in temperature and its steps merge. Decreasing the amount of alpha-cyclodextrin decreases the C(p) change on freezing. The endothermic freezing phenomenon differs from freezing of a pure liquid and is attributed to formation of a solid inclusion compound and its incongruent way of exothermic melting.     

Raman study of the hexafluoroaluminate ion in solid and molten FLINAK

Raman spectra have been obtained for matrix-isolated AlF6(3-) in an LiF/NaF/KF (FLINAK) eutectic mixture. Three Raman bands characteristic of the hexafluoroaluminate ion were identified in the solids formed from FLINAK melts which contained small amounts (5-11 mol%) of either AlF3 or Na3AlF6. The three allowed Raman-active bands of the matrix-isolated octahedral complex ion, nu 1(A1g), nu 2(Eg), and nu 5(F2g), were observed at 560.5, 380, and 325 cm-1, respectively, for the solid sample at 25 degrees C. Wavenumbers and relative intensities were similar to those of Na3AlF6 (cryolite), K3AlF6, and K2NaAlF6 (elpasolite) and other crystals known to contain discrete, octahedral AlF6(3-) ions. Peak positions, half-widths, and relative intensities for the bands were measured for samples at temperatures different from room temperature through the melting transition and into the molten state. The transition from high-temperature solid to molten salt at about 455 degrees C occurred gradually without perceptible change in the peak positions, half-widths, or relative intensities. For a sample in molten FLINAK at 455 degrees C, the nu 1(A1g), nu 2(Eg), and nu 5(F2g) modes of the AlF6(3-) ion were observed at 542, 365, and 324 cm-1, respectively. Raman depolarization experiments were consistent with these assignments, and the low value of the depolarization ratio of the nu 1(A1g) mode at 542 cm-1 indicated that the sample was molten above 455 degrees C. Differential thermal analysis also indicated that the FLINAK samples melted at about 455 degrees C. Raman measurements were performed for samples at temperatures from 25 to 600 degrees C in a silver dish, on a hot stage, in an argon-filled atmosphere, under a microscope. Additional Raman experiments were performed on samples at temperatures from 25 to 750 degrees C in a conventional graphite windowless cell, in an argon-filled quartz tube, in a standard furnace. Over the concentration range 4.8-11 mol% AlF3 (CR 23-8.0) in FLINAK, only bands due to the AlF6(3-) ion were detected. There was no evidence to support the presence of other aluminum complexes in these melts.     

Thermal behavior and film formation from an organogermanium polymer/nanoparticle precursor

In situ high-resolution transmission electron microscopy (HRTEM) was used to investigate the effect of heating on an organo-Ge polymer/nanoparticle composite material containing 4-8 nm diameter alkyl-terminated Ge nanoparticles. The product was obtained from the reduction of GeCl4 with Na(naphthalide) with subsequent capping of the -Cl surface with n-butyl Grignard reagent. The in situ HRTEM micrographs show that the product undergoes significant changes upon heating from room temperature to 600 degrees C. Two pronounced effects were observed: (i) Ge nanoparticles coalesce and remain crystalline throughout the entire temperature range, and (ii) the organo-Ge polymer acts as a source for the in situ formation of additional Ge nanoparticles. The in situ-formed Ge nanoparticles are approximately 2-3 nm in diameter. These in situ-formed nanoparticles (2-3 nm) are so dense that, together with the original ones, they build up an almost continuous crystalline film in the temperatures between 300 and 500 degrees C. Above 480 degrees C, melting of the in situ formed Ge nanoparticles (2-3 nm) is observed, while nanoparticles greater than 5 nm remain crystalline. After cooling to room temperature, the 2-3 nm Ge nanoparticles recrystallized.     

Heating effect on the DSC melting curve of flaxseed oil

Flaxseed oil is rich in the alpha-linolenic acid. The effect of heating on the thermal properties of flaxseed oil extracted from flax seeds has been investigated. The flaxseed oils were heated at a certain temperature (75, 105, and 135 °C, respectively) for 48 h. The melting curve (from ?75 to 100 °C) of flaxseed oil was determined by differential scanning calorimetry (DSC) at intervals of 4 h. Three DSC parameters of exothermic event and endothermic event, namely, peak temperature (T _peak), enthalpy, and temperature range were determined. The initial flaxseed oil exhibited an exothermic peak, two endothermic peaks, and two endothermic shoulders between ?68 and ?5 °C in the melting profile. Heating temperature had a significant influence on the oxidative deterioration of flaxseed oil. The melting curve and parameters of flaxseed oil were almost not changed when flaxseed oil was heated at 75 °C. However, the endothermic peaks of melting curve decreased dramatically with the increasing of heating time when heating temperature was above 105 °C. There is almost no change of melting heat flow of flaxseed oil when heating time exceeded 32 h at 135 °C. The preliminary results suggest that the DSC melting profile can be used as a fast and direct way to assess the deterioration degree of flaxseed oil.     

EFFECT OF GROWTH TEMPERATURE ON LIPID COMPOSITION and ULTRAVIOLET SENSITIVITY OF HUMAN CELLS

Human skin fibroblasts were incubated at either 25 or 37 degrees C before UV irradiation. Cells incubated at 25 degrees C were more resistant to near UV radiation than cells grown at 37 degrees C, but cells grown at the lower temperature were more sensitive to 254 nm radiation. Fatty acid analysis of membranes of cells showed that cells incubated at the lower temperature contained significantly higher amounts of linoleic acid (18:2) and linolenic acid (18:3) than cells incubated at 37 degrees C. To determine if this difference in fatty acid content of the membranes was responsible for the UV survival characteristics of cells incubated at different temperatures, cells were enriched with either linoleate or linolenate during a 37 degrees C incubation period. Gas chromatography revealed that cells incorporated the supplied fatty acid. Fatty acid enriched cells were then irradiated with near UV, and survival characteristics were compared to those obtained with cells grown at the lower incubation temperature. The results suggest that the different proportion of fatty acid content of the cells is not the cause of different UV sensitivities of cells grown at 25 degrees C compared to cells grown at 37 degrees C.     

Determination of optimum processing temperature for transformation of glyceryl monostearate

The purpose of this study was to clarify the mechanism of transformation from alpha-form to beta-form via beta'-form of glyceryl monostearate (GM) and to determine the optimum conditions of heat-treatment for physically stabilizing GM in a pharmaceutical formulation. Thermal analysis repeated twice using a differential scanning calorimeter (DSC) were performed on mixtures of two crystal forms. In the first run (enthalpy of melting: DeltaH1), two endothermic peaks of alpha-form and beta-form were observed. However, in the second run (enthalpy of melting: DeltaH2), only the endothermic peak of the alpha-form was observed. From a strong correlation observed between the beta-form content in the mixture of alpha-form and beta-form and the enthalpy change, (DeltaH1-DeltaH2)/DeltaH2, beta-form content was expressed as a function of the enthalpy change. Using this relation, the stable beta-form content during the heat-treatment could be determined, and the maximum beta-form content was obtained when the heat-treatment was carried out at 50 degrees C. An inflection point existed in the time course of transformation of alpha-form to beta-form. It was assumed that almost all of alpha-form transformed to beta'-form at this point, and that subsequently only transformation from beta'-form to beta-form occurred. Based on this aspect, the transformation rate equations were derived as consecutive reaction. Experimental data coincided well with the theoretical curve. In conclusion, GM was transformed in the consecutive reaction, and 50 degrees C was the optimum heat-treatment temperature for transforming GM from the alpha-form to the stable beta-form.     

Pressure‐induced amorphization and disordering on cooling in semi‐crystalline polymers: calorimetric evidence for inverse melting in one component system

We report some unusual phase behaviour, of general implication for condensed matter, on the polymer poly‐4‐methyl pentene‐1 (P4MP1) induced by changes in pressure (P) and temperature (T), as observed by in‐situ X‐ray diffraction and high pressure DSC. Upon increasing pressure beyond a threshold value, the polymer, crystalline at ambient conditions, looses its crystalline order isothermally. The process is reversible. This behaviour is observed in two widely separated temperature regions, one below the glass transition temperature (< 50°C) and one close to the melting temperature (250°C), thus showing solid state amorphization and inversion in the melting temperature with increasing pressure. This further suggests inverse melting, i.e. re‐entrant of the two widely separated liquid and amorphous phases along the T‐axis at fixed P. This is confirmed experimentally as disordering in the crystalline structure on cooling. The inverse melting in P4MP1 raises the possibility of exothermic melting and endothermic crystallization as anticipated by Tammann (1903), see reference 1. The anticipated exothermic melting and endothermic crystallization is confirmed experimentally in the one component system P4MP1. We are observing similar features in a range of polymers.     

Simultaneous XRD-DSC measurements of water-2-propanol at sub-zero temperatures.

A simultaneous low-temperature X-ray powder-diffractometric (XRD)-DSC technique was applied to the solid state and melting process of frozen aqueous solutions of 2-propanol. 1H NMR spectra were also obtained at low temperatures. The chemical shifts of the CH3 proton and the CH proton can be classified into four temperature regions: higher than -20 degrees C, around -20 degrees C, -50 to -20 degrees C, and lower than -50 degrees C. In the XRD data, five small diffraction peaks for 2 theta at 21.0 degrees, 25.2 degrees, 27.8 degrees, 31.1 degrees and 32.1 degrees can be attributed to the peritectic, while five diffraction peaks at 22.5 degrees, 24 degrees, 25.6 degrees, 33.4 degrees and 39.8 degrees can be attributed to ice; these peaks are due to the hexagonal form of ice, which disappears upon melting. However, the diffraction peak at 33.4 degrees showed a different pattern than the other peaks due to hexagonal ice. These results indicate that the temperature dependence of the diffraction peak at 33.4 degrees for 2 theta is related to the formation of hydrogen bonds between 2-propanol and water. The simultaneous XRD-DSC technique was effective for investigating this water-alcohol mixture at low temperatures.     

TG and DTA Study of the Thermal Dehydration of Metal-exchanged Zeolite-4A Samples

Zeolite-4A is a hydrated aluminosilicate which becomes more hydrated when exchanged with transition metals. In this work, the dehydration kinetics of cobalt, nickel and copper(II)-exchanged zeolite-4A were studied by means of TG and DTA over the temperature range from 20 to 500°C, and the numbers of water molecules in the metal-exchanged zeolite samples were calculated. It was observed that, as the ionic radius of the hydrated metal increased, the number of water molecules also increased. The loss of water from the zeolite samples generally occurred in the temperature range 100–300°C and was manifested in the DTA graphs by an extended endothermic effect. The DTA curves demonstrated that the peak position shifted towards lower temperatures as the metal concentration increased or, in other words, the water of hydration increased. The kinetic parameters (order of reaction and activation energy) were calculated via the Coats and Redfern method. The process of dehydration was found to follow first-order kinetics. This revised version was published online in August 2006 with corrections to the Cover Date.     

Physiochemical properties of phenobarbital solid dispersion with phosphatidylcholine

We prepared a phenobarbital (PB) solid dispersion (SD) with phosphatidylcholine (PC). PB was present in an amorphous state in SD if its mole fraction was under 0.75. An infrared (IR) spectra study suggested a hydrogen bond between NH in PB and phosphate in PC, with a ratio of about 1:1. When the mole fraction of PB was less than 0.50, differential scanning calorimetry (DSC) curves showed endothermic peaks at 57, 90 and 145 degrees C, and an exothermic peak at 60 degrees C. The IR spectrum and X-ray diffraction pattern changed after holding at 70 degrees C, so at this point it is considered that the metastable state of SD changed into a stable state, and extra energy was released. When the mole fraction of PB was high, PB also arranged near hydrophobic group because an endothermic peak was observed at 46-52 degrees C, which was lower than fully hydrated PC. PB is similar to indomethacin (IM) in molecular shape and to phenytoin (PHT) in chemical structure. Its DSC curve and IR spectra are similar to PHT, and the limit ratio of its amorphous state is the same as IM. It is considered that the chemical structure is an important factor in its interaction to PC, and also, the molecular shape is important to arrange into PC lattice.     

Melting and swelling behaviors of UV-irradiated gelatin gel microcapsules

Gelatin gel microcapsules with a narrow size distribution have been prepared for the use of regenerative therapy by means of SPG (Shirasu porous glass) emulsification and UV-induced cross linking, and the melting and swelling behaviors of the gel membrane of the microcapsules were observed. The gel melting temperature was proportional to the 2/3 power of UV irradiation time t for tor=1 h. The average cross-sectional area of the microcapsules that remains insoluble normalized by that at 25 degrees C monotonically increased with temperature for tor=1 h. Repeated quenching of the gel microcapsules between two temperatures (25 and 40 degrees C) induced a reversible size change, which was attributed to the helix-coil transition of collagen molecules locally. From a theoretical consideration of gel particles, the observed gel melting behavior was explained well, and the scaled volume of the microcapsules was expressed as a function of scaled temperature with four fitting parameters for t相似文献   

Effect of physical aging on nucleation of amorphous indomethacin

Differential scanning calorimetry has been used to study glassy indomethacin aged at 0 and -10 degrees C for periods of time up to 109 and 210 days, respectively. The results demonstrate the emergence of a small melting peak of the alpha-polymorph after aging for 69 days at 0 degrees C and for 147 days at -10 degrees C (i.e., approximately 55 degrees C below the glass-transition temperature) that provides evidence of nucleation occurring in the temperature region of the beta-relaxation. The evolution of an endothermic recovery peak temperature features a plateau at longer annealing times that suggests that the glass has made significant progress toward reaching the supercooled liquid state. It has been found that the melting peaks become detectable after the recovery peak has reached the plateau. The results highlight the importance of studying physical aging in the temperature region of the beta-relaxation as a means of evaluating the physical stability of amorphous pharmaceutical materials.     

Rheological and DSC changes in poly(vinyl alcohol) gels induced by immersion in water

Poly(vinyl alcohol) (PVA) gels were prepared by freezing and thawing aqueous solutions at temperatures from ?20 to 15°C. The temperature was varied periodically by use of a computer. The endothermic DSC peak was observed for the PVA gels at about 60°C for five specimens of different degrees of saponification (DS). Another endothermic peak was also observed in the range 67–80°C, and this peak shifted to higher temperature with increasing DS. These endothermic peaks shifted to lower temperature on immersion of the PVA gels in water. The dynamic Young's modulus E′ at room temperature was also decreased by immersion of PVA gels in water; E′ decreased monotonically with increasing temperature for PVA gels without immersion in water, while it increased up to a certain temperature and then decreased with increasing temperature for PVA gels in water. The X-ray diffraction showed a characteristic crystalline pattern for PVA gels of higher DS, and this peak was intensified by stretching the gel.     

Experimental determination of the NH4NO3/(NH4)2SO4/H2O phase diagram

We have studied the thermodynamic properties of the ammonium nitrate/ammonium sulfate/water system using differential scanning calorimetry and infrared spectroscopy of thin films at low temperatures. This is the first study focused on low temperatures, as previous experimental work on this system has been at 273 K and above. We have combined our experimental results with melting point data from the literature at high temperatures to create a solid/liquid phase diagram of the ammonium nitrate/ammonium sulfate/water system for temperatures below 343 K. Using phase diagram theory and Alkemade lines, we predict which solids are stable at equilibrium for all concentrations within the studied region. We also observed the decomposition of a solid at low temperatures which has not previously been reported. Finally, we have compared our predicted solids and final melting temperatures to the Aerosol Inorganics Model (AIM).     

二元贮冷水合盐熔解热的差示扫描量热法研究

用差示扫描量热法（differential scanning calorimetry)对二元贮冷水合盐的相变温度与熔解热进行了研究，实验结果对认识多元贮冷水合盐的相变过程的相变机理及选配贮冷水合盐材料，具有重要意义。     

Thermal and optical properties of Tm3+ doped tellurite glasses

Ultraviolet, visible (UV/VIS) and differential thermal analysis (DTA) measurements were carried out in order to investigate the optical and thermal properties of various 0.5 mol.% Tm2O3 containing (1 - x)TeO2 + xLiCl glasses in molar ratio. The samples were prepared by fusing the mixture of their respective reagent grade powders in a platinum cricuble at 750 degrees C for 30 min. DTA curves taken in the 23-600 degrees C temperature range with a heating rate of 10 degrees C/min reveal a change in the value of the glass transition temperature, Tg, while melting was not observed for the glasses containing LiCl content less than 50 mol.%. These glasses were found to be moisture-resistant. However, the glasses with LiCl content higher than 50 mol.%, in which a melting peak was observed at Tc = 401 degrees C, were moisture-sensitive. Absorption measurements in the UV/VIS region of the glasses without Tm2O3 content show that the Urbach cutoff occurs at about 320 nm and, is relatively independent of the LiCl content. Six absorption bands were observed in the Tm2O3 doped glasses corresponding to the absorption of the 1G4, 3F2, 3F3 and 3F4, 3H5 and 3H4 levels from the 3H6 ground level of Tm3+ ions. The spectra also show that the integrated absorption cross-section of each band depends on the glass composition. Judd-Ofelt theory was used to determine the Judd-Ofelt parameters as well as the radiative transition probabilities for the metastable levels of Tm3+ ions in (0.3)LiCl + (0.7) TeO2: 0.01 Tm2O3 glass which is moisture-resistant.