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1.
Abstract The van der Waals approach to predict liquid-vapor coexistence, becomes exact in the limit of weak, long-ranged attractive forces. However, for shorter ranged attractions, the liquid range shrinks and eventually disappears altogether. When the width of the attractive well becomes very small (less than 7% of the diameter of particles), an iso-structural solid-solid transition, reminiscent of the liquid-vapor transition, appears in the crystalline phase. This transition, that should be experimentally observable in certain colloidal suspensions, ends in a critical point. In quasi-two dimensional systems (e.g. confined colloids), this critical point induces the formation of a stable hexatic phase. 相似文献
2.
We investigated the relaxation behavior of lipid membranes close to the chain-melting transition using pressure jump calorimetry with a temperature accuracy of ∼10-3 K. We found relaxation times in the range from seconds up to about a minute, depending on vesicular state. The relaxation times are within error proportional to the heat capacity. We provide a statistical thermodynamics theory that rationalizes the close relation between heat capacity and relaxation times. It is based on our recent finding that enthalpy and volume changes close to the melting transition are proportional functions. 相似文献
3.
The kinetics of the main phase transition of dimyristoylphosphatidyl choline (DMPC) unilamellar vesicles were investigated in the time range from microseconds to seconds. Iodine laser-temperature jump (ILTJ) experiments showed three discrete relaxation phenomena. Time resolved cryo-electron microscopy (CEM) was applied to produce images of intermediate states typical for the relaxation times of lipid vesicles in the micro- to millisecond time window. A careful measurement of the rate of temperature decrease observed during the production of vitrified lamellae of aqueous samples on a copper grid was performed. The best conditions resulted in average rates of cooling of 3 x 10(4) K/s. By comparing the images from CEM of DMPC vesicle samples vitrified above, at, and below the phase transition temperature a structural model was designed, which explains the temperature jump relaxation times in the micro- to millisecond time range by the formation and disappearance of coexisting clusters of crystalline, intermediate, and fluid lipid areas inside the DMPC bilayers. 相似文献
4.
We have investigated the effects of methanol, ethanol, and 1-propanol on the phase transitions of L-alpha-dimyristoylphosphatidylethanolamine using differential scanning calorimetry and Fourier transform infrared spectroscopy. Alcohols lower the temperature of the gel (L beta) to liquid-crystalline (L alpha) phase transition and also lower the temperature of the unhydrated crystalline (Lc) to liquid-crystalline phase transition. When the lipid/alcohol dispersions are incubated at 2 degrees C for 1-18 h, a dehydrated crystalline phase forms, which gives rise to a phase transition at about 55 degrees C. This dehydrated crystalline phase forms more quickly at higher alcohol concentrations. Although alcohol at low concentration lowers the enthalpy of the observed melting transition, at high concentrations 1-propanol markedly increases this enthalpy. The phase giving rise to this high-enthalpy melting process is distinct from both the unhydrated crystalline phase and the gel phase. Infrared spectra suggest that this phase contains significant amounts of alcohol in a solid solution with the lipid. 相似文献
5.
The thermal behaviors of α-D-glucose in the melting and glass transition regions were examined utilizing the calorimetric methods of standard differential scanning calorimetry (DSC), standard temperature-modulated differential scanning calorimetry (TMDSC), quasi-isothermal temperature-modulated differential scanning calorimetry (quasi-TMDSC), and thermogravimetric analysis (TGA). The quantitative thermal analyses of experimental data of crystalline and amorphous α-D-glucose were performed based on heat capacities. The total, apparent and reversingheat capacities, and phase transitions were evaluated on heating and cooling. The melting temperature (T(m)) of a crystalline carbohydrate such as α-D-glucose, shows a heating rate dependence, with the melting peak shifted to lower temperature for a lower heating rate, and with superheating of around 25K. The superheating of crystalline α-D-glucose is observed as shifting the melting peak for higher heating rates, above the equilibrium melting temperature due to of the slow melting process. The equilibrium melting temperature and heat of fusion of crystalline α-D-glucose were estimated. Changes of reversing heat capacity evaluated by TMDSC at glass transition (T(g)) of amorphous and melting process at T(m) of fully crystalline α-D-glucose are similar. In both, the amorphous and crystalline phases, the same origin of heat capacity changes, in the T(g) and T(m) area, are attributable to molecular rotational motion. Degradation occurs simultaneously with the melting process of the crystalline phase. The stability of crystalline α-D-glucose was examined by TGA and TMDSC in the melting region, with the degradation shown to be resulting from changes of mass with temperature and time. The experimental heat capacities of fully crystalline and amorphous α-D-glucose were analyzed in reference to the solid, vibrational, and liquid heat capacities, which were approximated based on the ATHAS scheme and Data Bank. 相似文献
6.
The thermal behaviors of α-d-glucose in the melting and glass transition regions were examined utilizing the calorimetric methods of standard differential scanning calorimetry (DSC), standard temperature-modulated differential scanning calorimetry (TMDSC), quasi-isothermal temperature-modulated differential scanning calorimetry (quasi-TMDSC), and thermogravimetric analysis (TGA). The quantitative thermal analyses of experimental data of crystalline and amorphous α-d-glucose were performed based on heat capacities. The total, apparent and reversing heat capacities, and phase transitions were evaluated on heating and cooling. The melting temperature (Tm) of a crystalline carbohydrate such as α-d-glucose, shows a heating rate dependence, with the melting peak shifted to lower temperature for a lower heating rate, and with superheating of around 25 K. The superheating of crystalline α-d-glucose is observed as shifting the melting peak for higher heating rates, above the equilibrium melting temperature due to of the slow melting process. The equilibrium melting temperature and heat of fusion of crystalline α-d-glucose were estimated. Changes of reversing heat capacity evaluated by TMDSC at glass transition (Tg) of amorphous and melting process at Tm of fully crystalline α-d-glucose are similar. In both, the amorphous and crystalline phases, the same origin of heat capacity changes, in the Tg and Tm area, are attributable to molecular rotational motion. Degradation occurs simultaneously with the melting process of the crystalline phase. The stability of crystalline α-d-glucose was examined by TGA and TMDSC in the melting region, with the degradation shown to be resulting from changes of mass with temperature and time. The experimental heat capacities of fully crystalline and amorphous α-d-glucose were analyzed in reference to the solid, vibrational, and liquid heat capacities, which were approximated based on the ATHAS scheme and Data Bank. 相似文献
7.
X-ray analysis of the kinetics of Escherichia coli lipid and membrane structural transitions 总被引:1,自引:0,他引:1
Synchrotron radiation was used to follow the time course of the transitions, induced by temperature jump, in Escherichia coli membranes and their lipid extracts isolated from a fatty acid auxotroph grown with different fatty acids. We measured the relaxation times associated with the phase transitions as well as with the conformational transition of the hydrocarbon chains and observed different behavior as a function of chemical composition. Relaxation times of about 1-2 s were found at a hexagonal to lamellar phase transition and within a lamellar phase whose parameters display important variations with temperature when the conformational transition takes place. On the other hand, no delay was observed for a phase transition where large lipid or water diffusion was not needed. We have shown that phase transitions and conformational transitions are, to a large extent, uncoupled and that the relaxation times corresponding to the latter transition could be related to the size of the ordered domains. In all cases, the order to disorder conformational transition is more rapid than the disorder to order transition. Finally, the relaxation times of the disorder to order transition observed with the membranes and with their lipid extracts were found to be strongly correlated, indicating that the proteins do not play a role in this transition. 相似文献
8.
We have used 2H-nmr to study backbone dynamics of the 2H-labeled, slowly exchanging amide sites of fully hydrated, crystalline hen egg white lysozyme. Order parameters are determined from the residual quadrupole coupling and values increase from S2 = 0.85 at 290 K to S2 = 0.94 at 200 K. Dynamical rates are determined from spin-lattice relaxation at three nmr frequencies (38.8, 61.5, and 76.7 MHz). The approach used here is thus distinct from solution nmr studies where dynamical amplitudes and rates are both determined from relaxation measurements. At temperatures below 250 K, relaxation is independent of the nmr frequency indicating that backbone motions are fast compared to the nmr frequencies. However, as the temperature is increased above 250 K, relaxation is significantly more efficient at the lowest frequency, which shows, in addition, the presence of motions that are slow compared to the nmr frequencies. Using the values of S2 determined from the residual quadrupole coupling and a model-free relaxation formalism that allows for fast and slow internal motions, we conclude that these slow motions have correlation times in the range of 0.1 to 1.0 microsecond and are effectively frozen out at 250 K where fast motions of the amide planes with approximately 15 ps effective correlation times and 9 degrees rms amplitudes dominate relaxation. The fast internal motions increase slightly in amplitude as the temperature rises toward 290 K, but the correlation time, as is also observed in solution nmr studies of RNase H, is approximately constant. These findings are consistent with hypotheses of dynamic glass transitions in hydrated proteins arising from temperature-dependent damping of harmonic modes of motion above the transition point. 相似文献
9.
The partial specific heat capacity and volume of globular proteins and dispersions of phosphatidylcholines in aqueous solutions have been determined over a broad temperature range using a precise scanning microcalorimeter and a vibrational densimeter. It is shown that the temperature-induced, gel-to-liquid crystalline phase transition in phosphatidylcholines proceeds without a noticeable change in heat capacity but with a significant increase in the specific volume, whereas heat denaturation in proteins takes place without a noticeable change in the volume but with a significant increase in heat capacity. This principal difference between temperature-induced conformational phase transitions in proteins and lipids demonstrates clearly that heat denaturation of proteins, in contrast to the gel-to-liquid crystalline phase transition in lipids, cannot be regarded as a process similar to melting. Consequently, the 'molten globule' does not appear to be a suitable model for a heat-denatured protein. 相似文献
10.
High-sensitivity, temperature-controlled DSC measurements at a low heating rate and creation of differential DSC traces scaled with respect to the reference material (completely dehydrated starch or completely dehydrated fiber, or their respective blends) permitted investigation of the influence of fiber on phase transformations in the wheat-starch-water system in the course of thermal gelatinization. Thermal effects associated with water interactions over the temperature range from 283 to 384 K under atmospheric pressure were determined. These thermal effects and previous structural studies permit us to make the following observations: (1) The main endothermic transition associated with melting of the crystalline part of the starch granule followed by a helix-coil transition in amylopectin occurs over the temperature range 319-333 K independent of the water and fiber contents. Adding fiber causes that transition to disappear both in the native blends and in water suspensions at low water contents. After adding more water and heating, recrystallization is observed and the transition reappears. (2) The fiber content has practically no influence on the slow exothermic transformation, which follows melting and helix-coil transition in amylopectin, proving that the slow transformation has a specific chemical character. In this reaction, the free ends of the unwound helices of amylopectin reassociate with parts of amylopectin molecules other than their original helix duplex partner, forming physical junctions and creating more general amorphous hydrogen bonded associations. (3) The high-temperature transition and small, but reproducible, distortions on the peaks of the main endothermic transition for water contents near 70-80 wt % are associated with smectic and nematic transitions, respectively. These are significantly influenced by the fiber content; higher fiber content causes an almost complete disappearance of these transitions. (4) The slow exothermic effect appearing almost from the very beginning of the heating in the starch-water system, associated with softening and uptake of water in the amorphous growth rings of the starch granule, is significantly hindered by added fiber. 相似文献
11.
Polymorphic phases of galactocerebrosides: spectroscopic evidence of lamellar crystalline structures
Fourier transform infrared spectroscopy was applied to study the structural and thermal properties of bovine brain galactocerebroside (GalCer) containing amide linked non-hydroxylated or alpha-hydroxy fatty acids (NFA- and HFA-GalCer, respectively). Over the temperature range 0-90 degrees C, both GalCer displayed complex thermal transitions, characteristic of polymorphic phase behavior. Upon heating, aqueous dispersions of NFA- and HFA-GalCer exhibited high order-disorder transition temperatures near 80 and 72 degrees C, respectively. En route to the chain melting transition, the patterns of the amide I band of NFA-GalCer were indicative of two different lamellar crystalline phases, whereas those of HFA-GalCer were suggestive of lamellar gel and crystalline bilayers. Cooling from the liquid-crystalline phase resulted in the formation of another crystalline phase of NFA-GalCer and a gel phase of HFA-GalCer, with a phase transition near 62 and 66 degrees C, respectively. Prolonged incubation of GalCer bilayers at 38 degrees C revealed conversions among lamellar crystalline phases (NFA-GalCer) or between lamellar gel and crystalline bilayer structures (HFA-GalCer). Spectral changes indicated that the temperature and/or time induced formation of the lamellar crystalline structures of NFA- and HFA-GalCer was accompanied by partial dehydration and by rearrangements of the hydrogen bonding network and bilayer packing mode of GalCer. 相似文献
12.
The transformation between a gel and a fluid phase in dipalmitoyl-phosphatidylcholine (DPPC) bilayers has been simulated using a coarse grained (CG) model by cooling bilayer patches composed of up to 8000 lipids. The critical step in the transformation process is the nucleation of a gel cluster consisting of 20-80 lipids, spanning both monolayers. After the formation of the critical cluster, a fast growth regime is entered. Growth slows when multiple gel domains start interacting, forming a percolating network. Long-lived fluid domains remain trapped and can be metastable on a microsecond time scale. From the temperature dependence of the rate of cluster growth, the line tension of the fluid-gel interface was estimated to be 3+/-2 pN. The reverse process is observed when heating the gel phase. No evidence is found for a hexatic phase as an intermediate stage of melting. The hysteresis observed in the freezing and melting transformation is found to depend both on the system size and on the time scale of the simulation. Extrapolating to macroscopic length and time scales, the transition temperature for heating and cooling converges to 295+/-5 K, in semi-quantitative agreement with the experimental value for DPPC (315 K). The phase transformation is associated with a drop in lateral mobility of the lipids by two orders of magnitude, and an increase in the rotational correlation time of the same order of magnitude. The lipid headgroups, however, remain fluid. These observations are in agreement with experimental findings, and show that the nature of the ordered phase obtained with the CG model is indeed a gel rather than a crystalline phase. Simulations performed at different levels of hydration furthermore show that the gel phase is stabilized at low hydration. A simulation of a small DPPC vesicle reveals that curvature has the opposite effect. 相似文献
13.
The thermotropic phase behavior of cholesterol monohydrate in water was investigated by differential scanning calorimetry, polarizing light microscopy, and x-ray diffraction. In contrast to anhydrous cholesterol which undergoes a polymorphic crystalline transition at 39 degrees C and a crystalline to liquid transition at 151 degrees C, the closed system of cholesterol monohydrate and water exhibited three reversible endothermic transitions at 86, 123, and 157 degrees C. At 86 degrees C, cholesterol monohydrate loses its water of hydration, forming the high temperature polymorph of anhydrous cholesterol. At least 24 hours were required for re-hydration of cholesterol and the rate of hydration was dependent on the polymorphic crystalline form of anhydrous cholesterol. At 123 degrees C, anhydrous crystalline cholesterol in the presence of excess water undergoes a sharp transition to a birefringent liquid crystalline phase of smectic texture. The x-ray diffraction pattern obtained from this phase contained two sharp low-angle reflections at 37.4 and 18.7 A and a diffuse wide-angle reflection centered at 5.7 A, indicating a layered smectic type of liquid crystalline structure with each layer being two cholesterol molecules thick. The liquid crystalline phase is stable over the temperature range of 123 to 157 degrees C before melting to a liquid dispersed in water. The observation of a smectic liquid crystalline phase for hydrated cholesterol correlates with its high surface activity and helps to explain its ability to exist in high concentrations in biological membranes. 相似文献
14.
Differential scanning calorimetry and x-ray diffraction techniques have been used to investigate the structure and phase behavior of hydrated dimyristoyl lecithin (DML) in the hydration range 7.5 to 60 weight % water and the temperature range -10 to +60 degrees C. Four different calorimetric transitions have been observed: T1, a low enthalpy transition (deltaH approximately equal to 1 kcal/mol of DML) at 0 degrees C between lamellar phases (L leads to Lbeta); T2, the low enthalpy "pretransition" at water contents greater than 20 weight % corresponding to the transition Lbeta leads to Pbeta; T3, the hydrocarbon chain order-disorder transition (deltaH = 6 to 7 kcal/mol of DML) representing the transition of the more ordered low temperature phases (Lbeta, Pbeta, or crystal C, depending on the water content) to the lamellar Lalpha phase; T4, a transition occurring at 25--27 degrees C at low water contents representing the transition from the lamellar Lbeta phase to a hydrated crystalline phase C. The structures of the Lbeta, Pbeta, C, and Lalpha phases have been examined as a function of temperature and water content. The Lbeta structure has a lamellar bilayer organization with the hydrocarbon chains fully extended and tilted with respect to the normal to the bilayer plane, but packed in a distorted quasihexagonal lattice. The Pbeta structure consists of lipid bilayer lamellae distorted by a periodic "ripple" in the plane of the lamellae; the hydrocarbon chains are tilted but appear to be packed in a regular hexagonal lattice. The diffraction pattern from the crystalline phase C indexes according to an orthorhombic cell with a = 53.8 A, b = 9.33 A, c = 8.82 A. In the lamellae bilayer Lalpha strucure, the hydrocarbon chains adopt a liquid-like conformation. Analysis of the hydration characteristics and bilayer parameters (lipid thickness, surface area/molecule) of synthetic lecithins permits an evaluation of the generalized hydration and structural behavior of this class of lipids. 相似文献
15.
The interaction of melittin, a polypeptide consisting of 26 amino acid residues, with dimyristoyl phosphatidylcholine bilayers was investigated by vibrational Raman spectroscopy. Spectral peak height intensity ratios, involving vibrational transitions in both the 3000 cm?1 acyl chain methylene carbon-hydrogen stretching mode region and the 1100 cm?1 acyl chain carbon-carbon skeletal stretching mode interval, served as temperature profile indices for monitoring the bilayer order-disorder processes. For a lipid : melittin molar ratio of 14 : 1 two order-disorder transitions were observed. In comparison to a gel to liquid crystalline phase transition of 22.5°C for the pure lipid, the lower transition, exhibiting a 2°C width, is centered at 17°C and is associated with a depression of the main lipid phase transition of dimyristoyl phosphatidylcholine. The second thermal transition, displaying a 7°C interval, occurs at approx. 29°C and is associated with the melting behavior of approximately seven immobilized boundary lipids which surround the inserted hydrophobic segment of the polypeptide. For a lipid : melittin molar ratio of 10 : 1 two thermal transitions are also observed at 11 and 30°C. As before, they represent, respectively, the main gel to liquid crystalline phase transition and the melting behavior of approximately four boundary lipids attached to melittin. From these data alternative schemes are suggested for disposing the immobilized lipids around the hydrophobic portion of the polypeptide within the bilayer. 相似文献
16.
Liquid-like water confined in stacks of biological membranes at 200 k and its relation to protein dynamics
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Confined water is of considerable current interest owing to its biophysical importance and relevance to cryopreservation. It can be studied in its amorphous or supercooled state in the "no-man's land", i.e., in the temperature range between 150 and 235 K, in which bulk water is always crystalline. Amorphous deuterium oxide (D(2)O) was obtained in the intermembrane spaces of a stack of purple membranes from Halobacterium salinarum by flash cooling to 77 K. Neutron diffraction showed that upon heating to 200 K the intermembrane water space decreased sharply with an associated strengthening of ice diffraction, indicating that water beyond the first membrane hydration layer flowed out of the intermembrane space to form crystalline ice. It was concluded that the confined water undergoes a glass transition at or below 200 K to adopt an ultraviscous liquid state from which it crystallizes to form ice as soon as it finds itself in an unconfined, bulk-water environment. Our results provide model-free evidence for translational diffusion of confined water in the no-man's land. Potential effects of the confined-water glass transition on nanosecond membrane dynamics were investigated by incoherent elastic neutron scattering experiments. These revealed no differences between flash-cooled and slow-cooled samples (in the latter, the intermembrane space at temperatures <250 K is occupied only by the first membrane hydration layers), with dynamical transitions at 150 and 260 K, but not at 200 K, suggesting that nanosecond membrane dynamics are not sensitive to the state of the water beyond the first hydration shell at cryotemperatures. 相似文献
17.
The primary X-ray peak profile characterizing the interchain structure in the dipalmitoylglycerophosphocholine membrane has been measured as a function of temperature. The scattering between 23 and 34.6° C is characterized by an asymmetric crystalline reflection accounting for 85% of the total intensity, the remaining 15% being liquid-like in character. At a pre-transition temperature of 34.6° C, the reflection profile becomes (nearly) symmetrical, indicating a change in tilt angle of the chains with respect to the membrane surface. This change is accompanied by an increase of 20% in the amount of liquid-like scattering, indicating that the pre-transition mechanism includes a partial melting of the chains. At the melting point, 41.5° C, the crystalline reflection disappears, and the liquid component of the scattering increases to a point where it includes all the scattered intensity. The relative values of the integrated intensities at each temperature are tabulated, and the significance of the peak widths and shapes are discussed. 相似文献
18.
Effects of hydrostatic pressure on bilayer phase behavior and dynamics of dilauroylphosphatidylcholine.
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Deuterium nuclear magnetic resonance spectroscopy was used to study the thermotropic phase behavior of dilauroylphosphatidylcholine (DLPC) bilayers at pressures up to 221 MPa. Pressure was found to separate the liquid crystal to gel transition from the gel to ordered crystalline phase transition. The jump in chain order observed on cooling through the transition into the gel phase was found to be small and thus consistent with the trend in longer chain saturated diacyl phosphatidylcholines. On cooling, DLPC was observed to enter an unusual state above the transition into the gel phase. This unusual state displayed fluid-like conformational order but short transverse relaxation times. It was found to be much better pronounced and to span a broader temperature range at elevated pressure than at lower pressures. Transverse relaxation measurements of deuterons on the chain alpha-carbons revealed a substantial slowing of molecular motions within the temperature range of the unusual fluid phase. The observation of such a phase at high pressure appears to be consistent with recent reports of an unusual fluid phase, Lx, in DLPC at ambient pressure. 相似文献
19.
The thermotropic properties of coenzymes Q10, Q9, Q8, and Q7 have been examined by differential scanning calorimetry and wide-angle X-ray diffraction. Typical scanning calorimetry cooling curves of coenzyme Q from the liquid state exhibit a single exothermic phase transition into a crystalline state at a temperature that decreases as the length of the polyisoprenoid side-chain substituent decreases. Upon subsequent heating, the molecules undergo a series of thermal events which precede the main crystalline-to-liquid endothermic phase transition. The temperature of these transitions increases with increasing chain length. The crystallization phase transition temperature depends markedly on the rate at which the sample is cooled and increases with decreasing scan rate; the temperature of the melting endotherm is not markedly affected by the scan rate. Detailed calorimetric studies of coenzyme Q10 indicate that two crystalline states are formed, one at relatively high cooling rates to low temperatures and the other when preparations are cooled slowly from the liquid state to relatively high temperatures. Heating the crystalline phase formed by rapid cooling causes its transformation into the phase observed by cooling slowly. X-ray diffraction analysis confirmed the existence of these two crystal phases in coenzymes Q9 and Q10 and the transformation from the rapidly crystallized form to the more ordered form associated with slower cooling rates. At body temperature (310 K) under equilibrium conditions coenzyme Q10 exists in an ordered crystalline phase; the implications of the thermotropic behavior of coenzyme Q10 on mitochondrial functionin vitro andin vivo are discussed. 相似文献
20.
The sensitivity of the melting transition temperature of aqueous dispersions of dipalmitoyl- and distearoylphosphatidylcholine to hydrostatic pressure is used to allow measurement of the rates of isothermal freezing and melting of the lipids by rapidly changing the pressure. The degree of order of the lipids is measured by monitoring a ratio of two points in the Raman spectrum of the lipids which changes sharply at the melting temperature. Use of this Raman order ratio allows correlation between the order of the sample and the rates of transition in a manner which is impossible by monitoring only turbidity. Our longest relaxation times range upwards from a few seconds for both compounds. The freezing rates are slowest when the samples are initially fully melted, and the melting rates are slowest when the samples are initially frozen. These results imply that nucleation of the growing phase dominates the kinetics of both freezing and melting. 相似文献