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Phase transition from a gel to a fluid phase of cubic symmetry in dimyristoylphosphatidylcholine/myristic acid (1:2, mol/mol) bilayers.

Aqueous dispersions (pH 4.0) of a 2:1 (mol/mol) mixture of myristic acid with dimyristoylphosphatidylcholine undergo a sharp transition at 45-47 degrees C from a lamellar gel phase to a fluid phase which is optically isotropic. This fluid phase gives rise to 31P-NMR spectra, and 2H-NMR spectra of the chain-deuterated components, which are also isotropic. X-ray diffraction studies of the fluid phase at 49 degrees C, reveal reflections with spacings in the ratio square root of 2: (square root of 3): square root of 4: square root of 6: square root of 8, accompanied by a strong diffuse scatter. These reflections index on a cubic lattice of primitive space group Pn3 or Pn3m, or possibly the body-centered group Im3m, with a lattice constant of 21.2 nm. The dimensions of the phase are consistent with a structure composed of two systems of tetrahedrally (octahedrally) oriented inverted lipid cylinders, found for other cubic lipid phases with Pn3m (Im3m) symmetry. At higher temperatures the cubic phase gradually converts, with increasing temperature, to a coexisting inverted hexagonal phase.

Dimyristoylphosphatidylcholine↗

Thermotropic lipid phase transition and the behavior of hydrolytic enzymes in the kidney cortex brush border membrane.

Functional interactions of lipids and proteins were examined in brush-border membranes isolated from the kidney cortex by studying the temperature dependence of the hydrolytic enzyme activities. A close relationship was observed for the membrane proteins and the thermotropic lipid phase transitions. Three lines of evidences were provided for such dependence: a) Arrhenius relationship of the membrane-bound enzyme activities, and the effect of temperature in native and partially delipidated membranes, b) differential scanning calorimetric study of the membrane lipid phase transitions in the native and delipidated membranes, multilamellar vesicles prepared from the membrane extracted lipids, and in vesicles from dimyristoyl phosphatidylcholine, and c) the excimer (dimer)-formation studies of the membrane extrinsic fluorescent probe, pyrene, and the resultant membrane microviscosity. The brush-border membranes were partially delipidated with BuOH and 2,2,2-trifluoroethanol. The functional interactions of the delipidated membranes, which were greatly lost on lipid removal, were largely restored by the addition of exogenous lipids in the reconstitution process, which indicate the critical dependence of the membrane integral proteins on the neighboring lipid molecules in the bulk lipid phase.

Animals↗

Calorimetric study of phase transitions in a liquid-crystal-based microemulsion.

A lyotropic inverse micelle phase composed of water, thermotropic liquid-crystal octylcyanobiphenyl (8CB), and surfactant (DDAB) was studied by using high-resolution calorimetry on several mixtures with 3%, 8%, and 15% micelle concentration. Calorimetric results show strong depression of the isotropic to nematic (I-N) phase-transition temperature. Broad heat-capacity anomalies show the existence of a wide coexistence range of isotropic, nematic, and smectic-A phases, which mimics the behavior of a new nearly stable thermodynamic phase. An observation of the rather sharp almost bulklike nematic to smectic-A (N-A) transition at low-temperatures indicates that our heat capacity results are consistent with the phase separation scenario in which significant number of micelles is expelled during I-N conversion leaving almost pure nematic phase at lower temperatures. It was found that micelles get almost completely remixed on heating the mixture back to the isotropic phase.

Journal Article↗

Phospholipid phase transitions in model and biological membranes as studied by infrared spectroscopy.

Fourier transform infrared (FT-IR) spectroscopy is an extremely powerful yet non-perturbing physical technique for monitoring the conformation and dynamics of all portions of the phospholipid molecule. In this brief review we summarize some recent FT-IR spectroscopic studies of phospholipid phase transitions in model lipid bilayer and in biological membranes which illustrate the great utility of this technique. We show that FT-IR spectroscopy can accurately monitor the gel to liquid-crystalline phase transition and can provide a large amount of detailed information about phospholipid structure and organization in both the gel and liquid-crystalline states of lipid bilayers.

Lipid Bilayers↗

Phase transition behavior, protein adsorption, and cell adhesion resistance of poly(ethylene glycol) cross-linked microgel particles.

Thermoresponsive poly(N-isopropylacrylamide) (pNIPAm) microgel particles cross-linked with various concentrations of PEG diacrylates of 3 different PEG chain lengths were synthesized via free-radical precipitation polymerization in order to investigate the phase transition and protein adsorption behavior as the hydrophilicity of the network is increased. Photon correlation spectroscopy (PCS) reveals that, as the concentration of PEG cross-linker incorporated into the particles is increased, an increase in the temperature and breadth of the phase transition occurs. Qualitative differences in particle density using isopycnic centrifugation confirm that higher PEG concentrations result in denser networks. The efficient incorporation of PEG cross-linker was confirmed with (1)H NMR, and variable temperature NMR studies suggest that, in the deswollen state, the longer PEG cross-links protrude from the dense globular network. This behavior apparently manifests itself as a decrease in nonspecific protein adsorption with increasing PEG length and content. Furthermore, when electrostatically attached to a glass surface, the particles containing the longer chain lengths exhibited enhanced nonfouling behavior and were resistant to cell adhesion in serum-containing media. The excellent performance of these particulate films and the simplicity with which they are assembled suggests that they may be applicable in a wide range of applications where nonfouling coatings are required.

Adsorption↗

Structures and phase transitions of the A7PSe6 (A = Ag, Cu) argyrodite-type ionic conductors. II. Beta- and gamma-Cu7PSe6

The crystal structures of two of the three polymorphic forms of the Cu7PSe6 argyrodite compound are determined by means of single-crystal X-ray diffraction. In the high-temperature form, at 353 K, i.e. 33 K above the first phase transition, gamma-Cu7PSe6 crystallizes in cubic symmetry, space group F43m. The full-matrix least-squares refinement of the structure leads to the residual factors R = 0.0201 and wR = 0.0245 for 31 parameters and 300 observed independent reflections. In the intermediate form, at room temperature, beta-Cu7PSe6 crystallizes again in cubic symmetry, but with space group P2(1)3. Taking into account a merohedric twinning, the refinement of the beta-Cu7PSe6 structure leads to the residual factors R = 0.0297 and wR = 0.0317 for 70 parameters and 874 observed, independent reflections. The combination of a Gram-Charlier development of the Debye-Waller factor and a split model for copper cations reveals the possible diffusion paths of the d10 species in the gamma-Cu7PSe6 ionic conducting phase. The partial ordering of the Cu+ d10 element at the phase transition is found in concordance with the highest probability density sites of the high-temperature phase diffusion paths. A comparison between the two Cu7PSe6 and Ag7PSe6 analogues is carried out, stressing the different mobility of Cu+ and Ag+ and their relative stability in low-coordination chalcogenide environments.

Journal Article↗

Characterization of phase transitions during freeze-drying by in situ X-ray powder diffractometry.

The purpose of this research was to develop the technique of in situ freeze-drying in the sample chamber of an X-ray powder diffractometer (XRD) and to monitor the phase transitions during the freeze-drying of aqueous solutions of sodium nafcillin (I) and mannitol (II). Aqueous solutions of I and II were frozen under controlled conditions in the sample chamber of an XRD. This variable temperature XRD was modified so that the sample chamber could be evacuated and the samples dried under reduced pressures. Thus the entire freeze-drying cycle was carried out in the XRD holder and the solid-state was monitored during the various stages of the process. Frozen solutions of I when annealed at -4 degrees C, resulted in crystallization of the solute as 'sodium nafcillin hydrate' (unknown stoichiometry). Primary drying at -10 degrees C, resulted in partial dehydration to a poorly crystalline sodium nafcillin hemihydrate. There was no crystallization of mannitol when solutions of II were cooled and subjected to primary drying at -50 degrees C. During the drying, the intensities of the characteristic X-ray lines of ice (d-spacings of 3.94, 3.70 and 3.48 A) were quantified. This enabled real time monitoring of the complete sublimation of crystalline ice. When the secondary drying was carried out at -25 degrees C, mannitol crystallized as an anhydrous mixture of the delta- and beta-polymorphs. In a second set of experiments, the frozen solutions were warmed to -25 degrees C and subjected to primary drying. Mannitol crystallized and its XRD pattern matched that of mannitol hydrate reported recently (Yu et al., Pharm. Res., 14S (1997) S-445). When the secondary drying was carried out at -10 degrees C, there was no change in the XRD pattern suggesting the formation of a dehydrated hydrate. This in situ XRD technique enabled us to characterize the phase transitions during freeze-drying. It would be useful in developing a mechanistic understanding of the alterations in the solid-state during freeze-drying of complex, multi-component, pharmaceutical systems.

Crystallization↗

Is GH therapy useful to preserve bone mass in transition-phase patients with GH deficiency?

GH deficient (GHD) adult patients, either from child- or adulthood onset, have impaired health (impairment in body composition and structure functions as well as derangement in lipoprotein and in carbohydrate metabolism leading to increased cardiovascular morbidity), which improves with GH replacement. For patients with childhood-onset GHD, the so called "transition phase", defined as the period between reaching the final height and the completion of the development of such organs, can be considered as the most important phase of life for the development of important target organs: heart, bones and muscles. Particularly, children with GHD may not attain the peak bone mass (PBM) at the time of discontinuation of GH therapy, as the complete achievement of PBM is likely reached later on, during the transition phase to adulthood. In addition, patients with GHD generally have a delayed timing of PBM compared to normal individuals. GH treatment should be continued until the attainment of PBM, independently of the final height achieved. Individual titration of the recombinant human GH (rhGH) dose is recommended, and measurement of IGF-I levels is needed for monitoring the adequacy of replacement. The GH dose for replacement in the transition adolescent is still higher than in adulthood; after puberty, the rhGH dose should be progressively decreased in the following years (probably up to 25 yr of age) in order to obtain the achievement of optimal PBM.

Adolescent↗

Thermodynamic phase transition parameters of human lens dihydrosphingomyelin.

Dihydrosphingomyelin (DHS) is the major phospholipid in the human lens. The influence of this phospholipid on membrane structure and function is not known. In this study we used infrared spectroscopy to determine the thermodynamic and molecular structural properties of the hydrocarbon chains of DHS membranes isolated from human lenses. The phase transition temperature of human lens DHS was 9 degrees C higher than for bovine brain sphingomyelin membranes and 14 and 7 degrees C higher than human lens cortical and nuclear membranes, respectively. This increase in the phase transition temperature results in 20% increase in lipid order at 36 degrees C in comparison to that of native membranes and bovine brain sphingomyelin. DHS is likely to provide structural order to the hydrocarbon chain region and upholds the integrity of native membranes under oxidative conditions.

Animals↗

Dye permeability at phase transitions in single and binary component phospholipid bilayers.

By encapsulating a pH-sensitive dye, phenol red, in multilamellar liposomes of DMPC, DPPC and DMPC/DPPC mixtures, the permeability of these phospholipid bilayers to dye as a function of temperature has been studied. For both DMPC and DPPC liposomes, dye release begins well below the main gel-to-liquid-crystalline phase transition (24 degrees C and 42 degrees C, respectively) at temperatures corresponding to the onset of the pretransition (about 14 degrees C and 36 degrees C, respectively) with DPPC liposomes exhibiting a permeability anomaly at the main phase transition (42 degrees C). The perturbation occurring in the bilayer structure that allows the release of encapsulated phenol red (approx. 5 A diameter) is not sufficient to permit the release of encapsulated haemoglobin (approx. 20 A diameter, negatively charged). In liposomes composed of a range of DMPC/DPPC mixtures, dye release commences at the onset of the pretransition range (determined by optical absorbance measurements) and increases with increasing temperature until the first appearance of liquid crystalline phase after which no further dye release occurs. Interestingly, the dye retaining properties of DMPC and DPPC liposomes well below their respective pretransition temperature regions are very different: DMPC liposomes release much encapsulated dye at incubation temperatures of 5 degrees C whilst DPPC liposomes do not.

Animals↗

The transitional phase: the closing journey for patients and family caregivers.

The ability to identify physical waypoints along the continuum of illness may give end-stage patients and their families opportunities for goal reframing and risk reduction. That period which exists between active participation in the activities of daily living and a bedbound status, herein described as the transitional phase, is characterized by the four precursive, or seminal, behaviors of anorexia, increased sleep, weakness, and confusion, and the two cardinal behaviors of incontinence and falls. It is a time of heightened anxiety for families and risk of injury for patients. The ability to identify these behaviors as part of a definable phase, with a beginning and an end, allows the health care clinician or hospice worker to educate the family, assisting with goal reassignment, risk reduction, and diminishment of anxiety. Family understanding of the finite nature of the transitional phase may also reduce the need for placement outside the home for those wishing their loved one to die at home, and provide the caregiver with meaningful participation in end-of-life problem solving.

Attitude to Death↗

Studies on the phase transitions of lysoderivatives of ethanolamine glycerophospholipids from human brain.

The phase transition temperature of 1,2-distearoylglycerophosphocholine is reduced in presence of equimolar amounts of 1-O-(1'-alkenyl)-glycerophosphoethanolamine (ethanolamine lysoplasmalogen) from 53.3 degrees C-54.1 degrees C to 44.0 degrees C-44.9 degrees C at different pH (4.0; 7.2; 9.0; 10.5). 1-Acyl-glycerophosphoethanolamine leads to a smaller reduction of the 1,2-distearoyl-glycerophosphocholine transition temperature: 45.0 degrees C-46.2 degrees C at the same pH-values. 1-Alkyl-glycerophosphoethanolamine (hydrogenated ethanolamine lysoplasmalogen) possesses a transition temperature, which is 3.3 degrees C-4.9 degrees C higher than the hydrogenated 1-acyl-glycerophosphoethanolamine at each pH investigated. At pH 9.0 and, more pronounced, at pH 10.5 we find a reduction of the transition temperature for both these substances, whereas their transition temperature is nearly unchanged at pH 4.0 and 7.2. Our results clearly show that the ether-bonding in the lysoderivative of plasmalogen is responsible for the closer packing compared to the 1-acyl-glycerophosphoethanolamine.

Brain Chemistry↗

Magnetic phase transition in a heteromolecular hydrogen-bonded complex of nitronylnitroxide radicals.

An organic molecular acid-base complex has been synthesized from pyridine-substituted biradical 2 in a triplet (S = 1) ground state and a benzoic acid derivative of monoradical 3 with S = 1/2. The two constituent molecules are bound by an OH-N hydrogen bond in a crystalline solid state. The complex has been found to exhibit an antiferromagnetic phase transition at 5 K. The complex is the first example of a hydrogen-bonded heterospin, heteromolecular complex exhibiting a magnetic phase transition in purely organic molecule-based materials.

Journal Article↗

Criteria of phase transitions in a complex plasma.

New empirical rules for different phase transitions (including the melting of cubic lattices and the transitions between body-centered-cubic and face-centered-cubic structures) are proposed. The arrangements of charged macroparticles in a complex "dusty" plasma are numerically investigated for the conditions of laboratory experiments on weakly ionized gas discharges.

Journal Article↗

Bimodality as a signal of a liquid-gas phase transition in nuclei?

We use the heavy-ion phase-space exploration model to discuss the origin of the bimodality in charge asymmetry observed in nuclear reactions around the Fermi energy. We show that it may be related to the important angular momentum (spin) transferred into the quasiprojectile before secondary decay. As the spin overcomes the critical value, a sudden opening of decay channels is induced and leads to a bimodal distribution for the charge asymmetry. In the model, it is not assigned to a liquid-gas phase transition but to specific instabilities in nuclei with high spin. Therefore, we propose to use these reactions to study instabilities in rotating nuclear droplets.

Journal Article↗

Effects of probucol on phase transition and fluidity of phosphatidylcholine membranes: a spin label study.

Spin labeling methods were applied to study the structure and dynamics of phosphatidylcholine membranes as a function of temperature and the mole fraction of probucol. Multilamellar liposomes made of dimyristoylphosphatidyclcholine, dipalmitoylphosphatidylcholine both saturated, and egg yolk phosphatidylcholine, an unsaturated membrane, were used. In fluid phase membranes probucol was found to increase the order and decrease the motional freedom of alkyl chains of lipids as shown with stearic acid spin labels. The effect of probucol on order and motional freedom is more pronounced in the membrane center (16-doxylstearic acid spin label position) than in the near polar headgroup region (5-doxylstearic acid spin label position). The presence of unsaturation in alkyl chains significantly decreased the ordering effect of probucol. The main phase transition temperature of saturated bilayers was lowered by 2 degrees C in the presence of 3 mol% of probucol and significantly broadened at higher concentrations as measured with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) partitioning. Also, pretransition was no longer observed in the presence of probucol. In gel phase membranes, the effect of probucol was complex. Close to the main phase transition the motion of alkyl chains was increased, showing a regulatory effect of probucol on membrane fluidity. It is proposed that probucol is located in the membrane center as opposed to vitamin E, which locates its phenolic -OH group at the membrane surface; therefore, it inhibits lipid peroxidation in this region which is less accessible to vitamin E.

1,2-Dipalmitoylphosphatidylcholine↗