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PubMed1974

Lateral phase separation of lipids in plasma membranes: effect of temperature on the mobility of membrane antigens.

Cooling populations of newly formed mouse human heterokaryons has effects on the intermixing of mouse and human surface antigens which indicate the occurrence of phase separations in membrane lipids. Antigen mixing, previously shown to be due to diffusion in the plane of the membrane, is retarded when cells are cooled from 37 degrees to 21 degrees C, but is then speeded by further cooling to 15 degrees C. This result is in accord with observations on phase separations of lipids in artificial and bacterial membranes.

Animals↗
PubMed2004

Measurement of density distributions for colloidal beta-FeOOH rods in suspensions exhibiting phase separation: the role of long-range forces in smectic ordering.

We prepared monodisperse colloidal beta-FeOOH rods with length-to-width ratios L/W of 3.6-7.0 (L=210-330 nm and W=40-58 nm). Density gradients of the rods occurred in the suspensions by gravity, inducing a phase separation. The denser phase showed smectic (Sm) liquid crystalline structures exhibiting iridescent colors in a wide range of pH from 1.2 (at which the rods interact attractively) to 4.7 (repulsively). The lower density phase was disordered, but frequently emitted diffuse colors locally (at pH>2.6), implying the occurrence of short-range order. The nematic phase was not observed in the beta-FeOOH systems, being consistent with theoretical predictions. The particle density distributions were measured over the whole region of the suspensions (separated into two phases) at various pH values using a rapid freezing method. A phase diagram was determined thereby, where the critical (minimal) packing fraction of the particles for the Sm phase showed a nonlinear decrease from 0.43 to 0.12 with increasing pH. Rod-rod spacings in the Sm phase estimated experimentally at various pH were well explained using Derjaguin-Landau-Verwey-Overbeek (DLVO) type pair potentials. It is suggested that Sm ordering can be induced by attractive minima at pH<2.2, while driven by soft repulsions at pH>2.6. The former Sm ordering is expected to be the condensation-type phase transition and the latter the disorder-order transition.

Journal Article↗
PubMed1985

Calcium-induced lateral phase separations in phosphatidylcholine-phosphatidic acid mixtures. A Raman spectroscopic study.

The effects of calcium ions on mixed membranes of dimyristoylphosphatidic acid (DMPA) and dimyristoylphosphatidylcholine (DMPC) with either the PA or the PC component deuterated have been studied by Raman spectroscopy. The spectra of the pure components show that the acyl chains of hydrated DMPA bilayers are less tightly packed and have more trans bonds than those of DMPC. This behavior appears to be due to the particular arrangement of the polar head groups of DMPA for which the glycerol chain is oriented parallel to the bilayer surface. In agreement with the calorimetrically determined phase diagram [Graham, I., Gagné, J., & Silvius, J. R. (1985) Biochemistry (preceding paper in this issue)], the Raman results show that, in the absence of calcium, DMPA and DMPC are completely miscible at an equimolar ratio but undergo extensive phase separation in the presence of excess calcium. DMPC in phase-separated DMPC-DMPA (Ca2+) mixtures has a conformation that is very similar to that of pure DMPC bilayers, but it is packed more tightly since, depending on the temperature, it is at least partly incorporated into either a solid solution in DMPA or a DMPA-Ca2+-rich "cochleate" phase. This latter shows the same characteristics as the cochleate phase of pure DMPA-Ca2+ which is highly ordered and does not give rise to a thermotropic transition between 5 and 100 degrees C. However, the cochleate phase in DMPA (Ca2+)-DMPC mixtures contains some 20 mol % of DMPC trapped in small domains. These clusters do not melt cooperatively but become as fluid as pure DMPC at 50 degrees C.

Calcium↗
PubMed2001

Polymer-induced membrane contraction, phase separation, and fusion via Marangoni flow.

Experiments have shown that the depletion of polymer in the region between two apposed (contacting or nearly contacting) bilayer membranes leads to fusion. In this paper we show theoretically that the addition of nonadsorbing polymer in solution can promote lateral contraction and phase separation of the lipids in the outer monolayers of the membranes exposed to the polymer solution, i.e., outside the contact zone. This initial phase coexistence of higher- and lower-density lipid domains in the outer monolayer results in surface tension gradients in the outer monolayer. Initially, the inner layer lipids are not exposed to the polymer solution and remain in their original "unstressed" state. The differential stresses on the bilayers give rise to a Marangoni flow of lipid from the outer monolayers in the "contact zone" (where there is little polymer and hence a uniform phase) to the outer monolayers in the "reservoir" (where initially the surface tension gradients are large due to the polymer-induced phase separation). As a result, the low-density domains of the outer monolayers in the contact zone expose their hydrophobic chains, and those of the inner monolayers, to the solvent and to each other across the narrow water gap, allowing fusion to occur via a hydrophobic interaction. More generally, this type of mechanism suggests that fusion and other intermembrane interactions may be triggered by Marangoni flows induced by surface tension gradients that provide "action at a distance" far from the fusion or interaction zone.

Cell Membrane↗
PubMed2002

Slaughterhouse wastewater treatment: evaluation of a new three-phase separation system in a UASB reactor.

The anaerobic treatment of the wastewater from the meat processing industry was studied using a 7.2 1 UASB reactor. The reactor was equipped with an unconventional configuration of the three-phase separation system. The effluent was characterized in terms of pH (6.3-6.6), chemical oxygen demand (COD) (2,000-6,000 mg l(-1)), biochemical oxygen demand BOD5 (1,300-2,300 mg 1(-1)), fats (40-600 mg l(-1)) and total suspended solids (TSS) (850-6,300 mg l(-1)) The reactor operated continuously throughout 80 days with hydraulic retention time of 14, 18 and 22 h. The wastewater from Rezende Industrial was collected after it had gone through pretreatment (screening, flotation and equalization). COD, BOD and TSS reductions and the biogas production rate were the parameters considered in analyzing the efficiency of the process. The average production of biogas was 111 day(-1) (STP) for the three experimental runs. COD removal varied from 77% to 91% while BOD removal was 95%. The removal of total suspended solids varied from 81% to 86%. This fact supports optimal efficiency of the proposed three-phase separation system as well as the possibility of applying it to the treatment of industrial effluents.

Abattoirs↗
PubMedDate not supplied

Phase separation modulation and aggregation prevention: mechanism of the non-solvent addition method in the presence and absence of polyisobutylene as an additive.

The mechanism by which microcapsule aggregation is diminished in the presence of low concentrations of adjunct non-walling polymers such as polyisobutylene (PIB) in organic solvents is uncertain. It is here investigated by phase separation studies employing the non-solvent addition method (cyclohexane) in parallel with microencapsulation experiments, using Eudragit wall polymers and tetrahydrofurane (THF) as solvent with and without PIB. Polymer incompatibility leads to formation of two dilute liquid phases and emulsification from the outset. Progressive solvent transfer to the PIB phase modulates the rate of wall polymer desolvation and maintains the concentrated wall polymer phase in a fluid state during the critical microencapsulation stages of wall polymer entrapment--and spreading. A three-phase system is formed when gelling ensues (L1 + L2 + gel). In the absence of PIB, phase separation leads immediately to deposition of the wall polymer in gel form (L1 + gel) leading to adhesion. Phase diagrams are presented.

Capsules↗
PubMed2000

Lens cytoplasmic phase separation.

Cytoplasmic transparency is a unique feature of lens cells. The cytoplasm is a concentrated solution of crystallin proteins with minor constituents that include cytoskeletal proteins and lens specific intermediate filaments. Under normal physiological conditions, the proteins exist as a single transparent phase. With normal aging, progressive modification of the interactions between lens proteins occurs so that conditions within the lens become favorable for phase separation. These conditions produce intracellular inhomogeneities that approach or exceed the dimensions of the wavelength of visible light (400 to 700 nm) and light scattering from lens cells increases. The resulting opacification is the primary factor in the visual loss experienced in cataract, the leading cause of blindness in the world. We study biochemical factors that regulate the cytoplasmic phase separation and maintain normal cellular transparency.

Animals↗
PubMed2005

Adsorbate-induced alloy phase separation: a direct view by high-pressure scanning tunneling microscopy.

The influence of high pressures of carbon monoxide (CO) on the stability of a Au/Ni(111) surface alloy has been studied by high-pressure scanning tunneling microscopy. We show that CO induces a phase separation of the surface alloy at high pressures, and by means of time-lapsed STM movies we find that Ni atoms are removed from the surface layer during the process. Density functional theory calculations reveal the thermodynamic driving force for the phase separation to be the Au-induced compression of the CO overlayer with a resulting CO-CO repulsion. Furthermore, the atomistic mechanism of the process is shown to be kink-site carbonyl formation and evaporation which is found to be enhanced by the presence of Au.

Journal Article↗
PubMed2006

Automated sample treatment by flow techniques prior to liquid-phase separations.

Sample preparation (SP) is an integral and important part of an analytical process. Lately, SP has been the topic of increased interest in research and development of novel advanced technologies. Major needs in this aspect are miniaturization, automation, and enrichment. Among other methodologies, flow techniques can be conveniently and effectively coupled to liquid-phase separation technologies for on-line sample preparation. This paper reviews the current trends in on-line automated sample preparation by flow-through techniques prior to liquid-phase separations. Strategies and interfaces developed to couple flow techniques with liquid chromatography, capillary electrophoresis, and mass spectrometry are described. Advantages and limitations of the coupling are discussed. The paper also highlights certain selected applications of these coupled systems.

Chromatography, Liquid↗
PubMed1973

Lateral phase separations in membrane lipids and the mechanism of sugar transport in Escherichia coli.

Changes in slope of Arrhenius plots for transport can, in some instances, be detected at two different temperatures for cells that have a relatively simple fatty-acid composition in the membrane lipids. These characteristic temperatures correlate with the characteristic temperatures that define changes of state in membrane phospholipids as revealed by the paramagnetic resonance of the spin label TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl). The higher of these characteristic temperatures is that at which the formation of solid patches of membrane lipids is first detected. The lower is the end point of the course of lateral phase separations, at which all the membrane lipids are in a solid phase. For cells enriched for elaidic acid, the rate of transport increase by as much as 2-fold as the temperature is decreased by less than 1 degrees , at the higher characteristic temperature. At this characteristic temperature, lateral phase separations begin in the membrane phospholipids. This is also the temperature where one predicts a striking increase in the lateral compressibility of the membrane lipids. These data are thus interpreted to indicate that a component of the transport system vertically penetrates one or both monolayer faces of the membrane during transport, or that some other event involving the lateral compression of the phospholipids is important for transport.

Biological Transport, Active↗
PubMed2002

Influence of product phase separation on phospholipase A(2) hydrolysis of supported phospholipid bilayers studied by force microscopy.

In situ atomic force microscopy studies reveal a marked influence of the initial presence of hydrolysis products on the hydrolysis of supported phospholipid bilayers by phospholipase A(2). By analysis of the nano-scale topography of a number of supported bilayers with different initial product concentrations, made by Langmuir-Blodgett deposition, we show that small depressions enriched in products are efficiently promoting enzyme degradation of the bilayer. These small depressions, which are indicative of phase separation, are initially present in samples with 75% products. The kinetics of phospholipase A(2) exhibit under certain conditions an initial phase of slow hydrolysis, termed the latency phase, followed by a marked increase in the hydrolysis rate. The appearance of the phase-separated bilayer is strikingly similar to that of bilayers at the end of the latency phase. By analysis of individual nano-scale defects we illustrate a quantitative difference in the growth rates of defects caused by product aggregation and other structural defects. This difference shows for the first time how the enzyme prefers one type of defect to another.

Agkistrodon↗
PubMedDate not supplied

Modulation of membrane proteins by vertical phase separation and membrane lipid fluidity. Basis for a new approach to tumor immunotherapy.

Cell differentiation and proliferation entail a series of membranal events, which lead to the modulation of proteins at the cell surface. In the case of malignant differentiation this offers the tumor cell the possibility of escaping immune surveillance. Vertical phase separation of membrane proteins appears to play an important role during modulation of membrane proteins. The data reviewed here strongly suggests that the membrane lipid fluidity modulates expression of membrane proteins by vertical phase separation. When the membrane fluidity was elevated the surface expression of some membrane proteins increased, whereas it decreased when the membrane became more rigid. These proteins (e.g. H-2 antigens, hormone receptors and others were termed "syndromic". The membrane proteins which displayed the opposite behaviour with respect to the lipid fluidity were referred to as "antidromic" proteins e.g. human blood group antigens, Thy 1.2 and neuroreceptors). The possibility that the tumor cell plasma membrane contains cryptic antidromic antigens which may become exposed when the membrane lipid fluidity is manipulated has triggered a potentially new experimental approach in the treatment of neoplastic diseases. Autologous tumor cells pretreated to decrease their membrane lipid fluidity were shown to have an increased capability of eliciting specific immune responses when compared to normal control cells subjected to the same treatment.

Anesthetics, Local↗
PubMed2006

Lateral phase separation in lipid-coated microbubbles.

In the design of lipid-coated microbubble ultrasound contrast agents for molecular imaging and targeted drug delivery, the surface distribution of the shell species is important because it dictates such properties as ligand location, brush coverage, and amount of drug loading. We used a combination of spectroscopy and microscopy techniques to test the prevailing notion that the main phosphatidyl choline (PC) and lipopolymer species are completely miscible within the monolayer shell. NMR spectroscopy showed that the shell composition is roughly equivalent to the bulk lipid ratio. FTIR spectroscopy showed a sharp melting peak corresponding to the main phase-transition temperature of the main PC species, with no observed pretransitions while scanning from room temperature, indicating a single PC-rich ordered phase. Electron and fluorescence microscopy showed a heterogeneous microstructure with dark (ordered) domains and bright (disordered) regions. Domain formation was thermotropic and reversible. Fluorescent labeling of the lipopolymer following shell formation showed that it partitions preferentially into the disordered interdomain regions. The ordered domains, therefore, are composed primarily of PC, and the disordered interdomain regions are enriched in lipopolymer. Phase heterogeneity was observed at all lipopolymer concentrations (0.5 to 20 mol %), and the degree of phase separation increased with lipopolymer content. The composition and temperature dependence of the microstructure indicates that phase separation is driven thermodynamically rather than being a kinetically trapped relic of the shell-formation process. The overall high variation in microstructure, including the existence of anomalous three-phase coexistence, highlights the nonequilibrium (history-dependent) nature of the monolayer shell.

Coated Materials, Biocompatible↗
PubMed2002

Fabrication of a pure porous chitosan bead matrix: influences of phase separation on the microstructure.

The material properties and the microstructure of the scaffold are important parameters that determine the suitability of a material for tissue growth and controlled drug release. Because of its non-toxic, biocompatible, biodegradable, and antithrombogenic nature, chitosan has generated enormous interest for such applications. Chitosan bead-type scaffolds having various microstructures without any other material introduction were fabricated. For fabricating pure chitosan beads, a modified wet process and an extended thermally induced phase separation (TIPS) process were adapted. In the modified wet process, an acidic chitosan solution was phase-separated by changing its pH using an NaOH solution. The microstructure of the chitosan beads became looser with a decrease in the initial chitosan concentration, an increase in the acetic acid concentration, as well as with the addition of PEG to the dope solution. In contrast, the microstructure densified with an increase in the NaOH concentration in the coagulation bath. Through the modified wet process, porous chitosan beads with a relatively small pore size (0.01-13 microm) and moderate porosity (33-71%) could be prepared. In the extended TIPS process, chitosan solutions cast at different temperatures below 0 degrees C resulted in different microstructures wherein the microstructure densified with an increase in the quenching rate. The chitosan beads fabricated via extended TIPS had large pore sizes (26-120 microm) and high porosity (85-92%). All of these matrices showed good interconnected pores.

Biocompatible Materials↗
PubMed2002

Inhomogeneous magnetism in single crystalline Sr(3)CuIrO(6+delta): implications to phase-separation concepts.

The single crystalline form of an insulator, Sr(3)CuIrO(6+delta), is shown to exhibit unexpectedly more than one magnetic transition (at 5 and 19 K) with spin-glass-like magnetic susceptibility behavior. On the basis of this finding, viz., inhomogeneous magnetism in a chemically homogeneous material, we propose that the idea of "phase separation" described for manganites is more widespread in different ways. The observed experimental features enable us to make a comparison with the predictions of a recent toy model on magnetic phase separation in an insulating environment.

Journal Article↗
PubMed2004

Imaging of percolative conduction paths and their breakdown in phase-separated (La1-yPry)0.7Ca0.3MnO3 with y=0.7.

Local magnetization and current distribution in (La(1-y)Pr(y))0.7Ca0.3MnO3 (y=0.7) crystals are studied by a magneto-optical (MO) imaging technique. MO images below 120 K visualize inhomogeneous magnetization and conduction paths that manifest the percolative conduction originated from the mesoscopic phase separation into ferromagnetic metals and antiferromagnetic insulators. Application of large amounts of current switches the current distribution from inhomogeneous to homogeneous concomitantly with a steep increase in resistivity. These phenomena are discussed in view of current induced collapse of the phase separation through a local heating.

Journal Article↗
PubMed2003

Electrically controllable microlens array fabricated by anisotropic phase separation from liquid-crystal and polymer composite materials.

Anisotropic phase separation has been used to fabricate an electrically switchable microlens array from nematic liquid crystals. Nematic liquid-crystal-based microlens arrays have been built with diameters of approximately 400 microm and natural focal lengths as small as 1.6 mm. The focal length of each microlens in the array can be changed in milliseconds by an applied electric field. These devices, which have no internal substructures to scatter light, offer higher efficiency and greater light throughput than polymer dispersed devices.

Journal Article↗