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PubMed1982

Effect of retinol and retinoic acid on permeability, electrical resistance and phase transition of lipid bilayers.

Retinol and retinoic acid have been incorporated into the artificial membrane systems, planar bimolecular lipid membranes and liposomes, and their effects on several membrane parameters have been measured. 1. Retinol and retinoic acid increased the permeability of egg lecithin liposomes to K+, I- and glucose when incorporated into the membranes at levels as low as 0.5 membrane mol%. Retinoic acid influenced permeability more than did retinol for each of the solutes tested. 2. Retinol and retinoic acid both decreased the electrical resistance of egg lecithin-planar bimolecular lipid membranes from 0.5 to 8 membrane mol%. Retinoic acid effected a larger change than did retinol. 3. Retinol and retinoic acid increased the permeability of dimyristoylphosphatidylcholine and dipalmitoylphosphatidylcholine liposomes to water at 1.0 and 3.0 membrane mol%. A larger effect on water permeability was measured for retinoic acid than for retinol. 4. Retinol and retinoic acid at 1.0 and 3.0 membrane mol% were shown to lower the phase-transition temperature of liposomes composed of dimyristoylphosphatidylcholine or dipalmitoylphosphatidylcholine. Phase-transition temperatures were monitored by abrupt changes in water permeability and liposome size associated with the transition. Retinoic acid lowered the phase-transition temperature of dimyristoylphosphatidylcholine liposomes more than did retinol, while both retinoids had almost the same effect on dipalmitoylphosphatidylcholine liposomes.

Dimyristoylphosphatidylcholine↗
PubMed1997

A-myb is expressed in bovine vascular smooth muscle cells during the late G1-to-S phase transition and cooperates with c-myc to mediate progression to S phase.

The Myb family of transcription factors is defined by homology within the DNA binding domain and includes c-Myb, A-Myb, and B-Myb. The protein products of the myb genes all bind the Myb-binding site (MBS) [YG(A/G)C(A/C/G)GTT(G/A)]. A-myb has been found to display a limited pattern of expression. Here we report that bovine aortic smooth muscle cells (SMCs) express A-myb. Sequence analysis of isolated bovine A-myb cDNA clones spanning the entire coding region indicated extensive homology with the human gene, including the putative transactivation domain. Expression of A-myb was cell cycle dependent; levels of A-myb RNA increased in the late G1-to-S phase transition following serum stimulation of serum-deprived quiescent SMC cultures and peaked in S phase. Nuclear run-on analysis revealed that an increased rate of transcription can account for most of the increase in A-myb RNA levels. Treatment of SMC cultures with 5,6-dichlorobenzimidazole riboside, a selective inhibitor of RNA polymerase II, indicated an approximate 4-h half-life for A-myb mRNA during the S phase of the cell cycle. Expression of A-myb by SMCs was stimulated by basic fibroblast growth factor, in a cell density-dependent fashion. Cotransfection of a human A-myb expression vector activated a multimerized MBS element-driven reporter construct approximately 30-fold in SMCs. The activity of c-myb and c-myc promoters, which both contain multiple MBS elements, were similarly transactivated, approximately 30- and 50-fold, respectively, upon cotransfection with human A-myb. Lastly, A-myb RNA levels could be increased by a combination of phorbol ester plus insulin-like growth factor 1. To test the role of myb family members in progression through the cell cycle, we comicroinjected c-myc and myb expression vectors into serum-deprived quiescent SMCs. The combination of c-myc and either A-myb or c-myb but not B-myb synergistically led to entry into S phase, whereas microinjection of any vector alone had little effect on S phase entry. Thus, these results suggest that A-myb is a potent transactivator in bovine SMCs and that its expression induces progression into S phase of the cell cycle.

Animals↗
PubMed1985

Kinetics and mechanism of the lamellar gel/lamellar liquid-crystal and lamellar/inverted hexagonal phase transition in phosphatidylethanolamine: a real-time X-ray diffraction study using synchrotron radiation.

A study of the kinetics and mechanism of the thermotropic lamellar gel/lamellar liquid-crystalline and lamellar/inverted hexagonal phase transition in dihexadecylphosphatidylethanolamine (DHPE) at various hydration levels has been carried out. Measurements were made by using a real-time X-ray diffraction method at the Cornell High Energy Synchrotron Source. This represents an extension of an earlier study concerning the lamellar gel/lamellar liquid-crystalline phase transition in dipalmitoylphosphatidylcholine [Caffrey, M., & Bilderback, D. H. (1984) Biophys. J. 45, 627-631]. With DHPE, the chain-melting and the nonbilayer transitions were examined under active heating and passive cooling conditions by using a temperature jump to effect phase transformation. Measurements were made at hydration levels ranging from 0% to 60% (w/w) water, and in all cases, the transitions were found to be repeatable, be reversible, and have an upper bound on the transit times (time required to complete the transition) of less than or equal to 3 s. The shortest transit time recorded for the chain-melting and lamellar/hexagonal transitions was less than 1 s. At 8% (w/w) water, the transit times were still on the order of seconds even though the transition does not involve the intermediate L alpha phase. Note, the measured transit times are gross values incorporating the intrinsic transit time in addition to the time required to heat or cool the sample through the transition temperature range and to supply or remove the latent heat of the transition. Regardless of the direction of the transition, both appear to be two state to within the sensitivity limits of the real-time method. From simultaneous wide- and low-angle measurements at the lamellar chain-melting transition, loss of long-range order in the lamellar gel phase appears to precede the chain-melting process. On the basis of the real-time X-ray diffraction measurements, a mechanism is proposed for the lamellar/hexagonal phase transition. The mechanism does not involve large or energetically expensive molecular rearrangements, leads directly to a hexagonal lattice coplanar with the lamellar phase, incorporates facile reversibility, repeatability, and cooperativity, accounts for an observed, apparent memory in the hexagonal phase of the original lamellar phase orientation, and is consistent with the experimental observation of a predominantly two-state transition. In conjunction with the kinetic measurements, the DHPE/water phase diagram was constructed. At and above 12% (w/w) water, the thermotropic transition sequence is L beta'/L alpha/HII.(ABSTRACT TRUNCATED AT 400 WORDS)

Gels↗
PubMed2002

Overexpression of RCN1 and RCN2, rice TERMINAL FLOWER 1/CENTRORADIALIS homologs, confers delay of phase transition and altered panicle morphology in rice.

TERMINAL FLOWER 1 (TFL1)/CENTRORADIALIS (CEN)-like genes play important roles in determining plant architecture, mainly by controlling the timing of phase transition. To investigate the possibility of similar mechanisms operating in the control of inflorescence architecture in rice, we analysed the functions of RCN1 and RCN2, rice TFL1/CEN homologs. Constitutive overexpression of RCN1 or RCN2 in Arabidopsis caused a late-flowering and highly branching phenotype, indicating that they possess conserved biochemical functions as TFL1. In 35S::RCN1 and 35S::RCN2 transgenic rice plants, the delay of transition to the reproductive phase was observed. The transgenic rice plants exhibited a more branched, denser panicle morphology. Detailed observation of the panicle structure revealed that the phase change from the branch shoot to the floral meristem state was also delayed, leading to the generation of higher-order panicle branches. These results suggest rice has a pathway that can respond to the overexpressed TFL1/CEN-like functions, and the molecular mechanisms controlling the phase transition of meristems are conserved between grass and dicot species, at least to some extent.

Arabidopsis↗
PubMed1988

Calorimetric and electron spin resonance examination of lipid phase transitions in human stratum corneum: molecular basis for normal cohesion and abnormal desquamation in recessive X-linked ichthyosis.

Lipids appear to play a critical role as regulators of stratum corneum desquamation. In this study, we observed discrete lipid phase transitions at physiologic temperatures in both normal human scale (NHS) and in lipid extracts of NHS by differential scanning calorimetry. In contrast, such thermal transitions were not observed in recessive x-linked ichthyosis scale (RXLIS). To gain further insight into the molecular basis of the lipid phase transitions in NHS vs. RXLIS, comparable samples were evaluated by electron spin resonance, utilizing the perdeuterated probe, di-t-butyl nitroxide. Upon electron spin resonance analysis, both NHS and RXLIS demonstrated thermal phase transitions in the physiologic range; however, the nature of the lipid environments in each type varied. Whereas the environment of the spin probe was more polar in NHS than in RXLIS, the spin probe partitioned into a more "fluid" environment in RXLIS; i.e., the spin probe was more mobile in RXLIS than in NHS lipid matrices. Because an alteration in the cholesteryl sulfate:cholesterol ratio is the primary lipid abnormality in RXLIS, model cholesterol-fatty acid-cholesteryl sulfate mixtures were prepared in proportion to the lipid composition of NHS and RXLIS. Differences were observed in both thermal transitions and in lipid microenvironments in these mixtures that paralleled those observed in scale samples. Based on these results, a model is proposed that invokes abnormal hydrogen bonding, due to increased cholesteryl sulfate, as the mechanism for the abnormal desquamation in recessive X-linked ichthyosis.

Butanes↗
PubMed2006

Intrinsic paramagnetic defects probe the superionic phase transition in mechanochemically synthesized AgI nanocrystals.

Electron paramagnetic resonance (EPR) of two intrinsic paramagnetic centers generated by soft mechanochemistry of Ag and I to yield zinc blende gamma-AgI nanoparticles (approximately 38 nm) has been used for the first time to probe the gamma-alpha (body centered cubic) superionic phase transitions in AgI at (423 +/- 1) K. These results are agreeable with the differential scanning calorimetric studies. A transmission electron microscope picture shows the average crystallite size in the range of approximately 30-40 nm. A hole-type Ag-related paramagnetic center (Ag2+) with an average g = 2.21025 value is remarkably sensitive to the first-order phase transition exhibiting sharp drops at the phase transition temperature (T(t)) and complete reversibility. The T(t) is characterized by a sharp, abrupt rise in the inverse paramagnetic susceptibility 1/chi by 1 order (7.4 x 10(10) to 3.17 x 10(11) in kg m(-3)) which reflects changes in the bonding of the material. Furthermore, a sharp signal at g = 2.0019 (deltaH(PP) = 10 G) due to an electron-excess center (Ag0) as a result of Ag metal nanoclusters also formed during the mechanochemical reaction (MCR) yields an abrupt and drastic decrease in the intensity observed at T(t) = 423 K. From high-temperature (323 to 433 K) I-V characteristics, the evolution of nonohmic behavior is observed on the order of 10(-9)-10(-6) A with increasing temperature until below T(t) which becomes ohmic thereafter. The reason could be the creation of an electronic defect such as Ag0 metal nanoclusters formed during the near-equilibrium mechanochemical reaction, with the increased excess free energy favoring the formation of gamma-AgI nanoparticles.

Journal Article↗
PubMed2005

Segregation and phase transition in mixed lipid films.

Energy dispersion X-ray diffraction (EDXD) was applied to investigate the structure of partly dehydrated mixed films formed by the phospholipid dimyristoyl phosphatidylcoline (DMPC) and any of the three diastereomers of the dicationic gemini surfactant (2S,3S)-2,3-dimethoxy-1,4-bis(N-hexadecyl-N,N-dimethylammonium) butane dibromide. As the surfactant to lipid molar ratio (R(S/L)) increases, the gemini monotonically solubilizes the lipid bilayer promoting the formation of a cubic phase of space group Pmn segregating from the residual lamellar phase of the lipid. Finally, at R(S/)(L) = 1, the phase transition is complete. The mixed film at the highest surfactant to lipid molar ratio (R(S/L) = 2.3) was hydrated by a vapor saturated atmosphere. At full hydration, a cubic to lamellar phase transition occurs. Coarse grain dynamic investigations, carried out as a function of both the surfactant to lipid molar ratio and the number of water molecules for amphiphile unit, allowed us to elucidate the structure of the emerging cubic phase and the hydration-induced structural pathway of the cubic to lamellar phase transition observed by EDXD.

Dehydration↗
PubMed1985

Phase transition properties of 1,2- and 1,3-diacylphosphatidylethanolamines with modified head groups.

The phase transition properties of dilute aqueous suspensions of "nonhydrated" (i.e., lipid suspensions which had not been heated above room temperature or above the main phase transition temperature of the fully hydrated lipid, whichever was lower) and hydrated 1,2(alpha)- and 1,3(beta)-dipalmitoylphosphatidylethanolamines with modified head groups have been determined by high-sensitivity differential scanning calorimetry at a scan rate of 0.1 K min-1. In both the 1,2 and 1,3 series, the head-group modifications of the phosphoethanolamine moiety included N-methyl, N,N-dimethyl, and N,N,N-trimethyl (phosphocholine). In the 1,2 series, additional modifications were dinitrophenyl, trinitrophenyl, N-(dinitrophenyl)aminocaproyl, N-(trinitrophenyl)aminocaproyl, and N-4-nitro-2,1,3-benzoxadiazole. Also included in this study were 1,2-dihexadecylphosphatidylethanolamine and the corresponding N-methyl-substituted lipid. In general, increasing bulkiness of the head-group substituent caused increasing lowering of the transition temperature, the most extreme cases among the hydrated lipids being the 45 degrees C lowering produced by the N-(dinitrophenyl)aminocaproyl substitution and its trinitrophenyl analogue in the 1,2 series. No simple trend is evident in the changes produced in the calorimetric enthalpy of transitions.

Acylation↗
PubMed2005

Anomalous heat capacity above the isotropic-chiral-smectic-C phase transition.

A phenomenological model is developed to describe the isotropic-chiral-smectic-C phase transition. The anomalous part of the heat capacity of the chiral-smectic-C liquid crystals above the isotropic-chiral-smectic-C phase transition is calculated using Landau's fluctuation theory. The temperature dependence of the heat capacity above the transition point is calculated first for the Gaussian model and then taking the cubic and the quartic terms as a perturbation. The theoretical results are found to be in good agreement with experiment.

Journal Article↗
PubMed2006

Power law relaxation and glassy dynamics in Lebwohl-Lasher model near the isotropic-nematic phase transition.

Orientational dynamics in a liquid crystalline system near the isotropic-nematic (IN) phase transition is studied using molecular dynamics simulations of the well-known Lebwohl-Lasher model. As the IN transition temperature is approached from the isotropic side, we find that the decay of the orientational time correlation functions (OTCF) slows down noticeably, giving rise to a power law decay at intermediate time scales. The angular velocity time correlation function also exhibits a rather pronounced power law decay near the IN boundary. In the mean squared angular displacement at comparable time scales, we observe the emergence of a subdiffusive regime which is followed by a superdiffusive regime before the onset of the long-time diffusive behavior. We observe signature of dynamical heterogeneity through pronounced non-Gaussian behavior in orientational motion particularly at lower temperatures. This behavior closely resembles what is usually observed in supercooled liquids. We obtain the free energy as a function of orientational order parameter by the use of the transition matrix Monte Carlo method. The free energy surface is flat for the system considered here and the barrier between isotropic and nematic phases is vanishingly small for this weakly first-order phase transition, hence allowing large scale, collective, and correlated orientational density fluctuations. This might be responsible for the observed power law decay of the OTCFs.

Journal Article↗
PubMed1989

Effect of acyl chain composition on salt-induced lamellar to inverted hexagonal phase transitions in cardiolipin.

Salt-induced fluid lamellar (L alpha) to inverted hexagonal (HII) phase transitions have been studied in diphosphatidylglycerols (cardiolipins) with different acyl chain compositions, using 31P nuclear magnetic resonance (NMR) spectroscopy. Cardiolipins with four myristoyl chains, tetramyristoyl cardiolipin (TMCL), and with four oleoyl chains, tetraoleoyl cardiolipin (TOCL), were synthesized chemically. TMCL was found to undergo a thermotropic lamellar gel to lamellar liquid-crystalline phase transition at 33-35 degrees C. This lipid exhibited an axially symmetric 31P-NMR spectrum corresponding to a lamellar phase at all NaCl concentrations between 0 and 6 M. In the case of TOCL, formation of an HII phase was induced by salt concentrations of 3.5 M NaCl or greater. These observations, taken together with earlier findings that bovine heart cardiolipin aqueous dispersions adopt an HII phase at salt concentrations of 1.5 M NaCl or greater, indicate that increasing unsaturation and length of the acyl chains favour formation of the HII phase in diphosphatidylglycerols.

Calorimetry, Differential Scanning↗
PubMed1999

Renormalization of the phase transition in lead phosphate, Pb3(PO4)2, by high pressure: lattice parameters and spontaneous strain.

The unit-cell parameters of lead phosphate, Pb(3)(PO(4))(2), have been measured by single-crystal X-ray diffraction in a diamond-anvil cell under hydrostatic conditions to a maximum pressure of 6 GPa. The compound undergoes an improper ferroelastic phase transition at 1.81 +/- 0.01 GPa at 298 +/- 1 K from a low-pressure monoclinic phase (space group C2/c) to a high-pressure trigonal phase. The space group of the high-pressure phase is R3;m or R3m and the phase boundary is the same as that crossed at ca 450 K at room pressure. The evolution of the spontaneous strain components arising from the phase transition is linear with pressure, indicating an effective critical exponent for the phase transition of beta = 0.50 +/- 0.03. Thus, the application of pressure strongly renormalizes the effective critical exponent of the order parameter from the value of 0.236 found in high-temperature experiments.

Journal Article↗
PubMed2000

First-order phase transition with a logarithmic singularity in a model with absorbing states.

Recently, Lipowski [Phys. Rev. E 62, 4401 (2000)] investigated a stochastic lattice model which exhibits a discontinuous transition from an active phase into infinitely many absorbing states. Since the transition is accompanied by an apparent power-law singularity, it was conjectured that the model may combine features of first- and second-order phase transitions. In the present work it is shown that this singularity emerges as an artifact of the definition of the model in terms of products. Instead of a power law, we find a logarithmic singularity at the transition. Moreover, we generalize the model in such a way that the second-order phase transition becomes accessible. As expected, this transition belongs to the universality class of directed percolation.

Journal Article↗
PubMed2003

Phase Transition of Thylakoid Membranes Modulates Photoinhibition in the Cyanobacterium Anabaena siamensis.

A shift of the growth temperature from 40 degrees C to 18 degrees C promoted an increase in the degree of fatty acids unsaturation and a decrease, from 26 degrees C to 0 degrees C, of the phase transition temperature of thylakoid membranes in Anabaena siamensis. The pattern of photoinhibition of photosynthesis at distinct temperatures varied as a function of the phase transition temperature. In the absence of streptomycin, a pronounced photoinhibition at temperatures near the phase transition (26 degrees C) was observed in cells grown at 40 degrees C, while protection from photodamage was observed at chilling temperatures (15 degrees C to 5 degrees C). In this same range of temperature, such a protection was not verified if cells were grown at 18 degrees C. In both types of cells, however, the rate of photoinactivation in the presence of streptomycin was progressively decreased by lowering the temperature of photoinhibition. When recovery from photoinhibition was followed at the respective temperature in which cells were grown, the restoration profile of the photosynthetic O(2) evolution to initial levels was essentially the same in both types of cells. The protective effect of low temperatures against photoinhibition was attributed to a decreased solubility and diffusion of oxygen in the thylakoid membranes due to an increase of the membrane viscosity that would avoid the photogeneration of reactive oxygen species around PS II.

Journal Article↗
PubMed1981

Interaction of tubulin with phospholipid vesicles. I. Association with vesicles at the phase transition.

Purified soluble tubulin will interact with highly sonicated small unilamellar vesicles of dipalmitoyl phosphatidylcholine. This results in the leakage of a fluorescent dye, carboxyfluorescein, from the internal aqueous space of the vesicles at the lipid phase transition. The amount of dye leaked from the vesicles is determined by the tubulin to vesicle ratio and partial dye leakage reflects the uniform leakage of carboxyfluorescein from all of the vesicles. Once tubulin interacts with dipalmitoyl phosphatidylcholine vesicles at the phase transition, it is unavailable to interact with additional vesicles. This interaction represents the formation of stable tubulin-vesicle recombinants as shown by density gradient centrifugation. Such recombinants are only formed by interacting the protein with the vesicles at the lipid phase transition temperature. The interaction is insensitive to ionic strength (0.001 to 4 M NaCl) and the recombinants remain stable for days.

Animals↗
PubMed2002

Critical behavior of nonequilibrium phase transitions to magnetically ordered states.

We describe nonequilibrium phase transitions in arrays of dynamical systems with cubic nonlinearity driven by multiplicative Gaussian white noise. Depending on the sign of the spatial coupling we observe transitions to ferromagnetic or antiferromagnetic ordered states. We discuss the phase diagram, the order of the transitions, and the critical behavior. For global coupling we show analytically that the critical exponent of the magnetization exhibits a transition from the value 1/2 to a nonuniversal behavior depending on the ratio of noise strength to the magnitude of the spatial coupling.

Journal Article↗
PubMed2006

Vibrational sum frequency generation studies of the (2 x 2)-->(radical19 x radical19) phase transition of CO on Pt(111) electrodes.

The potential-dependent (2x2)-3CO-->(radical19x radical19)R23.4 degrees-13CO adlayer phase transition on Pt(111) with 0.1M H(2)SO(4) electrolyte was studied using femtosecond broadband multiplex sum frequency generation (SFG) spectroscopy combined with linear scan voltammetry. Across the phase boundary the SFG atop intensity jumps, and at the same time the SFG spectrum of threefold CO sites is transformed into a bridge site spectrum with a small decrease in integrated SFG intensity. The SFG atop intensity jump and three fold-to-bridge intensity drop are noticeably different from what would be expected for these structures on the basis of coverage alone. This occurs because the SFG signal is sensitive to both the coverage and changes in the local field that result from a changing adlayer structure. We derive an equation that allows us to correct the SFG intensities for these effects using information derived from infrared absorption-reflection spectroscopy (IRAS) and second-harmonic generation (SHG) measurements. With this correction, the SFG results agree well with what would be expected for a transition between perfect adlattices. A small (approximately 20%) discrepancy in the SFG determination of atop coverage is attributed to either a small amount of surface disorder or uncertainties in the SFG, SHG, and IRAS measurements. SFG is also used to examine the reversibility hysteresis and kinetics of the phase transition and its dependence on electrolyte composition. The phase transition is reversible with an approximately 150 mV anodic overpotential and the forward (2x2)-->(radical19x radical19) transition is slower than the reverse. Repeated cycles of phase transition indicate that the 25 microm electrolyte layer used here does not appreciably distort the potential-coverage relationships.

Journal Article↗
PubMed2004

First-order superradiant phase transitions in a multiqubit cavity system.

We predict the existence of novel first-order phase transitions in a general class of multiqubit cavity systems. Apart from atomic systems, the associated superradiant phase transition should be observable in a variety of solid-state experimental systems, including the technologically important case of interacting quantum dots coupled to an optical cavity mode.

Journal Article↗