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PubMed1995

Aspects of self- and cross-association hydrophobicity in a single chain binary mixture. A computer study.

The differential scanning calorimetry (DSC) traces for binary mixtures of single chain amphiphiles present more than one transition temperature, while the traces for pure single chain amphiphiles have a single (or at most two) transition temperature(s). These secondary transition temperatures can appear owing to the selective association processes between the components of the lipid mixtures. This paper presents an attempt to examine theoretically the association of single chain amphiphiles between (a) two identical molecules (self-association) and (b) two different molecules (cross-association). Association probabilities, the mean association probabilities and the overall ratio of efficiency, were evaluated for 36 binary mixtures of single chain amphiphiles. A test system for evaluation of differential effects of the hydrophobic chain length on the mean association probabilities was considered. Self-association of longer hydrophobic chains and cross-association phenomena show a high probability compared with the self-association of shorter hydrophobic chains. We found that "the efficacious length of association" in a binary mixture of single chain amphiphiles is 8 methylene groups.

Calorimetry, Differential Scanning↗
PubMed1994

Dynamic mechanical analysis of two crosslinked copolymer systems.

OBJECTIVES: This research investigated the dynamic mechanical properties of two model dental restorative copolymers to elucidate the influence of pendent group length and addition of crosslinking agent. METHODS: Two different monomethacrylate resins [(methyl methacrylate (MMA) or 2-ethoxyethylmethacrylate (EEM)] were added to various molar fractions (0, 5, 10, 20, 40, 60, 80 and 100%) of a difunctional monomer [triethylene glycol dimethacrylate (TEGDMA)], resulting in two different copolymer systems (TMMA and TEEM). Bar-shaped specimens were heat-cured and tested for their dynamic mechanical properties at a fixed frequency (1Hz): flexural storage modulus and loss factor. Transition temperatures associated with peaks were determined using tan delta, phase angle and loss factor. The properties of one specimen were also examined using a range of applied frequencies. RESULTS: Below the Tg, all resin systems had similar storage moduli. An increase in pendent group length lowered transition temperatures and demonstrated greater influence on temperature changes than did a change in crosslinker content. With increasing crosslinker, the transition temperatures increased. The values ascribed to transition temperatures were dependent upon the analysis method used: tan delta gave highest values, followed by phase angle, with loss factor values the lowest. Storage and loss moduli values and their ratio increased with increasing frequency of applied signal. Loss factor analysis provided the most elucidation of sub-Tg transitions. SIGNIFICANCE: Restorative polymers with specific desired physical and mechanical properties can be achieved by both judicious selection of monomer structure as well as by the controlled addition of the crosslinking agent.

Analysis of Variance↗
PubMed1985

Effect of tryptophan derivatives on the phase properties of bilayers.

Binding of several tryptophan derivatives and tryptophan-containing peptides to bilayers is examined by monitoring fluorescence enhancement as a function of lipid concentration. The thermodynamic and spectral parameters of the solutes in the bilayers of vesicles and liposomes do not exhibit any anomalous dependence upon the gel or the liquid-crystalline phase state of the bilayer. Effects of these solutes on the phase-transition profiles of the bilayers of liposomes and vesicles are examined, and the lowering of the phase-transition temperature is correlated with the mole fraction of the solute in the bilayer. The partition coefficients do not change at the main phase-transition temperature. These observations contradict the thermodynamic explanation of the solute-induced lowering of the phase-transition temperature which is based on the Van't Hoff relationship for distribution of the solute in the two coexisting phases at the phase-transition temperature. It is postulated that solute molecules bound to defect sites in bilayers modulate the phase properties of bilayers. These defect sites are induced in the gel phase of bilayers of liposomes above the subtransition temperature.

Chemical Phenomena↗
PubMed1984

Haptenic activity of galactosyl ceramide and its topographical distribution on liposomal membranes. Effects of temperature and phospholipid composition.

The relation between the immune reactions of phosphatidylcholine liposomes containing galactosyl ceramide and the physical properties of the glycolipid in membranes was studied. The immune-agglutination of dipalmitoyl phosphatidylcholine liposomes was affected both by reaction temperature and by cholesterol content. Fatty acyl chain length of phosphatidylcholine also influenced the immune-agglutination. The electron spin resonance and calorimetric studies indicated that the fatty acyl chain length of phosphatidylcholine and cholesterol content, as well as temperature, affect the physical properties of galactosyl ceramide in liposomal membranes. In the absence of cholesterol, most galactosyl ceramide molecules were clustered on the phosphatidylcholine liposomes below the chain-melting transition temperature of the phospholipid, whereas they were randomly distributed in the membrane above the transition temperature. Upon addition of cholesterol to the membranes below the chain-melting transition temperature, the number of glycolipid molecules in the cluster phase decreased. Cholesterol increased the ordering of galactosyl ceramide molecules in the phase of random distribution on membranes above the transition temperature. The change in topographical distribution of galactosyl ceramide in membranes was parallel with that of immune-reactivity.

Agglutination Tests↗
PubMed1983

Differential polarized phase fluorometric studies of phospholipid bilayers under high hydrostatic pressure.

Differential polarized phase fluorometry was used to quantify the rotational rate (R) and limiting anisotropy (r infinity) of the membrane probe diphenylhexatriene (DPH) in solvents and lipid vesicles exposed to hydrostatic pressures ranging from 1 bar to 2 kbar. These measurements reveal the effect of pressure on the phase-transition temperatures of the phosphatidylcholine vesicles, and the effects of pressure on order parameter of the acyl side-chain region of the membranes, the latter as indicated by r infinity. In addition to the well-known elevation of the transition temperature (Tc) with pressure, our results demonstrate that increased pressure restores the order of the bilayers to that representative of temperatures below the transition temperature. We also found that solvents which allowed free isotropic rotation of DPH at 1 bar no longer allowed free rotation when sufficiently compressed; moreover, the apparent DPH rotational rate increased with r infinity. Pressure studies using both DPH and the charged DPH analogue, trimethylammonium DPH (TMA-DPH) indicated that the Tc of dipalmitoylphosphatidylcholine vesicles increased 23 K/kbar and an apparent volume change of 0.036 ml/mol lipid at the phase transition. Assuming, as has been proposed, that TMA-DPH is localized near the glycerol backbone region of the bilayers, these results indicate a similar temperature- and pressure-dependent phase transition in this region and the acyl side-chain region of the membrane.

Cell Membrane↗
PubMedDate not supplied

Temperature-dependent changes in activation energies of the transport systems for nucleosides, choline and deoxyglucose of cultured Novikoff rat hepatoma cells and effects of cytochalasin B and lipid solvents.

The initial rates of transport of uridine, thymidien, purines, choline and 2-deoxy-D-glucose by cultured Novikoff rat hepatoma cells were determined as a function of temperature between 5 and 41 degrees C. Arrhenius plots of all transport systems exhibited sharp breaks in slope; between 17 and 23 degrees for uridine, thymidine and hypoxanthine-guanine transport and between 29 and 32 degrees for choline and 2-deoxy-D-glucose transport. The activation energies for the transport systems changed from 15-26 kcal/mole below the transition temperatures to 4-9 kcal/mole above the transition temperatures. Propagation of the cells in the presence of cis-6-octadecenoic acid which results in marked changes in the lipid composition of cell membrane, had little effect on the temperature characteristics of the various transport systems. Similarly, propagation of the cells for 24 hr in media containing Tween 40 or nystatin had no effect on the capacity of the cells to transport the various substrates or on the temperature dependence of the transport systems. The presence of ethanol, phenethyl alcohol or Persantin at concentrations that inhibited thymidine and 2-deoxy-D-glucose transport between 40 and 70% also did not alter the transition temperatures or activation energies for the transport of these substrates. Cytochalasin B, on the other hand, shifted the transition temperature for 2-deoxy-D-glucose transport to higher temperatures in a concentration-dependent manner, whereas it had no effect on the temperature dependence of thymidien transport.

Biological Transport, Active↗
PubMed2000

Charge changes in loop 2 affect the thermal unfolding of the myosin motor domain bound to F-actin.

The thermal unfolding of Dictyostelium discoideum myosin head fragments with alterations in the actin-binding surface loop 2 was studied by differential scanning calorimetry. Lengthening of loop 2 without concomitant charge changes led to decreases in the transition temperature of not more than 1.8 degrees C. Insertions with multiple positive or negative charges had a stronger destabilizing effect and led to reductions in the thermal transition temperature of up to 3.7 degrees C. In the presence of nucleotide, most mutants displayed similar or higher transition temperatures than M765. Only constructs M765(11/+6) and M765(20/+12) with long positively charged inserts showed transition temperatures that were more than 2 degrees C below the values measured for M765 in the presence of ADP, ADP-V(i), and ADP-BeF(3). Interaction with F-actin in the presence of ADP shifted the thermal transition of M765 by 6 degrees C, from 49.1 to 55.1 degrees C. The actin-induced increase in thermal stability varied between 1.2 and 9.1 degrees C and showed a strong correlation with the mutant constructs' affinity for actin. Our results show that length and charge changes in loop 2 do not significantly affect nucleotide-induced structural changes in the myosin motor domain, but they affect structural changes that occur when the motor domain is strongly bound to actin and affect the coupling between the actin- and nucleotide-binding sites.

Actins↗
PubMed1986

Fluorescence polarization studies on Escherichia coli membrane stability and its relation to the resistance of the cell to freeze-thawing. I. Membrane stability in cells of differing growth phase.

Physical properties of Escherichia coli membrane lipids in logarithmic- and stationary-phase cells were studied by measuring the fluorescence polarization change of cis- and trans-parinaric acid as a function of temperature. In aqueous dispersions of phospholipids extracted from cytoplasmic and outer membranes of cells of differing growth phase, a similar polarization increase was observed over the range from physiological temperature to below 0 degrees C, and nearly the same transition ratios were obtained in all samples. The cytoplasmic membrane of both of the growth-phase cells showed a higher polarization ratio above the transition temperatures, compared to that in the aqueous dispersion of phospholipids. The polarization ratios below the transition temperatures of these specimens were lower than the value obtained with the lipids, especially in the stationary-phase specimens. The outer membrane specimens showed a similar polarization change but the transition temperature ranges were considerably higher both in the logarithmic- and the stationary-phase specimens, compared to those in the cytoplasmic membrane specimens. Freeze-thawing of logarithmic-phase cells showed the emergence of activity of certain enzymes which are known to be located in the membranes. The stationary-phase cells did not suffer from any such deleterious effect and maintained a high level of cell viability in a similar treatment. These results indicate that in the stationary-phase cell membranes lipids are in a highly ordered state, and the lipid state causes a membrane stability which results in the high resistance of the cell to freeze-thawing.

Cell Membrane↗
PubMed1985

Reversible helix/coil transitions of left-handed Z-DNA structures. Comparison of the thermodynamic properties of poly(dG).poly(dC), poly[d(G-C)].poly[d(G-C)], and poly(dG-m5dC).poly(dG-m5dC).

In contrast to poly(dG).poly(dC), which remains in the B-DNA conformation under all experimental conditions the polynucleotides with the strictly alternating guanine/cytosine or guanine/5'-methylcytosine sequences can change from the classical right-handed B-DNA structure to the left-handed Z-DNA structure when certain experimental conditions such as ionic strength or solvent composition are fulfilled. Up to now the investigation of the helix/coil transition of left-handed DNA structures was not possible because the transition temperature exceeds 98 degrees C. By applying moderate external pressure to the surface of the aqueous polymer solution in the sample cell the boiling point of the solvent water is shifted up the temperature scale without shifting the transition temperature, so that we can measure the helix/coil transition of the polynucleotides at all experimental conditions applied. It can thus be shown that the Z-DNA/coil transition is cooperative and reversible. The Tm is 125 degrees C for poly(dG-m5dC).poly(dG-m5dC) in 2mM Mg2+, 50mM Na+, pH 7.2 and 115 degrees c for poly[d(G-C)].poly[d(G-C)] in 3.04M Na+. The transition enthalpy per base pair was determined by the help of an adiabatic scanning microcalorimeter.

DNA↗
PubMed1986

Magnetic field-induced drug permeability in liposome vesicles.

Liposome vesicles maintained in a uniform static magnetic field release a chemotherapeutic drug (ARA-C, MW = 243) at temperatures approaching the phase-transition region where these liposomes are not normally leaky. Drug release is rapid, and a maximum difference between treated and unexposed liposomes of 30% of the total maximal release of ARA-C was observed within 1 min in a magnetic field. Dose-effect studies conducted between 0.01 and 7.5 T (1 T = 10(4) G) reveal that this permeability effect has a sigmoidal dependence on magnetic flux density. The ED50 is 15 mT, with a 95% confidence interval of 6.50-34.9 mT. Magnetic field exposures were conducted using a superconducting magnet with the liposomes maintained at +/- 0.08 degrees C. For comparison, samarium-cobalt permanent magnets induced a comparable drug release at 0.4 T. These results indicate that a static magnetic field of 10 mT or greater can increase passive transport in phospholipid membrane bilayers maintained at or near their membrane phase-transition temperature. Lipid clustering which occurs at prephase-transition temperatures may predispose phospholipid domains to diamagnetic orientation in a magnetic field and thereby facilitate drug release.

Cytarabine↗
PubMed1987

Fluorescence lifetime distributions of 1,6-diphenyl-1,3,5-hexatriene in phospholipid vesicles.

The fluorescence emission properties of 1,6-diphenyl-1,3,5-hexatriene (DPH) in 1,2-dipalmitoyl-3-sn-phosphatidylcholine and 1,2-dimyristoyl-3-sn-phosphatidylcholine multilamellar vesicles have been measured by using multifrequency phase fluorometry. The fluorescence decay of DPH in the phospholipid vesicles has been analyzed by assuming either that the decay is made up of a discrete sum of exponential components or that the decay is made up of one or more continuous distributions of lifetime components. The fit of the decay curve using exponentials required at least two terms, and the reduced X2 was relatively large. The fit using a continuous distribution of lifetime values used two continuous components. Several symmetric distribution functions were used: uniform, Gaussian, and Lorentzian. The distribution function that best described the decay was the Lorentzian. The full width at half-maximum of the Lorentzian distribution was about 0.6 ns at temperatures below the phase transition temperature. At the phospholipid phase transition and at higher temperatures, the distribution became quite narrow, with a width of about 0.1 ns. It is proposed that the lifetime distribution is generated by a continuum of different environments of the DPH molecule characterized by different dielectric constants. Below the transition temperature in the gel phase, the dielectric constant gradient along the membrane normal determines the distribution of decay rates. Above the transition, in the liquid-crystalline phase, the translational and rotational mobility of the DPH molecule increases, and the DPH experiences an average environment during the excited-state lifetime. Consequently, the distribution becomes narrower.(ABSTRACT TRUNCATED AT 250 WORDS)

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1983

Gel to liquid-crystalline phase transitions of aqueous dispersions of polyunsaturated mixed-acid phosphatidylcholines.

The thermotropic properties of aqueous dispersions of synthetic mixed-acid polyunsaturated 1,2-diacyl-3-sn-phosphatidylcholines (PC) have been studied by differential scanning calorimetry. The gel to liquid-crystalline phase transition temperature (Tc) of 1-stearoyl-2-linoleoyl-sn-glycero-3-phosphocholine (SLPC) was -16.2 +/- 1.6 degrees C (means +/- SD, nine dispersions, three separate synthetic preparations); that for a preparation of 1-stearoyl-2-linolenoyl-PC (SLnPC) was -13 degrees C and for a preparation of 1-stearoyl-2-arachidonoyl-PC (SAPC) was -12.6 +/- 1.0 degrees C (three dispersions, one preparation). The temperatures of maximum heat flow (Tmax) for the lipid transitions were -14.4 +/- 1.3, -11, and -10.7 +/- 0.9 degrees C and the enthalpies were 3.3 +/- 1.0, 6.6, and 5.3 +/- 1.8 kcal X mol-1 for SLPC, SLnPC, and SAPC, respectively. The transition temperatures and enthalpies are rationalized on the basis of existing data on the effect of double-bond position on Tc and are interpreted with the use of a statistical mechanical model. The trend of the transition temperatures with the introduction of multiple double bonds reflects opposing effects due to increased molecular area and decreasing degrees of freedom of rotation about carbon-carbon bonds.

Calorimetry, Differential Scanning↗
PubMed1987

Evaluation of electrical conductivity-temperature curves using a mathematical model: temperature-dependent changes during thawing of frozen aqueous pharmaceuticals.

The information contained in the electrical conductivity curves of pharmaceuticals measured as a function of temperature can be represented by a small set of parameters. This is achieved by approximating the electrical conductivity curve as a number of consecutive steps, using a suitable empirical model. The three parameters describing each step are: transition temperature, slope factor and step height. The validity of the calculated transition temperatures was established by applying the model to electrical conductivity curves measured on aqueous solutions of KCl, NaCl and on a KCl-NaCl mixture. It appears that the transition temperatures calculated for these inorganic salts are in good agreement with the respective eutectic temperatures reported in the literature. Subsequently, the method was applied to the corticosteroids prednisolone sodium succinate and prednisolone disodium phosphate. The mathematical model yields a satisfactory fit for both experimental conductivity curves. The actual consequences of freeze-drying an aqueous solution of prednisolone sodium succinate below and above the respective transition temperatures calculated are discussed in relation to the experimental conductivity data.

Chemistry, Pharmaceutical↗
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↗
PubMed1979

Antagonism between high pressure and anesthetics in the thermal phase-transition of dipalmitoyl phosphatidylcholine bilayer.

The antagonizing action of hydrostatic pressure against anesthesia is well known. The present study was undertaken to quantitate the effects of hydrostatic pressure and anesthetics upon the phase-transition temperature of dipalmitoyl phosphatidylcholine vesicles. The drugs used to anesthetize the phospholipid vesicles included an inhalation anesthetic, halothane, a dissociable local anesthetic, lidocaine and an undissociable local anesthetic, benzyl alcohol. All anesthetics decreased the phase-transition temperature dose-dependently. In the case of lidocaine, the depression was pH dependent and only uncharged molecules were effective. The application of hydrostatic pressure increased the phase-transition temperature both in the presence and the absence of anesthetics. The temperature-pressure relationship was linear over the entire pressure range studied up to 340 bars. Through the use of Clapeyron-Clausius equation, the volume change accompanying the phase-transition of the membrane was calculated to be 27.0 cm3/mol. Although the anesthetics decreased the phase-transition temperature, the molar volume change accompanying the phase-transition was not altered. The anesthetics displaced the temperature-pressure lines parallel to each other. The mole fraction of the anesthetics in the liquid crystalline membrane, calculated from the van't Hoff equation, was independent of pressure. This implies that pressure does not displace the anesthetics from the liquid membrane, and the partition of these agents remains constant. The volume change of the anesthetized phospholipid membranes is entirely dependent upon the phase-transition and not on the space occupied by the anesthetics.

Anesthetics↗
PubMed1974

Electrostatic effects on lipid phase transitions: membrane structure and ionic environment.

Ordered --> fluid phase transitions in bilayers of charged lipids are accompanied by a decrease in electrostatic free energy mainly as a result of bilayer expansion. For uniform charge distribution the Gouy-Chapman theory of the electrical double layer predicts a decrease of the transition temperature with increasing charge density. We studied the effects of pH and mono- and divalent cations on the phase transition of lecithin, cephalin, phosphatidylserine, and phosphatidic acid bilayers. Phosphatidic acid with two ionizable protons was selected for a systematic investigation. A change in pH from 7 to 9 increases the charge per polar group from one to two elementary charges. This lowers the transition temperature by about 20 degrees C in agreement with the theory. In this pH region rather small changes in pH suffice to induce the phase transition at constant temperature. Divalent cations (Mg(++) and Ca(++)) increase the transition temperature by charge neutralization and thus can be used to induce the fluid --> ordered transition at constant temperature. In contrast, monovalent cations (Li(+), Na(+), K(+)) lower the transition temperature, or fluidize the bilayer structure at a given temperature. Rather small changes in ionic environment can induce gross alterations in bilayer structure; divalent and monovalent cations have antagonistic effects. This result parallels current theories on nerve excitation and sensory transduction where cation-induced structural changes in biomembranes are invoked.

Calcium↗
PubMed2006

A review of poloxamer 407 pharmaceutical and pharmacological characteristics.

Poloxamer 407 copolymer (ethylene oxide and propylene oxide blocks) shows thermoreversible properties, which is of the utmost interest in optimising drug formulation (fluid state at room temperature facilitating administration and gel state above sol-gel transition temperature at body temperature promoting prolonged release of pharmacological agents). Pharmaceutical evaluation consists in determining the rheological behaviour (flow curve or oscillatory studies), sol-gel transition temperature, in vitro drug release using either synthetic or physiological membrane and (bio)adhesion characteristics. Poloxamer 407 formulations led to enhanced solubilisation of poorly water-soluble drugs and prolonged release profile for many galenic applications (e.g., oral, rectal, topical, ophthalmic, nasal and injectable preparations) but did not clearly show any relevant advantages when used alone. Combination with other excipients like Poloxamer 188 or mucoadhesive polymers promotes Poloxamer 407 action by optimising sol-gel transition temperature or increasing bioadhesive properties. Inclusion of liposomes or micro(nano)particles in Poloxamer 407 formulations offers interesting prospects, as well. Besides these promising data, Poloxamer 407 has been held responsible for lipidic profile alteration and possible renal toxicity, which compromises its development for parenteral applications. In addition, new findings have demonstrated immuno-modulation and cytotoxicity-promoting properties of Poloxamer 407 revealing significant pharmacological interest and, hence, human trials are in progress to specify these potential applications.

Animals↗
PubMed2003

The effect of fructan on membrane lipid organization and dynamics in the dry state.

Fructans are a group of fructose-based oligo- and polysaccharides, which appear to be involved in membrane preservation during dehydration by interacting with the membrane lipids. To get further understanding of the protective mechanism, the consequences of the fructan-membrane lipid interaction for the molecular organization and dynamics in the dry state were studied. POPC and DMPC were investigated in the dry state by (2)H, (31)P NMR, and Fourier transform infrared spectroscopy using two types of fructan and dextran. The order-disorder transition temperature of dry POPC was reduced by 70 degrees C in the presence of fructan. Fructan increased the mobility of the acyl chains, but immobilized the lipid headgroup region. Most likely, fructans insert between the headgroups of lipids, thereby spacing the acyl chains. This results in a much lower phase transition temperature. The headgroup is immobilized by the interaction with fructan. The location of the interaction with the lipid headgroup is different for the inulin-type fructan compared to the levan-type fructan, since inulin shows interaction with the lipid phosphate group, whereas levan does not. Dextran did not influence the phase transition temperature of dry POPC showing that reduction of this temperature is not a general property of polysaccharides.

Dextrans↗