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Differential effect of triiodothyronine and thyroxine on the liposomal membrane in liquid-crystalline and gel state.

The effect of thyroid hormones on the degree of order or fluidity of dimyristoyl, dipalmitoyl or egg yolk phosphatidyl choline liposomes was evaluated by fluorescence spectroscopy methods. The freedom of molecular motion above the phase transition temperature was decreased, while below the transition, the mobility was actually increased by the incorporation of triiodothyronine to liposomes. While thyroxine decreases the fluidity in the liquid crystalline state, it cannot increase the fluidity in the gel state. A differential effect of triiodothyronine and thyroxine on the release of the liposomal content was found, depending on the liquid crystalline or gel state of the liposomes. These facts were correlated with the differential incorporation of the hormones to liposomes above and below the phase transition temperature of dimyristoyl and dipalmitoyl phospholipid choline. In gel state, a low incorporation of thyroxine compared with triiodothyronine was found.

1,2-Dipalmitoylphosphatidylcholine↗

Electron paramagnetic resonance of Cu2+:Mb single crystal. Conformational changes.

Copper introduced into met-myoglobin crystals occupies various sites as indicated by electron paramagnetic resonance parameters. Cu2+ (A) is probably liganded to histidine A10, lysine A14, and asparagine GH4 (Banaszak et al., 1965) and shows superhyperfine interaction with a single (imidazole) nitrogen. Cu2+ (B) and Cu2+ (C) correspond to other anisotropic sites described in less detail. Cu2+ (A) exhibits a transition to an isotropic form with a transition temperature of 40.5 degrees C. This transition indicates a conformational change in myoglobin and could correspond to a motion of A helix away from the GH section. The transition temperature is 7 degrees C higher than the one previously reported (Atanasov, 1971) for myoglobin in solution.

Animals↗

Temperature difference between bulk and surface transition in freely suspended smectic films.

We report an ellipsometric study of freely suspended films of a chiral liquid-crystal compound possessing the phase sequence smectic-C-smectic-A-isotropic with a very broad (67 K) smectic-A phase range. We observe a smectic-C-smectic-A surface transition which is situated more than 60 K above the bulk smectic-C-smectic-A transition temperature. Possible reasons for this unusually large temperature shift are discussed.

Journal Article↗

Characterization and thermophysical properties of unsaturated polyester-layered silicate nanocomposites.

The thermophysical properties of unsaturated polyester (UPE) nanocomposites reinforced by organo-montmorillonite clay nanoplatelets are reported. The organo-clay nanoplatelets were sonicated in acetone for 2 hours to be dispersed in the UPE matrix. Vacuum extraction removed not only the acetone but also the styrene present in the UPE solution. The same mechanical and thermophysical properties of UPE were regained after adding the lost amount of styrene to the UPE solution. Both delaminated and intercalated clay morphologies were observed by transmission electron microscopy. It was found that the sonication process was effective to delaminate clay nanoplatelets for more homogeneous dispersion, dependent on organic chemical modifications for clay nanoplatelets. A higher storage modulus enhancement was obtained when the organo-clay nanoplatelets were delaminated and more homogeneously dispersed. The reinforcing effect of both delaminated and intercalated clay nanoplatelets was theoretically evaluated with the Halpin-Tsai equations. It was evaluated that the aspect ratio of delaminated clay nanoplatelets was approximately 150. The increase of the storage modulus below and above the glass transition temperature was achieved without reducing glass transition temperature and Izod impact strength with increasing clay content.

Materials Testing↗

Effect of mitoxantrone liposomes on multidrug-resistant breast cancer cells.

A major obstacle in efficacy of breast cancer chemotherapy is the emergence of multidrug resistance. We investigated modulation of multidrug resistance by liposome-encapsulated mitoxantrone in a drug resistant human breast MCF7R cell line and the influence of liposome composition. Neutral high phase-transition temperature and anionic low phase-transition temperature phospholipid liposomes, reduced the resistance factor from 142 to 15 and 38, respectively. The higher cytotoxicity obtained with mitoxantrone-encapsulation was not necessarily related to higher intracellular uptake. Our data suggest that liposomes, according to their lipid composition, may alter the P-glycoprotein function by plasma membrane stabilization and modulate multidrug resistance in human cancer.

Antineoplastic Agents↗

[Thermal and viscoelastic properties and problems on measurement methods of JIS for inlay waxes (author's transl)].

The thermal and viscoelastic properties of commercial inlay waxes were investigated by measurements of JIS (Japanese Industrial Standard), differential thermal analysis, dilatometry and dynamic viscoelasticity. The crystal transition from orthorhombic to hexagonal caused by paraffin was observed in inlay waxes. The thermal expansion of waxes was influenced by crystal transition temperature. The cooling shrinkage of internal wax pattern is smaller in wax having larger expansion from 25 degrees C to 37 degrees C. The viscoelastic properties of inlay waxes shifted to low temperature region with decreasing in crystal transition temperature. The various properties of inlay waxes greatly changed at temperature of peak for loss tangent. There were some problems on measurement methods of JIS and the reexamination of thermal expansion and flow was suggested. Commercial inlay waxes, respectively, have various different properties, but from these results the qualities of waxes can not be determined so it's necessary to choose a suitable wax according to various conditions.

Elasticity↗

Melting of a DNA hairpin without hyperchromism.

UV absorbance spectroscopy is the most common method for detecting nucleic acid structural transitions and obtaining thermodynamic parameters. UV-detected melting has been used to determine stabilities of nucleic acid hairpins, duplexes, triplexes, and higher order structures and to determine thermodynamic effects of unusual or modified bases and mismatched base-pairs. We report that in some cases UV absorbance spectroscopy is an inadequate analytical technique for these purposes. Some critical transitions are invisible to UV absorbance spectroscopy. For example, the conversion of dodecamer d(CGCAAATTCGCG) from hairpin to random coil is not accompanied by hyperchromism. Circular dichroism (CD) spectroscopy (263 nm) clearly detects two transitions for this dodecamer, each giving a pronounced change in ellipiticity. The concentration dependence of the low-temperature transition and the concentration independence of the high-temperature transition indicate that the predominant state converts from duplex to hairpin to random coil as the temperature increases. These assignments are confirmed by comparison to oligonucleotides of similar sequence that undergo a hairpin to coil transition only. In contrast to CD spectroscopy, UV absorbance spectroscopy shows only a single transition. The transition detected by UV absorbance spectroscopy corresponds to the low-temperature transition detected by CD. UV absorbance spectroscopy does not detect the second transition at any wavelength (from 218 to 310 nm) (by changes) in either absorbance or its derivative with temperature.

Circular Dichroism↗

Effect of Temperature on Respiration of Mitochondria and Shoot Segments from Cold hardened and Nonhardened Wheat and Rye Seedlings.

The effect of temperature on respiration of mitochondria and tissue segments from three wheat (Triticum aestivum L.) and one rye (Secale cereale L.) cultivar grown at 2 and 24 C has been examined. Discontinuities in Arrhenius plots of respiratory activity against temperature were observed for mitochondria and tissue segments from seedlings grown at both temperatures. The rates of respiration decreased abruptly below the transition temperatures, resulting in increased energy of activation values for respiration. Transition temperatures were observed from 6 to 10 C during tissue segment respiration, and from 10 to 14 C during respiration by isolated mitochondria. Respiratory control and efficiency of phosphorylation were not affected markedly by either reaction temperature or growth temperature of the seedlings. No correlation was observed between the cold hardiness of the cultivars and the temperature at which structural transitions occurred in the mitochondria. Dry matter content of the seedlings increased markedly during growth at 2 C, but no appreciable changes in the levels of mitochondrial protein were observed. The results support the view that changes other than fatty acid unsaturation are involved in the abrupt change in mitochondrial membrane properties at low temperature.

Journal Article↗

Damage spreading on two-dimensional trivalent structures with Glauber dynamics: hierarchical and random lattices.

The damage spreading of the Ising model on various two-dimensional trivalent structures with Glauber dynamics is investigated. It is shown that topology plays an important role in determining the damage spreading transition temperatures of the trivalent structures. When damage is considered in terms of only the topological properties of the cellular patterns, the transition temperature above which damage is saturated is found to be determined by the cells with the highest edge number. When the area of cells is also taken into account in the computation of damage, the damage spreading transition temperatures are all lowered. These results are verified by simulation on a set of hierarchical lattices constructed by recursive application of the star-triangle transformation on the vertices of the hexagonal structure, as well as soap froth and randomized lattice structures using Voronoi construction.

Journal Article↗

Effect of cations on the volume of the helix-coil transition of poly[d(A-T)].

The pressure dependence of the helix-coil transition temperature of poly[d(A-T)] has been measured in aqueous solutions of NaCl, KCl, and CsCl at concentrations between 0.02 and 1 M. In all cases the transition temperature increases with pressure. For solutions of NaCl, KCl and dilute CsCl the change in the transition temperature is linear with pressure up to 200 MPa. In more concentrated CsCl solutions the change in Tm with pressure was hyperbolic. The molar volume change of the transition (delta Vt) was calculated using the Clapeyron equation. At the lower salt concentrations, the derived values of delta Vt increase with the radius of the cation (Na+ < K+ < Cs+). At the higher salt concentrations delta Vt of poly[d(A-T)] in Na+ and K+ became equal; however, in CsCl solutions delta Vt was approximately twice as large as delta Vt in solutions containing the other two ions. In solutions of NaCl and KCl, delta Vt increased linearly with the logarithm of the salt concentration while in aqueous CsCl the concentration dependence of delta Vt was hyperbolic. The results are interpreted in terms of the role played by the radius of the cation in deciding the strength of the interactions formed with water.

Cations↗

Depth dependence of the perturbing effect of placing a bulky group (oxazolidine ring spin labels) in the membrane on the membrane phase transition.

Electron paramagnetic resonance (EPR) and differential scanning calorimetry (DSC) have been used to study the effect on the phase transition of dimyristoylphosphatidylcholine membranes of incorporating various stearic acid spin labels (SASL's) that contain the bulky oxazolidine ring at various positions along the stearyl chain. SASL's lowered the phase transition temperature and decreased the size of the cooperative unit, with the effects stronger in the order of 9- > 12- > 5- > 16-SASL > stearic acid (no label). Incorporation of stearic acid without the spin label slightly increases the phase transition temperature. Incorporation of 9-SASL (3 mol% of lipid) decreased the transition temperature by 1.8 degrees C and the cooperative unit to 1/5 of that without the spin label, while the effect of 16-SASL was slight. The effect on transition enthalpy was small. It is concluded that the perturbing effect of placing a bulky group on the alkyl chain on phase transition is through inducing packing defects in the gel-phase.

Calorimetry, Differential Scanning↗

Superconductivity at 39 K in magnesium diboride.

In the light of the tremendous progress that has been made in raising the transition temperature of the copper oxide superconductors (for a review, see ref. 1), it is natural to wonder how high the transition temperature, Tc, can be pushed in other classes of materials. At present, the highest reported values of Tc for non-copper-oxide bulk superconductivity are 33 K in electron-doped Cs(x)Rb(y)C60 (ref. 2), and 30 K in Ba(1-x)K(x)BiO3 (ref. 3). (Hole-doped C60 was recently found to be superconducting with a Tc as high as 52 K, although the nature of the experiment meant that the supercurrents were confined to the surface of the C60 crystal, rather than probing the bulk.) Here we report the discovery of bulk superconductivity in magnesium diboride, MgB2. Magnetization and resistivity measurements establish a transition temperature of 39 K, which we believe to be the highest yet determined for a non-copper-oxide bulk superconductor.

Journal Article↗

Heat-induced secondary structure and conformation change of bovine serum albumin investigated by Fourier transform infrared spectroscopy.

Fourier transform infrared (FT-IR) spectra were measured for an aqueous solution (pD = 5.40) of defatted monomer bovine serum albumin (BSA) over a temperature range of 25-90 degrees C to investigate temperature-induced secondary structure and conformation changes. The curve fitting method combined with the Fourier self-deconvolution technique allowed us to explore details of the secondary structure and conformation changes in defatted BSA. Particularly striking in the FT-IR spectra was an observation of the formation of an irreversible intermolecular beta-sheet of BSA on heating above 70 degrees C. A band at 1630 cm(-1) in the spectra was assigned to short-segment chains connecting alpha-helical segments. The transition temperature for the short-segment chains connecting alpha-helical segments is lower by 17-18 degrees C, when compared to those of the alpha-helix, turn, and intermolecular beta-sheet structures of BSA, suggesting that the alpha-helix and turn structures of BSA are cooperatively denatured on heating. Moreover, the results give an important feature in heat-induced denaturation of BSA that the conformation changes occur twice around both 57 and 75 degrees C. The appearance of two peaks is interpreted by the collapse of the N-terminal BSA domain due to the crevice in the vicinity between domains I and II at low-temperature transition and by the change in cooperative unit composed of the other two BSA domains at high-temperature transition.

Animals↗

Interaction of tryptophan with lecithin liposomes: NMR and turbidity studies.

A study on the interactions between tryptophan (Trp) and dipalmitoylphosphatidyl choline (DPPC) liposomes conducted with the NMR technique and taking turbidity measurements is reported. Trp is shown to be incorporated into the bilayer only when interaction occurs above gel-liquid transition. Disappearance of turbidity changes at the phase transition temperatures are shown to occur with Trp incorporation. 1H and 13C NMR relaxation times T1 of DPPC are seen to be reduced. Acyl chain signal intensity is shown to decrease and the corresponding line-width to increase as a function of Trp concentration. DPPC 31P [1H] Nuclear Overhauser Effect (NOE) is depressed by the presence of Trp above gel-liquid transition temperature whereas NOE remains high below phase transition temperature when Trp is present in the bilayer. Effects are shown to be the same in both H2O and in 2H2O. A membrane modification that may account for the previously observed inhibition of polysaccharide induced cell aggregation is hypothesized.

Kinetics↗

Thermotropic phase behavior of model membranes composed of phosphatidylcholines containing iso-branched fatty acids. 1. Differential scanning calorimetric studies.

The thermotropic phase behavior of aqueous dispersions of phosphatidylcholines containing one of a series of methyl iso-branched fatty acyl chains was studied by differential scanning calorimetry. These compounds exhibit a complex phase behavior on heating which includes two endothermic events, a gel/gel transition, involving a molecular packing rearrangement between two gel-state forms, and a gel/liquid-crystalline phase transition, involving the melting of the hydrocarbon chains. The gel to liquid-crystalline transition is a relatively fast, highly cooperative process which exhibits a lower transition temperature and enthalpy than do the chain-melting transitions of saturated straight-chain phosphatidylcholines of similar acyl chain length. In addition, the gel to liquid-crystalline phase transition temperature is relatively insensitive to the composition of the aqueous phase. In contrast, the gel/gel transition is a slow process of lower cooperativity than the gel/liquid-crystalline phase transition and is sensitive to the composition of the bulk aqueous phase. The gel/gel transitions of the methyl iso-branched phosphatidylcholines have very different thermodynamic properties and depend in a different way on hydrocarbon chain length than do either the "subtransitions" or the "pretransitions" observed with linear saturated phosphatidylcholines. The gel/gel and gel/liquid-crystalline transitions are apparently concomitant for the shorter chain iso-branched phosphatidylcholines but diverge on the temperature scale with increasing chain length, with a pronounced odd/even alternation of the characteristic temperatures of the gel/gel transition.(ABSTRACT TRUNCATED AT 250 WORDS)

Calorimetry, Differential Scanning↗

Determination of the phase behaviour of phosphatidylethanolamine admixed with other lipids and the effects of calcium chloride: implications for protein kinase C regulation.

The phase behaviour of 1-palmitoyl-2-oleoylphosphatidylethanolamine (POPE) was studied by differential scanning calorimetry and 31P-NMR spectroscopy. Modulation of the phase behaviour of POPE by 1-palmitoyl-2-oleoylphosphatidylserine (POPS). 1-palmitoyl-2-oleoylphosphatidylcholine (POPC), 1,2-di-olein (DOG), CaCl2, MgCl2, and combinations of these substances was studied. The bilayer-forming lipids, POPS and POPC, raise the bilayer-to-hexagonal phase-transition temperature of POPE. The POPC has a greater effect than POPS, probably because the former lipid is more miscible with POPE. Addition of 10 mM CaCl2 has little effect on the phase-transitions of POPE/POPC mixtures, but it greatly decreases the effectiveness of POPS in raising the bilayer-to-hexagonal phase-transition temperature of POPE. The effectiveness of DOG in lowering the phase-transition temperature of POPE is also greatly reduced in the presence of 10 mM CaCl2. This phenomenon may play a role in the negative feedback regulation of protein kinase C.

Calcium Chloride↗

Delivery of antitumor drug to bladder cancer by use of phase transition liposomes and hyperthermia.

It has been proposed that liposomes (phospholipid bilayer vesicles) could be used to entrap enzymes or drugs and then be administered intravenously to patients as a natural molecule to be metabolized. After liposome degradation, the entrapped molecules would be released at higher concentrations in target tissues. In 1979, it was shown that liposomes containing a chemotherapeutic agent could preferentially release the agent at the transition temperature of the lipids. In an effort to deliver high dose methotrexate (MTX) to animal transitional cell carcinomas (TCC), we used liposomes with phase transition temperature a few degrees above 37 C. Experimentally induced bladder TCC tumors (induced with N-(4-(5-nitro-2-furyl)-2 thiazolyl) formamide) were transplanted into hind legs of C3H/Bi mice. These animals received tritiated MTX encapsulated in phase transition liposomes. Tumors were heated to 42 +/- 0.5 C (by ultrasound) before receiving the liposomes containing tritiated molecules of MTX. After an appropriate time sequence the tumors were removed and MTX uptake of each tumor was noted and compared to the controls having unheated tumors. Heated TCC tumors accumulated 11.9-fold more MTX than nonheated tumors receiving the same dose. Animals receiving free MTX did not exhibit a temperature dependent difference. This indicates that the phase transition temperature of specifically engineered liposome may be used to increase delivery of high dose methotrexate to transitional cell carcinomas.

Animals↗

The effect of cholesterol incorporation on the temperature dependence of water permeation through liposomal membranes prepared from phosphatidylcholines.

The permeation of water through liposomal membranes composed of phosphatidylcholine plus varying amounts of cholesterol was studied as a function of temperature. 1. Increasing amounts of cholesterol caused a gradual disappearance of the abrupt change in the rate of water permeation near the gel to liquid-crystalline phase transition temperature of dipalmitoylphosphatidylcholine and dimyristoylphosphatidylcholine liposomes. At cholesterol concentrations above about 30 mol % there was no longer a discontinuity in the rate of water permeation. 2. The incorporation of cholesterol produces a steep change in the activation energy of the water permeation above the transition temperature of the saturated lecithin occurring at about 15 mol % of cholesterol. Below the transition temperature there was a gradual decrease in the activation energy of the water permeation in the region of 0 to 33 mol % of cholesterol. 3. In systems containing unsaturated phosphatidylcholines cholesterol also enhanced the activation energy of the water permeation although to a lesser extent. The results indicate that the position of the cis-double bond in the fatty acid chain is very important in this respect. 4. In systems in which cholesterol increased the temperature dependence of the water permeation there is also an enhancement of the temperature dependence of the isotonic glycerol and erythritol swelling by the same number of kcal/mol.

Biological Transport↗