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PubMed1978

Effects of bile salts on the structural integrity of liposomes.

The effects of the bile salts, sodium taurocholate and sodium glycocholate on the structural integrity of liposomes of different lipid compositions were studied. The bile salt concentrations were in the range encountered in the human intestine and the incubations were conducted at 37 degrees C. Two measures of liposome integrity were used: (a) changes in their light-scattering properties; and (b) release of entrapped potassium chromate. The results show that "fluid" liposomes, i.e., those prepared from phospholipids whose phase transition temperatures are below 37 degrees C, were totally disrupted in the presence of 10 mM bile salts at pH 7.4, and their entire contents were released. In the case of liposomes prepared from phospholipids with phase transition temperatures above 37 degrees C, the effect of the bile salts became less pronounced as the phase transition temperature increased. Nevertheless, a considerable proportion of the entrapped marker compound was released from liposomes with phase transition temperatures as high as 60 degrees C. The relevance of these results to the reported liposome-mediated gastrointestinal uptake of insulin is discussed.

Bile Acids and Salts↗

PubMed1998

Thermodynamic analysis of human plasma apolipoprotein C-1: high-temperature unfolding and low-temperature oligomer dissociation.

Thermal and chemical unfolding of lipid-free apolipoprotein C-1 (apoC-1), a 6-kDa protein component of very low density and high-density lipoproteins, was analyzed by far-UV CD. In neutral 1 mM Na2HPO4 solutions containing 6-7 micrograms/mL protein, the apoC-1 monomer is approximately 30% alpha-helical at 0-22 degrees C and unfolds reversibly from about 22-80 degrees C with Tm = 51 +/- 3 degrees C and van't Hoff enthalpy delta Hv(Tm) = 19 +/- 3 kcal/mol. The apparent free energy of the monomer stabilization determined from the chemical unfolding at 0 degree C, delta G(0 degree C) = 2.8 +/- 0.8 kcal/mol, decreases by about 1 kcal/mol upon heating to 25 degrees C. A small apparent heat capacity increment suggests the absence of a substantial hydrophobic core for the apoC-1 molecule. At pH 7, increasing apoC-1 concentration above 10 micrograms/mL leads to self-association and formation of additional alpha-helices that unfold upon both heating and cooling from room temperature. The CD data indicate that the high-temperature transition reflects a complete monomer unfolding and the low-temperature transition reflects oligomer dissociation into stable monomers. This suggests the importance of hydrophobic interactions for apoC-1 self-association. Close proximity between the high- and low-temperature transitions and the absence of a plateau in the chemical unfolding curves recorded from oligomeric apoC-1 indicate marginal oligomer stability and suggest that in vivo apoC-1 transfer is mediated via the complexes with other apolipoproteins and/or lipids.

Acetates↗

PubMed2001

Mild isolation procedure discloses new protein structural properties of beta-lactoglobulin.

To explore the potentially available functional properties of beta-lactoglobulin in, for example, the processing of food products, it is important to isolate the protein by a procedure that avoids all possible denaturing conditions, such as low pH, high ionic strength, or low or elevated temperatures that could cause the protein to undergo irreversible conformational changes. In this work, a mild isolation protocol for beta-lactoglobulin from bovine milk is presented, applicable to semi large-scale isolations (50 to 200 g). The protein could be isolated with a high efficiency (>80%) and a good purity (>98%). Biochemical characterization of the material demonstrated no lactosylation of the protein, nor the formation of irreversibly associated dimers. Also, no proteose peptones could be detected. The ability of beta-lactoglobulin to undergo conformational changes is studied by far and near-ultraviolet circular dichroism and differential scanning calorimetry. A "global" unfolding of the protein is detected around 72 (tertiary level) and 77 degrees C (secondary level). The dimer-monomer dissociation occurring around 52 degrees C could also be monitored at a secondary structural level. Remarkably, a low temperature transition around 30 degrees C was observed, where approximately 10 beta-stranded residues unfold cooperatively, not been reported previously. This low temperature transition is irreversible at temperatures higher than 35 degrees C or upon freezing the material at -20 degrees C. The addition of 20% glycerol could prevent this irreversible conformational change. The effect of the low temperature transition on the protein's functionality remains to be investigated.

Animals↗

PubMed1999

Microphase separation in low density lipoproteins. Evidence for a fluid triglyceride core below the lipid melting transition.

The structural organization of the neutral lipid core in human low density lipoproteins (LDL) was investigated in physicochemically defined, distinct human LDL subspecies in the density range of 1. 0244-1.0435 g/ml by evaluation of the core lipid transition temperature, chemical composition, and the behavior of spin-labeled core lipids. Calorimetric studies were performed on more than 60 LDL preparations, and the transition temperature, which varied between 19 and 32 degreesC, was correlated to the chemical composition and revealed a discontinuity at a critical cholesteryl ester to triglyceride ratio of approximately 7:1. For electron spin resonance studies, several LDL preparations were probed with spin-labeled cholesteryl esters and triglycerides, respectively. In LDL with a high triglyceride content, both labels exhibited similar mobility behavior. In contrast, in LDL with only small concentrations of triglycerides, the behavior of labeled cholesteryl esters and labeled triglycerides differed distinctly. The cholesteryl esters were strongly immobilized below the transition temperature, whereas the triglycerides remained fluid throughout the measured temperatures. These results suggest that the critical cholesteryl ester to triglyceride mass ratio of 7:1 corresponds to two concentric compartments with a radial ratio of 2:1, where the liquid triglycerides occupy the core, and the cholesteryl esters form the frozen shell. At higher triglyceride contents, the triglyceride molecules insert into the cholesteryl ester shell and depress the peak transition temperature of the LDL core, whereas at lower triglyceride contents, excess cholesteryl esters are dissolved in the core.

Calorimetry, Differential Scanning↗

PubMedDate not supplied

Modeling the kinetics of the pectin methylesterase catalyzed de-esterfication of pectin in frozen systems.

The applicability of the William, Landel, and Ferry (WLF) equation with a modification to take into account the effect of melt-dilution and an empirical log-logistic equation were evaluated to model the kinetics of diffusion-controlled reactions in frozen systems. Kinetic data for the pectin methylesterase catalyzed hydrolysis of pectin in four model systems with different glass transition temperatures: sucrose, maltodextrin (DE = 16.5-19.5), carboxymethylcellulose (CMC) and fructose in a temperature range of -24 to 0 degrees C were used. The modified WLF equation was evaluated with a concentration-dependent glass transition temperature (T(g)) as well as the glass transition temperature of the maximally freeze-concentrated matrix (T(g)') as reference temperatures. The equation with temperature-dependent T(g) described the reaction kinetics reasonably well in all the model systems studied. However the kinetics was better described by a linear relationship between log(V(0)/V(0ref)) and (T - T(ref)) in all cases except CMC. The log-logistic equation also described the kinetics reasonably well. The effect of melt-dilution on reactant concentration was found to be minimal in all cases.

Carboxylic Ester Hydrolases↗

PubMed2005

Dynamic mechanical thermal analysis of two light-cured dental composites.

OBJECTIVES: Clinical observations suggest that some composite resins are more often linked to post-operative sensitivity than others. These differences may relate to differences in modulus of elasticity and polymerization rates among materials. The aim of this study was to identify viscoelastic behavior of two light curable composites and determine whether significant differences in viscoelastic behavior exist between the two materials when light cured at each of three different irradiance values. METHODS: Two composites (Z100 and Z250 by 3M ESPE) were evaluated. Six specimens per composite and irradiance value (250, 500 and 850 mW/cm2) were made. The curing times were chosen to produce a fixed energy value of 30 J/cm2 independent of irradiation value. Dynamic mechanical thermal analysis (DMTA) was performed in single cantilever clamped mode. RESULTS: There were significant differences in transition temperatures between the two materials and the three frequencies at their glass transition temperatures, while significant differences did not exist at the lower transitions. The glass transition of Z250 was lower and narrower than that of Z100. Z250 exhibited lower storage modulus values. The irradiance values did not affect any of the transition temperatures significantly. SIGNIFICANCE: The lower and more distinct T(g) of Z250 suggests that Z250 cures more efficiently than Z100. The lower storage modulus of Z250 suggests that Z250 develops less stress in the tooth than Z100 during curing if shrinkage is the same for the two materials. The findings suggest that the material chosen, rather than irradiance, determines the stress level developed during light curing.

Composite Resins↗

PubMed1987

Changes in the Physical State of Membrane Lipids during Senescence of Rose Petals.

Changes in the physical state of microsomal membrane lipids during senescence of rose flower petals (Rosa hyb. L. cv Mercedes) were measured by x-ray diffraction analysis. During senescence of cut flowers held at 22 degrees C, lipid in the ordered, gel phase appeared in the otherwise disordered, liquid-crystalline phase lipids of the membranes. This was due to an increase in the phase transition temperature of the lipids. The proportion of gel phase in the membrane lipids of 2-day-old flowers was estimated as about 20% at 22 degrees C. Ethylene may be responsible, at least in part, for the increase in lipid transition temperature during senescence since aminooxyacetic acid and silver thiosulfate inhibited the rise in transition temperature. When flowers were stored at 3 degrees C for 10 to 17 days and then transferrd to 22 degrees C, gel phase lipid appeared in membranes earlier than in freshly cut flowers. This advanced senescence was the result of aging at 3 degrees C, indicated by increases in membrane lipid transition temperature and ethylene production rate during the time at 3 degrees C. It is concluded that changes in the physical state of membrane lipids are an integral part of senescence of rose petals, that they are caused, at least in part, by ethylene action and that they are responsible, at least in part, for the increase in membrane permeability which precedes flower death.

Journal Article↗

PubMed1975

A calorimetric and monolayer investigation of the influence of ions on the thermodynamic properties of phosphatidylcholine.

The effects of various ions and 2H2O on the thermal properties of phosphatidylcholine dispersions were studied using differential scanning calorimetry and the change in the surface potential of monolayers with temperature. The phosphatidylcholine in 2H2O dispersion exhibits a slightly higher transition temperature and lower enthalpy of melting than a phosphatidylcholine in H2O dispersion. Monovalent (H+, Na+, and Li+) and some divalent cations of chloride salts (Ba2+, Mg2+, and Sr2+) have no effect on the thermal properties of phosphatidylcholine, while halide salts of the di-positive ions Cd2+ and Ca2+ have an effect on both the enthalpy of melting and transition temperature. No effect attributable to the metal ion was observed in non-halide salts of cadmium. The chloride salt of La3+ has no effect on lipid thermal properties whereas that of Fe3+ affects the transition temperature. The enthalpy of melting of phosphatidylcholine in one molar solutions of potassium salts increases in the order: CNS minus greater than acetate greater than I minus. Such large, polarizable anions clearly interact with phosphatidylcholine and must therefore also confer a negative charge on the lipid. The potassium salt of SO4-2 minus has no effect. Possible origins of the observed trends are discussed.

Anions↗

PubMed2005

Thermodynamic behavior of poly(3-alkyl thiophene) blends: Equilibrium cocrystal formation and phase segregation.

The equilibrium cocrystal formation of poly(3-alkyl thiophene) (P3AT) blends has been studied by isothermal cocrystallization in a differential scanning calorimeter (DSC-7). The equilibrium melting points (T(m)0) of the cocrystals are measured using the Hoffman-Weeks extrapolation procedure. The equilibrium phase diagrams are of three different types: (a) concave upward, (b) linear, and (c) linear with phase separation at higher content of lower melting component. The phase diagram nature depends on the regioregularity difference and also on the difference in the number of carbon atoms in the pendent alkyl group of the components. The origin of biphasic nature of type "c" phase diagram has been explored from the glass transition temperature (Tg) measurement using a dynamic mechanical analyzer. The biphasic compositions show two glass transition temperatures (Tg) as well as two beta transition temperatures (T beta). The T(g)s of phase-separated regions correspond to almost the component values but the T(beta)s correspond to that of a lower (T beta) component value, and the other is higher than that of the higher (T beta) component value. Possible reasons are discussed from the interchain lamella thickness in the P3AT blends and molecular modeling using molecular mechanics program.

Journal Article↗

PubMed2002

Control of the anchoring behavior of polymer-dispersed liquid crystals: effect of branching in the side chains of polyacrylates.

A temperature-driven anchoring transition in a polymer/nematic fluid composite that is far from the bulk nematic-isotropic transition temperature is reported. A series of poly(methylheptyl acrylates) were studied to probe the subtle effects of the side chain structure of the polymer on control of the anchoring. A polymer-dispersed liquid crystal film made from TL205 and 1-methylheptyl acrylate shows only planar anchoring over the temperature range studied, while the films made from TL205 and each of the other methylheptyl acrylates or n-heptyl acrylate show the homeotropic-to-planar anchoring transition at temperatures between 70 and 78 degrees C. An interfacial model is proposed in which the different conformation of the side chains is suggested as the cause for the dramatic difference in the observed anchoring behavior.

Journal Article↗

PubMed1983

Structure and thermotropic properties of 1,3-dipalmitoyl-glycero-2-phosphocholine.

The structure and thermotropic properties of hydrated 1,3-dipalmitoyl-glycero-2-phosphocholine (beta-DPPC) have been studied by X-ray diffraction and differential scanning calorimetry. After prolonged storage at -3 degrees C, differential scanning calorimetry heating scans exhibit endothermic transitions at 27 degrees C and 37 degrees C, with transition enthalpies, delta H = 9.1 and 10.5 kcal/mol beta-DPPC, respectively (1 cal = 4.184 J). Upon cooling, the high temperature transition is completely reversible, whereas the low temperature transition is not. Prolonged incubation of hydrated beta-DPPC at low temperatures is necessary in order to regain the full enthalpy of the low temperature transition, indicating metastability of the low temperature form. X-ray diffraction studies indicate three different lamellar phases upon heating equilibrated beta-DPPC from -3 degrees C: (1) below 18 degrees C, a hydrated (14 mol water/mol beta-DPPC) "crystalline" bilayer phase, Lc, with an ordered hydrocarbon chain-packing mode and a bilayer periodicity d = 58 A; (2) between 30 degrees C and 35 degrees C, a hydrated (22 mol water/mol beta-DPPC) gel phase, L beta, with hexagonal chain-packing and d = 47 A; hydrocarbon chain interdigitation in this phase is suggested by the small bilayer periodicity, a sharp, symmetric wide-angle reflection at 1/4.2 A-1, an area per mol beta-DPPC at the interface of approximately 80 A2, electron density profiles and structure factor calculations using strip electron density models; (3) above 37 degrees C, a highly hydrated (48 mol water/mol beta-DPPC) liquid crystalline bilayer phase, L alpha, with d = 65 A. Previous nuclear magnetic resonance and neutron diffraction studies have suggested that in beta-DPPC the glycerol backbone adopts an orientation parallel to the bilayer surface, in contrast to its usual perpendicular orientation in alpha-DPPC. This conformation presumably results in an increased intramolecular chain separation, with consequent changes in the molecular packing, hydration and thermotropic behavior of beta-DPPC, compared to its positional isomer alpha-DPPC.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed1987

Effect of fish oil versus lard diets on the chemical and physical properties of low density lipoproteins of nonhuman primates.

Twenty-four adult male African green grivet monkeys were fed diets containing 42% of calories as lard or menhaden oil and 0.76 mg of cholesterol/kcal for a period of 8 months. Plasma samples from fasting animals were then taken and low density lipoproteins (LDL) were isolated by ultracentrifugation and agarose column chromatography. The LDL were analyzed chemically, and physical properties of the particles were studied by differential scanning calorimetry. The fish oil group had significantly smaller LDL (2.91 vs. 3.43 g/mumol), which contained fewer molecules per particle of all lipid constituents, except triglyceride, compared to the lard-fed animals. The fish oil-fed group had 15% of the total cholesteryl esters as n-3 fatty acyl species and the number of n-3, but not n-6, cholesteryl esters per LDL particle was proportional to LDL size. The numbers of saturated and monounsaturated cholesteryl ester species per LDL particle were highly correlated with LDL size for both diet groups. The LDL of the fish oil group had broad reversible thermotropic transitions that were 12-13 degrees C lower than those of the lard group. These transitions were indicative of order-disorder transitions of the LDL core cholesteryl esters. The peak transition temperature of LDL of the lard group was proportional to the ratio of saturated and monounsaturated to polyunsaturated cholesteryl ester species (CEFA ratio). However, the much lower peak transition temperature of the LDL of the fish oil group was not related to the CEFA ratio nor to the triglyceride content of the particles, but rather, to the n-3 cholesteryl ester content of the particles. Studies of cholesteryl ester model systems demonstrated that relatively small amounts of n-3 cholesteryl esters (less than 15% of total cholesteryl ester) could result in a lowering of the peak transition temperature of cholesteryl linoleate similar to that seen for intact LDL. We conclude that n-3 cholesteryl esters in small quantities have a marked disordering effect on the core cholesteryl esters of LDL, resulting in a striking depression of LDL transition temperature. In addition, we conclude that n-3 cholesteryl esters are preferentially utilized relative to n-6 cholesteryl esters to increase the number of cholesteryl esters per LDL particle with LDL enlargement in fish oil-fed animals.

Animals↗

PubMedDate not supplied

Temperature sensitization of liposomes by use of N-isopropylacrylamide copolymers with varying transition endotherms.

Three kinds of copolymers of N-isopropylacrylamide (NIPAM) with the same conformational transition temperature and varying transition endotherms were synthesized with N-acryloylpyrrolidine (APr), N,N-dimethylacrylamide (DMAM), and N-isopropylmethacrylamide (NIPMAM) as the comonomers. Two dodecyl groups were incorporated into the termini of these copolymers as an anchor for the fixation to a liposomal membrane. Egg yolk phosphatidylcholine liposomes having these copolymers were prepared and their temperature-sensitive contents release and association properties were investigated. While these copolymer exhibited a conformational transition at ca. 40 degrees C, DeltaH for the transition increased in the order of poly(APr-co-NIPAM) < poly(DMAM-co-NIPAM) < poly(NIPMAM-co-NIPAM). The liposomes containing poly(NIPMAM-co-NIPAM) showed a drastic release enhancement of entrapped calcein above the transition temperature, whereas the liposomes with poly(DMAM-co-NIPAM) and those with poly(APr-co-NIPAM) exhibited moderate and slight enhancement of calcein release above that temperature, respectively. On the contrary, the liposomes containing poly(APr-co-NIPAM) showed significant aggregation above the transition temperature, but the aggregation was hardly observed for the liposomes having poly(NIPMAM-co-NIPAM), indicating that poly(APr-co-NIPAM) more efficiently made the liposome surface hydrophobic. Thus, we concluded that the copolymer with a large DeltaH is suitable for obtaining functional liposomes with a temperature-sensitive contents release property, whereas the copolymer with a small DeltaH is appropriate for preparing functional liposomes with a temperature-sensitive surface property.

Acrylamides↗

PubMed1991

Structure and interactions of ether- and ester-linked phosphatidylethanolamines.

The ether-linked phospholipid 1,2-dihexadecylphosphatidylethanolamine (DHPE) was studied as a function of hydration and in fully hydrated mixed phospholipid systems with its ester-linked analogue 1,2-dipalmitoylphosphatidylethanolamine (DPPE). A combination of differential scanning calorimetry (DSC) and X-ray diffraction was used to examine the phase behavior of these lipids. By DSC, from 0 to 10 wt % H2O, DHPE displayed a single reversible transition that decreased from 95.2 to 78.8 degrees C and which was shown by X-ray diffraction data to be a direct bilayer gel to inverted hexagonal conversion, L beta----HII. Above 15% H2O, two reversible transitions were observed which stabilized at 67.1 and 92.3 degrees C above 19% H2O. X-ray diffraction data of fully hydrated DHPE confirmed the lower temperature transition to be a bilayer gel to bilayer liquid-crystalline (L beta----L alpha) phase transition and the higher temperature transition to be a bilayer liquid-crystalline to inverted hexagonal (L alpha----HII) phase transition. The lamellar repeat distance of gel-state DHPE increased as a function of hydration to a limiting value of 62.5 A at 19% H2O (8.6 mol of water/mol of DHPE), which corresponds to the hydration at which the transition temperatures are seen to stabilize by DSC. Electron density profiles of DHPE, in addition to calculations of the lipid layer thickness, confirmed that DHPE in the gel state forms a noninterdigitated bilayer at all hydrations. Fully hydrated mixed phospholipid systems of DHPE and DPPE exhibited two reversible transitions by DSC.(ABSTRACT TRUNCATED AT 250 WORDS)

Drug Interactions↗

PubMed2002

RNA hairpin-folding kinetics.

Based on the complete ensemble of hairpin conformations, a statistical mechanical model that combines the eigenvalue solutions of the rate matrix and the free-energy landscapes has been able to predict the temperature-dependent folding rate, kinetic intermediates, and folding pathways for hairpin-forming RNA sequences. At temperatures higher than a "glass transition" temperature, T(g), the eigenvalues show a distinct time separation, and the rate-limiting step is a two-state single exponential process determined by the slowest eigenmode. At temperatures lower than T(g), no distinct time separation exists for the eigenvalues, hence multiple (slow) eigenmodes contribute to the rate-determining processes, and the folding involves the trapping and detrapping of kinetic intermediates. For a 21-nt sequence we studied, T(g) is lower than the transition temperature, T(m), for thermodynamic equilibrium folding. For T > T(m), starting from the native state, the chain undergoes a biphasic unfolding transition: a preequilibrated quasi-equilibrium macrostate is formed followed by a rate-limiting two-state transition from the macrostate to the unfolded state. For T(g) < T < T(m), the chain undergoes a two-state on-pathway folding transition, at which a nucleus is formed by the base stacks close to the loop region before a rapid assembly of the whole hairpin structure. For T < T(g), the multistate kinetics involve kinetic trapping, causing the roll-over behavior in the rate-temperature Arrhenius plot. The complex kinetic behaviors of RNA hairpins may be a paradigm for the folding kinetics of large RNAs.

Base Sequence↗

PubMed1987

The effect of factor Va on lipid dynamics in mixed phospholipid vesicles as detected by steady-state and time-resolved fluorescence depolarization of diphenylhexatriene.

We have monitored the thermotropic behavior of mixed dimyristoylglycerophosphoserine (Myr2GroPSer)/dimyristoylglycerophosphocholine (Myr2GroPCho) and Myr2GroPSer/dipalmitoylglycerophosphocholine (Pam2GroPCho) vesicles in the presence of blood-clotting factor Va, using 1,6-diphenyl-1,3, 5-hexatriene as a lipid probe. The Ca2+-independent interaction of factor Va with these vesicles caused a small increase (1-2 degrees C) in the phase transition temperature, regardless of whether Myr2GroPChe was the lower or higher-melting component of the mixed vesicles. The major effect of factor Va was to increase the polarization of diphenylhexatriene when the mixed vesicles were in the liquid crystalline phase. The protein did not change the anisotropy in the bilayer gel state. The increase in the polarization value above the transition temperature closely correlated with the amount of phospholipid-bound factor Va, as verified by a direct binding technique. In addition, we found that the affinity of factor Va for Myr2GroPSer/Myr2GroPCho and Myr2GroPSer/Pam2GroPCho greatly increased at temperatures above the transition temperatures. Time-dependent fluorescence anisotropy measurements of diphenylhexatriene embedded in vesicles in the liquid crystalline state give fluorescence decay curves which can best be fitted by two exponential functions with two rotational correlation times and a constant term. Vesicles composed of Myr2GroPSer exhibit more ordering than Myr2GroPCho vesicles. However, the order parameter of mixed vesicles composed of 40% Myr2GroPSer and 60% Myr2GroPCho (mol/mol) approached that of Myr2GroPCho. Factor Va dramatically increased the longer rotational correlation time of diphenylhexatriene embedded in mixed vesicles in the liquid crystalline state from 3.7 ns to about 17 ns. The second rank-order parameter increased only slightly, but the calculated steady-state anisotropy increased by twofold. These results indicate that the acidic phospholipid-dependent binding of factor Va to mixed vesicles has an ordering effect on the acyl chains of the acidic phospholipids in the outer layer, but leaves the bulk of the phospholipids, mainly phosphatidylcholine, unaltered. None of the factor-Va-induced alterations in the anisotropy parameters point to the occurrence of lateral phase separation.

Diphenylhexatriene↗

PubMed1996

Reversible thermal unfolding of ribonuclease T1 in reverse micelles.

The reverse micellar system formed by the negatively charged surfactant AOT and the organic solvent isooctane is used to solubilize the protein RNase T1. The physicochemical properties of the entrapped protein have been studied using intrinsic tryptophan fluorescence and far-and near-UV CD. These studies indicate a similar structure for the protein in reverse micelles and in pH 7.0 buffer. Thermal unfolding has been studied as a function of W0, the molar ratio of water to AOT, in the solution. Measuring the change in fluorescence intensity as a function of temperature, we observe a reversible transition for W0 in the range 5-12. Heating rate dependencies carried out on these transitions (0.6-3.0 degrees C/min) indicate that the transition temperature and the apparent van't Hoff enthalpy change depend on the scanning rate as well as on W0. The values of the transition temperature, T(m) and the enthalpy change, delta H degrees(un), extrapolated to an infinitely slow scanning rate, are analyzed considering the electrostatic interaction of the charged residues of the protein with the charges of the surfactant molecules forming reverse micelles, the variation of the size of the reverse micelles, and the relative rates of unfolding, refolding, and irreversible denaturation.

Calorimetry, Differential Scanning↗

PubMed1997

Enthalpy is a proper criterion for comparability of monolayer and bilayer studies: isobaric temperature scanning measurements on glycolipid monolayers.

The thermotropic behaviour of glycolipid monolayers has been studied by isobaric temperature scanning measurements to elucidate conditions under which monolayers exhibit thermodynamic and structural properties comparable to those observed in bilayers. A selection of synthetic, stereochemically pure, glyceroglycolipids with identical, ether-linked alkyl chains of 12, 14, or 16 CH2-groups has been investigated. The head groups of the glycolipids consisted of glucose, galactose, maltose, lactose or maltotriose moieties with beta-configuration of the glycosidic bond. These glycolipids were chosen to permit a quantitative characterization of three effects, (i) the role of the length of the aliphatic chains, (ii) the influence of the size of the head group, and (iii) the influence of the stereochemistry of the sugar moieties on the structure and stability of the monolayers. To probe the effects of stereochemical alterations in the glycerol moiety 2,3-O-ditetradecyl-1-O-beta-D-glucosyl-sn-glycerol (14-2,3-Glc) was compared with 1,2-O-ditetradecyl-3-O-beta-D-glucosyl-sn-glycerol (14-1,2-Glc). It has been shown that in general several features of bilayers can be obtained from monolayer studies with reasonable accuracy, provided the proper parameters are chosen. The monolayer is stabilized by elongation of the aliphatic chains of the lipids and destabilized when the monosaccharide read groups is replaced by a di-, or trisaccharide, in a similar manner as in the bilayer. The stabilizing effect that has been observed in bilayer studies, when galactose instead of glucose is introduced as head group, has also been established in the monolayer studies. This stabilizing effect is even retained in the lipids having disaccharide head groups. On the basis of these monolayer studies in connection with WAXS and SAXS measurements on multilamellar systems, we suggest that identity of transition enthalpies of the chain melting L beta-L alpha transition is an appropriate criterion for estimating molecular areas and area changes of bilayers from monolayer measurements and vice versa. However, estimates of transition temperatures are poor using the enthalpy criterion. If identity of transition temperature is introduced as criterion, glycolipid monolayers must be compressed to about 43 +/- 3 mN m-1. Under these conditions the agreement between the calculated enthalpies and structural properties of monolayers and multilayers is poor. As a general conclusion it can be emphasized that for monolayer and bilayer systems of glycolipids there exists no such parameter as a universal pressure or a universal temperature that automatically renders monolayer data identical to bilayer data. Depending on which property (transition temperatures, transition enthalpies, lateral areas and transitional area changes) one wants to extrapolate from monolayer to bilayer different lateral pressures have to be applied.

Calorimetry, Differential Scanning↗