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PubMed1998

Dehydration of Hydrated Bilayer of Dipalmitoylphosphatidylcholine Caused by Beryllium Ion: Evidence from a Differential Scanning Calorimetry of Bilayer Phase Transition.

The effect of polyvalent metal ions Be2+, Mg2+, Ca2+, Sr2+, Ba2+, and La3+ on the phase transition behavior of hydrated bilayer of dipalmitoylphosphatidylcholine (DPPC) was investigated by differential scanning calorimetry (DSC) in relation to their ability to induce the aggregation of DPPC vesicles. The addition of the metal ions other than Be2+ provided DSC thermograms characteristic to a fully hydrated DPPC bilayer. By the addition of Be2+, the endothermic peak associated with the bilayer phase transition was shifted to that corresponding to partially dehydrated DPPC bilayer, which was reported by Kodama et al. (Biochem. Biophys. Acta 689, 567, 1982). This demonstrates that Be2+ causes dehydration of DPPC head group in hydrated bilayer and supports the speculation that the unusual property of Be2+ to induce the aggregation of PC vesicles is attributed to the destruction of repulsive hydration force due to the partial dehydration of vesicular surface. Copyright 1998 Academic Press.

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PubMed2000

A Simple Experimental Way of Measuring the Hamaker Constant A(11) of Divided Solids by Immersion Calorimetry in Apolar Liquids.

Recent progress in interpretation of immersion calorimetry has shown the link between the immersion enthalpy (Delta(imm)H) value in apolar liquid and the Lifshitz-van der Waals contribution to surface energy (gamma(LW)(S)) of divided solids. In this work we show that a simple relationship can be established between the Hamaker constant (A(11)) of a solid and its immersion enthalpy in a pure apolar solvent. The results are satisfying compared to those already available in the scientific literature. The main interest of this method is the measurement of the Hamaker constants of solids for which contact angle measurements are impossible to carry out and for those for which the complexity of the solid structure hampers the ab initio calculation. Values are given for some clay minerals. Copyright 2000 Academic Press.

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PubMed2001

Evaluation of Surface Enthalpy of Porous Aluminosilicates of the MCM-41 Type Using Immersional Calorimetry: Effect of the Pore Size and Framework Si:Al Ratio.

Surface properties of porous aluminosilicates of the MCM-41 type have been tested by immersional calorimetry. Two series of materials, referred to as SiAlxCn, where x is the Si : Al mole ratio and n the chain length of the surfactant template, having (1) x=32 and n=8, 12, 14, 16, 18 and (2) n=14 and x=8, 32, infinity, were used. The results of thermogravimetric analysis on these samples served to evaluate the surface density of hydroxyl groups. This parameter is rather sensitive to the pore size than to the aluminium content in the solid matrix. Based on the experimentally measured enthalpies of immersion in n-heptane, water, and formamide per unit BET specific surface area, estimates could be made of the apolar, Lewis acid, and Lewis base contributions to the total surface enthalpy of MCM-41 materials. The samples studied have a predominant surface acidic character, which is markedly enhanced by incorporating aluminium into the silica matrix. Surface acidity is also modified by changes in the porous structure, although the trends are less noticeable here. Nevertheless, the total surface enthalpy of MCM-41 aluminosilicates appears to be small in comparison with typical inorganic oxides, such as silica or alumina. Copyright 2001 Academic Press.

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PubMed1996

Effects of an acute decrease in non-esterified fatty acid levels on muscle glucose utilization and forearm indirect calorimetry in lean NIDDM patients.

The aim of the study was to evaluate an acute decrease in NEFA levels during an oral glucose tolerance test and its effects on glucose tolerance, muscle glucose uptake and muscle indirect calorimetry in ten lean non-insulin-dependent diabetic subjects. Two 75-g oral glucose tolerance tests were performed in random order. Placebo or 250 mg acipimox (to inhibit lipolysis) were administered orally 2 h before the start of the oral glucose tolerance test. Two hours after acipimox administration (time 0), non-esterified fatty acid, glycerol and 3-hydroxybutyrate levels decreased by 84, 68 and 77% respectively, compared to basal levels. Concomitantly, muscle lipid oxidation and non-oxidative glycolysis also decreased significantly. After placebo administration, non-esterified fatty acids, glycerol and 3-hydroxybutyrate and lipid oxidation increased by 29, 28, 106 and 33%, respectively (NS vs basal levels; p < 0.001 vs acipimox). There was a negative rate of net glucose storage (interpreted as glycogenolysis) during post-absorptive conditions and at time 0 after administration of both drugs. After oral glucose tolerance test, the incremental areas of blood glucose and insulin were significantly decreased by 18 and 19% after acipimox compared to placebo. In addition, the ratio between the incremental area of forearm muscle glucose uptake and the insulin levels was significantly increased by 45% during acipimox compared to placebo administration. Glucose oxidation and non-oxidative glycolysis were significantly higher while lipid oxidation was significantly lower after acipimox than after placebo. In conclusion, our study found that in lean non-insulin-dependent diabetic subjects, an acute decrease in non-esterified fatty acid levels improves glucose tolerance, muscle glucose uptake, glucose oxidation and non-oxidative glycolysis, but is unable to normalize glucose storage.

3-Hydroxybutyric Acid↗
PubMed2006

Dielectric analysis and Differential Scanning Calorimetry of water-in-oil microemulsions.

The system investigated is a multicomponent thermodynamically stable liquid consisting of water spherical droplets, (approximately 10 nm diameter), stabilized by a surfactant shell and dispersed in a continuous oil phase (microemulsions). A comparative analysis is carried out among the results obtained with three different experimental approaches, namely, dielectric analysis, Thermally Stimulated Depolarization, and Differential Scanning Calorimetry. The different measurement procedures are briefly described. The attention was focused on the system water concentration. Two microemulsions, differing only in the oil used as continuous phase, were studied. For any concentration a comparison between the results obtained with the different experimental methods was undertaken. The evolution with water addition of the water/oil interphase region was analysed in some detail.

Journal Article↗
PubMed2006

A quantitative differentiation method for plastic bags by infrared spectroscopy, thickness measurement and differential scanning calorimetry for tracing the source of illegal drugs.

Fifty shopping bags, commonly encountered in the packaging of drug doses, were characterized by thickness measurements, infrared spectroscopy and differential scanning calorimetry. By these very straightforward and inexpensive techniques, without sample preparation, nearly all the considered samples could be discriminated. Ninety-seven percent of the possible pairs of white, apparently similar dull polymer films were differentiated. The rather large degree of variability existing in grocery bags, even though they are mass produced, was shown, confirming that these items can be useful in tracing the source of illicit drug doses.

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PubMed2006

Ion calorimetry: Using mass spectrometry to measure melting points.

Calorimetry measurements have been used to probe the melting of aluminum cluster cations with 63 to 83 atoms. Heat capacities were determined as a function of temperature (from 150 to 1050 K) for size-selected cluster ions using an approach based on multicollision-induced dissociation. The experimental method is described in detail and the assumptions are critically evaluated. Most of the aluminum clusters in the size range examined here show a distinct peak in their heat capacities that is attributed to a melting transition (the peak is due to the latent heat). The melting temperatures are below the bulk melting point and show enormous fluctuations as a function of cluster size. Some clusters (for example, n = 64, 68, and 69) do not show peaks in their heat capacities. This behavior is probably due to the clusters having a disordered solid-like phase, so that melting occurs without a latent heat.

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PubMed2005

Study of mass transfer in oil-water-oil multiple emulsions by differential scanning calorimetry.

A multiple emulsion of the type O1/W/O2 is studied experimentally by means of differential scanning calorimetry (DSC). The aim of this work is to characterize and measure the time-dependent changes within the emulsion. In particular, interest is focused to quantify the concentration changes in the internal and external phases of the O1/W/O2 multiple emulsion. In order to accomplish the objective, the measurement and analysis carried out by DSC are based on the crystallization behavior of the emulsion. A volume of a few mm3 is periodically removed from the O1/W/O2 multiple emulsion. The sample is submitted to steady cooling and the crystallization thermogram is recorded. The experimental data provided by the crystallization thermogram makes it possible to quantify the crystallized mass for both phases, the internal and the external. In addition, the composition in each phase can also be deduced from the thermogram. To deduce the composition, a diagram of crystallization temperatures is elaborated, employing several mixtures of known composition. In addition to the main objective previously mentioned, the influence of formulation parameters such as surfactant concentration in the aqueous phase and the mass ratio of the internal and external phases are also analyzed. The experimental results made it possible to conclude that a mass transfer took place from the internal phase toward the external phase; this transfer is caused by the composition difference on both sides of the aqueous membrane. In this work we analyzed the mass transfer in the multiple emulsion carried out by a composition gradient through the aqueous membrane. The most likely mechanism of mass transfer through the aqueous membrane is a solution-diffusion of tetradecane enhanced by the micelles of the surfactant Tween 20. The model of mass transfer confirms that the osmotic pressure difference controls the kinetics of tetradecane transfer. It is also confirmed that an increment of surfactant concentration in the aqueous phase allows a faster kinetics of the tetradecane transfer.

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PubMed2005

Energetics of arsenate sorption on amorphous aluminum hydroxides studied using flow adsorption calorimetry.

Flow adsorption calorimetry was used to investigate the energetics of arsenate sorption on amorphous aluminum hydroxide (AHO) and its effect on surface charge and ion exchange. Arsenate sorption at pH 5.7 was exothermic and the molar heats of adsorption were quite variable, ranging from -3.0 to -66 kJ/mol. Repetitive exposure of the same sample to arsenate in the calorimeter showed that the AHO was able to regenerate a considerable amount of reactive surface over time periods as short as 15 to 20 min. The large variability in heats of arsenate adsorption and the ability to regenerate reactive surface is believed to result from the amorphous nature of the AHO used. Heats of Cl/NO3 exchange were much smaller and more consistent, ranging from about 3.0 to 6.0 kJ/mol. The molar ratio of exchangeable Cl:Al was about 6:1 for the AHO, indicating a highly porous material. At pH 5.7, arsenate sorption neutralized surface positive charge as measured by Cl/NO3 exchange. Only at the two highest loadings (>60,000 mg/kg) did arsenate sorption result in any negative surface charge as measured by Na/K exchange. These results showed that most of the arsenate was adsorbed by a mechanism that involved no increase in surface negative charge. The PZNC of the AHO decreased by about 1 pH unit when exposed to arsenate in the flow calorimeter. Exposure to arsenate in a batch system decreased the PZNC about 4 pH units. This difference in behavior between batch and flow systems was related to differences in the amount of arsenate adsorbed.

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PubMed2006

Measurement of cation binding to immobilized vanillin by isothermal calorimetry.

Isothermal calorimetry was used to determine enthalpy changes for interaction of divalent cobalt, nickel, copper, and zinc chlorides with silica gel functionalized with vanillin, Sil-Van. The thermal effect, Q(int), and the corresponding amount of cation that interacts, n(int), were obtained in the same experiment. Langmuir expressions for adsorption isotherms were applied to determine the maximum adsorption capacity to form a monolayer, N(mon), and the energy of interaction for a saturated monolayer per gram of Sil-Van, Q(mon). From knowledge of N(mon) and Q(mon), the molar enthalpy of interaction for formation of a monolayer of anchored cations per gram of Sil-Van, Delta(mon)H(m), was determined. Interactions between the Lewis-acidic cations and the donor atom attached to silica are reflected by Delta(mon)Hm values in the order Ni2+ > Cu2+ > Zn2+ congruent with Co2+.

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PubMed2006

Phase behavior of binary mixture of 1-dodecyl-3-methylimidazolium bromide and water revealed by differential scanning calorimetry and polarized optical microscopy.

Phase behavior of aqueous mixture of imidazolium ionic liquid, 1-dodecyl-3-methylimidazolium bromide, was investigated by means of differential scanning calorimetry and polarized optical microscopy. The mixture forms two types of lyotropic liquid-crystalline gels, one is composed of lamellar phase and the other is of hexagonal phase. T-X phase diagram of the mixture was constructed, which defines the regions of various phases appearing in this mixture.

Journal Article↗
PubMed1999

Differential scanning calorimetry: applications in drug development.

Differential scanning calorimetry (DSC) is frequently the pharmaceutical thermal analysis technique of choice because of its ability to provide detailed information about both the physical and energetic properties of a substance. This review provides an up-to-date overview of the applications of DSC in the drug development process. It should serve as a broad introduction to those starting work in this area, and also as a valuable reference for those already practising in this field.

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PubMed2006

Pressure-modulated differential scanning calorimetry. An approach to the continuous, simultaneous determination of heat capacities and expansion coefficients.

A new method is described that permits the continuous and synchronous determination of heat capacity and expansibility data. We refer to it as pressure-modulated differential scanning calorimetry (PMDSC), as it involves a standard DSC temperature scan and superimposes on it a pressure modulation of preselected format. The power of the method is demonstrated using salt solutions for which the most accurate heat capacity and expansibility data exist in the literature. As the PMDSC measurements could reproduce the parameters with high accuracy and precision, we applied the method also to an aqueous suspension of multilamellar DSPC vesicles for which no expansibility data had been reported previously for the transition region. Excellent agreement was obtained between data from PMDSC and values from independent direct differential scanning densimetry measurements. The basic theoretical background of the method when using sawtooth-like pressure ramps is given under Supporting Information, and a complete statistical thermodynamic derivation of the general equations is presented in the accompanying paper.

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PubMed2001

Photoacoustic calorimetry and quantum yields of Mo(CO)(6) ligand exchange in linear alkanes: determination of volume of reaction, energetics, and kinetics of nucleophile displacement of alkane from Mo(CO)(5)(alkane).

Photoacoustic calorimetry (PAC) and actinometry studies were used to determine the enthalpies and volumes of reaction for the production of a transient intermediate, Mo(CO)(5)-alkane, and for its subsequent reaction with tetrahydrofuran (THF). Both the enthalpy and the volume of reaction contribute to the photoacoustic signal and have been resolved by changing the solvent thermal expansion properties with a series of linear alkanes. The enthalpies for substitution of CO on Mo(CO)(6) by an alkane and of coordinated alkane on Mo(CO)(5)(alkane) by THF are 30 and -14 kcal/mol, respectively. Likewise, the volumes of reaction are 18 and -1 mL/mol. From available data for the Mo--CO bond energy, these results allow the calculation of the Mo-alkane and Mo-THF bond energies (11 and 25 kcal/mol, respectively). The Mo-alkane result is 7 kcal/mol less than that from our previous PAC study, which ignored the volume of reaction, and is in better agreement with the results of kinetic studies. The large absolute difference in the reaction volumes for each step is partially attributed to a void volume created during the formation of the Mo--THF bond. In general, the volume of reaction cannot be neglected in the calculation of enthalpies of ligand substitution from PAC studies. The quantum yields for photosubstitution of Mo(CO)(6), in contrast to Cr(CO)(6), were found to be insensitive to the chain length of the alkane solvent.

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PubMed2003

Calorimetry of polymer metallization: copper, calcium, and chromium on PMDA-ODA polyimide.

The heat of reaction has been measured for vapor deposition of metal atoms onto clean polymeric substrates. These calorimetric measurements introduce a new technique for the study of metal-polymer interfacial chemistry. Results for three systems are reported here, calcium, chromium, and copper on PMDA-ODA polyimide, and widely different reaction heats are observed in each case. Our results show that calcium deposition is very exothermic at low coverages, with an initial heat approaching 610 kJ/mol. In the case of chromium deposition, the initial heat is quite low, 125 kJ/mol or less, an affect we attribute to the energetic cost of polymer bond disruption. The data for copper deposition show that calorimetry can be used to study fine details of the nucleation and growth process of the metal island film.

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PubMed2005

Influence of reduction conditions on H2 adsorption in high-surface Rh/CeO2 catalysts as deduced by volumetry, calorimetry, and 1H NMR techniques.

1H NMR spectra corresponding to H2 adsorption on high-surface Rh/CeO2 catalysts (S(BET) approximately 55 m2/g) are formed by two lines, attributed to hydrogen adsorbed on ceria (resonance line A) and rhodium-metal particles (upfield-shifted line B). The evolution of 1H NMR spectra as a function of temperature, time, and type of reduction (static or dynamic) allows the study of the progressive establishment of the strong metal-support interaction (SMSI) in Rh/CeO2 catalysts. As the reduction progresses, the mean adsorption heat and the amount of hydrogen adsorbed on the metal, deduced from volumetry, NMR, and calorimetry techniques, decrease considerably. As a consequence of the decrease in metal activity, the amount of hydrogen transferred to the support CeO2 is also reduced (spill-over processes). Outgassing of samples at 773 K eliminates hydrogen species retained at the metal-support surface, and oxidation treatments at 473 and 673 K eliminate the electronic effect and physical blocking of metal particles. The oxidation at 673 K recuperates the total adsorption capacity of metal particles. On the basis of these treatments, the contribution of different processes to the SMSI effect is analyzed. Electronic perturbation of rhodium particles is higher when reductions are performed in dynamic conditions; however, the importance of physical blocking of metal particles increases in static reductions. High reducibility of ceria strengthens electronic effects in Rh/CeO2 compared to those observed in Rh/TiO2 catalysts.

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PubMed2005

Optimizing experimental parameters in isothermal titration calorimetry.

In isothermal titration calorimetry, the statistical precisions with which the equilibrium constant (K) and reaction enthalpy (DeltaH degrees ) can be estimated from data for 1:1 binding depend on a number of quantities, key among them being the products c identical with K[M](0) and h identical with DeltaH degrees [M](0), the stoichiometry range (R(m)(), ratio of total titrant X to total titrate M after the last injection), and the number of injections of titrant. A study of the statistical errors as functions of these quantities leads to the following prescription for optimizing throughput and precision: (1) Make 10 injections of titrant. (2) Set the concentrations in accord with the empirical equation R(m)() = 6.4/c(0.2) + 13/c (but no smaller than 1.1). (3) Make the starting concentration [M](0) as large as possible within the large-signal limits of the instrumentation but limited to c < 10(3) for estimating K. With this procedure, both K and [M](0) are predicted to have relative standard errors <1% over large ranges of K. Systematic errors in the concentrations, [X](0) and [M](0), are fully compensated by the "site number" or stoichiometry parameter (n). On the other hand, altering and freezing any of the fit parameters leads to a deterioration of the fit quality and to predictable changes in the other parameters. Fit divergence at very small c is avoidable through a simple redefinition of the fit parameters; however, unless n can be fixed from other information, DeltaH degrees may be statistically ill-defined in this region.

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PubMed2006

A combined pressure-controlled scanning calorimetry and Monte Carlo determination of the Joule-Thomson inversion curve. Application to methane.

A combination of a pressure-controlled scanning calorimetry (PCSC) and Monte Carlo simulations (MCS) is presented for an unequivocal determination of the Joule-Thomson inversion curve (JTIC) with high accuracy over wide ranges of pressure and temperature. The MCS performed with the fluctuation method are fast and easy to operate, but the results can vary significantly depend on the set of primary molecular data needed for the calculations. The PCSC is an experimental and more laborious technique, but supplies data of high quality. Thus, it can be used to check the MCS data and to verify the molecular parameters used for the calculations. Such a combined procedure was used in the present study for determination of the JTIC for methane, for which a correlation equation was established valid from 302.9 to 586.5 K. A combination of a direct experimental technique with molecular simulations permits also to better understand the complex behavior of the Joule-Thomson inversion phenomenon over wide ranges of pressure and temperature.

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