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PubMed2004

Calorimetry by immersion into liquid nitrogen and liquid argon: a better way to determine the internal surface area of micropores.

The aim of this work is to assess the internal surface area of a set of samples (either carbons or oxides, either porous or nonporous, either microporous or mesoporous) by microcalorimetry via immersion into liquid nitrogen or argon. We have made use of an isothermal, heat-flux microcalorimeter, initially designed and built in our laboratory for the sake of gas adsorption experiments at 77 or 87 K. It seems that immersion calorimetry into liquid nitrogen and argon makes it possible to go one step further in the determination of the internal surface area of micropores.

Argon↗
PubMed2005

Isothermal titration calorimetry and dynamic light scattering studies of interactions between gemini surfactants of different structure and Pluronic block copolymers.

The interactions between triblock copolymers of poly(ethylene oxide) and poly(propylene oxide), P103 and F108, EO(n)PO(m)EO(n), m=56 and n=17 and 132, respectively, and m-s-m type gemini surfactants, m=8, 10, 12, and 18, and s = 3, 6, 12, and 16, have been studied in aqueous solution using isothermal titration calorimetry and dynamic light scattering techniques. The enthalpograms of F108 as a function of surfactant concentration show one broad peak at polymer concentrations C(p) < or = 0.50 wt%, below the cmc of the copolymer at 25 degrees C. It is attributed to interactions between the surfactant and the triblock copolymer monomer. DLS results show hydrodynamic radii (R(h)) initially consistent with copolymer monomers that change to values consistent with gemini surfactant micelles as the surfactant concentration is increased. In P103 solutions at C(p) > or = 0.05 wt%, two peaks appear in the enthalpograms, and they are attributed to the interactions between the gemini surfactant and the micelle or monomer forms of the copolymer. An origin-based nonlinear fitting program was employed to deconvolute the two peaks and to obtain estimates of peak properties. An estimate of the fraction of copolymer in aggregated form was also obtained. The enthalpy change due to interactions between the surfactants and P103 aggregates is very large compared to values obtained for traditional surfactants. This suggests that extensive reorganization of copolymer aggregates and surrounding solvent occurs during the interaction. DLS results for the P103 systems containing C(p) > or = 0.05% show evidence of very large aggregates in solution, likely P103 micelle clusters. The transitions observed in the hydrodynamic radii are consistent with a breakdown of micelle clusters with addition of gemini surfactant, followed by mixed micelle formation and/or deaggregation into monomer P103. This is followed by interactions similar to those typically observed in surfactant-nonionic polymer systems. Mechanisms for the interaction and the observed structural changes are discussed.

Biophysics↗
PubMed2005

Interaction of Ag(I), Hg(II), and Cu(II) with 1,2-ethanedithiol immobilized on chitosan: thermochemical data from isothermal calorimetry.

The nature of interactions between metal ions Ag(I), Hg(II), Cu(II) and chitosan derivative of 1,2-ethanedithiol, QTDT, was investigated by isothermal calorimetry using the membrane breaking technique. Simultaneous determination of thermal effects, Q(int), and amount of cation that interacts, n(int), are described. The experimental data have been interpreted in terms of the Langmuir equation to determine the maximum adsorption capacity to form a monolayer, N(mon), and the energy of interaction for a saturated monolayer per gram of QTDT, Q(mon). With N(mon) and Q(mon), the molar enthalpy of interaction for formation of a monolayer of anchored cations per gram of QTDT, Delta(mon)H(m), was determined. The Delta(mon)H(m) values for Ag(I), Hg(II), and Cu(II) were -60.56, -58.05, and -84.36 kJ mol(-1), respectively. Negative values of DeltaG show the spontaneity of the interaction processes. The least entropically favourable processes, i.e., those which present more negative DeltaS values, seem to be compensated by the more favourable enthalpic parameter.

Calorimetry↗
PubMed2005

Prediction of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements.

We present a prediction (estimation, calculation, screening) method for the estimation of the self-accelerating decomposition temperature (SADT) for liquid organic peroxides from differential scanning calorimetry (DSC) measurements based on the concepts of thermal explosion theory originally introduced by Semonov which are adopted to our problem assuming nth-order reaction kinetics. For the peroxides under investigation, we demonstrate good agreement with the experimental SADT. This method can be used as a quick and easy applicable method for the estimation of the critical temperatures.

Calorimetry, Differential Scanning↗
PubMed2006

Isothermal calorimetry: impact of measurements error on heat of reaction and kinetic calculations.

Heat flow and power compensation calorimetry measures the power generation of a reaction via an energy balance over an appropriately designed isothermal reactor. However, the measurement of the power generated by a reaction is a relative measurement, and calibrations are used to eliminate the contribution of a number of unknown factors. In this work the effect of the error in the measurement of temperature of electric power used in the calibrations and the heat transfer coefficient and baseline is assessed. It has been shown that the error in all aforementioned quantities reflects on the baseline and it can have a very serious impact on the accuracy of the measurement. The influence of the fluctuation of ambient temperature has been evaluated and a means of a correction that reduces its impact has been implemented. The temperature of dosed material is affected by the heat loses if reaction is performed at high temperature and low dosing rate. An experimental methodology is presented that can provide means of assessment of the actual temperature of the dosed material. Depending on the reacting system, the heat of evaporation could be included in the baseline, especially if non-condensable gases are produced during the course of the reaction.

Algorithms↗
PubMed2006

31P NMR and isothermal titration calorimetry studies on polyoxomolybdates-catalyzed hydrolysis of ATP.

ATP hydrolysis in the presence of polyoxomolybdates at pH levels of 6, 4, and 2 has been investigated with a help of high pressure liquid chromatography (HPLC) analyses, 31P- and 1H NMR measurements, and isothermal titration calorimetry (ITC). The polyoxomolybdates-induced ATP-hydrolysis proceeded satisfactorily in pH < 6 media at 20 degrees C with an optimum pH level of 4, while it was significantly depressed at low temperature of < or = 5 degrees C. At pH levels of 6 and 4, ADP was a main product, and the involvement of [(PO4)2Mo5O15](6-)-like ATP-molybdate complex as an intermediate was implied. At pH 2 ATP was decomposed to AMP with small generation of ADP through the formation of the ATP-molybdate complex isostructural with [(O3POPO3)Mo6O18(H2O)4]4- as an intermediate. The ITC result at pH 4 showed an occurrence of two types of the exothermic binding reactions between molybdate and ATP with binding constants (K) of 6.61x10(4) and 9.40x10(3) M(-1) and molar enthalpy values (deltaH) of -6.32x10(4) and -4.73x10(3) J mol(-1), respectively. Together with the results of 1H NMR measurements, it is deduced that the molybdates interact with not only phosphate sites in the ATP side-chain, but also adenine-ring with an accompanying aggregation of molybdates at pH 4.

Adenosine Triphosphate↗
PubMed2005

Optimization of glibenclamide tablet composition through the combined use of differential scanning calorimetry and D-optimal mixture experimental design.

A systematic analysis of the influence of different proportions of excipients on the stability of a solid dosage form was carried out. In particular, a d-optimal mixture experimental design was applied for the evaluation of glibenclamide compatibility in tablet formulations, consisting of four classic excipients (natrosol as binding agent, stearic acid as lubricant, sorbitol as diluent and cross-linked polyvinylpyrrolidone as disintegrant). The goal was to find the mixture component proportions which correspond to the optimal drug melting parameters, i.e. its maximum stability, using differential scanning calorimetry (DSC) to quickly obtain information about possible interactions among the formulation components. The absolute value of the difference between the melting peak temperature of pure drug endotherm and that in each analysed mixture and the absolute value of the difference between the enthalpy of the pure glibenclamide melting peak and that of its melting peak in the different analyzed mixtures, were chosen as indexes of the drug-excipient interaction degree.

Calorimetry, Differential Scanning↗
PubMed2006

Isothermal titration calorimetry study of epicatechin binding to serum albumin.

The interaction of epicatechin with bovine serum albumin (BSA) was studied by isothermal titration calorimetry. The binding constant (K) and associated thermodynamic binding parameters (n, DeltaH) were determined for the interaction at three solution concentrations of BSA using a binding model assuming independent binding sites. These data show weak non-covalent binding of epicatechin to BSA. The interaction energetics varied with BSA concentration in the calorimeter cell, suggesting that the binding of epicatechin induced BSA aggregation. The free energy (DeltaG) remained constant within a range of 2 kJ mol(-1) and negative entropy was observed, indicating an enthalpy driven exothermic interaction. It is concluded that the non-covalent epicatechin-BSA complex is formed by hydrogen bonding.

Algorithms↗
PubMed2006

Differential scanning calorimetry as a screening technique in compatibility studies of DHEA extended release formulations.

Differential scanning calorimetry (DSC) was used as a screening technique for assessing the compatibility of DHEA as ternary complex with alpha-cyclodextrin and glycine (c-DHEA) with some excipients suitable for preparation of sustained-release matrix tablets by direct compression. The effect of sample mechanical treatment due to the compression process was also evaluated. In order to investigate the possible interactions between the components, the DSC curves of c-DHEA and each selected excipient were compared with those of their 1:1 w/w physical mixtures, before and after compression, in order to evaluate any possible solid state modification. FT-IR spectroscopy and X-ray powder diffractometry were used as complementary techniques to adequately implement and assist in interpretation of the DSC results. On the basis of DSC results, c-DHEA was found to be compatible with xanthan gum, hydroxypropylmethylcellulose, sodium starch glycolate (Explotab), polyvinylacetate-polyvinylpirrolidone (Kollidon SR) and sodium chloride. Some drug-excipient interaction was observed with dextrate hydrate (Emdex), mannitol and Magnesium stearate. Finally, the behaviour of the complete formulation, in the presence of all the excipients selected by means of the compatibility study, was investigated, in order to verify the absence of reciprocal interactions among the components.

Calorimetry, Differential Scanning↗
PubMedDate not supplied

Prospective study of resting energy expenditure changes in head and neck cancer patients treated with chemoradiotherapy measured by indirect calorimetry.

OBJECTIVE: The prevalence of malnutrition is high in patients with head and neck cancer due to tumor location and coadjuvant treatment. We studied changes in resting energy expenditure (REE) during treatment with chemoradiotherapy and compared the measured REE by indirect calorimetry (IC) with the value estimated by the Harris-Benedict (HB) formula. METHODS: Eighteen patients with head and neck cancer (15 men and 3 women, mean age 57 +/- 10.7 y, age range 30-71 y) entered the study. All patients were treated with radiotherapy (70.8 +/- 1 Gy, range 70-72) and received 37.4 +/- 3.5 fractions (range 32-42) and concurrent chemotherapy with cisplatinum (absolute doses of 400 to 1000 mg). Nutrition assessment included anthropometry (body mass index, triceps skinfold thickness, subscapular skinfold thickness, midarm circumference, and midarm muscle circumference) and tetrapolar bioimpedance (Holtain BC). The IC (kcal/24 h; Deltatrac II MBM-200) was performed after an overnight fast. Measurements were done before treatment, at weeks 2, 4, and 6 of treatment, at the end of treatment, and 2 wk after treatment. RESULTS: Body mass index decreased during treatment from 24.7 +/- 4.4 kg/m(2) (range 16.9-31.4) to 22.3 +/- 4.2 kg/m(2) (range 15.1-29.6). REE (kcal/24 h) changed significantly during treatment (IC P < 0.05, HB formula P < 0.001). REE measured by IC appeared as a U-shaped curve, but REE estimated by the HB formula decreased during treatment. The HB underestimated REE measurements compared with IC. These differences were statistically significant before treatment, at the end of treatment, and 2 wk after treatment (P < 0.05) and showed a limited clinical agreement with the Bland-Altman method. CONCLUSIONS: REE measured by IC significantly changed during chemoradiotherapy. It was higher before treatment, at the end of treatment, and 2 wk after treatment. The HB formula underestimated REE in these patients. IC is a suitable method for measuring REE in this cohort of patients.

Adult↗
PubMed2006

Indirect calorimetry: relevance to patient outcome.

Indirect calorimetry provides an important adjunctive monitor for the provision of nutrition support in the critically ill patient. Accuracy in determining caloric requirements may serve to optimize benefit from nutrition therapy and improve patient outcome. A number of strategies in nutrition management in the intensive care setting (eg, dosing of enteral nutrition, monitoring cumulative caloric balance, and deliberate but "permissive" underfeeding) necessitate the determination of a fairly specific goal for caloric provision. Inaccuracy leading to inappropriate under- or overfeeding may generate additional morbidity and adverse clinical consequences for patients already at high risk from hypermetabolic stress response to injury.

Calorimetry, Indirect↗
PubMed2004

Measurement of protein stability and protein denaturation in cells using differential scanning calorimetry.

Many methods exist for measuring and studying protein denaturation in vitro. However, measuring protein denaturation in cells under conditions relevant to heat shock presents problems due to cellular complexity and high levels of light scattering that interfere with optical techniques. A general method for measuring protein denaturation in cells using high sensitivity differential scanning calorimetry (DSC) is given. Profiles of specific heat (c(p) vs. temperature) are obtained providing information about transitions in cellular components including the denaturation of proteins. The specific approaches employed with erythrocytes, bacteria, and mammalian cells are described, and an identification of several features of the DSC profiles is given. Protein denaturation on the level of roughly 7-20% occurs for commonly used heat shocks in mammalian cells.

Animals↗
PubMed2005

The activity of wild-type and mutant phenylalanine hydroxylase and its regulation by phenylalanine and tetrahydrobiopterin at physiological and pathological concentrations: an isothermal titration calorimetry study.

The activity of phenylalanine hydroxylase (PAH) is regulated by the levels of both the substrate (L-Phe) and the natural cofactor (6R)-tetrahydrobiopterin (BH4). It has recently been observed that many PAH mutants associated with BH4-responsive phenylketonuria display abnormal kinetic and regulatory properties as shown by standard kinetic analyses. In this work, we have developed a high-sensitive and high-throughput activity assay based on isothermal titration calorimetry (ITC) in order to study the kinetic properties of wild-type PAH (wt-PAH) and the BH4-responsive c.204A>T (p.R68S) mutant at physiological and superphysiological concentrations of L-Phe and BH4. Compared to wt-PAH, the p.R68S mutant showed reduced apparent and equilibrium binding affinity for the natural cofactor and increased affinity and non-cooperative response for L-Phe, together with a strong substrate inhibition that is alleviated at high BH4 concentrations. For both wt-PAH and mutant, the apparent affinity for BH4 decreases at increasing L-Phe concentrations, and the affinity for the substrate also depends on the cofactor concentration. Our results indicate that the activity landscape for wt and mutant enzymes is more complex than expected from standard kinetic analyses and highlight the applicability of this ITC-based assay to characterize the activity and regulation of PAH at a wide range of substrate and cofactor concentrations. Moreover, the results aid to understand the activity dynamics of wild-type and mutant PAH under physiological and pathological conditions, as well as BH4-responsiveness in certain PKU mutations.

Animals↗
PubMed2003

Estimation of parvalbumin Ca(2+)- and Mg(2+)-binding constants by global least-squares analysis of isothermal titration calorimetry data.

The use of competitive isothermal titration calorimetry (ITC) to measure high-affinity binding constants has been largely restricted to systems with a single binding site or multiple identical sites. This study demonstrates the extension of this approach to proteins with two nonequivalent EF-hand Ca(2+)-binding sites--rat beta parvalbumin and the S55D/E59D variant of rat alpha parvalbumin. The method involves simultaneous (global) least-squares analysis of titrations with Ca(2+), with Mg(2+), with Ca(2+) in the presence of Mg(2+), and with Ca(2+) or Mg(2+) in the presence of a competitive chelator (EDTA or EGTA). The Ca(2+) and Mg(2+) binding constants obtained for rat beta agree well with estimates obtained by flow dialysis. Although the Ca(2+) affinity of alpha S55D/E59D is too high to measure by flow dialysis, it was amenable to analysis using the ITC-based approach. The combined S55D and E59D mutations increase the Ca(2+) and Mg(2+) affinities of the mutated binding site by factors of 14 and 26, respectively. This behavior is consistent with that seen previously for the rat beta S55D variant.

Amino Acid Substitution↗
PubMed2003

A study of statistical error in isothermal titration calorimetry.

In isothermal titration calorimetry (ITC), the two main sources of random (statistical) error are associated with the extraction of the heat q from the measured temperature changes and with the delivery of metered volumes of titrant. The former leads to uncertainty that is approximately constant and the latter to uncertainty that is proportional to q. The role of these errors in the analysis of ITC data by nonlinear least squares is examined for the case of 1:1 binding, M+X right arrow over left arrow MX. The standard errors in the key parameters-the equilibrium constant Ko and the enthalpy DeltaHo-are assessed from the variance-covariance matrix computed for exactly fitting data. Monte Carlo calculations confirm that these "exact" estimates will normally suffice and show further that neglect of weights in the nonlinear fitting can result in significant loss of efficiency. The effects of the titrant volume error are strongly dependent on assumptions about the nature of this error: If it is random in the integral volume instead of the differential volume, correlated least-squares is required for proper analysis, and the parameter standard errors decrease with increasing number of titration steps rather than increase.

Calorimetry↗
PubMed2000

Chlorpromazine interaction with glycerophospholipid liposomes studied by magic angle spinning solid state (13)C-NMR and differential scanning calorimetry.

Phosphatidylserine (PS) extracted from pig brain and synthetic dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) were used to make DPPC/DMPC and DPPC/PS large unilamellar liposomes with a diameter of approximately 1 microm. Chlorpromazine-HCl (CPZ), an amphipathic cationic psychotropic drug of the phenothiazine group, is known to partition into lipid bilayer membranes of liposomes with partition coefficients depending on the acyl chain length and to alter the bilayer structure in a manner depending on the phospholipid headgroups. The effects of adding CPZ to these membranes were studied by differential scanning calorimetry and proton cross polarization solid state magic angle spinning (13)C-nuclear magnetic resonance spectroscopy (CP-MAS-(13)C-NMR). CP-MAS-(13)C-NMR spectra of the DPPC (60%)/DMPC (40%) and the DPPC (54%)/DMPC (36%)/CPZ (10%) liposomes, show that CPZ has low or no interaction with the phospholipids of this neutral and densely packed bilayer. Conversely, the DPPC (54%)/PS (36%)/CPZ (10%) bilayer at 25 degrees C demonstrates interaction of CPZ with the phospholipid headgroups (PS). This CPZ interaction causes about 30% of the acyl chains to enter the gauche conformation with low or no CPZ interdigitation among the acyl chains at this temperature (25 degrees C). The DPPC (54%)/PS (36%)/CPZ (10%) bilayer at a sample temperature of 37 degrees C (T(C)=31.2 degrees C), shows CPZ interdigitation among the phospholipids as deduced from the finding that approximately 30% of the phospholipid acyl chains carbon resonances shift low-field by 5-15 ppm.

Calorimetry, Differential Scanning↗
PubMed2000

Fourier transform infrared spectroscopy and differential scanning calorimetry studies of fatty acid homogeneous ceramide 2.

Ceramides provide a major component of the barrier function of skin. An understanding of barrier organization requires a detailed characterization of ceramide phase behavior and molecular interactions. Toward this end, Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC) studies of ceramide 2 analogues (non-hydroxylated fatty acid N-acyl sphingosines) of specific chain lengths (C(14), C(16), C(18), C(20)) are presented. In addition, the molecular interactions of the individual chains in each molecule are elucidated through thermotropic FTIR studies of derivatives possessing perdeuterated fatty acid chains. DSC data showed a much smaller chain length variation (for the C(16), C(18), C(20) derivatives) in the main order-disorder transition temperature (approx. 93+/-1 degrees C) than is observed in the corresponding series of phosphatidylcholines, consistent with minimal ceramide hydration. The temperature dependence of the methylene stretching and scissoring modes revealed a solid-solid phase transition at 20-25 degrees C below the main order-disorder transition accompanied by chain packing alterations from orthorhombic-->hexagonal subcells. The chain packing transition was accompanied by enhanced penetration of water into the polar region. This was deduced from the temperature dependence of the amide I and II modes, which provide direct evidence for H-->D exchange. The CD(2) scissoring mode splitting of the deuterated fatty acid constituent of the C(16), C(18), C(20) chains revealed preferential segregation of microdomains (3-5 chains) of this species within the orthorhombic phase. In contrast, the sphingosine base chains appeared to be sufficiently separated so as to inhibit interchain vibrational coupling between them. FTIR spectroscopy provides a convenient means for characterizing domain formation, chain packing, and hydration sites of these phases, which are highly ordered under physiological conditions.

Calorimetry, Differential Scanning↗
PubMed2001

Differential scanning calorimetry and (2)H nuclear magnetic resonance and Fourier transform infrared spectroscopy studies of the effects of transmembrane alpha-helical peptides on the organization of phosphatidylcholine bilayers.

We have studied the effects of the incorporation of the alpha-helical transmembrane peptides Ac-K(2)-L(24)-K(2)-amide (L(24)) and Ac-K(2)-(L-A)(12)-K(2)-amide ((LA)(12)) on the thermotropic phase behavior of 1,2-dipalmitoyl-d(62)-sn-glycero-3-phosphocholine (DPPC-d(62)) and 1-palmitoyl-d(31)-2-oleoyl-sn-glycero-3-phosphocholine (POPC-d(31)) lipid bilayer model membranes by differential scanning calorimetry (DSC) and the conformational and orientational order of the phospholipid chains by Fourier transform infrared (FTIR) spectroscopy and (2)H nuclear magnetic resonance ((2)H-NMR) spectroscopy, respectively. Our DSC and FTIR spectroscopic studies indicate that the peptides L(24) and (LA)(12) both decrease the temperature and enthalpy of the gel/liquid-crystalline phase transition of DPPC-d(62) bilayers, with (LA)(12) having the greater effect in this regard. An examination of the frequencies of the CH(2) and CD(2) symmetric stretching bands of the infrared spectra of liquid-crystalline states of the peptide-free and peptide-containing DPPC-d(62) and POPC-d(31) samples, and a comparison with the orientational order as measured by (2)H-NMR spectroscopy as well as with the chain order as measured by electron spin resonance spectroscopy, lead us to conclude that the CH(2) (or CD(2)) stretching frequencies of lipid hydrocarbon chains are not a reliable measure of chain conformational order in lipid bilayers containing significant amounts of peptides or other lipophilic inclusions. In contrast, the results of our (2)H-NMR spectroscopic studies present a consistent picture in which both L(24) and (LA)(12) increased in a similar way the time-averaged orientational order of the lipid chains of their liquid-crystalline lipid bilayer hosts. The comparison of the effects L(24) and (LA)(12) on phosphatidylcholine bilayers indicates that the gel-to-liquid-crystalline phase transition appears to be more sensitive to small changes in transmembrane peptide surface topology than hydrocarbon carbon chain orientational order in the liquid-crystalline state.

Calorimetry, Differential Scanning↗