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Yeast cytochrome c peroxidase (CcP) and horse metmyoglobin (Mb) bind HN3 with similar affinities at 25 degrees C. The pH-independent equilibrium association constants for formation of the CcP.HN3 and Mb.HN3 complexes are (1.05 +/- 0.06)x10(5) and (1.6 +/- 0.8)x10(5) M(-1), respectively. However, the thermodynamic parameters for formation of the two complexes are quite different. The DeltaH0 values for formation of CcP.HN3 and Mb.HN3 are -16.4 +/- 0.7 and -9.0 +/- 0.5 kcal/mol, respectively, and the Delta S0 values are -32 +/- 2 and -16 +/- 2 cal/deg mol, respectively. The proton associated with HN3 is retained in both protein complexes at low pH but dissociates with apparent pKA values of 5.5 +/- 0.2 and > or =8.2 for the Mb.HN3 and CcP.HN3 complexes, respectively. CcP and Mb differ significantly in their reactivity toward the azide anion, N3-. CcP binds N3- very weakly, if at all, and only an upper-limit of 18 +/-5 M(-1) for the pH-independent equilibrium association constant for the CcP.N3- complex can be determined. Mb binds N3- with an association constant of (1.8 +/- 0.1)x10(4) M(-1). The ratio of the equilibrium association constants for HN3 and N3- binding provides a discrimination factor between the neutral and charged forms of the ligand. The discrimination factor is greater than 5800 for CcP but only nine for Mb. Protonation of the distal histidines in the two proteins influences binding of HN3. Protonation of His-64 in Mb enhances HN3 binding due to a gating mechanism while protonation of His-52 in CcP decreases the affinity for HN3 due to loss of base-assisted association of the ligand to the heme iron.
Concentration dependence of NaCl salting of 0-1.5 mM lysozyme solution in 0.1 M sodium acetate buffer, pH 4.25, was investigated for NaCl concentration varying up to 0.9 M. Calorimetric experiments demonstrated that depending on the salt concentration the estimated number of the binding sites on the lysozyme surface varied in the range of 5 up to 13, and the increase of salt concentration caused the decrease of the number of accessible sites. The small, but significant, local maximum centered at 0.63 M NaCl concentration indicated the specific salting-out of the lysozyme accompanied by binding of approximately 2-3 chloride anions. Generalized McMillan and Mayer's approach reduced to the third-order virial coefficients demonstrates the domination of lysozyme aggregation upon salt addition (a(21)-h(xxy)) and salt organization on the lysozyme surface (a(12)-h(xyy)) processes.
We report an extension of the recently published PMDSC method that permitted synchronous determination of heat capacity and expansibility when using slow, defined pressure formats in a DSC scan. Here we applied continuously opposing pressure changes that are fast compared to the time constants of the DSC instrument to study relaxation kinetics of phospholipids. Investigations of multilamellar vesicles of DPPC or DSPC in water revealed for both lipids relaxation times of about 30 s at the maximum of the main transition peak and about 15 s at the maximum of the pretransition. The relaxation times in the transition range are proportional to heat capacity of main- and pretransition. The molecular origin of the relaxation processes appears to stem from pressure-induced water fluxes between the interbilayer region and the bulk water phase.
Starch isolated from a hybrid maize (8535-23) was chemically modified by succinylation and acetylation. No pronounced difference was observed between the X-ray pattern of native starch and modified starch samples, and the samples gave the characteristic A pattern of cereal starches. Onset temperature (T(o)), peak temperature (T(p)), concluding temperature (T(c)) and enthalpy of gelatinisation (DeltaH), reduced after succinylation and acetylation, but gelatinisation temperature range increased following starch modifications. Modifications reduced starch retrogradation.
In this study we address the problem of the effect of canthaxanthin on the thermotropic properties of lipid membranes formed with lipids which differ in the thickness of their hydrophobic core, size of polar heads or presence of the ester carbonyl group. For all the lipids a decrease in main transition enthalpy has been observed, indicating that canthaxanthin alters the membrane properties in its gel phase. The strongest influence of canthaxanthin on main phase transition and pretransition has been observed for the lipid having the thinnest hydrophobic region. Component analysis indicates a distinct cooperativity change, which most probably colligates with the formation of new thermotropic phases. The effect of canthaxanthin has been almost negligible in the case of phosphatidylethanolamines. The absence of the ester carbonyl group results in different thermotropic behavior, especially for low canthaxanthin concentrations. The effect of canthaxanthin is explained in terms of its organization within the membrane.
The scope of this work is to carry out a systematic comparison of inverse gas chromatography (IGC) and microcalorimetry as tools for the study of the gas-phase adsorption of organic vapours (using hexane as model compound) on zeolitic materials (using different Mn, Co and Fe-exchanged NaX and CaA zeolites). Adsorption isotherms were recorded using both techniques in the temperature range of 150-250 degrees C, being observed that the shape of the isotherms obtained with the dynamic (IGC) and static (microcalorimetry) techniques was surprisingly similar in the pressure range at which both techniques are applicable (low surface coverages). Concerning to the measurement of the strength of the adsorption, calorimetric data provide two parameters related to the adsorption enthalpy: the initial differential heat and the isosteric adsorption enthalpy. A great coincidence was found between the last one and the adsorption enthalpy determined by IGC (4-20% of difference, depending on the studied material). The behaviour of the initial differential heat depends strongly on the studied material, being in some cases closely related to the other two parameters and temperature-independent (in the case on Mn-exchanged zeolites), whereas for the Co-CaA and Fe-CaA zeolites, it is temperature-dependent, being not correlated with the other parameters in this case. The main conclusion of this work is that IGC is an attractive alternative to the static microcalorimetric data for obtaining information on the adsorption of organic compounds on microporous materials.
Intracellular ice formation (IIF) plays a central role in cell damage during cryopreservation. We are investigating the factors which trigger IIF in Xenopus oocytes, with and without aquaporin water channels. Here, we report differential scanning calorimeter studies of Xenopus control oocytes which do not express aquaporins. Stage I to VI oocytes (which increase progressively in size) were investigated with emphasis on stage I and II because they are translucent and can also be studied under the cryomicroscope. Measurements were made in 1, 1.5, and 2M ethylene glycol (EG) in frog Ringers plus SnoMax. A multistep freezing protocol was used in which the samples were cooled until extracellular ice formation (EIF) occurred, partially remelted, slowly recooled through the EIF temperature, and then rapidly (10 degrees C/min) cooled. EIF in the 1, 1.5, and 2M EG occurred at -6.4, -7.8, and -8.9 degrees C, respectively. Freezing exotherms of individual stage I-VI oocytes were readily visible. A general trend was observed in which the IIF temperature of the early stage oocytes (I-III) was well below T(EIF) while the later stages (IV-VI) froze at temperatures much closer to T(EIF). Thus, in 1.5M EG, T(IIF) was -21.1, -25, and -26.6 degrees C in stages I-III, but was -17 and -8.5 degrees C for stage IV and V-VI. Concurrently, the percentage of oocytes in which IIF was observed fell dramatically from a high of 40 to 72% in early stages (I-III) to a low of only 7% in stage V-VI because, particularly in the later stages, IIF was hidden in the EIF exotherm. We conclude that early stage oocytes are a good model system in which to investigate modulators of IIF, but that late stage oocytes are damaged during EIF and infrequently supercool.
Efficient control of whole cell biotransformation requires quantitative real-time information about the thermodynamics and kinetics of growth and product formation. Heat production contains such information, but its technical application is restricted due to the high price of calorimetric devices, the difficulty of integrating them into existing bio-processes and the slow response times of established microcalorimeters. A new generation of chip or nanocalorimeters may overcome these weaknesses. We thus tested a highly sensitive chip calorimeter for its applicability in biotechnological monitoring. It was used to monitor aerobic growth of suspended and immobilized Escherichia coli DH5alpha DSM 6897 and anaerobic growth of suspended Halomonas halodenitrificans CCM 286(T). The chip data corresponded well with enthalpy balance calculations and measurements with a conventional calorimeter, indicating the applicability of the chip calorimeter for bio-process control.
Three model proteins, bovine serum albumin, hen's egg lysozyme and bovine serum fibrinogen, were adsorbed from aqueous solution onto finely dispersed ceramic particles, namely different kinds of alumina and hydroxyapatite particles. The influence of adsorption on protein secondary structure was investigated. The FTIR spectroscopic findings were compared with the results of DSC measurements. In almost all cases it was found that adsorption results in destabilisation and structural loss of the bound protein. A decrease in transition enthalpy is correlated with a loss in alpha-helical structure, which seems to be the most sensitive structure on adsorption-induced rearrangements. A total collapse of structure in the adsorbed proteins was not determined on any ceramic surface. Some residual structure is always retained. Structural changes in the D- or E-domains of fibrinogen could be independently observed by two different calorimetric signals. The two techniques applied in the present study -- micro-DSC and FTIR spectroscopy -- can be concluded to provide complementary information on adsorption-induced structural changes on both the molecular (thermal stability, overall structure) and the sub-molecular level (secondary structure).
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IC is the standard for determining energy expenditure in critically ill patients. The measured REE is an objective, patient-specific caloric reference that serves as the most accurate method of determining energy expenditure. Protocols addressing IC methodology are necessary to ensure technical accuracy and clinically useful results. The measured REE should be the caloric target without the addition of stress or activity factors for nutrition support regimens in the ICU. The RQ should be used primarily as an indicator of test validity. Optimal nutrition intervention requires continuous evaluation of all pertinent clinical data and careful monitoring of each patient's response to therapy.
The first X-ray and vibrational spectroscopic analysis of a new molecular complex between guanidinium and selenic acid is reported. The crystal of guanidinium hydrogenselenate at room temperature belongs to P2(1)/n space group of the monoclinic system with Z=4, a=8.330A, b=5.109A, c=14.855A and beta=92.65 degrees . Room temperature powder infrared and Raman spectra for the titled complex (1:1) were measured. The observed IR and Raman spectra are in accordance with this crystallographic structure. The differential scanning calorimetric (DSC) experiment on powder samples indicates on continuous phase transition at ca. 160K. To explain in detail the behavior of the crystal during the phase transition the infrared and Raman powder spectra in low temperature range (10-300K) were measured. The temperature dependencies of bands position and intensities for obtained spectra are analysed.
OBJECTIVE: This study compared measured resting energy expenditures to resting energy expenditures calculated using Harris-Benedict equations (HBEs) and the Cystic Fibrosis Consensus Committee equations (CFCCEs). DESIGN: We studied 31 preadolescent boys and girls with cystic fibrosis who ranged in age from 3.25 to 12.75 years old. The patients were afebrile and not in pulmonary distress. Measured resting energy expenditures were determined using a portable metabolic measurement cart with fully automated calibration and data management. The measured resting energy expenditures obtained were compared with values obtained using HBEs and CFCCEs. RESULTS: For each patient, the measured resting energy expenditure value was above the predicted resting energy expenditure values derived from HBEs (P < or = .0001) and CFCCEs (P < or = .01). APPLICATIONS: The HBEs and the CFCCEs underestimated the energy expenditures of the study population by 13% and 8%, respectively. These findings support the usefulness of the measurement of energy expenditures in determining the energy needs of preadolescent patients with cystic fibrosis. In clinical practice, the resting energy expenditures would be multiplied by activity coefficients to determine the total daily energy expenditures of this population.
Changes in the internal energy of lipids with temperature are related to both lipid volume and area changes. Close to the chain melting transition of lipid bilayers volume and enthalpy fluctuations generally follow proportional functions. This makes it possible to calculate the relationship between membrane excess heat capacity with lipid volume, area compressibility and the membrane bending modulus, if the area fluctuations of the two monolayers are assumed to be mainly decoupled. Thus, compressibility and elasticity display pronounced maxima at the chain melting transition. These maxima can also be related to pronounced minima of the sound velocity in the lipid transition range, which were found in ultrasonic experiments. In the present study heat capacity profiles and volume changes were obtained. The compressibilities and the bending modulus were then deduced from the specific heat. The relevance of these findings for structural transitions and for the curvature dependence of heat capacities is discussed.
We report a new phase transition in fully hydrated dispersions of dipalmitoylphosphatidylcholine (DPPC). This new transition, called the sub-subtransition, exhibits a transition enthalpy of 0.25 kcal/mol with a Tm at 6.8 degrees C. Unlike the subtransition, no extended low temperature incubation is required to observe the sub-subtransition. This new sub-subgel (SGII) phase may be a precursor to the subgel (SGI) phase, and this discovery is discussed in relation to the current knowledge regarding the polymorphic gel phases of both ester- and ether-linked lipids with identical acyl chains.
Prothrombin denaturation was examined in the presence of Na2EDTA, 5mM CaCl2, and CaCl2 plus membranes containing 1-palmitoyl-2-oleoyl-3-sn-phosphatidylcholine (POPC) in combination with either bovine brain phosphatidylserine (PS) or 1,2-dioleoyl-phosphatidylglycerol (DOPG). Heating denaturation of prothrombin produced thermograms showing two peaks, a minor one at approximately 59 degrees C previously reported to correspond to denaturation of the fragment 1 region (Ploplis, V. A., D. K. Strickland, and F. J. Castellino 1981. Biochemistry. 20:15-21), and a main one at approximately 57-58 degrees C, reportedly due to denaturation of the rest of the molecule (prethrombin 1). The main peak was insensitive to the presence of 5mM Ca2+ whereas the minor peak was shifted to higher temperature (Tm approximately 65 degrees C) by Ca2+. Sufficient concentrations of POPC/bovPS (75/25) large unilamellar vesicles to guarantee binding of 95% of prothrombin resulted in an enthalpy loss in the main endotherm and a comparable enthalpy gain in the minor endotherm accompanying an upward shift in peak temperature (Tm approximately 73 degrees C). Peak deconvolution analysis on the prothrombin denaturation profile and comparison with isolated prothrombin fragment 1 denaturation endotherms suggested that the change caused by POPC/PS vesicles reflected a shift of a portion of the enthalpy of the prethrombin 1 domain to higher temperature (Tm approximately 77 degrees C). The enthalpy associated with this high-temperature endotherm increased in proportion to the surface concentration of PS. By contrast, POPC/DOPG (50/50) membranes shifted the prethrombin 1 peak by 4 degrees C to a lower temperature and the fragment 1 peak by 5 degrees C to a higher temperature. The data lead to a hypothesis that the fragment 1 and prethrombin 1 domains of prothrombin do not denature quite independently and that binding of prothrombin to acidic-lipid membranes disrupts the interaction between these domains. It is further hypothesized that PS containing membranes exert the additional specific effect of decoupling the denaturation of two subdomains of the prethrombin 1 domain of prothrombin.
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