Reducing the time period of steady state does not affect the accuracy of energy expenditure measurements by indirect calorimetry

Achievement of steady state during indirect calorimetry measurements of resting energy expenditure (REE) is necessary to reduce error and ensure accuracy in the measurement. Steady state is often defined as 5 consecutive min (5-min SS) during which oxygen consumption and carbon dioxide production vary by +/-10%. These criteria, however, are stringent and often difficult to satisfy. This study aimed to assess whether reducing the time period for steady state (4-min SS or 3-min SS) produced measurements of REE that were significantly different from 5-min SS. REE was measured with the use of open-circuit indirect calorimetry in 39 subjects, of whom only 21 (54%) met the 5-min SS criteria. In these 21 subjects, median biases in REE between 5-min SS and 4-min SS and between 5-min SS and 3-min SS were 0.1 and 0.01%, respectively. For individuals, 4-min SS measured REE within a clinically acceptable range of +/-2% of 5-min SS, whereas 3-min SS measured REE within a range of -2-3% of 5-min SS. Harris-Benedict prediction equations estimated REE for individuals within +/-20-30% of 5-min SS. Reducing the time period of steady state to 4 min produced measurements of REE for individuals that were within clinically acceptable, predetermined limits. The limits of agreement for 3-min SS fell outside the predefined limits of +/-2%; however, both 4-min SS and 3-min SS criteria greatly increased the proportion of subjects who satisfied steady state within smaller limits than would be achieved if relying on prediction equations.

A potential role for isothermal calorimetry in studies of the effects of thermodynamic non-ideality in enzyme-catalyzed reactions

Attention is drawn to the feasibility of using isothermal calorimetry for the characterization of enzyme reactions under conditions bearing greater relevance to the crowded biological environment, where kinetic parameters are likely to differ significantly from those obtained by classical enzyme kinetic studies in dilute solution. An outline of the application of isothermal calorimetry to the determination of enzyme kinetic parameters is followed by considerations of the nature and consequences of crowding effects in enzyme catalysis. Some of those effects of thermodynamic non-ideality are then illustrated by means of experimental results from calorimetric studies of the effect of molecular crowding on the kinetics of catalysis by rabbit muscle pyruvate kinase. This review concludes with a discussion of the potential of isothermal calorimetry for the experimental determination of kinetic parameters for enzymes either in biological environments or at least in media that should provide reasonable approximations of the crowded conditions encountered in vivo. Copyright (C) 2004 John Wiley Sons, Ltd.

Gelatinisation of starch in mixtures of sugars. II. Application of differential scanning calorimetry

Differential scanning calorimetry was used to investigate the effect of mixtures of glucose and fructose, and five types of honeys on starch gelatinisation. At a 1:1 starch:water ratio, glucose generally increased the enthalpy (DeltaH(gel)) and temperatures (T-onset, T-peak and T-end) of gelatinisation more than fructose. Upon mixing, DeltaH(gel) of the low-temperature endotherm decreased in comparison to the sole sugars, but was fairly constant (7.7 +/- 0.33 J/g dry starch). DeltaH(gel) of the high-temperature endotherm increased with the fructose content. For both endotherms, the gelatinisation temperatures were unchanged (CV less than or equal to 3%) for the mixtures. With the honeys (moisture, 14.9-18.0%; fructose, 37.2-44.0%; glucose, 28.3-31.9%) added at 1.1-4.4 g per g dry starch, the enthalpy and temperatures of gelatinisation did not vary significantly (CV less than or equal to 6%). Typical thermograms are presented, and the results are interpreted in the light of the various proposed mechanisms for starch gelatinisation in sugar-water systems, total sugar content and possible sugar-sugar interactions. The thermograms were broader in the presence of the sugars and honeys, and a biphasic character was consistently exhibited. The application of an exponential equation to the gelatinisation temperatures of the starch-honey mixtures revealed an opposing influence of fructose and glucose during gelatinisation. The mechanism of starch gelatinisation may be better understood if techniques could be perfected to quantify breakage and formation of hydrogen bonds in the starch granules, and suggested techniques are discussed. (C) 2004 Elsevier Ltd. All rights reserved.

Investigation of the starch gelatinisation phenomena in water-glycerol systems: application of modulated temperature differential scanning calorimetry

The use of modulated temperature differential scanning calorimetry (MTDSC) has provided further insight into the gelatinisation process since it allows the detection of glass transition during gelatinisation process. It was found in this work that the glass transition overlapped with the gelatinisation peak temperature for all maize starch formulations studied. Systematic investigation on maize starch gelatinisation over a range of water-glycerol concentrations with MTDSC revealed that the addition of glycerol increased the gelatinisation onset temperature with an extent that depended on the water content in the system. Furthermore, the addition of glycerol promoted starch gelatinisation at low water content (0.4 g water/g dry starch) and the enthalpy of gelatinisation varied with glycerol concentration (0.73-19.61 J/g dry starch) depending on the water content and starch type. The validities of published gelatinisation models were explored. These models failed to explain the glass transition phenomena observed during the course of gelatinisation and failed to describe the gelatinisation behaviour observed over the water-glycerol concentrations range investigated. A hypothesis for the mechanisms involved during gelatinisation was proposed based on the side chain liquid crystalline polymer model for starch structure and the concept that the order-disorder transition in starch requires that the hydrogen bonds (the major structural element in the granule packing) to be broken before the collapse of order (helix-coil transition) can take place. (C) 2004 Elsevier Ltd. All rights reserved.

Wheat grain cooking process as investigated by modulated temperature differential scanning calorimetry

The thermal properties of soft and hard wheat grains, cooked in a steam pressure cooker, as a function of cooking temperature and time were investigated by modulated temperature differential scanning calorimetry (MTDSC). Four cooking temperatures (110, 120, 130 and 140 degrees C) and six cooking times (20, 40, 60, 80, 100 and 120 min) for each temperature were studied. It was found that typical non-reversible heat flow thermograms of cooked and uncooked wheat grains consisted of two endothermic baseline shifts localised around 40-50 degrees C and then 60-70 degrees C. The second peaks of non-reversible heat flow thermograms (60-70 degrees C) were associated with starch gelatinisation. The degree of gelatinisation was quantified based on these peaks. In this study, starch was completely gelatinised within 60-80 min for cooking temperatures at 110-120 degrees C and within 20 min for cooking temperatures at 130-140 degrees C. MTDSC detected reversible endothermic baseline shifts in most samples, localised broadly around 48-67 degrees C with changes in heat capacity ranging from 0.02 to 0.06 J/g per degrees C. These reversible endothermic baseline shifts are related to the glass transition, which occurs during starch gelatinisation. Data on the specific heat capacity of the cooked wheat samples are provided. (C) 2005 Elsevier Ltd. All rights reserved.

Specific heat capacity of Australian honeys from 35 to 165C as a function of composition using differential scanning calorimetry

Modulated temperature differential scanning calorimetry was used to investigate the specific heat capacity (C-p) of 10 Australian honeys within the processing and handling temperatures. The values obtained were found to be different from the literature values at certain temperatures, and are not predictable by the additive model. The C-p of each honey exhibited a cubic relationship (P < 0.001) with the temperature (T, C). In addition, the moisture (M, %), fructose (F, %) and glucose (G, %) contents of the honeys influenced their C-p. The following equation (r(2) = 0.92) was proposed for estimating C-p of honey, and is recommended for use in the honey industry and in research: C = 996.7 + 1.4 x 10(-3)T + 5.6 x 10(-5)T(2) - 2.4 x 10(-7)T(3) - 56.5M - 25.8F - 31.0G + 1.5(M * F) + 1.8(M * G) + 0.8(F * G) - 4.6 x 10(-2) (M * F * G).