The question of high- or low-temperature glass transition in frozen fish. Construction of the supplemented state diagram for tuna muscle by differential scanning calorimetry

The thermal behavior of fresh tuna muscle, rehydrated freeze-dried tuna muscle, and tuna sarcoplasmic protein fraction was studied by three types of differential scanning calorimetry (DSC): conventional DSC, alternating DSC, and sensitive micro-DSC. The relationship between glass transition temperature, T(g), and water content was established. Only a low-temperature glass transition was detected for fresh tuna and freeze-dried tuna rehydrated to high water contents, whereas for sarcoplasmic protein fraction both a low-temperature and an apparent high-temperature glass transition were detected for samples of high water content. Construction of the supplemented state diagrams for whole tuna muscle and for tuna sarcoplasmic protein fraction confirmed the low-temperature transition to be glass transition of the maximally freeze-dehydrated phase. The apparent upper transition of sarcoplasmic protein fraction was shown not to be a glass transition but rather to originate from the onset of melting of ice, and the temperature of this event should be denoted T(m)'. The glass transition temperature and the concentration of the maximally freeze dehydrated tuna muscle are -74 degrees C and 79% (w/w), respectively.     

Use of differential scanning calorimetry (DSC) as a new technique for detection of adulteration in honeys. 1. Study of adulteration effect on honey thermal behavior.

Differential scanning calorimetry (DSC) was used to study the thermal behavior of authentic honeys (Lavandula, Robinia, and Fir honeys) and industrial sugar syrups. Thermal or thermochemical parameters such as the glass transition temperature (Tg), enthalpies of fusion (DeltaH(fus)), and heat capacity variation (DeltaC(p)) were measured. The syrups and honeys showed significant differences in thermal phenomena, as well as in their amplitude and position on the temperature scale. Results showed good reproducibility of the method for all samples studied. The effect of adulteration of honey with different amounts of syrup (5, 10, 20, 40, and 60%) was investigated. A linear relationship was found between the percentage of added syrup and the glass transition temperature. A similar relationship was obtained from the enthalpy of fusion results in the temperature range of 40-90 degrees C. Under applied conditions, the effects of adulteration of honeys by industrial syrups appeared to be detectable from a level as low as 5%.     

State diagram of temperature vs date solids obtained from the mature fruit

Mature dates were dried achieving an increase in the level of solids from 70.8% to 92.4% (wet basis). Small deformation dynamic oscillation was employed to identify changes in the viscoelastic properties of dates as a function of solids. Samples were cooled or heated at a constant scan rate of 1 degrees C/min. At high temperatures, e.g., 70 degrees C, the storage and loss modulus (G' and G' ', respectively) remained relatively independent of the time or frequency of observation, thus delineating the plateau zone. Cooling resulted in rapid development of both moduli with G' ' overtaking G'. This is known as the glass transition region and was used to define the rheological T(g). Eventually, the glassy state is reached where the storage modulus becomes dominant once more and approaches values of 10(9.5) Pa. The values of T(g) were used to determine the metastable glass transition curve of mature dates. At lower levels of solids, i.e., between 11.7% and 64%, freezing experiments were employed to identify the equilibrium melting curve of ice. The state diagram yielded a maximally freeze-concentrated solute at 70% solids with the characteristic temperature of glass formation being -50 degrees C. Data on equilibrium and kinetic events were modeled using the Chen and Gordon-Taylor equations yielding the rheological T(g) for date solids at their effective molecular weight.     

Reaction rate modeling in cryoconcentrated solutions: alkaline phosphatase catalyzed DNPP hydrolysis

The hydrolysis of disodium p-nitrophenyl phosphate catalyzed by alkaline phosphatase was chosen as a model to study the kinetics of changes in frozen food products. The initial reaction rate was determined in concentrated sucrose solutions down to -24 degrees C, and the enzymatic characteristics K(M) and V(max) were calculated. The experimental data were compared to the kinetics predicted by assuming that the reaction was viscosity dependent. Indeed, an analysis of the enzymatic reaction demonstrated that both the diffusion of the substrate and the flexibility of the enzyme segments were controlled by the high viscosity of the media. When the temperature was too low for the viscosity to be measured simply, the Williams-Landel-Ferry equation was used to predict the viscosity, taking, as reference temperature, the glass transition temperature (T(g)) corresponding to the concentration of the freeze-concentrated phase at the test temperature. Predicted values of the reaction rate were very close to the experimental ones in the studied temperature range.     

Honey protein as internal standard for stable carbon isotope ratio detection of adulteration of honey

Using the difference in stable carbon isotope ratio between a honey and its protein fraction permits objective evaluation of possible adulteration of honey with small amounts (7-20%) as well as larger amounts of corn or cane sugar. The present uncertainty in interpretation of results from pure honey with delta 13C values outside the generally accepted limits for pure honey of -27.5% to -23.5% is eliminated; likewise TLC testing to resolve questionable samples with delta 13C values between -23.5 and -21.5% is not needed. Fifty certified samples of pure honey were used to establish criteria for purity, and 38 other samples with delta 13C values in the "questionable" or "adulterated" range for the AOAC official method were tested. A difference of 1.0% or more between honey and protein fractions is proposed to indicate adulteration.     

Thermomechanical Transitions of Rice Kernels

Thermomechanical analysis (TMA) and differential scanning calorimetry (DSC) were used to investigate the thermal transitions of long‐grain rice kernels. Three distinct thermomechanical transitions were identified as rice kernels were heated from 0 to 200°C. The identified transitions were a low temperature transition with onset at ≈45°C, an intermediate temperature transition at ≈80°C, and a high temperature transition at ≈180°C. Low temperature transition with onset from ≈60°C at 5% moisture content (MC) to 30°C at 20% MC was identified as the glass transition of the rice kernels. Intermediate temperature transition from 60 to 100°C, depending on MC, may be caused by rapid evaporation of moisture in the rice kernels. High temperature transition was associated with melting of the crystalline structure of rice starch. The temperatures of all three transitions decreased as MC increased, confirming that moisture acted as a plasticizer in rice kernels.     

Effect of temperature and glassy states on the molecular mobility of solutes in frozen tuna muscle as studied by electron spin resonance spectroscopy with spin probe detection

The mobility of solutes in frozen food systems (tuna muscle, sarcoplasmic protein fraction of tuna muscle, and carbohydrate-water) has been studied using the temperature dependence of the shape of electron spin resonance (ESR) spectra of the spin probe 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL). The spin probe was incorporated into the tuna meat from an aqueous solution of TEMPOL or by contact with a layer of TEMPOL crystals. The melting/freezing of freeze-concentrated solutes in frozen tuna meat was observed to take place over a range of temperatures from -25 to -10 degrees C. Lower temperatures gave ESR powder spectra due to the decreased mobility of the spin probe, and the temperature dependence of the mobility of the spin probe did not show abrupt changes at the glass transition temperatures of the systems. The mobility of nonglass forming solutes is concluded to be decoupled from the glass forming components. Similar behavior was also observed for TEMPOL in frozen, aqueous carbohydrate systems. The temperature dependence of the mobility of TEMPOL in the frozen systems was analyzed using the Arrhenius equation, and the logarithm of the Arrhenius preexponential factor tau(a) was found to be linearly correlated with the activation energy for all of the tuna and carbohydrate samples, indicating a common molecular mechanism for the observed mobility of TEMPOL in all of the systems. The linear correlation also suggests that the observed mobility of TEMPOL in the frozen aqueous systems is dominated by enthalpy-entropy compensation effects, where the mobility of TEMPOL is thermodynamically strongly coupled to the closest surrounding molecules.     

Changes in the physical state of sucrose during dark chocolate processing

Dark chocolate tablets were manufactured using 100% crystalline sucrose, 50% crystalline and 50% amorphous sucrose, and 100% amorphous sucrose. The physical state of sucrose was determined by differential scanning calorimetry (DSC) and X-ray diffraction. DSC scans of dark chocolate samples containing amorphous sucrose were characterized by a glass transition at 63 degrees C, a sucrose crystallization peak at 105 degrees C, and a melting endotherm at 188 degrees C. Independent of the amount of amorphous or crystalline sucrose used for the preparation of dark chocolate, all final chocolate products provided a single melting endotherm at 188 degrees C and a crystalline X-ray diffraction pattern. These results indicated that sucrose crystallized during production of dark chocolate and that no amorphous sucrose was present in the final chocolate products.     

Monitoring chemical and physical changes during thermal flavor generation

On-line techniques were developed to monitor chemical and physical changes occurring during the heating of skim milk powder (SMP). Atmospheric pressure chemical ionization mass spectrometry (APCIMS) followed the generation and release of volatile compounds from SMP in a packed-bed reactor. Operating conditions were optimized to avoid condensation of high boiling compounds such as maltol, and the system was highly reproducible (CV < 7%). Differential scanning calorimetry (DSC) of SMP identified a potential glass transition at an onset temperature of 67.9 degrees C and a series of exothermic events that were related to different stages of the Maillard reaction. No lactose crystallization was found after heating. Using a heated stage reflectance FTIR device, spectra were obtained at different temperatures. Analysis of the data showed a correlation between the intensity ratio at wavenumbers 1017 and 1064 cm(-1) and the glass transition measured by DSC. This FTIR system was not sensitive enough to detect Maillard intermediates. Combining data from the three techniques provides a fuller picture of the physical changes during the Maillard reaction and their effects on the chemical reactions.     

Thermal characteristics of soil organic matter measured by DSC: A hint on a glass transition

Glass transitions have been reported for purified humic acids only. In this study, a glass transition was detected in a sample of a sandy forest soil by Differential Scanning Calorimetry (DSC). The glass transition temperature was 79°C for air‐dried samples and 77°C for pre‐moistened samples. In addition to the glass transition, an exothermic process around 30°C was detected in pre‐moistened samples. This could be due to water loss of soil organic matter. However, the nature of this process is not yet understood. This study showed that the macromolecular behaviour of SOM, as indicated by DSC, reacts to the moisture state of soil organic matter.     

Differential Scanning Calorimetry Glass Transition Temperatures of White Bread and Mold Growth in the Putative Glassy State

Differential scanning calorimetry (DSC) was used to determine the onset and end temperatures of the glass transition (T_g) for white bread equilibrated between 53 and 84% rh. Calorimetric T_g end values were ≈20°C higher than onset values, indicating that it is probably more correct to refer to a “glass transition range” rather than a glass transition temperature. Slices of white bread inoculated with a mixture of xerophilic molds were equilibrated to 75% rh (equilibrium moisture content of 14.5 g of water/100 g of dry material) and stored at 26°C. In a parallel experiment, some of the equilibrated bread samples were stored without mold inoculation and subjected to spontaneous contamination from the immediate surroundings. As suggested by measured T_g, bread stored at 75% rh and 26°C appeared to be glassy. After storage, samples of bread (inoculated or not) were spoiled by xerophilic molds, suggesting that T_g, as measured by DSC, cannot be considered as an absolute threshold for mold growth inhibition.     

Honey as a protective agent against lipid oxidation in ground turkey.

Lipid oxidation is a major deteriorative factor in meats. Sources of natural antioxidants that are as effective as commercially available antioxidants are desired. The objective of this research was to investigate honey as an inhibitor of lipid oxidation in ground poultry. The antioxidant content of different varieties of honey was investigated spectrophotometrically and honey's effectiveness in reducing oxidation of ground poultry determined by monitoring thiobarbituric acid reactive substances (TBARS). Buckwheat honey had the highest antioxidant content and acacia honey the lowest. Honeys of different floral sources differed in their protection against lipid oxidation. Buckwheat honey (5%, w/w) reduced TBARS approximately 70%, whereas acacia honey reduced TBARS approximately 34% at 3 days of storage at 4 degrees C. In comparison to butylated hydroxytoluene and tocopherol (0.02% of total fat), honey (at 5% of the weight of the meat) was much more effective at preventing oxidation. Honey has great potential as an antioxidant source and may result in greater acceptability of meat products and prevent negative health implications of oxidized meats.     

Effects of glycerol and moisture gradient on thermomechanical properties of white bread

The thermomechanical properties of breadcrumb were investigated using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The main transition (T(1), near 0 degrees C) shifted to lower temperature with added glycerol due to freezing point depression. The low-temperature transition (T(3), approximately -50 degrees C), found only in high-glycerol (8.8%) bread, suggested that of excess or phase-separated glycerol. The high-temperature transition (T(2), 60-85 degrees C) appeared only in aged breadcrumbs; its temperature range was correlated well with the amylopectin melting transition (DSC) but its tan delta amplitude did not correlate well with the amylopectin melting enthalpy (r(2) = 0.72). On the other hand, the change of E' ' (viscous behavior) suggested that T(2) might be related to the change in the amorphous region. Domain-to-domain (amorphous) and crumb-to-crust moisture migrations are two critical phenomenological changes associated with aging and could lead to significant local dehydration of some amorphous regions contributing to mechanical firming during storage.     

Temperature effect on lactose crystallization, maillard reactions, and lipid oxidation in whole milk powder

Whole milk powder with an initial water content of 4.4% (w/w) and a water activity of 0.23 stored in hermetically sealed vials for up to 147 days below (37 and 45 degrees C) and above (55 degrees C) the glass transition temperature (T(g) determined to have the value 48 degrees C) showed a strong temperature dependence for quality deterioration corresponding to energies of activation close to 200 kJ/mol for most deteriorative processes. The glass transition was found not to cause any deviation from Arrhenius temperature dependence. Lactose crystallization, which occurred as a gradual process as monitored by isothermal calorimetry, is concluded to liberate bound water (a(w) increase to 0.46) with a modest time delay (approximately 2 days at 55 degrees C) and with concomitant surface browning as evidenced by an increasing Hunter b-value. Browning and formation of bound hydroxymethyl-furfural determined by HPLC seem to be coupled, while formation of another Maillard reaction product, furosine, occurred gradually and was initiated prior to crystallization. Initiation of lipid oxidation, as detected by lipid-derived radicals (high g-value ESR spectra), and progression of lipid oxidation, as detected by headspace GC, seem not to be affected by lactose crystallization and browning, and no indication of browning products acting as antioxidants could be determined.     

Nonenzymatic browning in food models in the vicinity of the glass transition: effects of fructose,glucose, and xylose as reducing sugar

Effects of a reducing sugar, fructose, glucose, or xylose, and glass transition on the nonenzymatic browning (NEB) rate in maltodextrin (MD), poly(vinylpyrrolidone) (PVP), and water systems were studied. Glass transition temperatures (T(g)) were determined using DSC. Water contents were determined gravimetrically, and NEB rates were followed at several temperatures spectrophotometrically at 280 and 420 nm. Reducing sugar did not affect water contents, but xylose reduced the T(g) of the solid models. Sugars showed decreasing NEB reactivity in the order xylose > fructose > glucose in every matrix material. The NEB reactivity and temperature dependence of the single sugars varied in different matrices. The NEB rates of the solid models increased at temperatures 10-20 degrees C above the T(g), and nonlinearity was observed in Arrhenius plots in the vicinity of T(g). The temperature dependence of nonenzymatic browning could also be modeled using the WLF equation.     

Glass transition and water effects on sucrose inversion by invertase in a lactose-sucrose system

Enzymatic changes are often detrimental to quality of low-moisture foods. In the present study, effects of glass transition and water on sucrose inversion in a lactose-sucrose food model were investigated. Amorphous samples were produced by freeze-drying lactose-sucrose (2:1)-invertase (20 mg invertase/49.4 g of carbohydrate) dissolved in distilled water. Sorption isotherms were determined gravimetrically at 24 degrees C. Sucrose hydrolysis was determined by monitoring glucose content using a test kit and the amounts of fructose, glucose, and sucrose using HPLC. The glass transition temperatures, T(g), at various water contents were measured using differential scanning calorimetry (DSC). The BET and the GAB sorption models were fitted to experimental data up to a(w) 0.444 and 0.538, respectively. Water sorption and DSC results suggested time-dependent crystallization of sugars at a(w) 0.444 and above. Significant sucrose hydrolysis occurred only above T(g), concomitantly with crystallization. Sucrose hydrolysis and crystallization were not likely in glassy materials.     

Elucidation of the effect of formaldehyde and lipids on frozen stored cod collagen by FT-Raman spectroscopy and differential scanning calorimetry

The effect of frozen storage (-10 and -30 degrees C), formaldehyde, and fish oil on collagen, isolated from cod muscle, was investigated. Salt- and acid-soluble collagen fractions as well as insoluble collagen indicated changes in solubility on frozen storage. Differential scanning calorimetry (DSC) showed a highly cooperative transition at 28.2 degrees C for isolated collagen. Changes in the thermodynamic properties of collagen were observed on frozen storage at -10 degrees C compared with the control at -30 degrees C because of changes in structure. In the presence of formaldehyde, there were no changes in the DSC collagen transition; however, in the presence of fish oil there was an increase in enthalpy and an extra peak was observed at 44.6 degrees C, indicating collagen-fish oil interaction. Structural changes resulted in a decrease in the solubility of collagen in salt and acid solution. FT-Raman spectra obtained for collagen at -10 degrees C and -30 degrees C confirmed the alteration of the conformation of collagen not only at -10 degrees C but also in the presence of formaldehyde and fish oil.     

Anhydrous goat's milk fat: thermal and structural behavior. 1. Crystalline forms obtained by slow cooling

The thermal and structural behaviors of anhydrous goat's milk fat (AGMF) have been determined as a function of temperature using a powerful technique allowing simultaneous time-resolved synchrotron X-ray diffraction as a function of temperature (XRDT) and high-sensivity differential scanning calorimetry (DSC) measurements from the same sample. This first paper, aiming at the characterization of the physical properties of AGMF, we examine crystalline organizations made by triacylglycerols (TG) upon slow cooling at /dT/dt/ = 0.1 degrees C/min from 45 to -20 degrees C in order to approach system equilibrium. Three overlapped exotherms were observed by DSC upon cooling, whereas four endotherms were found on the subsequent heating at 1 degrees C/min. XRDT evidenced that AGMF crystallizes under four different lamellar structures, two with double-chain length packings at 41.5 and 38.2 angstroms and two with triple-chain lengths of 72 and 64.7 angstroms stacking. Simultaneous wide-angle XRDT has shown that initial nucleation mainly occurs in a packing of beta' type from approximately 26 degrees C, although some transient presence of alpha was detected. The absence of polymorphic transition, on heating, until final melting (approximately 40 degrees C) demonstrated the relative stability of the structures formed.     

Differential Scanning Calorimetric Study on the Effects of Frozen Storage on Gluten and Dough

Water transport from the gluten to the starch paste during frozen storage of a dough was studied by analysis of the differential scanning calorimetry (DSC) peak shape for gluten and dough. The results indicate that in gluten stored at ‐15°C, the water content in the gluten phase decreased by ≈1% over the first three weeks. An apparent steady state was attained over this period and the amount of ice did not increase further. Such changes were not observed for samples stored at ‐25°C. Qualitatively similar observations were made for dough stored at either ‐15 or ‐25°C. The greater sensitivity of dough to frozen storage is tentatively attributed to a slightly lower glass transition temperature in dough.     

Aging of whey protein films and the effect on mechanical and barrier properties

This work focuses on the aging of whey protein isolate (WPI) films plasticized with glycerol (G) and sorbitol (S). The films were cast from heated aqueous solutions at pH 7 and dried at 23 degrees C and 50% relative humidity (RH) for 16 h. They were stored in a climate room (23 degrees C, 50% RH) for 120 days, and the film properties were measured at regular intervals. The moisture content (MC) of the WPI/G films decreased from 22% (2 days) to 15% (45 days) and was thereafter constant at 15% (up to 120 days). This affected the mechanical properties and caused an increased stress at break (from 2.7 to 8.3 MPa), a decreased strain at break (from 33 to 4%), and an increased glass transition temperature (T(g)) (from -56 to -45 degrees C). The barrier properties were, however, unaffected, with constant water vapor permeability and a uniform film thickness. The MC of the WPI/S films was constant at approximately 9%, which gave no change in film properties.