Frozen State Transitions in Freeze-Concentrated Lactose-Protein-Cornstarch Systems

Differential scanning calorimetry study of frozen state transitions of mixtures of lactose, proteins, cornstarch, and water revealed that maximum freeze-concentration was achieved by annealing at temperatures T′_m-1. The onsets of glass transition of maximally freeze-concentrated solids, T′_g, were lower and onsets of ice melting, T′_m, were higher for mixtures of proteins and polysaccharide than those of lactose. The established state diagrams showed solids concentrations C′_g, of the maximally freeze-concentrated systems of, 82, 78, 78, 78, and 75% for lactose, lactose/albumin, lactose/gelatin, lactose/cornstarch, and lactose/cornstarch/gelatin solutions, respectively. The state diagrams established with experimental and predicted T_g values are useful in characterization of thermal phenomena and physical state of the systems at various water contents and in the freeze-concentrated state.     

Rates of Crystallization of Dried Lactose-sucrose Mixtures

The isothermal crystallization kinetics of glassy lactose/sucrose mixtures were studied at several storage temperatures (close to T_g and T_m). The kinetic parameters implicit in the Avrami equation were determined. Activation energies for transport (E_D) and surface nucleation (W*) were also found and correlated to the molar composition of the lactose/sucrose mixtures. A monotonic increase in the half crystallization time (t_1/z), Avrami index (n), % crystallization per day, activation energy for transport (E_D) and surface nucleation energy (W*) and a decrease in the crystallization velocity constants (K) were related to the increase in the lactose content of lactose/sucrose mixtures.     

Water and Molecular Weight Effects on Glass Transitions in Amorphous Carbohydrates and Carbohydrate Solutions

The effects of water, freeze-concentration and effective molecular weight (M_e) on glass transition (T_g) of maltose and maltodextrins were studied, and methods to predict T_g were used to establish state diagrams. T_g of maximally freeze-concentrated solutes (T′_g) and onset of ice melting (T′_m) increased with M_e, and for high molecular weight polysaccharides T′_g and T′_m were predicted to have the same temperature value. Ice formation at T′_gm was time dependent. Unfrozen water in maximally freeze-concentrated matrices was about 20% independently of M_e. The state diagrams can be used to evaluate physical state of frozen and dehydrated foods.     

Glass transition and crystallization behaviour of freeze-dried lactose-salt mixtures

Glass transition temperatures were determined for dehydrated lactose/salt mixtures with various water contents and water activities, and state diagrams were established. Crystallization behaviour was studied for pure amorphous lactose stored at various relative water vapour pressures (RVP). Furthermore, glass transitions temperatures and time-dependent lactose crystallization of freeze-dried lactose and lactose/CaCl₂, lactose/NaCl, lactose/MgCl₂ and lactose/KCl mixtures in molar ratios of 9:1 were determined. Glass transition temperatures (T_g) of lactose powder as determined by differential scanning calorimetry (DSC) was lower than that of lactose/CaCl₂ (9:1)_, and lactose/MgCl₂ (9:1), but it was slightly higher than the T_g of lactose/NaCl (9:1), and lactose/KCl (9:1). Lactose/KCl had the lowest glass transition temperature, but it had about the same crystallization temperature as lactose/NaCl, and lactose/MgCl₂. The glass transition temperatures decreased as water contents increased. The critical water contents and water activities at 23 °C were predicted using data on glass transition temperature and water sorption. Pure lactose had a different critical water activity and water content from lactose/salt mixtures. The critical values of lactose/CaCl₂ (9:1) were the highest. Loss of sorbed water, indicating lactose crystallization, was observed in lactose and lactose/salt mixtures stored above the critical RVP.     

Characterization of Physical and Mechanical Properties of Miscible Lactose‐Sugars Systems

Lactose‐sugars systems were produced by spray drying. They were lactose, lactose–glucose (4:1) mixtures, lactose–maltose (4:1) mixtures, lactose–sucrose (4:1) mixtures, lactose–trehalose (4:1) mixtures, and lactose–corn syrup solids (CSS) (4:1) mixtures. The physical characteristics, water sorption behavior, glass transition, and mechanical properties of miscible lactose‐sugars systems were investigated. Lactose–glucose mixtures had larger particle size than other lactose‐sugars systems after spray drying. The presence of glucose or sucrose in lactose‐sugars mixtures decreased the glass transition temperatures of amorphous systems, while the presence of maltose and trehalose had only minor impact on the glass transition temperatures. Moreover, glucose accelerated the crystallization of amorphous system at 0.44 a_w, but its presence delayed the loss of sorbed water at higher water activities (≥0.54 a_w). Mechanical property study indicated that glucose and sucrose in amorphous system could result in an increase of molecular mobility, while the presence of CSS could decrease the free volume and maintain the stiffness of the miscible systems.     

Rheological and Thermal Properties of Extruded Mixtures of Rice Starch and Isolated Soy Protein

Many foods gain new mechanical, thermal and textural properties after being processed due to interactions between carbohydrates and proteins. This effect is characteristic for each foodstuff. The properties of extruded isolated soy protein (ISP) and rice starch were studied considering the following extrusion variables: starch proportion with respect to ISP (0–100%), pH (3–9), moisture content (20–30%) and temperature (140–180ºC). The following characteristics were measured: Water absorption index (WAI), water solubility index (WSI), glass transition temperature (T_g), melting temperature (T_m), viscosity at 90ºC and at 50ºC, storage (G′), loss modulus (G′′) and tan δ. The results indicate that the extruded starch exhibits higher WAI and WSI values than untreated starch. For extruded ISP these values are much lower than for untreated ISP. Extrudates with higher starch proportion had higher T_g and T_m values; pH has a significant effect (p<0.05), at pH 3 higher T_g values were observed, and at pH 9 higher values of T_m. The highest viscosities at 90ºC and 50ºC were observed for extrudates with a higher starch proportion and pH 9. Extruded mixtures showed a more elastic than viscous behavior and an extruded 1:1 blend of starch‐ISP exhibited the behavior of a viscous liquid.     

X-ray diffraction analysis of lactose crystallization in freeze-dried lactose–whey protein systems

Water sorption, time-dependent crystallization and XRD patterns of lactose and lactose–WPI mixtures were studied with glass transition data. The results indicated that the sorbed water of lactose–WPI mixtures was fractional and water content of individual amorphous components in lactose–WPI mixtures at each a_w from 25 °C to 45 °C could be calculated. Crystallization occurred in pure lactose whereas partial crystallization was typical of lactose–WPI mixtures (protein content ≤ 50%) at intermediate and high a_w (> 0.44 a_w) from 25 °C to 45 °C. The extents of crystallization were significantly delayed by WPI. The T_g values of lactose–WPI systems showed the composition-dependent property in systems and might indicate the occurrence of phase separation phenomena during 240 h storage. XRD showed no anhydrous β-lactose and mixed α-/β-lactose with molar ratios of 4:1 crystals in crystallized lactose–WPI systems (70:30 and 50:50 solids ratios). Reduced crystallization in the presence of WPI was more pronounced possibly because of reduced nucleation and diffusion during crystal-growth. The present study showed that WPI could present an important role in preventing sugar crystallization.     

Plasticizing Effect of Water on Thermal Behavior and Crystallization of Amorphous Food Models

Dehydrated sugar solutions were used as models of thermal behavior of amorphous foods, and of the effect of temperature, moisture content and time on physical state of such foods. The transition temperatures determined were glass transition (T_g), crystallization (T_cr) and melting (T_m) which all decreased with increasing moisture. T_g of a sucrose/ fructose model had a slightly lower value than the empirical “sticky point,” at all moisture contents studied. Crystallization of sucrose was delayed by addition of fructose or starch. Crystallization above T_g was time-dependent, and the relaxation time of this process followed the WLF equation.     

Glass Transition Study in Model Food Systems Prepared with Mixtures of Fructose,Glucose, and Sucrose

Abstract: The glass transition temperature of model food systems prepared with several glucose/fructose/sucrose mass fractions was studied using differential scanning calorimetry (DSC). A distance‐based experimental design for mixtures of 3 components was used to establish the proportion of sugars of the model systems. Thus, 32 compositions including individual sugars and sugar mixtures, both binary and ternary were prepared and analyzed. Thermograms showing the complete process of heating–cooling–reheating were used to determine the precise glass transition temperature during cooling () or reheating () in amorphous sugars. The Scheffe cubic model was applied to experimental results to determine the influence of sugar composition on the glass transition temperature (P < 0.05). The final model proved to be appropriate (R² > 0.97, CV < 9%, model significance <0.0001) to predict the T_g values of any dry mixture of amorphous fructose, glucose, and sucrose. Practical Application: The experimental values of T_g and the mathematical model proposed in this work may be of great use for making available T_g data that involves the mixture of more than 2 sugars and thus could be used as a tool for predicting the storage stability and quality of dehydrated products such as fruit powders.     

Glass Transition and Crystallization of Amorphous Trehalose-sucrose Mixtures

Our objective was to investigate the glass transition and crystallization of trehalose-sucrose mixtures at various moisture contents. Samples were freeze-dried, rehumidified, and scanned with Differential scanning calorimetry (DSC) to obtain T_g values for all mixtures and pure sugars. Amorphous cotton candy samples for crystallization studies were prepared, humidified, and monitored for crystallinity as a function of time using powder X-ray diffraction (XRD). The T_g of pure dry trehalose was found to be 106 °C, while sucrose had a T_g of 60 °C. Glass transition, as expected, occurred at an intermediate temperature for sucrose-trehalose mixtures. Of the dry samples, only those containing less than 16% trehalose showed sucrose crystallization during scanning. In cotton candy made from a 25% trehalose-75% sucrose mixture, humidified to 33%, sucrose did not crystallize after 30 days, whereas pure sucrose cotton candy at that humidity crystallized completely after 11 days. These data show that trehalose may be a useful crystallization inhibitor in foods with high sucrose content, although small amounts of trehalose did not significantly raise the T_g.     

Calorimetric study of the glass transition occurring in aqueous glucose: Fructose solutions

Glass transition temperatures (T_g) for dilute and concentrated glucose: fructose: water solutions have been determined by differential scanning calorimetry. The supplemented phase diagrams (glucose: fructose 1:4, 1:2, 1:1, 2:1, 4:1 (w/w)) are presented and from these the temperature (T_g') and concentration (C'_g) of the maximally freeze-concentrated glass have been determined. Theoretical predictions of T_g for binary (glucose: fructose) and tertiary (glucose: fructose: water) systems according to the Couchman–Karasz and Gordon-Taylor equations are given and discussed. Annealing vitrified glucose: fructose glasses above their T_g allows the glass concentration to approach C'_g as a result of ice formation. Viscosity measurements of fructose and fructose: glucose mixtures allow for a calculation of T_g of the non-aqueous solutions.     

WATER PLASTICIZATION EFFECTS ON CRYSTALLIZATION BEHAVIOR OF LACTOSE IN A CO-LYOPHILIZED AMORPHOUS POLYSACCHARIDE MATRIX AND ITS RELEVANCE TO THE GLASS TRANSITION

ABSTRACT

Crystallization of lactose in a co-lyophilized amorphous polysaccharide matrix was investigated under various hydration conditions to test the possible relation between the ability of the polymer to raise the glass transition temperature (T_g) of the lactose-pullulan blend, relative to pure lactose, and the crystallization kinetics. Both calorimetric (DSC) non-isothermal measurements and x-ray diffraction analysis of samples stored at a constant temperature revealed a marked retardation in lactose crystallization in the presence of pullulan; i.e., the rate constant values, as determined by the Avrami analysis, declined and the ‘half-time’ (t_1/2c) for lactose crystallization increased with decreasing ratio of lactose/pullulan. The inhibitory action of pullulan on crystallization of lactose could not be solely attributed to T_g-related effects on molecular mobility of the composite systems. At a pullulan weight fraction range of 0.25–0.33 (w/w of total solids) the influence of the polymeric additive on T_g was marginal over the entire water content range examined, although crystallization was delayed as compared with pure lactose. Modeling of the temperature-dependence of t_1/2c for the combined lactose-pullulan systems with the Williams-Landel-Ferry (WLF) equation was feasible only when the coefficients C₁ and C₂ were allowed to vary instead of assuming their ‘universal’ values.     

Influence of milk proteins on the development of lactose-induced stickiness in dairy powders

The stickiness behaviour of a range of spray dried dairy powders differing in protein/lactose ratio was determined using a fluidised bed apparatus. Powders with higher protein/lactose ratios were less susceptible to sticking. Stickiness was related to both the glass transition temperature (T_g) and the temperature increment by which T_g must be exceeded before sticking occurred (T?T_g). T?T_g values of approximately 10, 22, 29, 45 and 90 °C were found for powders containing 15.5, 26.9, 39.5, 55.7 and 83.4% protein respectively. Composition had different effects on T_g and T?T_g. The rate at which water was sorbed and desorbed by powders increased with protein content. With increasing protein content, preferential sorption of water by non-amorphous constituents delayed the rate at which lactose underwent the requisite change from the ‘glassy’ to the ‘rubbery’ form in order that powder particles became sticky.     

Residual Moisture Content as Related to Collapse of Freeze-dried Sugar Matrices

Amorphous sugars were prepared by freeze-drying 20% (w/w) aqueous solutions of lactose, sucrose, trehalose and maltose. The dried samples were further dehydrated over P₂O₅ for 1 wk at 25, 35 or 45°C, and the residual moisture content was determined using oven drying or a thermogravimetric balance. Results indicated a small amount of residual moisture (usually 1–2%) which was not removed by the desiccation treatment for 1 wk at 25°C over P₂O₅. The dried samples, heated at a temperature near the published “anhydrous” glass transition temperatures (T_g) exhibited different behavior depending on whether they were heated in open or sealed vials. Structural collapse, a sharply visible shrinkage of the matrix, was found in all samples in sealed vials, while those samples in open vials did not collapse. Thus, removal of the last amount of residual moisture by heating in uncovered vials increased T_g, preventing or delaying collapse.     

Effects of methylcellulose,xanthan gum and carboxymethylcellulose on thermal properties of batter systems formulated with different flour combinations

The functionalities of hydrocolloid–flour mixtures in terms of the thermal properties of their resulting batter systems were investigated, and the effects of different thermal processes such as cooking–freezing–thawing (CFT) and freezing–cooking (FC) on thermal properties of the various batter systems were determined in this study. Differential scanning calorimetry (DSC) was used to determine thermal property parameters including gelatinization temperature (T_G), total enthalpies of gelatinization (ΔH_G), glass transition temperature (T_g), melting peak temperature (T_m), and total melting enthalpies (ΔH_m). The different thermal processes did not significantly affect either T_G or ΔH_G of batter systems, but they influenced the glass transition behavior and the ΔH_m of batter systems. The thermal processes also showed different effects on the batter systems containing different hydrocolloids such as methylcellulose (MC), carboxymethylcellulose (CMC), and xanthan gum (XG). The hydrocolloids shifted T_G upwards, depressed T_g, and increased T_m of batters. The effect of these hydrocolloids on glass transition temperature was more pronounced in raw samples (FC process) than in cooked samples and increased with increasing levels of CMC and MC used in the formulations. Batters with MC showed increased ΔH_m for all the thermal processes. CMC only showed significant effect on ΔH_m for cooked samples (CFT process). MC and CMC showed more pronounced effects on T_g for raw uncooked rice- and corn flour-based batters than on raw uncooked wheat flour-based batters. However, this special effect was not obvious in the batters containing 0.2% XG.     

Water–solids interactions,matrix structural properties and the rate of non-enzymatic browning

The kinetics of non-enzymatic browning (NEB) was studied in freeze-dried model and food systems in a wide range of relative humidity (R.H.) values.PVP, lactose, lactose–starch solutions and food (milk, cabbage, apple, potato, and chicken meat) systems were freeze-dried, equilibrated at 11–85% of R.H. and incubated at 70 °C. Thermal transitions were determined by DSC. The kinetics of NEB development was analyzed. In PVP systems the maximum rate occurred at 33% R.H., at which T_g was close to the storage temperature. Above 33% R.H. the samples presented a fluid aspect at 70 °C and the NEB rate decreased when increasing R.H. In tissues containing structuring water insoluble biopolymers and presenting an intermediate degree of collapse, the maximum rate of NEB occurred at relative humidities in a range of 50–80%, when the samples were well above T_g at the storage temperature. In the lactose systems the maximum rate occurred at R.H. close to 40%, at conditions at which lactose was highly crystalline.     

State diagram of salmon (Salmo salar) gelatin films

BACKGROUND: A state diagram presents different physical states of a biomaterial as a function of solid content and temperature. Despite their technological interest, little information is available on protein systems such as gelatin/water mixtures. The objective of this work was to develop state diagrams of salmon gelatin (SG) and bovine gelatin (BG) in order to determine maximal freeze concentration parameters (T′_g, T′_m and X_s′) and to relate possible differences to their biochemical characteristics. RESULTS: Biochemical characterisation of SG showed lower molecular weight and iminoacid concentration compared with BG. Likewise, the glass transition temperature (T_g) was lower for SG at X_s > 0.8, which was associated with its lower molecular weight. Unexpectedly, the depression of freezing temperature (T_f) was greater for SG at X_s > 0.1, which was associated with its higher ash content. Isothermal annealing produced effective values of T′_g ≈ ? 52 °C, T′_m ≈ ? 46 °C and X′_s ≈ 0.6 for both gelatins. Interestingly, the enthalpy change associated with T′_m (ΔH) was significantly higher for SG than for BG after annealing, indicating a higher proportion of ice present at about ? 50 °C. CONCLUSION: Maximal freeze concentration parameters were similar between the two gelatins, though differences in biochemical properties were evident. The results show that there are likely different ways of interaction of SG and BG with water. Copyright © 2011 Society of Chemical Industry     

Influence of protein concentration on surface composition and physico-chemical properties of spray-dried milk protein concentrate powders

Surface composition, moisture sorption behaviour and glass–rubber transition temperature (T_gr) were determined for spray-dried milk protein concentrate (MPC) powders over a range of protein contents (35–86 g 100 g⁻¹). Surface characterisation of MPC powders indicated that fat and protein were preferentially located on the surface of the powder particles, whereas lactose was located predominantly in the bulk. Moisture sorption analysis at 25 °C showed that MPC35 exhibited lactose crystallisation, whereas powders with higher protein contents did not and continually absorbed moisture upon humidification up to 90% RH. The GAB equation, fitted to sorption isotherms of MPCs, gave increases in monolayer moisture value (m_m) with protein content. T_gr, measured with a rheometer, decreased significantly (P < 0.05) with increasing water content and increased with increasing protein content (P < 0.05). In conclusion, increasing protein concentration of MPCs resulted in altered surface composition and increased m_m value and T_gr values.     

Amino Acids as Plasticizers for Starch-based Plastics

Amino acids of differing hydrophobicity were tested as plasticizers in starch-glycerol (4:1 weight ratio) blends and were compared to the more conventional plasticizers, urea, sucrose and ammonium chloride. In mechanical tests (tensile strength and percent elongation) on extruded ribbons containing up to 20 weight percent plasticizer, glycine and isoleucine hydrochloride were found to be extremely poor plasticizers. However, lysine behaved similarly to sucrose. Proline compared favorably to urea. Moreover, at concentrations of 23 and 29 weight percent, proline was superior to urea in its ability to increase the percent elongation of the starch-glycerol mixture. The glass transition temperature (T_g) for the standard starch-glycerol samples was 40°C, as determined by differential scanning calorimetry. Added lysine hydrochloride, sucrose, proline and urea effected the T_g similarly. At 5 weight percent all T_g's increased, while at 20 weight percent they dropped to room temperature or below. Isoleucine, at low or high concentration, yielded a T_g of 60°C, consistent with very brittle material. Biodegradation experiments were conducted on selected formulations by monitoring CO₂ evolution after inoculation with Aspergillus niger. Little CO₂ accumulated from the standard starch-glycerol mixture or sucrose plasticized blends, likely due to a lack of combined nitrogen. In contrast, proline and urea-plasticized blends were rapidly metabolized.     

The effect of starch gelatinization and solute concentrations on T g′ of starch model system

The effect of starch gelatinization on glass transitions in a starch/water model system and how the concentrations of added solutes (sucrose and sodium chloride) affect the glass transition temperatures of the gelatinized starch solution was investigated. The starch suspension samples were heat treated in a Differential Scanning Calorimeter (DSC) under different time and temperature regimes to achieve different degrees of gelatinization. The gelatinization characteristics (onset, peak and end temperatures and enthalpy) and the glass transition values of a potato starch were determined using the DSC. The results showed that the starch concentrations had no effect on gelatinization characteristics and the T_g′ of the gelatinized potato starch but had clearly increased their ΔC_p in the T_g′ region. Annealing at a temperature slightly below the T_g′ of −5 °C, led to maximal freeze‐concentration in the total/partial gelatinized starch and a higher T_g′ value at about −3 °C was obtained. The T_g′ values of the totally gelatinized starch samples were slightly lower than those of partially gelatinized samples. The T_g′ of the gelatinized starch decreased with increasing concentrations of sucrose or sodium chloride. Sodium chloride had a stronger depressing effect on T_g′ than sucrose. © 2000 Society of Chemical Industry