On modeling changes in food and biosolids at and around their glass transition temperature range

Temperature‐induced mechanical and other changes in biosolids are regulated by three types of kinetics, depending on whether the material is in the glassy state, undergoing a transition, or fully plasticized. The transition itself can take place over a considerable temperature range, which in many food and biological systems happens to be the most pertinent to their functionality and stability. At the transition onset, the plot of stiffness vs. temperature has a downward concavity. It is reversed only at an advanced stage of plasticization after much of the stiffness has already been lost. Consequently, the WLF, Arrhenius, or any other model that implies a continuous upward concavity cannot account for changes in the transition region, and it is unsafe to use them to predict properties through extrapolation.

The mechanical changes in the transition region can be described by a model with the mathematical structure of Fermi's function. Its applicability has been demonstrated with published data on a variety of foods and biosolids. Because the plot of stiffness vs. moisture, or water activity, has the same general shape as that of the stiffness vs. temperature plot, it too can be described by a model with the same mathematical format.

Because moisture lowers the transition center temperature in a manner that can be described by a simple algebraic expression, the combined effects of temperature and moisture can be incorporated into a single general model. The latter can be used to create three‐dimensional displays of the stiffness‐temperature‐moisture characteristic relationships of biosolids at and around their transition. At temperatures well above that of the transition, though, where a plot of log stiffness vs. temperature has a clear upper concavity, this model is no longer applicable, and the changes are better described by the WLF or an alternative model.     

Influence of osmodehydrofreezing with different sugars on the quality of frozen rambutan

The objective of this research was to study the effect of osmotic pretreatment with different sugars on the quality of frozen rambutan. Rambutan pieces were osmotically dehydrated in 50% sucrose, trehalose and maltitol solutions. The amount of water loss and solid gain during osmotic dehydration were determined. The increase of water loss and solid gain were not significantly different among the syrups ( P  > 0.05). For osmodehydrofreezing, the fruit pieces were immersed for 1 h before freezing at −40 °C with an untreated sample used for comparison. The physical and chemical properties of samples stored at −18 °C for 3, 60 and 120 days were studied. Pretreatment with sucrose received the highest scores in terms of taste, texture and acceptability. The glass transition temperature values of treated samples, especially those treated with trehalose, increased significantly compared to the untreated sample, but they were all much lower than the storage temperature of −18 °C. All of the experimental samples were in a rubbery state, and therefore the glass transition concept could not be used to predict quality.     

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.     

Characterization of Branched Oligosaccharides Produced by Bacillus licheniformis Maltogenic Amylase

Highly concentrated branched oligosaccharides (HBOS) were prepared from liquefied corn starch by a continuous process using an immobilized Bacillus licheniformis maltogenic amylase (BLMA) and yeast fermentation. Physicochemical properties of HBOS were evaluated and compared with those of sucrose and commercial oligosaccharides. An HBOS solution showed flow behavior nearly Newtonian. At relative humidities of 32% and 90%, HBOS exhibited high moisture retention and absorption properties. HBOS were relatively stable against heating at pH 3. Addition of 10–20% HBOS to starch increased its gelatinization temperature by 5–10°C. The glass transition temperature of freeze-concentrated HBOS was higher than that of sucrose, suggesting the potential of HBOS for use in the storage of frozen foods.     

Kinetics of non-enzymatic browning in amorphous solid systems: distinguishing the effects of water activity and the glass transition

Debates have emerged recently on whether water activity or the state of the system as dictated by the glass transition temperature (T_g) impacts the rates of chemical reactions in reduced-moisture solid systems. The objective of this study was to evaluate the kinetics of brown pigment formation in polyvinylpyrrolidone model systems of different molecular weights so that the effects of water activity and the glass transition could be distinguished. Browning rates at different T_gs, but constant water activity, were significantly different except when all were in the glassy state. As the system changed from a glassy state to a rubbery state, the rate of browning increased 7-fold. The rate of browning also increased as water activity increased from 0.33 to 0.54, but then appeared to plateau with further increases in water activity. Thus, the rate of brown pigment formation is influenced significantly by the glass transition temperature of the system and less by the water activity. In addition, the concentration of reactants in the aqueous microenvironment had a significant impact on the rate of brown pigment formation.     

Glycine Loss and Maillard Browning as Related to the Glass Transition in a Model Food System

The effects of water activity and the glass transition on the rate constants for glycine loss and brown pigment formation due to the Maillard reaction were evaluated in a model food system. Equimolar glucose and glycine were incorporated into amorphous polyvinylpyrrolidones of various molecular weights and moisture contents. Glycine loss and brown pigment formation were quantified during storage at 25°C. At constant water activity, rate constants were higher in systems with lower glass transition temperatures. Glycine rate constants decreased upon matrix collapse, but browning rate constants were not affected by collapse. Changes associated with the glass transition influence bimolecular reactions and should be considered during product formulation and shelf-life testing.     

Nonenzymatic Browning in Amorphous Food Models: Effects of Glass Transition and Water

ABSTRACT: The effect of glass transition on nonenzymatic browning (NEB) rates of amorphous, L-lysine, and D-xylose containing maltodextrin (MD)- or polyvinylpyrrolidone (PVP)-based food models, equilibrated into a_w of 0.23, 0.33, or 0.44 was studied. Glass transition temperature, T_g, was measured using DSC and NEB rates, followed spectrophotometrically. Use of citrate buffer as a pH regulator was evaluated. The NEB rates were higher in PVP than in MD models. Arrhenius plots showed nonlinearity in the vicinity of the T_g. Increasing a_w decreased T_g, but did not affect NEB rates around the T_g. The temperature difference (T - T_g) was not a sufficient measure of material stability.     

A quasi-chemical model for the growth and death of microorganisms in foods by non-thermal and high-pressure processing

Predictive microbial models generally rely on the growth of bacteria in laboratory broth to approximate the microbial growth kinetics expected to take place in actual foods under identical environmental conditions. Sigmoidal functions such as the Gompertz or logistics equation accurately model the typical microbial growth curve from the lag to the stationary phase and provide the mathematical basis for estimating parameters such as the maximum growth rate (MGR). Stationary phase data can begin to show a decline and make it difficult to discern which data to include in the analysis of the growth curve, a factor that influences the calculated values of the growth parameters. In contradistinction, the quasi-chemical kinetics model provides additional capabilities in microbial modelling and fits growth-death kinetics (all four phases of the microbial lifecycle continuously) for a general set of microorganisms in a variety of actual food substrates. The quasi-chemical model is differential equations (ODEs) that derives from a hypothetical four-step chemical mechanism involving an antagonistic metabolite (quorum sensing) and successfully fits the kinetics of pathogens (Staphylococcus aureus, Escherichia coli and Listeria monocytogenes) in various foods (bread, turkey meat, ham and cheese) as functions of different hurdles (a_w, pH, temperature and anti-microbial lactate). The calculated value of the MGR depends on whether growth-death data or only growth data are used in the fitting procedure. The quasi-chemical kinetics model is also exploited for use with the novel food processing technology of high-pressure processing. The high-pressure inactivation kinetics of E. coli are explored in a model food system over the pressure (P) range of 207–345 MPa (30,000–50,000 psi) and the temperature (T) range of 30–50 °C. In relatively low combinations of P and T, the inactivation curves are non-linear and exhibit a shoulder prior to a more rapid rate of microbial destruction. In the higher P, T regime, the inactivation plots tend to be linear. In all cases, the quasi-chemical model successfully fit the linear and curvi-linear inactivation plots for E. coli in model food systems. The experimental data and the quasi-chemical mathematical model described herein are candidates for inclusion in ComBase, the developing database that combines data and models from the USDA Pathogen Modeling Program and the UK Food MicroModel.     

Linear and non-linear kinetics in the synthesis and degradation of acrylamide in foods and model systems

Isothermal acrylamide formation in foods and asparagine-glucose model systems has ubiquitous features. On a time scale of about 60 min, at temperatures in the approximate range of 120-160 degrees C, the acrylamide concentration-time curve has a characteristic sigmoid shape whose asymptotic level and steepness increases with temperature while the time that corresponds to the inflection point decreases. In the approximate range of 160-200 degrees C, the curve has a clear peak, whose onset, height, width and degree of asymmetry depend on the system's composition and temperature. The synthesis-degradation of acrylamide in model systems has been recently described by traditional kinetic models. They account for the intermediate stages of the process and the fate of reactants involved at different levels of scrutiny. The resulting models have 2-6 rate constants, accounting for both the generation and elimination of the acrylamide. Their temperature dependence has been assumed to obey the Arrhenius equation, i.e., each step in the reaction was considered as having a fixed energy of activation. A proposed alternative is constructing the concentration curve by superimposing a Fermian decay term on a logistic growth function. The resulting model, which is not unique, has five parameters: a hypothetical uninterrupted generation-level, two steepness parameters; of the concentration climbs and fall and two time characteristics; of the acrylamide synthesis and elimination. According to this model, peak concentration is observed only when the two time constants are comparable. The peak's shape and height are determined by the gap between the two time constants and the relative magnitudes of the two "rate" parameters. The concept can be extended to create models of non-isothermal acrylamide formation. The basic assumption, which is yet to be verified experimentally, is that the momentary rate of the acrylamide synthesis or degradation is the isothermal rate at the momentary temperature, at a time that corresponds to its momentary concentration. The theoretical capabilities of a model of this kind are demonstrated with computer simulations. If the described model is correct, then by controlling temperature history, it is possible to reduce the acrylamide while still accomplishing much of the desirable effects of a heat process.     

Lactose crystallization delay in model infant foods made with lactose, beta-lactoglobulin, and starch

Handling and storage alter infant food powders due to lactose crystallization and interactions among components. Model infant foods were prepared by colyophilization of lactose, β-lactoglobulin (β-LG), and gelatinized starch. A mixture design was used to define the percentage of each mixture component to simulate a wide range of infant food powders. The kinetics of crystallization was studied by a gravimetric method (dynamic vapor sorption) at 70% relative humidity (RH). After freeze-drying, lactose was amorphous and crystallized at 70% RH. The delay before crystallization depends on the contents of β-LG and starch in the formulations. A mathematical model was proposed to predict crystallization time (delay) at 70% RH. For the formulation containing 50% lactose, 25% β-LG, and 25% starch, lactose was still amorphous after 42 h at 70% RH, whereas pure amorphous lactose crystallized after approximately 70 min. Calculated and experimental results of adsorbed moisture from the formulations were compared. Adsorbed water of formulation containing lactose could not be calculated from moisture sorption properties of each component at a given RH because β-LG and gelatinized starch prevented lactose crystal growth.     

Changes in Starch Pasting Properties Due to Sugars and Emulsifiers as Determined by Viscosity Measurement

The effects of sugars, emulsifiers, and their interactions on starch pasting properties were determined by the Rapid Visco-Analyser (RVA). Solutions of 50% sugars in water were used. The disaccharides, sucrose and lactose, delayed pasting more than did the monosaccharide, dextrose. Sugars’effects on starch pasting delay and on starch paste consistency varied with the starch. Addition of the same emulsifier (1%) to different starches did not result in the same change in paste consistency in the presence of high amounts of sugar. Both sucrose ester F-160 (SE) and polysorbate 60 (PS) reduced the hot paste consistency of starch-sugar mixtures, with SE having a greater effect than PS.     

On the need for another type of predictive model in structured foods

Most of the models discussed up till now in predictive microbiology do not take into account the variability of microbial growth with respect to space. In structured (solid) foods, microbial growth can strongly depend on the position in the food and the assumption of homogeneity can thus not be accepted: space must be considered as an independent variable. Indeed, experimental evidence exists of bacteria competition on agar not showing the same behavior as the competition in a well-mixed liquid culture system. It is conjectured that this is due to the spatially structured habitat. Therefore, in the current paper, a prototype two species competition model proposed in previous work by the authors is extended to take space into account. The extended model describes two phenomena: (i) local evolution of biomass and (ii) transfer of biomass through the medium. The structure of the food product is taken into account by limiting the diffusion through the medium. The smaller mobility of the micro-organisms in solid foods allows spatial segregation which causes pattern formation. Evidence is given for the fact that taking space into account indeed has an influence on the behavior (coexistence/extinction) of the populations. Although the reported simulations are by no means to be interpreted as accurate predictions, the proposed model structure allows one to highlight (i) important characteristics of microbial growth in structured foods and (ii) future research trends in predictive microbiology.     

On water dynamics and germination time of mold spores in concentrated sugar and polyol solutions

The relative effect of concentrated solutions of selected glass formers on germination time at 28 °C of mold spores of Aspergillus flavus, A. niger and Eurotium herbariorum was determined. Solutes included glucose, fructose, mannose, glycerol, sucrose, maltose and propylene glycol. The effect of fructose concentration on the germination time of A. parasitions was also studied. The results did not agree with previous literature experimental data used to support a ‘water dynamics’ approach of microbial stabilization in concentrated sugar and polyol solutions.     

A model of moisture-induced plasticization of crunchy snacks based on fermi' distribution function

The irregular force-deformation relationships of commerical cheese balls and Zwiebacks at nine levels of water activity in the range 0.11–0.85 were recorded with a computer-interfaced Universal testing machine. They were characterized by two empirical stiffness parameters, the force at 10 and 20% deformation, and two jaggedness measures, the apparent fractal dimension of the normalized force-deformation curve and the mean magnitude of its power spectrum. The plots of all four parameters versus the water activity had a stable region followed by a substantial drop at a characteristic water activity level, of the kind expected when a material undergoes a glass transition. The phenomenon over the entire experimental water activity range, could be described by a model whose mathematical formal is a slightly modified version of Fermi' distribution function that is P(a_w) = P_s/{1 + exp[(a_w — a_wcp)]/b_p} + c_p where P(a_w) is any of the stiffness or jaggedness parameters, P_s and c^p constants whose sum is the magnitude of the parameter when the material is in the dry state (c_p is the residual level after plasticization), a_wcp is a characteristic water activity level representing the region where the major textural changes take place, and b_p a constant representing the steepness of the relationship at the transition region.     

浅述玻璃化转变温度与食品成分的关系

食品体系的玻璃化转变温度会对食品的加工和贮藏过程及食品的品质产生重要影响。重视食品体系的玻璃化转变温度并分析其影响因素,可帮助人们更好的了解食品加工和贮藏特性,提高产品品质。该文就水分含量、碳水化合物、蛋白质、平均分子量及食品添加剂等因素与一定的食品体系的玻璃化转变温度的关系进行了综述。     

Rates of starch hydrolysis and changes in viscosity in a range of common foods subjected to simulated digestion in vitro

A range of common starch-rich foods and pure starches was analysed for available carbohydrates and dietary fibre content, and subjected to a simulated digestion procedure in vitro. The initial rates of free sugar release differed markedly between foods; the time required for the release of 50% of the starch content of some legumes was up to 100 fold longer than that for foods such as potatoes and rice. A significant correlation (r=0.806; P<0.01) between the time required for hydrolysis and the total dietary fibre content of the foods was observed. The viscosity of the food samples declined during the course of digestion, but always remained markedly higher than that of pure starch. The rate of hydrolysis of starch appears to be the most important factor governing the human glycaemic response to foods described by other authors, but the final viscosity of partially digested foods may be of some significance.     

Water activity,water glass dynamics,and the control of microbiological growth in foods

Water is probably the single most important factor governing microbial spoilage in foods, and the concept of water activity (a_w) has been very valuable because measured values generally correlate well with the potential for growth and metabolic activity. Despite some drawbacks (e.g., solute effect), the concept of a_w has assisted food scientists in their effort to predict the onset of food spoilage as well as to control food‐borne disease hazards in food products. In the last decade the concept of a_w has been challenged. It has been suggested that reduced‐moisture food products (e.g., low and intermediate) may be nonequilibrium systems and that most of them are in the amorphous metastable state, which is very sensitive to changes in moisture content and temperature. It has been proposed that the glass transition temperature T_g (temperature at which the glass‐rubber transition occurs), is a parameter that can determine many product properties, the safety of foods among them. The concept of water dynamics, originating in a food polymer science approach, has been suggested instead of a_w to better predict the microbial stability of intermediate‐moisture foods. The usage of a_w to predict microbial safety of foods has been discouraged on the basis that (1) in intermediate‐moisture foods the measured water vapor pressure is not an equilibrium one, and because a_w is a thermodynamic concept, it refers only to equilibrium; and (2) the microbial response may differ at a particular a_w when the latter is obtained with different solutes.

This review analyzes these suggestions on the basis of abundant experimental evidence found in the literature. It is concluded that nonequilibrium effects (e.g., inability of water to diffuse in a semimoist food) appear to be in many cases slow within the time frame (food's shelf life) of the experiments and/or so small that they do not affect seriously the application of the a_w concept as a predictor of microbial stability in foods.

The claims that a food science polymer approach to understanding the behavior of aqueous sugar glasses and concentrated solutions may be used to predict the microbial stability of food systems is not substantiated by experimental evidence. This approach does not offer, at the present time, a better alternative to the concept of a_w as a predictor of microbial growth in foods.

It is also recognized that a_w has several limitations and should be always used carefully, and this must include precautions regarding the possible influences of nonequilibrium situations. This aspect may be summarized by simply saying that anyone who is going to employ the term water activity must be aware of the implications of its definition.     

Intrinsic viscosities and apparent specific volumes of amino acids and sugars. ‘Effective size’ and taste of sapid molecules

Intrinsic viscosities ([η]) and apparent specijic volumes (V) are compared for a number of amino acids and simple sugars and their derivatives. While the sugars and their derivatives fit within a narrow range for both parametevs ([η])=2.27–2.61 cm³ g^?1; V=0.60–4.69 cm³ g^?1), the amino acids cover a much wider band ([η]) = 1.29–4.20 cm³ g^?1; V=0.562–0.712 cm³ g^?1). The intrinsic viscosity value of any particular amino acid is always greater than the corresponding apparent specijc volume, and ranges (at 10 mg g^?1) between two and seven times the value of the apparent specific volume. For the sugars and sugar derivatives, on the other hand, the intrinsic viscosities are always three to four times greater than the values of the corresponding apparent specijic volumes. When concentration is increased, all apparent specific volumes increase but they remain relatively constant if they are expressed as parachors (Vγ^1/4). Differences between the sugars and amino acids originate in the greater structural diversification of the latter molecules which in turn accords with their greater range of taste qualities.     

A review on the use of cyclodextrins in foods

Cyclodextrins (CDs) are cyclic oligomers widely used in the food industry as food additives, for stabilization of flavours, for elimination of undesired tastes or other undesired compounds such as cholesterol and to avoid microbiological contaminations and browning reactions. In this review the characteristics of the most important CDs at industrial level (α-CD, β-CD and γ-CD) and their main properties from a technological point of view, such as solubility and their capability to form inclusion complexes are described. In addition, the present state-of-the-art on the use of these compounds in the food industry was reviewed.     

On the size of monomers and polymers of beta-casein.

The size and number average molecular weight have been determined for beta-casein monomers and polymers from electron micrographs using the freeze-etching procedure with spray-frozen specimens. For the spherical beta-casein monomers we found a mol. wt of 22600 and a diam. about 10 nm, which compared quite well with data obtained from ultracentrifugation, light scattering and viscosity measurements. Polymer sizes were in agreement with molecular weight determinations from ultracentrifugation and light scattering, assuming that the volume and weight of the particles are proportional.