Relationship between ice recrystallisation rates and the glass transition in frozen sugar solutions

The increase in ice crystal size that occurs through recrystallisation when many frozen products such as ice cream and frozen desserts are stored is one of the major factors contributing to the perceived deterioration of the product by the consumer. In order to reduce the rate of deterioration, a detailed understanding of the fundamental mechanism is needed. This study demonstrates that ice recrystallisation rates in a series of frozen sugar solutions are strongly correlated with the molecular mobilities of the water and solute molecules as measured by time domain nuclear magnetic resonance. The study also demonstrates that the proximity to the glass transition temperature as described by state diagrams correlates well with the measured ice recrystallisation rates. The temperature dependence in these systems is described by Williams, Landel and Ferry theory. © 2002 Society of Chemical Industry     

水分含量对草莓玻璃化转变温度的影响

在冻干和低温保存中,玻璃化转变温度是一个非常重要的参数。本文用差示扫描量热仪测量得到不同湿基水分含量的草莓汁的玻璃化转变温度。实验发现水分含量较高时(>50%),草莓发生的是部分玻璃化转变,不同湿基水份含量草莓汁的Tg’基本相同,水分对其的影响较小。而水分含量较低时(<45%),草莓降温时往往出现完全玻璃化转变,不同湿基水分含量草莓的Tg有很大不同,完全玻璃化转变温度随着水分含量的减少而升高,拟合得到Tg随水分变化的公式。     

蔗渣碱法制浆蒸煮黑液增浓过程中的相变化

利用DSC的热分析法探讨了蔗渣浆黑液在蒸发浓缩中的相转变过程。当蔗渣黑液中固形物含量接近40%时，黑液聚合物由水的连续相转变为聚合物（由有机物和无机物组成）的连续相。此时，黑液由凝固点（冰点）温度过渡到玻璃化转变点温度，相应地，黑液的物化性能如粘度等变化很大。     

Dielectric properties of frozen maltodextrin solutions with added NaCl across the glass transition

The change in the dielectric properties of frozen 200 g kg^?1 maltodextrin solutions upon warming has been recorded using a capacitance meter and a dielectric thermal analysis instrument. The capacitance and permittivity increased by several orders of magnitude after melting, and higher values were obtained at a higher measurement frequency or with added NaCl, while a marked increase (labelled T_rise) was seen close to the glass transition temperatures measured by differential scanning calorimetry. The transition temperatures shifted to more negative values by 4–6 °C upon the addition of 0.1 mol kg^?1 NaCl, consistent with the freezing point depression of the freeze‐concentrated solutions. Copyright © 2004 Society of Chemical Industry     

草莓玻璃化转变温度的DSC测量

在测量溶液的部分玻璃化转变温度时,往往无法直接测得溶液在最大冻结浓缩状态下的部分玻璃化转变温度(Tg’),而是测得部分结晶玻璃化转变温度(Tgf)。本文用差示扫描量热仪,采用不经过退火处理的连续扫描法、分步扫描法对草莓打浆液、榨汁草莓经抽滤的草莓汁液和浓缩掉三分之一水分的浓缩草莓汁进行了玻璃化转变温度的测量。研究发现,用同一种方法测得的三者的玻璃化转变温度相差不大。在-48℃以下退火,玻璃化转变温度随着退火温度的增大而增大,在-48℃以上退火,玻璃化转变温度随着退火温度的增大而减小,并有很好的线性关系,从Tgf确定Tg’的新方法是两侧Tgf的交点对应的温度为Tg’。得到草莓的Tg’为-52.8℃。     

南美白对虾肉玻璃化转变温度测定的影响因素

为准确测定南美白对虾肉的玻璃化转变温度(Tg),对影响其Tg测定的因素(包括差示扫描量热仪(DSC)测定过程中程序扫描次数、退火温度和时间、加热速率、样品湿基含水率)进行了系统研究。结果表明,含非冻结水的虾肉宜采用单扫描程序。含冻结水的虾肉冰晶体出现始、末对应的温度范围为-22℃~-53℃,在此温度范围内退火30 min,焓变ΔH先降低后增加,当ΔH达到最小值171.1 J/g时,与之对应的温度为-35℃,即为虾肉适宜的退火温度。虾肉Tg随退火时间的延长而降低,且在超过30 min后逐渐趋于稳定,因此适宜退火时间为30 min。虾肉Tg随升温速率的降低而降低,并在速率低于5℃/min后逐渐趋于恒定,适宜升温速率范围5℃/min。Tg随虾肉含水率的增加而降低,含水率25.88%时,Tg降低趋势明显;而含水率25.88%时,Tg降低幅度很小并逐渐趋于恒定。本研究结果可为南美白对虾肉DSC扫描程序的确定提供理论依据。     

赤藓糖醇对南美白对虾肉玻璃化转变温度与状态图的影响

南美白对虾肉（PV）冻藏期间极易出现蛋白质变性,为提高虾肉贮藏稳定性,研究了PV与按虾肉质量添加5%赤藓糖醇的虾肉（PV-E）的吸附等温线;测定了PV与PV-E的玻璃化转变温度（Tg）和冻结点温度（TF）。采用Gordon-Taylor方程与Chen’s方程拟合数据,探讨添加赤藓糖醇对虾肉状态图的影响。结果表明,PV与PV-E水分吸附均为III型等温线,GAB模型为描述虾肉水分吸附特性的最适模型。PV与PV-E的Tg随着湿基含水率升高而降低;相同含水率时,PV-E的Tg高于PV。PV与PV-E的TF随着固形物含量的增加而降低。PV与PV-E最大冷冻浓缩溶液时的玻璃化转变温度T’g分别为-77.09℃和-62.23℃,与之对应的溶质含量分别为0.672 g/g和0.686 g/g。赤藓糖醇可作为一种新型抗冻剂,用于提高虾肉冻藏期间的贮藏稳定性。      

The measurement of the glass transition temperature of sucrose and maltose solutions with added NaCl

The effect of added NaCl on the glass transition temperatures of 200 and 300 g kg⁻¹ sucrose and maltose solutions was determined using DSC and capacitance measurements. Negative shifts of around 4 °C were seen upon the addition of 0.1 mol kg⁻¹ NaCl, consistent with the freezing point depression expected for the maximally freeze‐concentrated solutions. Changes in the capacitance were seen which matched both the onset of the devitrification event and the main heat capacity step seen in DSC scans. © 2000 Society of Chemical Industry     

Effect of Calcium Maltobionate on the Glass Transition Temperature of Model and Hand-made Hard Candies

Glass transition temperature (T_g) is an important parameter for the physical quality control of hard candies. In order to understand the applicability of calcium maltobionate to hard candy, effect of calcium maltobionate addition on the T_g of model and hand-made hard candies was investigated. Freeze-dried calcium maltobionate-sugar (sucrose containing a small amount of glucose-fructose mixture) and calcium maltobionate-reduced isomaltulose mixtures were prepared as model candies, and their anhydrous T_g was evaluated using a differential scanning calorimetry. The anhydrous T_g increased linearly with the molar fraction of calcium maltobionate. From these results, it was expected that calcium maltobionate can improve the physical stability of normal and sugarless candies. For comparison, various commercial candies were employed, and their T_g was evaluated using a thermal rheological analysis. The T_g values were in the range of 28–49 °C. The T_g values were higher than 25 °C, which is significant with respect to the physical stability of the candies. Calcium maltobionate-sugar and calcium maltobionate-reduced isomaltulose candies were prepared as hand-made candies. The calcium maltobionate-reduced isomaltulose candies had higher T_g than the calcium maltobionate-sugar candies at each calcium maltobionate content, although reduced isomaltulose has a lower T_g than sugar. At a high calcium maltobionate content, calcium maltobionate-reduced isomaltulose candy had an equivalent T_g to the commercial sugarless candies, and thus practically acceptable stability was expected. In the case of calcium maltobionate-sugar candies, there was a possibility that the hydrolysis of sugar reduced their T_g. Vacuum-concentration will be useful to improve the T_g of the candies.     

冻干溶液玻璃化转变温度的实验研究

本文利用差示扫描量热仪(DSC)研究了降温速率和溶质比对叔丁醇/蔗糖/水三元系统玻璃化转变温度Tg’的影响。实验结果表明,降温速率的增大会使溶液的玻璃化转变温度明显降低。对于10%叔丁醇/10%蔗糖/水溶液,当降温速率大于10℃/min时,Tg’为-42℃。对于叔丁醇与蔗糖的浓度比小于0.2的溶液,降温时叔丁醇不会发生结晶。     

Optimisation of production and storage stability of the starter bacteria Streptococcus thermophilus and Lactobacillus plantarum

The growth of Lactobacillus plantarum and Streptococcus thermophilus was modelled by fitting isothermal calorimetric traces to arbitrary mathematical functions. There was a correlation between certain features on the thermal trace and parameters derived from a Baranyi fit to viable count data. In the presence of 75 g L^?1 lactose, S. thermophilus showed a slower rate of growth than in the presence of 5 g L^?1 lactose when measured by both viable count and heat flow. A simple equation described the variation in glass transition temperature with water activity for all preparations. A master curve fit for all mortality data for S. thermophilus showed the importance of a transition temperature for the survival of freeze‐dried preparations of bacteria. The temperature at which survival began to be impaired was 15–20 °C below the glass transition temperature determined by differential scanning calorimetry. Copyright © 2007 Society of Chemical Industry     

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.     

Effect of maltodextrin weight fraction on the amorphous state and critical storage conditions of freeze-dried juices

Diagrams relating to water activity (a_w), equilibrium moisture content (X_w) and glass transition temperature (Tg) are valuable tools for predicting amorphous fruit powders' storage procedure and stability. Thus, T_g–a_w–X_w diagrams were constructed to characterise the amorphous state and define the critical values of water content (X_wc) and water activity (a_wc) of freeze-dried juices of strawberry, pineapple, kiwi and prickly pear prepared with maltodextrin at the dry mass fraction (W_MD) of 0, 0.4 and 0.8. The T_g and sorption data were fitted with a polynomial equation and the Guggenheim–Anderson–de Boer (GAB) model respectively. A Tukey test was performed to evaluate the difference between critical values of the powders (P < 0.05). The a_wc and X_wc increase with W_MD and depend on the chemical composition of the powders. The highest critical values were found in pineapple powders, ranging from 0.174 to 0.632 and 0.029 to 0.142 dry basis (d.b.), and the lowest ones in kiwi juice powders ranging from 0.029 to 0.550 and 0.013 to 0.129 (d.b.). For W_MD of 0.8, however, regardless of juice composition, stable powders in an amorphous state were obtained up to an a_w of 0.52 at 25°C.     

Stability of anthocyanins in frozen and freeze-dried raspberries during long-term storage: in relation to glass transition

Abstract: Anthocyanins, natural plant pigments in the flavonoid group, are responsible for the red color and some of the nutraceutical benefits of raspberries. This study explores anthocyanin degradation in frozen and freeze‐dried raspberries during storage in relation to glass transition temperatures. Frozen raspberries were stored at ?80, ?35, and ?20 °C, while freeze‐dried raspberries were stored at selected water activity (a_w) values ranging from 0.05 to 0.75 at room temperature (23 °C) for more than a year. The characteristic glass transition temperatures (T′_g) of raspberries with high water content and glass transition temperature (T_g) of raspberries with small water content were determined using a differential scanning calorimeter. The pH differential method was used to determine the quantity of anthocyanins in frozen and freeze‐dried raspberries at selected time intervals. The total anthocyanins in raspberries fluctuated during 378 d of storage at ?20 and ?35, and ?80 °C. Anthocyanin degradation in freeze‐dried raspberries ranged from 27% to 32% and 78% to 89% at a_w values of 0.05 to 0.07 and 0.11 to 0.43, respectively, after 1 y. Anthocyanins were not detectable in freeze‐dried raspberries stored at a_w values of 0.53 to 0.75 after 270 d. First order and Weibull equations were used to fit the anthocyanin degradation in freeze‐dried raspberries. The 1^st‐order rate constant (k) of anthocyanin degradation ranged from 0.003 to 0.023 days^?1 at the selected water activities. Significant anthocyanin degradation occurred in both the glassy and rubbery states of freeze‐dried raspberries during long‐term storage. However, the rate of anthocyanin degradation in freeze‐dried raspberries stored in the glassy state was significantly smaller than the rate of anthocyanin degradation in the rubbery state.     

Determining the effects of annealing time on the glass transition temperature of Pueraria lobata (Willd.) Ohwi starch

To probe the effects of annealing time on the glass transition temperature (T_g) and digestibility of Pueraria lobata (Willd.) Ohwi starch, the starch crystal structure and moisture distribution through the components of P. lobata (Willd.) Ohwi starch were investigated. Annealing times of 0, 1, 3, 6, 12 and 24 h were employed to determine the effect of starch T_g using differential scanning calorimetry (DSC) with the support of ¹H low‐field NMR, polarised light microscopy and ¹³C CP/MAS NMR. The T_g values of the starch increased with longer annealing times. The ¹H low‐field NMR results showed that the T₂ relaxation time decreased and starch–water interactions increased as the annealing time increased. Compared with native starch, annealed starch had higher contents of slowly digested starch (SDS) and resistant starch (RS). The starch crystal structure was not destroyed after annealing, but the relative crystallinity percentage increased slightly.     

Slow Molecular Mobility in the Amorphous Solid State of Fructose: Fragility and Aging

ABSTRACT:  The molecular mobility of β-D-fructose was studied by thermally stimulated depolarization currents (TSDC) in the amorphous solid state. The amorphous solid samples were prepared in such a way that the tautomeric mixture was near the equilibrium composition. A broad secondary relaxation was observed, that merges, at high temperatures, with the alpha relaxation. The alpha relaxation temperature provided by the TSDC technique is  T_g  = 13 °C (at 4 K min⁻¹). The fragility index calculated from TSDC data is  m  = 34, significantly lower when compared with the values reported in the literature obtained from Dielectric Relaxation Spectroscopy (DRS). The physical significance of the fragility obtained by the 2 dielectric techniques is discussed. The influence of physical aging on the secondary relaxation in amorphous fructose was analyzed as the glass structurally relaxes. A complex behavior was observed such that the faster components (lower temperature) of the secondary relaxation are negligibly dependent on aging and may be ascribed to intramolecular modes of motion, while the slower motional modes (higher temperature) show a significant dependence on aging and correspond to the genuine Johari–Goldstein β-relaxation.     

Effects of time/temperature treatments on potato (Solanum tuberosum) starch: a comparison of isolated starch and starch in situ

Previously, time/temperature treatments of starch have been performed mainly on starch/water systems. In this study the same time/temperature treatments were applied to starch/water systems and to potato starch in situ. Two potato varieties (Solanum tuberosum cultivars Asterix and Bintje) were used. The effect of time/temperature treatments on gelatinisation behaviour was evaluated using differential scanning calorimetry (DSC). A blanching process was simulated by heating samples to 74 °C and then cooling them to 6 °C. A DSC scan showed that starch was completely gelatinised after this treatment. Retrogradation of amylopectin increased during storage at 6 °C from 0 to 24 h after blanching. Annealing of starch, with the aim of altering cooking properties, was performed by heating samples to temperatures below the gelatinisation onset temperature. Treating samples at 50 °C for 24 h caused a shift in gelatinisation onset temperature of 11–12 °C for isolated starch and 7–11 °C for in situ samples. The extent of the annealing effect depended on the difference between onset and annealing temperatures, and prolonged treatment time increased the effect. Starch/water systems and tissue samples behaved similarly when exposed to time/temperature treatments. The most apparent difference was the shift of gelatinisation to higher temperatures in tissue samples. Copyright © 2003 Society of Chemical Industry     

Differential scanning calorimetry: gelatinisation of sago starch in the presence of sucrose and sodium chloride

The effect of sucrose and sodium chloride (NaCl) on sago starch gelatinisation was investigated by differential scanning calorimetry (DSC). The gelatinisation of starch in the presence of low levels of water and high levels of sucrose was studied. The gelatinisation temperature was found to increase in the presence of sucrose, whereas the gelatinisation enthalpy was unaffected. The gelatinisation temperature range was not as broad in the presence of sucrose as without sucrose. Furthermore, the shape of the gelatinisation endotherm was changed by the addition of sucrose. The double endotherm obtained in limited water–starch systems was changed into a single endotherm, similar to the endotherm obtained in excess water–starch systems at higher temperature. DSC was also used to examine the effects of water and NaCl content on the phase transitions of sago starch. Samples were adjusted to starch–water weight ratios of 2:3 and 3:2 in NaCl concentrations from 1 to 5 M . The gelatinisation temperature of sago starch increased and then decreased as the NaCl concentration increased. NaCl created similar effects on the endotherms with excess water content and on the first endotherm with limited water content. © 1999 Society of Chemical Industry     

Indicators of resilience during the transition period in dairy cows: A case study

The transition period is a demanding phase in the life of dairy cows. Metabolic and infectious disorders frequently occur in the first weeks after calving. To identify cows that are less able to cope with the transition period, physiologic or behavioral signals acquired with sensors might be useful. However, it is not yet clear which signals or combination of signals and which signal properties are most informative with respect to disease severity after calving. Sensor data on activity and behavior measurements as well as rumen and ear temperature data from 22 dairy cows were collected during a period starting 2 wk before expected parturition until 6 wk after parturition. During this period, the health status of each cow was clinically scored daily. A total deficit score (TDS) was calculated based on the clinical assessment, summarizing disease length and intensity for each cow. Different sensor data properties recorded during the period before calving as well as the period after calving were tested as a predictor for TDS using univariate analysis of covariance. To select the model with the best combination of signals and signal properties, we quantified the prediction accuracy for TDS in a multivariate model. Prediction accuracy for TDS increased when sensors were combined, using static and dynamic signal properties. Statistically, the most optimal linear combination of predictors consisted of average eating time, variance of daily ear temperature, and regularity of daily behavior patterns in the dry period. Our research indicates that a combination of static and dynamic sensor data properties could be used as indicators of cow resilience.