Impact of caramelization on the glass transition temperature of several caramelized sugars. Part I: Chemical analyses

This study aims to investigate the relationship between caramelization of several sugars including fructose, glucose, and sucrose and their glass transition temperature (Tg). Differential scanning calorimetry (DSC) was used for creating caramelized sugar samples as well as determining their glass transition temperature, which was found to decrease first and then increase as the holding time at the highest temperature increased. The extent of caramelization was quantified by UV-vis absorbance measurement and high-performance liquid chromatography analysis. Results showed that the amount of small molecules from the degradation of sugar increased very fast at the beginning of heating, and this increase slowed down in the later stage of caramelization. On the other hand, there was a lag phase in the formation of large molecules from the degradation of sugar at the beginning of heating, followed by a fast increase in the later stage of caramelization. The obtained results clearly indicate the impact of melting condition on the T g of sugars through formation of intermediates and end products of caramelization. Generally, when the heating condition is relatively mild, small molecules are formed first by decomposition of the sugar, which leads to a decrease of the overall Tg, and as the heating time becomes longer and/or the heating condition becomes more severe, polymerization takes over and more large molecules are formed, which results in an increase of the overall Tg. Mathematical modeling of the relationship will be presented as part II of the study in a separate paper.     

Impact of melting conditions of sucrose on its glass transition temperature.

The impact of the melting conditions of sucrose crystals on the glass transition temperature (T(g)) of the sucrose melt was studied. Final temperature, heating rate, and the residence time at the final temperature were the experimental conditions considered. The glass transition temperature of the different glasses was measured by differential scanning calorimetry, and the degradation of sucrose during the thermal treatments was studied by high-performance liquid chromatography. The results showed that the T(g) is sensitive to the degradation of sucrose: T(g) decreases with the appearance of small molecules and then increases with the appearance of polymerization products. Thus, the choice of thermal treatment is of the utmost importance for the determination of the T(g) of pure sucrose.     

牛肉部分玻璃化转变温度研究

利用调制式差示扫描量热仪(MDSC)对牛肉糜和牛肉肌动球蛋白的部分玻璃化转变温度进行了测定，得出平均转变温度约为－52.54℃。实验研究了明胶、海藻酸钠和羧甲基纤维素钠对牛肉糜部分玻璃化转变温度的影响，结果表明3种添加剂对牛肉糜部分玻璃化转变温度均无显著影响。利用程序降温仪对牛肉糜进行冻结与解冻实验，结果表明在本实验的降温速率1～5℃/min范围内，降温速率越高，所需的冻结终温越低。     

Porosity and the effect of structural changes on the mechanical glass transition temperature

Continuing an investigation on the fundamentals and applications of a recently proposed concept, i.e., the mechanical or network glass transition temperature, we now report data on the macrostructural changes in dehydrated apple tissue in relation to apparent porosity. Care was taken to keep the moisture content of the matrix constant (approximately 81%) while the volume fraction of total pores ranged from 0.38 to 0.79. Reproducible mechanical profiles identified the first derivative of shear storage modulus as a function of temperature to be the appropriate indicator of the mechanical Tg at the conjunction of the William-Landel-Ferry/free volume theory and the modified Arrhenius equation. Information on the microstructural characteristics and morphology of porous apple preparations was also made available via modulated differential scanning calorimetry and scanning electron microscopy. The work reveals and discusses discrepancies in the Tg-porosity relationship obtained from calorimetry and mechanical analysis attributable to the different extent to which the two techniques respond to degrees of molecular mobility.     

Nonenzymatic browning reaction of essential amino acids: effect of pH on caramelization and Maillard reaction kinetics.

The interaction between glucose and essential amino acids at 100 degrees C at pH values ranging from 4.0 to 12.0 was investigated by monitoring the disappearance of glucose and amino acids as well as the appearance of brown color. Lysine was the most strongly destroyed amino acid, followed by threonine which induced very little additional browning as compared with that undergone by glucose. Around neutrality, the nonenzymatic browning followed pseudo-zero-order kinetics after a lag time, while the glucose and amino acid losses did not follow first-order kinetics at any of the pH values tested. Glucose was more strongly destroyed than all of the essential amino acids, the losses of which are really small at pH values lower than 9.0. However, glucose was less susceptible to thermal degradation in the presence of amino acids, especially at pH 8.0 with threonine and at pH 10.0 with lysine. The contribution of the caramelization reaction to the overall nonenzymatic browning above neutrality should lead to an overestimation of the Maillard reaction in foods.     

A Synoptic Climatological Approach to Assess Climatic Impact on Air Quality in South-central Canada. Part II: Future Estimates

Using within-weather-group air pollution prediction models developed in Part I of this research, this study estimates future air pollution levels for a variety of pollutants (specifically, carbon monoxide – CO, nitrogen dioxide – NO₂, ozone – O₃, sulphur dioxide – SO₂, and suspended particles – SP) under future climate scenarios for four cities in south-central Canada. A statistical downscaling method was used to downscale five general circulation model (GCM) scenarios to selected weather stations. Downscaled GCM scenarios were used to compare respective characteristics of the weather groups developed in Part I; discriminant function analysis was used to allocate future days from two windows of time (2040–2059 and 2070–2089) into one of four weather groups. In Part I, the four weather groups were characterised as hot, cold, air pollution-related, and other (defined as relatively good air quality and comfortable weather conditions). In estimating future daily air pollution concentrations, three future pollutant emission scenarios were considered: Scenario I – emissions decreasing 20% by 2050, Scenario II – future emissions remaining at the same level as at the end of the twentieth century, and Scenario III – emissions increasing 20% by 2050. The results showed that, due to increased temperatures, the average annual number of days with high O₃ levels in the four selected cities could increase by more than 40–100% by the 2050s and 70–200% by the 2080s (from the current areal average of 8 days) under the three pollutant emission scenarios. The corresponding number of low O₃ days could decrease by 4–10% and 5–15% (from the current areal average of 312 days). For the rest of the pollutants, future air pollution levels will depend on future pollutant emission levels. Under emission Scenarios II and III, the average annual number of high pollution days could increase 20–40% and 80–180%, respectively, by the middle and late part of this century. In contrast, under Scenario I, the average annual number of high pollution days could decrease by 10–65%.     

Effect of transglutaminase treatment on the glass transition of soy protein

The effect of microbial transglutaminase (MTG) treatment on the glass transition temperature (T(g)) of two fractions which were isolated from a soy protein sample was studied. The T(g) of each fraction measured by differential scanning calorimetry was lowered by the MTG treatment, which generated cross-links in the samples, and this result agreed with the result of dynamic mechanical analysis. From the (1)H NMR measurement, the line width of the (1)H signal of the MTG-treated sample was observed to be greater than that of the MTG-nontreated sample at similar water content, which implied that there was relatively more immobilized water in the MTG-treated sample. The MTG treatment seemed to cause the increment in immobilized water, which might affect the T(g) of the soy protein sample.     

苹果碰撞响应数学模型的研究

通过苹果的碰撞损伤试验，建立了描述苹果碰撞过程的加速度——时间曲线的数学模型，分析了该模型中各参数对碰撞特性及损伤的影响     

Kinetics of a bioactive compound (caffeine) mobility at the vicinity of the mechanical glass transition temperature induced by gelling polysaccharide

An investigation of the diffusional mobility of a bioactive compound (caffeine) within the high-solid (80.0% w/w) matrices of glucose syrup and κ-carrageenan plus glucose syrup exhibiting distinct mechanical glass transition properties is reported. The experimental temperature range was from 20 to -60 °C, and the techniques of modulated differential scanning calorimetry, small deformation dynamic oscillation in shear, and UV spectrometry were employed. Calorimetric and mechanical measurements were complementary in recording the relaxation dynamics of high-solid matrices upon controlled heating. Predictions of the reaction rate theory and the combined WLF/free volume framework were further utilized to pinpoint the glass transition temperature (T(g)) of the two matrices in the softening dispersion. Independent of composition, calorimetry yielded similar T(g) predictions for both matrices at this level of solids. Mechanical experimentation, however, was able to detect the effect of adding gelling polysaccharide to glucose syrup as an accelerated pattern of vitrification leading to a higher value of T(g). Kinetic rates of caffeine diffusion within the experimental temperature range were taken with UV spectroscopy. These demonstrated the pronounced effect of the gelling κ-carrageenan/glucose syrup mixture to retard diffusion of the bioactive compound near the mechanical T(g). Modeling of the diffusional mobility of caffeine produced activation energy and fractional free-volume estimates, which were distinct from those of the carbohydrate matrix within the glass transition region. This result emphasizes the importance of molecular interactions between macromolecular matrix and small bioactive compound in glass-related relaxation phenomena.     

气力滚筒式排种器种子吸附边界模型及验证

为了探索气力滚筒式播种机对不同规格小粒蔬菜种子吸附性能的影响,该文对种子在吸种孔外部气流场中处于临界运动时与吸种孔的位置关系进行了理论分析。通过分析吸种孔外部气流场的气体的流动状态以及种子在气流场中的绕流阻力与其到吸种孔距离的关系,并对种子在气流场中运动临界状态进行受力分析,从而推导出种子吸附边界的数学模型。分析吸附边界大小对种子吸附性能的影响,以菜心种子、芥兰种子、辣椒种子为试验对象,排种器真空度在1 k Pa~12 k Pa变化,吸种孔半径为0.25 mm,导种板为无振动和振幅为0.4 mm。试验结果与模型分析结果一致:种子吸附的前提条件是种子持续不断的进入吸附边界内,种子的吸附性能与种子边界的大小和种子形状和大小有关;对于小粒蔬菜种子,扁平种子的单粒率低于球形种子,球形种子的直径越小,越难获得高的单粒率。对于小粒扁平种子和直径较小的小粒球形种子,合理的供种方法和增大排种器真空度使吸种孔不空种,再清除吸种孔上的多余种子,是实现排种器精密播种的一种途径。研究结果为气力滚筒式播种机的精密播种研究提供参考。     

Determination of molecular weight of agars and effect of the molecular weight on the glass transition

A novel procedure to determine the molecular weight (MW) and MW distributions for various agars is described. The MW values of commercial agars, an agarose, an agaropectin, and hydrolyzed agaroses were determined by size exclusion chromatography-low angle laser light scattering, using 4.0 M guanidine hydrochloride as eluent to avoid gelation. The MW for the commercial agars was between 106 400 and 243 500 with polydispersity between 1.283 and 6. 600. The MW of the agarose separated from a commercial agar was lower than that of the agaropectin. To prepare agaroses with different MW values, the obtained agarose was hydrolyzed. The MW of the agarose decreased with hydrolysis time, and the polydispersity, on the contrary, increased. The glass transition temperature (T(g)) of agarose with different MW values and that of agaropectin were measured by differential scanning calorimetry. The T(g) of the agarose was higher than that of the agaropectin with higher MW. The T(g) of agarose increased with MW.     

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.     

Effects of heating conditions on the glass transition parameters of amorphous sucrose produced by melt-quenching

This research investigates the effects of heating conditions used to produce amorphous sucrose on its glass transition (T(g)) parameters, because the loss of crystalline structure in sucrose is caused by the kinetic process of thermal decomposition. Amorphous sucrose samples were prepared by heating at three different scan rates (1, 10, and 25 °C/min) using a standard differential scanning calorimetry (SDSC) method and by holding at three different isothermal temperatures (120, 132, and 138 °C) using a quasi-isothermal modulated DSC (MDSC) method. In general, the quasi-isothermal MDSC method (lower temperatures for longer times) exhibited lower T(g) values, larger ΔC(p) values, and broader glass transition ranges (i.e., T(g end) minus T(g onset)) than the SDSC method (higher temperatures for shorter times), except at a heating rate of 1 °C/min, which exhibited the lowest T(g) values, the highest ΔC(p), and the broadest glass transition range. This research showed that, depending on the heating conditions employed, a different amount and variety of sucrose thermal decomposition components may be formed, giving rise to wide variation in the amorphous sucrose T(g) values. Thus, the variation observed in the literature T(g) values for amorphous sucrose produced by thermal methods is, in part, due to differences in the heating conditions employed.     

Decoupling structural and environmental determinants of sap velocity: Part II. Observational application

In this work we present experimental evidence in support of a new approach for investigating the dependence of sap velocity on atmospheric water demand and soil moisture supply. In this method, sap velocity is defined as the product of two components: the first describes the ‘shape’ of the radial profile of sap velocity, which is consistent through time and is likely linked to the species-specific anatomical and structural properties of the conducting xylem; the second, which we define as stem conductance, captures the time-dependent component of sap velocity that is mostly governed by shifts in atmospheric water demand and individual tree water supply. The heat pulse technique was used to estimate radial profiles of sap velocity and transpiration from a sample of 16 mature sugar maples (Acer saccharum) located along a topographic transect in a mixed deciduous forest. Our results demonstrate that: (1) stem conductance is strongly correlated with bulk air conditions (with confidence intervals for all the sampled trees greater than 99% and average R² of 0.43, 0.57, 0.54 for vapor pressure deficit (VPD), PPFD and net radiation, respectively) and atmospheric water demand (average R² equal to 0.73) on an hourly basis and that it is independent of tree size; (2) sensitivity of stem conductance to atmospheric water demand in sugar maples is also correlated to variation in local soil water availability (P-value = 0.014, R² = 0.43) which arises due to a mild topographic gradient (i.e. 20 m of relative relief along 140 m) and relatively shallow soil. Although the sampled trees were subjected to a wide range of atmospheric water demands and soil moistures, the response to changes in environmental conditions is entirely explainable by dynamics of stem conductance rather than the relative fraction of sap flow along the radial profile, as some of the previous studies reported. Overall, our results confirm our theoretical approach and the possibility of partitioning sap velocity variability between either xylem properties or changes in environmental conditions.     

Maillard reaction kinetics in model preservation systems in the vicinity of the glass transition: experiment and theory

Rates of reactant consumption for the Maillard reaction between lysine and glucose were measured for a noncrystallizing trehalose-sucrose-water matrix in the glass transition region. At temperatures above the glass transition temperature (T(g)), the consumption rates showed Arrhenius temperature dependence with activation energies of 135 and 140 kJ mol(-1) for lysine and glucose, respectively. Finite reaction rates were observed for glassy samples that were faster than that of one of the nonglassy samples. A comparison of experimental results with predicted diffusion-controlled reaction rate constants indicated that the reaction was reaction-controlled at temperatures above T(g) and approached the diffusion-influenced regime in the glassy state. The needs for further research on reactant diffusivity, the theory of the orientation dependence of reactivity, and a detailed understanding of the reaction mechanism and kinetics were identified.     

Twenty years of conservation tillage research in subarctic Alaska: II. Impact on soil hydraulic properties

Soil management practices are needed in the subarctic that stabilize the soil against the forces of wind and water as well as conserve soil water for crop production. There is a paucity of information, however, regarding the long-term effects of conservation tillage on soil hydraulic properties in subarctic Alaska. The objective of this study was therefore to characterize infiltration, water retention, and saturated hydraulic conductivity of a soil 20 years after establishing tillage and straw management treatments in interior Alaska. The strip plot experimental design, established on a silt loam and maintained in continuous barley (Hordeum vulgare L.), included tillage as the main treatment and straw management as the secondary treatment. Tillage treatments included no tillage, autumn chisel plow, spring disk, and intensive tillage (autumn and spring disk) while straw treatments included retaining or removing stubble and loose straw from the soil surface after harvest. Soil properties were measured after sowing in spring 2004; saturated hydraulic conductivity was measured by the falling-head method, infiltration was measured using a double-ring infiltrometer, and water retention was assessed by measuring the temporal variation in in-situ soil water content. No tillage resulted in greater saturated hydraulic conductivity and generally retained more water against gravitational and matric forces than other tillage treatments. Infiltration was greater in autumn chisel plow than other tillage treatments and was presumably suppressed in no tillage by an organic layer overlying mineral soil. Infiltration was also enhanced by retaining straw on rather than removing straw from the soil surface after harvest. No tillage is not yet a sustainable management practice in this region due to lack of weed control strategies. In addition, the formation of an organic layer in no tillage has important ramifications for the soil hydrological and thermal environment. Therefore, minimum tillage (i.e., autumn chisel plow or spring disk) appears to be a viable management option for maximizing infiltration in interior Alaska.     

Twenty years of conservation tillage research in subarctic Alaska: II. Impact on soil hydraulic properties

Soil management practices are needed in the subarctic that stabilize the soil against the forces of wind and water as well as conserve soil water for crop production. There is a paucity of information, however, regarding the long-term effects of conservation tillage on soil hydraulic properties in subarctic Alaska. The objective of this study was therefore to characterize infiltration, water retention, and saturated hydraulic conductivity of a soil 20 years after establishing tillage and straw management treatments in interior Alaska. The strip plot experimental design, established on a silt loam and maintained in continuous barley (Hordeum vulgare L.), included tillage as the main treatment and straw management as the secondary treatment. Tillage treatments included no tillage, autumn chisel plow, spring disk, and intensive tillage (autumn and spring disk) while straw treatments included retaining or removing stubble and loose straw from the soil surface after harvest. Soil properties were measured after sowing in spring 2004; saturated hydraulic conductivity was measured by the falling-head method, infiltration was measured using a double-ring infiltrometer, and water retention was assessed by measuring the temporal variation in in-situ soil water content. No tillage resulted in greater saturated hydraulic conductivity and generally retained more water against gravitational and matric forces than other tillage treatments. Infiltration was greater in autumn chisel plow than other tillage treatments and was presumably suppressed in no tillage by an organic layer overlying mineral soil. Infiltration was also enhanced by retaining straw on rather than removing straw from the soil surface after harvest. No tillage is not yet a sustainable management practice in this region due to lack of weed control strategies. In addition, the formation of an organic layer in no tillage has important ramifications for the soil hydrological and thermal environment. Therefore, minimum tillage (i.e., autumn chisel plow or spring disk) appears to be a viable management option for maximizing infiltration in interior Alaska.     

Establishment of trees on mixtures of pulverized fuel ash and Gypsum. Part II: Nutrition and trace elements

Nutrients and trace elements were determined in the foliage of nine tree species grown in mixtures of pulverized fuel ash (PFA) and gypsum. No serious macronutrient deficiencies were observed. Treatments with PFA consistently increased foliar levels of boron, potassium and molybdenum, and the poor performance of some tree species in pure PFA was attributed to boron toxicity. Gypsum hindered the uptake of boron when mixed with PFA, however, and co-disposal of the two wastes could be used to minimize problems associated with boron toxicity.     

Predicting bare soil temperature. II. Experimental testing of multi-day models

Two agroclimatic models described earlier are tested against measurements of temperature at the soil surface, T₀, and in bulk soil, T(z,t), at an experimental site near Aberdeen during spring, summer and autumn. Soil temperature is predicted most accurately in spring and autumn, when the constant-windspeed model ENBL1 predicts the mean within 0.3 K of measurement. Thedynamic-windspeed model ENBL2 predicts within 0.1 K in all intervals, and with error<0.3 K to depth z=32 cm in spring and autumn. A sensitivity analysis of the output diurnal wave, T₀(t), shows that maximum input economy requires only time-dependent shortwave radiation, R_s(t), and air temperature, T_a(t), other inputs being constant. Two or three harmonics in ENBL1 should suffice, requiring four or six measurements per day, depending mainly on the time-structure of the primary driving function R_s.     

Effects of pH and the gel state on the mechanical properties, moisture contents, and glass transition temperatures of whey protein films.

The mechanical properties, moisture contents (MC), and glass transition temperature (T(g)) of whey protein isolate (WPI) films were studied at various pH values using sorbitol (S) as a plasticizer. The films were cast from heated aqueous solutions and dried in a climate chamber at 23 degrees C and 50% relative humidity (RH) for 16 h. The critical gel concentrations (c(g)) for the cooled aqueous solutions were found to be 11.7, 12.1, and 11.3% (w/w) WPI for pH 7, 8, and 9, respectively. The cooling rate influenced the c(g), in that a lower amount of WPI was needed for gelation when a slower cooling rate was applied. Both cooling rates used in this study showed a maximum in the c(g) at pH 8. The influence of the polymer network on the film properties was elucidated by varying the concentration of WPI over and under the c(g). Strain at break (epsilon(b)) showed a maximum at the c(g) for all pH values, thus implying that the most favorable structure regarding the ability of the films to stretch is formed at this concentration. Young's modulus (E) and stress at break (sigma(b)) showed a maximum at c(g) for pH 7 and 8. The MC and epsilon(b) increased when pH increased from 7 to 9, whereas T(g) decreased. Hence, T(g) values were -17, -18, and -21 degrees C for pH 7, 8, and 9, respectively. E and sigma(b) decreased and epsilon(b) and thickness increased when the surrounding RH increased. The thickness of the WPI films also increased with the concentration of WPI.