Modeling the effect of water activity and storage temperature on chemical stability of coffee brews

This work was addressed to study the chemical stability of coffee brew derivatives as a function of water activity (aw) and storage temperature. To this purpose, coffee brew was freeze-dried, equilibrated at increasing aw values, and stored for up to 10 months at different temperatures from -30 to 60 degrees C. The chemical stability of the samples was assessed by measuring H3O+ formation during storage. Independently of storage temperature, the rate of H3O+ formation was considerably low only when aw was reduced below 0.5 (94% w/w). Beyond this critical boundary, the rate increased, reaching a maximum value at ca. 0.8 aw (78% w/w). Further hydration up to the aw of the freshly prepared beverage significantly increased chemical stability. It was suggested that mechanisms other than lactones' hydrolysis, probably related to nonenzymatic browning pathways, could contribute to the observed increase in acidity during coffee staling. The temperature dependence of H3O+ formation was well-described by the Arrhenius equation in the entire aw range considered. However, aw affected the apparent activation energy and frequency factor. These effects were described by simple equations that were used to set up a modified Arrhenius equation. This model was validated by comparing experimental values, not used to generate the model, with those estimated by the model itself. The model allowed efficient prediction of the chemical stability of coffee derivatives on the basis of only the aw value and storage temperature.     

Influence of crystallization on the oxidative stability of extra virgin olive oil

The aim of this study was to evaluate the influence of the extra virgin olive oil (EVOO) physical state on the kinetics of oxidative reactions. To this purpose, EVOO was stored at increasing temperatures from 3 to 60 degrees C and the oxidation was followed by measuring both primary and secondary oxidation products. Results highlighted that crystallization plays an important role in determining EVOO stability. Below the melting point, the oxidation rate was found to be higher than that expected on the basis of the Arrhenius equation. The observed deviation from the Arrhenius equation was attributed to the physicochemical changes occurring as a consequence of phase transitions. In particular, the increase in unsaturated triacylglycerol concentration and the decrease of polyphenol content in the liquid phase surrounding fat crystals were indicated as the main factors causing the deviation. By taking into account these changes it was possible to describe the temperature dependence of the oxidation rate in the entire range of temperatures considered. This model appears to be promising in the challenge to find mathematical models able to predict the stability and, hence, the shelf life of lipid-containing foods.     

Shelf-life modeling of bakery products by using oxidation indices

The aim of this work was to develop a shelf-life prediction model of lipid-containing bakery products. To this purpose (i) the temperature dependence of the oxidation rate of bakery products was modeled, taking into account the changes in lipid physical state; (ii) the acceptance limits were assessed by sensory analysis; and (iii) the relationship between chemical oxidation index and acceptance limit was evaluated. Results highlight that the peroxide number, the changes of which are linearly related to consumer acceptability, is a representative index of the quality depletion of biscuits during their shelf life. In addition, the evolution of peroxides can be predicted by a modified Arrhenius equation accounting for the changes in the physical state of biscuit fat. Knowledge of the relationship between peroxides and sensory acceptability together with the temperature dependence of peroxide formation allows a mathematical model to be set up to simply and quickly calculate the shelf life of biscuits.     

Stability of isoflavones in soy milk stored at elevated and ambient temperatures

Soy isoflavones are widely recognized for their potential health benefits. The increased use of traditional and new food products calls for the assessment of their stability during processing and storage. The present study examines the stability of genistein and daidzein derivatives in soy milk. Soy milk was stored at ambient and elevated temperatures, and the change in isoflavone concentration was monitored with time. Genistin loss in time showed typical first-order kinetics, with rate constants ranging from 0.437-3.871 to 61-109 days(-1) in the temperature ranges of 15-37 and 70-90 degrees C, respectively. The temperature dependence of genistin loss followed the Arrhenius relation with activation energies of 7.2 kcal/mol at ambient temperatures and 17.6 kcal/mol at elevated temperatures. At early stages of soy milk storage at 80 and 90 degrees C, the 6' '-O-acetyldaidzin concentration increased, followed by a slow decrease. The results obtained in this study can serve as a basis for estimating the shelf life of soy milk as related to its genistin content.     

Lycopene degradation and isomerization kinetics during thermal processing of an olive oil/tomato emulsion

The stability of lycopene in an olive oil/tomato emulsion during thermal processing (80-140 °C) was studied. Initially, the degradation of total lycopene (all-E plus Z-forms) occurred quickly at temperatures above 100 °C. However, a nonzero plateau value, depending on the processing temperature, was attained after longer treatment times. Besides degradation, the isomerization of total-Z-lycopene as well as the individual isomerization of all-E-, 5-Z-, 9-Z-, and 13-Z-lycopene was studied in detail. After prolonged heating, the isomer conversion reached a temperature-dependent equilibrium state. The degradation of total lycopene and the isomerization could be described by a fractional conversion model. The temperature dependency of the corresponding reaction rate constants was quantified by the Arrhenius equation. The activation energy of degradation was estimated to be 28 kJ/mol, and the activation energy of overall (all-E and total-Z) isomerization was estimated to be 52 kJ/mol.     

Kinetic study on the changes in the susceptibility of egg white proteins to enzymatic hydrolysis induced by heat and high hydrostatic pressure pretreatment

A kinetic study was conducted on the effect of heat pretreatment in the temperature range of 50-85 degrees C at atmospheric pressure and of high hydrostatic pressure pretreatment (100-700 MPa) at four temperatures (10, 25, 40, and 60 degrees C) on the susceptibility of egg white solutions (10% v/v, pH 7.6) to subsequent enzymatic hydrolysis by a mixture of trypsin and alpha-chymotrypsin at 37 degrees C and pH 8.0. Both heat pretreatment at atmospheric pressure and high-pressure pretreatment resulted in an increase in degree of hydrolysis (DH) after 10 min of enzymatic reaction (DH10) of egg white solutions, as measured using the pH-stat method, which could be described by a fractional conversion model (based on an apparent first-order reaction kinetic model). The temperature dependence of the corresponding rate constants could be described by the Arrhenius equation. At elevated pressure, a negative apparent activation energy was obtained, implying an antagonistic effect of pressure and temperature. The pressure dependence of the rate constants could be described by the Eyring equation, and negative activation volumes were observed, which demonstrates the positive effect of pressure on the susceptibility of egg white solutions to subsequent enzymatic hydrolysis.     

NMR转折点温度对食品储存过程中Maillard反应速率影响

采用核磁共振(NMR)技术对以葡萄糖、海藻糖、蔗糖、赖氨酸构成的模型食品进行磁共振实验,绘制体系NMR状态图并计算转折点温度,同时在不同温度下进行储藏实验,考察体系中葡萄糖的变化,评估不同储藏温度下的Maillard反应速率.结果表明:模型食品体系含水量不同、非反应组分含量不同,其NMR转折点温度有所不同.低水分含量的体系具有相对高的NMR转折点温度.即使在相同的储藏温度下,含水量相同而非反应组分含量不同的情况下,体系的Maillard反应速率也有所不同.储藏温度处于体系的NMR转折点之下时,体系的Maillard反应速率明显要比在NMR转折点温度之上要慢.由此,可以通过改变食品的配方、含水量等改变体系的NMR转折点温度,可以有效地延长食品的货架期.因此,核磁共振状态图对于评估最佳的储藏温度,以及通过配方设计来延长食品的货价期具有指导意义.     

Temperature sensitivity of anaerobic labile soil organic carbon decomposition in brackish marsh

The global warming has a potential for acceleration of labile soil organic carbon decomposition. Arrhenius equation is one of the useful equation for predicting temperature sensitivity of carbon decomposition, with the activation energy of rate constant being a key factor. The purpose of this study is the evaluation of temperature sensitivity of labile soil organic carbon decomposition under anaerobic condition in wetland soil using the activation energy of rate constant among different vegetation types. The soil samples were incubated at three different temperatures (10, 20, and 30°C) under anaerobic condition and carbon decomposition rates (sum of CO₂ and CH₄ production) were measured by gas chromatography. The first-order kinetic model with Arrhenius equation was used for approximate of anaerobic carbon decomposition. For determination of activation energy of rate constant, non-linear least-squares method was conducted between observed carbon decomposition rate and predicted carbon decomposition rate which calculated by Arrhenius equation. The activation energy of rate constant of anaerobic labile soil organic carbon decomposition was different among vegetation types. We successfully determined the activation energy of rate constant of CO2 or CH4 production from Phragites, Juncus, and Miscanthus+Cirsium-dominated vegetation soil with Arrhenius equation. Hence, this study suggests that Arrhenius equation was useful for evaluation of temperature sensitivity of labile soil organic carbon decomposition not only aerobic condition, but also anaerobic condition among several vegetation types in the wetland ecosystem. Moreover, gaseous carbon production from soil under Juncus yocoscensis dominated soil appeared higher activation energy and temperature sensitivity than that from soil under other vegetation types.     

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

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

Degradation kinetics of the antioxidant additive ascorbic acid in packed table olives during storage at different temperatures

The kinetics of ascorbic acid (AA) loss during storage of packed table olives with two different levels of added AA was investigated. Three selected storage temperatures were assayed: 10 degrees C, ambient (20-24 degrees C), and 40 degrees C. The study was carried out in both pasteurized and unpasteurized product. The effect of pasteurization treatment alone on added AA was not significant. In the pasteurized product, in general AA degraded following a first-order kinetics. The activation energy calculated by using the Arrhenius model averaged 9 kcal/mol. For each storage temperature, the increase in initial AA concentration significantly decreased the AA degradation rate. In the unpasteurized product, AA was not detected after 20 days in samples stored at room temperature and AA degradation followed zero-order kinetics at 10 degrees C, whereas at 40 degrees C a second-order reaction showed the best fit. In both pasteurized and unpasteurized product, the low level of initial dehydroascorbic acid disappeared during storage. Furfural appeared to be formed during storage, mainly at 40 degrees C, following zero-order kinetics.     

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.     

基于乙醇质量分数的草莓果实腐烂指数预测模型

为应用电子鼻快速检测草莓物流过程中果实腐烂状况,建立了一种基于乙醇质量分数的果实腐烂指数预测模型。将草莓果实贮藏于不同温度（273、278、283、288、293和298 K）下,测定其腐烂指数和乙醇质量分数的变化。首先,基于Arrhenius动力学方程建立了草莓果实乙醇质量分数与贮藏时间和温度之间的动力学预测模型;其次,基于零级反应方程式建立了腐烂指数与贮藏时间和温度之间的动力学预测模型;最后,根据果实腐烂指数和乙醇质量分数变化的线性关系,进一步建立了基于乙醇质量分数的果实腐烂指数预测模型。在275、280、285、290、295和300 K贮藏温度下对上述3个预测模型进行验证,预测的相对误差（RE）分别为0.76%、5.89% 和7.08%,预测精度较高。将基于果实乙醇质量分数的腐烂指数预测模型与传统的腐烂指数动力学预测模型进行比较,发现二者的预测精度无显著差异。因此,基于乙醇质量分数的腐烂指数预测模型可以较好地预测在273～300 K贮藏温度下草莓果实的腐烂状况,从而为应用电子鼻无损检测果实品质提供理论依据。     

Inactivation of orange pectinesterase by combined high-pressure and -temperature treatments: a kinetic study

Pressure and/or temperature inactivation of orange pectinesterase (PE) was investigated. Thermal inactivation showed a biphasic behavior, indicating the presence of labile and stable fractions of the enzyme. In a first part, the inactivation of the labile fraction was studied in detail. The combined pressure-temperature inactivation of the labile fraction was studied in the pressure range 0.1-900 MPa combined with temperatures from 15 to 65 degrees C. Inactivation in the pressure-temperature domain specified could be accurately described by a first-order fractional conversion model, estimating the inactivation rate constant of the labile fraction and the remaining activity of the stable fraction. Pressure and temperature dependence of the inactivation rate constants of the labile fraction was quantified using the Eyring and Arrhenius relations, respectively. By replacing in the latter equation the pressure-dependent parameters (E(a), k(ref)(T)()) by mathematical expressions, a global model was formulated. This mathematical model could accurately predict the inactivation rate constant of the labile fraction of orange PE as a function of pressure and temperature. In a second part, the stable fraction was studied in more detail. The stable fraction inactivated at temperatures exceeding 75 degrees C. Acidification (pH 3.7) enhanced thermal inactivation of the stable fraction, whereas addition of Ca(2+) ions (1 M) suppressed inactivation. At elevated pressure (up to 900 MPa), an antagonistic effect of pressure and temperature on the inactivation of the stable fraction was observed. The antagonistic effect was more pronounced in the presence of a 1 M CaCl(2) solution as compared to the inactivation in water, whereas it was less pronounced for the inactivation in acid medium.     

基于酶动力学方程的双孢蘑菇气调贮藏呼吸速率模型

为了给气调贮藏设计提供理论设计依据,采用酶动力学方程,建立了双孢蘑菇呼吸速率随贮藏时间变化的理论模型;研究了在贮藏温度为5℃、气体体积分数为20%O_2、80%N2的贮藏条件下,贮藏时间对双孢蘑菇采后呼吸速率的影响,并建立了双孢蘑菇呼吸速率随贮藏时间变化的数学模型,模型决定系数R~2为0.9766、0.9331。模型与实测值进行配对T检验差异不显著(P0.05),呼吸速率值的绝对误差小于5 m L/(kg·h),相对误差变化范围为0.06%~24.95%。在已建模型基础上,研究不同贮藏温度(5、10、15、20℃)对已建模型参数的影响,利用Arrhenius方程来描述贮藏温度对果蔬呼吸速率的影响,建立了包含温度和贮藏时间因子的呼吸速率模型,模型决定系数R~2为0.9073、0.9350。验证试验结果表明,模型与实测值进行配对T检验差异不显著(P0.05),呼吸速率值的绝对误差小于17 m L/(kg·h),相对误差变化范围为1.00%~25.25%。该模型可为双孢蘑菇气调贮藏期间呼吸速率的预测及贮藏品质研究提供参考。     

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

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

Kinetics of maneb degradation during thermal treatment of tomatoes

The kinetics of maneb degradation in tomato homogenates at high temperatures and at two pH values (4 and 9) and the rate of formation of the toxic metabolite, ethylenethiourea (ETU), were studied. Maneb was measured as carbon disulfide by headspace gas-chromatography and ETU by high-performance liquid chromatography with photodiode array detection. First-order kinetics adequately described the degradation of maneb in tomato homogenates. The degradation rate constants exhibited an Arrhenius temperature dependence in the range from 50 to 90 degrees C and the apparent activation energy (E(a)) was calculated to be 36 KJ mol(-1) in homogenates with natural pH (4). Raising temperature from 60 to 75 and to 90 degrees C, ETU formation was significantly increased. Interestingly, the selectivity toward ETU showed a downward trend when the total conversion increased at longer heating times. When the pH of the tomato homogenates was adjusted to 9, the degradation of maneb proceeded faster at both 60 and 90 degrees C. The combination of alkaline pH and the highest temperature (90 degrees C) resulted in the maximum ETU conversion rates. The results of the present study on the fate of maneb and ETU residues during tomato processing, may prove valuable in estimating potential risk from dietary exposure.     

速冻莲藕片贮藏过程中品质变化动力学模型

为了探寻贮藏温度对速冻莲藕片品质的影响及预测其货架期,该文研究在贮藏温度?5、?15和?25℃条件下,速冻莲藕片维生素C、色泽和硬度随着贮藏时间的变化,建立了3个指标变化动力学模型。结果表明:随着贮藏温度的升高,速冻莲藕片维生素C、色泽和硬度的变化速率逐渐增加,?5℃条件下贮藏的速冻莲藕片品质快速下降,?15和?25℃条件下贮藏前期莲藕片品质下降不显著(P0.05),随着时间的延长,?25℃部分玻璃态贮藏的莲藕片品质最佳;不同贮藏温度下速冻莲藕片维生素C和硬度变化符合一级反应,总色差和亮度变化符合零级反应,速冻莲藕片维生素C、色泽和硬度反应速率常数符合Arrhenius方程,并建立莲藕片货架期动力学模型,通过对其验证发现模型拟合度良好(R20.9),能预测速冻莲藕片贮藏期各品质指标变化和不同温度下的货架期寿命。研究结果可为速冻莲藕片低温贮藏品质变化和货架寿命预测提供理论依据。     

Modeling of the fine‐scale temperature response of arylsulfatase activity in soil

Fine‐scale (1.0–2.2 °C) temperature dependence of soil arylsulfatase activity (arylsulfate sulfohydrolase, EC 3.1.6.1) was measured at 0 to 75 °C in a Danish sandy, arable soil. Assays were done with field‐moist soil samples in the absence of toluene as plasmolytic agent – a procedure that primarily measures the extracellular enzymes. The aim was to evaluate the use of temperature models to describe the temperature response of soil arylsulfatase activity. In addition, we searched for increases in activity at high temperatures (e.g., 50–60 °C), which might be associated with unmasking (exposure) of intracellular enzymes. Arylsulfatase activities ranged from 1.1 to 60.3 μg p‐nitrophenol (g dry weight soil)^–1 h^–1, with an optimum temperature at 58.1 °C. The temperature response below 58.1 °C could be described by the Arrhenius equation (r² = 0.978, n = 83) and the simple Ratkowsky equation (r² = 0.977, n = 83). The expanded Ratkowsky equation, which covered the entire temperature range (0–75 °C), was less satisfactory (r² = 0.958, n = 90) because the model underestimated the reaction rates near the optimum temperature. The activation energy (E_a) calculated from the Arrhenius equation was 42.2 kJ mol^–1. This was higher than previously found for other soils (16.5–34.7 kJ mol^–1), possibly due to the use of toluene in these studies. Further analysis of the temperature response showed that no increase in activity occurred due to potential unmasking of intracellular enzymes by disintegration of bacterial cell membranes at high temperatures. Thus, the use of high incubation temperatures did not facilitate the differentiation between intra‐ and extracellular enzyme activity.     

红枣汁中维生素C热降解的动力学研究(简报)

为了了解加热温度对红枣汁中维生素C含量变化的影响,降低红枣汁在加工过程中维生素C的损失,该文以红枣澄清汁为材料,采用可逆的一级反应模型研究了不同加热温度下还原型维生素C(AA)的降解规律并推导出氧化型维生素C(DHAA)含量变化的数学模型.在此基础上利用Arrhenius方程计算得到AA和DHAA的降解反应活化能.结果表明,在303,313,323,333,343 K温度条件下,可逆的一级反应模型适用于表达红枣汁中AA的降解规律,非线性回归决定系数γ2均大于0.98.DHAA的数学模型也能较好地预测DHAA在红枣汁中的含量变化规律.在不同的加热温度下,AA与DHAA均能发生降解反应,但DHAA的降解速率较AA低,DHAA的降解主要发生在AA的降解反应达到平衡之后.AA热降解反应活化能较低,表明红枣汁中的AA对热处理较敏感.该研究为优化红枣汁的加工工艺、提高红枣汁的品质提供理论依据.     

黏弹性材料动态力学性能的分数阶时温等效模型与验证

为构造一种更加精准的黏弹性时温等效模型,基于黏弹性阻尼材料的分数阶本构关系和Vogel-Fulcher-Tammann黏度方程,结合WLF(Williams-Landel-Ferry)方程,提出了黏弹性阻尼材料动态力学性能的分数阶时温等效模型(fractional time-temperature superposition model,FTTSM),导出频率转化因子,并给出参数识别方法。在DMA(dynamic thermomechanical analysis)试验数据的基础上,对比研究了FTTSM和WLF两种模型,并应用分数阶Kelvin-Voigt模型对二者在参考温度5℃的主曲线进行了验证。结果表明,FTTSM和WLF所表征的频率转化因子在温度范围(–80~80℃)内最大相对误差为0.984 4%,FTTSM主曲线和WLF主曲线相对于Kelvin-Voigt模型理论预测值的均方根误差(RMSE)分别为1.291和1.834 MPa,验证了FTTSM的精确性。另外FTTSM主曲线扩展的最低频域低于WLF主曲线2个数量级,证明FTTSM对黏弹性动态力学特性具有更广泛的预测能力。为黏弹性材料动态性能预测、物理老化、蠕变损伤演化机理等研究提供理论参考。