Nonenzymatic browning kinetics of a carbohydrate-based low-moisture food system at temperatures applicable to spray drying

Effects of water contents on nonenzymatic browning (NEB) rates of amorphous, carbohydrate-based food model systems containing L-lysine and D-xylose as reactants were studied at different temperatures (40, 50, 60, 70, 80, and 90 degrees C) applicable to spray drying conditions. Water sorption was determined gravimetrically, and data were modeled using the Brunauer-Emmett-Teller and Guggenheim-Anderson-deBoer equations. Glass transition, Tg was measured by DSC. NEB was followed spectrophotometrically. The rate of browning increased with water content and temperature, but a lower T-Tg was needed for browning at decreasing water content. Water content seemed to affect the activation energy of NEB, and higher water contents decreased the temperature dependence of the NEB. At higher temperatures, the NEB became less water content dependent and enhanced browning in spray-drying. The temperature dependence of nonenzymatic browning could also be modeled using the Williams-Landel-Ferry (WLF) equation, but the WLF constants were dependent on the water content.     

Glass transition and water effects on sucrose inversion by invertase in a lactose-sucrose system

Enzymatic changes are often detrimental to quality of low-moisture foods. In the present study, effects of glass transition and water on sucrose inversion in a lactose-sucrose food model were investigated. Amorphous samples were produced by freeze-drying lactose-sucrose (2:1)-invertase (20 mg invertase/49.4 g of carbohydrate) dissolved in distilled water. Sorption isotherms were determined gravimetrically at 24 degrees C. Sucrose hydrolysis was determined by monitoring glucose content using a test kit and the amounts of fructose, glucose, and sucrose using HPLC. The glass transition temperatures, T(g), at various water contents were measured using differential scanning calorimetry (DSC). The BET and the GAB sorption models were fitted to experimental data up to a(w) 0.444 and 0.538, respectively. Water sorption and DSC results suggested time-dependent crystallization of sugars at a(w) 0.444 and above. Significant sucrose hydrolysis occurred only above T(g), concomitantly with crystallization. Sucrose hydrolysis and crystallization were not likely in glassy materials.     

Modeling bleaching of tomato derivatives at subzero temperatures

This work was addressed to obtain a predictive model of the rate of bleaching in tomato derivatives at subzero temperatures. To this aim, a tomato puree was freeze-dried and equilibrated at increasing solid fractions. The bleaching rate was assessed by measuring tomato color during storage for up to 18 months at temperatures from -30 to 0 degrees C. The temperature dependence of the tomato-bleaching rate was neither predictable using the Arrhenius equation nor simply related to tomato physical state. The lack of a clear Arrhenius relation was attributed to the occurrence of temperature-dependent phenomena, such as ice crystallization and oxygen solubility modifications, which strongly changed the local concentration of reactants. A modified Arrhenius equation predicting the tomato-bleaching rate in the entire temperature range was proposed. Tomato concentration, and hence its physical state, affected the temperature dependence of bleaching, modifying apparent activation energy and frequency factor of the modified Arrhenius equation. In light of these considerations, a mathematical model was set up and validated to accurately predict the tomato-bleaching rate on the basis of only its concentration and storage temperature.     

基于差示扫描量热法和热力学模型的生物柴油结晶行为分析

棕榈酸甲酯(C16:0)、硬脂酸甲酯(C18:0)和油酸甲酯(C18:1)是生物柴油的主要组成部分。为了深入探究生物柴油的结晶行为,该文基于差示扫描量热法(differential scanning calorimetry,DSC)分析了这3种脂肪酸酯的物性参数,研究发现饱和脂肪酸甲酯C16:0和C18:0的熔点和熔化焓远远高出不饱和脂肪酸甲酯C18:1的值,C16:0和C18:0的熔点分别为301.57、310.92 K,C18:1的熔点为255.01 K。对脂肪酸酯组成的二元溶液进行DSC扫描,DSC曲线出现了2个放热峰,并且溶液的结晶点要低于首先析出的饱和脂肪酸酯纯物质时的熔点;随着饱和脂肪酸酯质量分数的增加溶液的结晶点温度也相应提高。将生物柴油当作由多元脂肪酸甲酯的混合溶液时,C16:0和C18:0等饱和脂肪酸甲酯作为溶质,C18:1等不饱和脂肪酸甲酯作为溶剂,建立了热力学模型计算溶液的结晶点温度。将脂肪酸甲酯的混合溶液近似为理想溶液时对此模型进一步简化,并利用简化模型计算得到4种生物柴油的结晶温度,与实测值进行比较得到了很好的验证效果。该研究可为优化生物柴油低温流动性的技术措施提供参考。     

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.     

莲子热风干燥过程对其淀粉热特性及凝胶化的影响

为解决莲子干燥过程中淀粉形态结构变化造成莲子结壳、硬化,不利于干燥以及复水难、易返生问题,该文利用差示扫描量热技术(differential scanning calorimetry,DSC)对新鲜莲子以及不同热风干燥(70、80、90℃)莲子的淀粉热特性与凝胶化过程进行了研究.研究发现,莲子淀粉在低水分环境(42.2%,以质量比计)时存在2个明显的吸热峰,高水分环境(71.1%,以质量比计)时存在1个明显的吸热峰;莲子在干燥过程中不断失水,并伴随着淀粉凝胶化.方差分析(analysis of variance,ANOVA)表明,高温干燥显著影响莲子淀粉的热特性,其淀粉凝胶化温度(峰起温度To、峰顶温度Tp以及峰止温度Te)部分显著升高.相同干燥条件下,莲子淀粉糊化焓ΔH受水分显著影响,但干燥温度、升温速率对其影响不显著(P>0.01).采用Kissinger、Crane方程获得了淀粉凝胶化动力学参数(活化能Ea、指前因子Z以及反应级数n).莲子淀粉的非等温凝胶化反应可近似为一级反应,高温干燥后其Ea值出现增加,并随着水分增加呈现降低趋势.研究结果可为确定莲子高品质干燥工艺以及干莲子、莲子淀粉后续加工过程提供技术支持.     

Temperature effect on lactose crystallization, maillard reactions, and lipid oxidation in whole milk powder

Whole milk powder with an initial water content of 4.4% (w/w) and a water activity of 0.23 stored in hermetically sealed vials for up to 147 days below (37 and 45 degrees C) and above (55 degrees C) the glass transition temperature (T(g) determined to have the value 48 degrees C) showed a strong temperature dependence for quality deterioration corresponding to energies of activation close to 200 kJ/mol for most deteriorative processes. The glass transition was found not to cause any deviation from Arrhenius temperature dependence. Lactose crystallization, which occurred as a gradual process as monitored by isothermal calorimetry, is concluded to liberate bound water (a(w) increase to 0.46) with a modest time delay (approximately 2 days at 55 degrees C) and with concomitant surface browning as evidenced by an increasing Hunter b-value. Browning and formation of bound hydroxymethyl-furfural determined by HPLC seem to be coupled, while formation of another Maillard reaction product, furosine, occurred gradually and was initiated prior to crystallization. Initiation of lipid oxidation, as detected by lipid-derived radicals (high g-value ESR spectra), and progression of lipid oxidation, as detected by headspace GC, seem not to be affected by lactose crystallization and browning, and no indication of browning products acting as antioxidants could be determined.     

Optimization of Near‐Infrared Reflectance Model in Measuring Gelatinization Characteristics of Rice Flour with a Rapid Viscosity Analyzer (RVA) and Differential Scanning Calorimeter (DSC)

This study compared the calibration models generated by combinations of different mathematical and preprocessing treatments as well as regression algorithms to optimize the analysis of gelatinization properties of rice flour by using near‐infrared spectroscopy, in comparison with conventional techniques of differential scanning calorimetry (DSC) and rapid viscosity analysis (RVA). A total of 220 milled rice flours were used for model construction. A model generated by the modified partial least squares regression (MPLS) with mathematical treatment “2, 8, 8, 2” (second‐order derivative computed based on eight data points, and eight and two data points in the second smoothing, respectively) and detrend preprocessing was identified as the best for simultaneously measuring onset temperature (T_o), peak temperature (T_p), and conclusion temperature (T_c) of DSC. MPLS/“2, 8, 8, 2”/weighted multiplicative scattering correction preprocessing was identified as the best for RVA properties. The results indicated that near‐infrared reflectance spectroscopy could be used to rapidly predict gelatinization properties of rice flour for the purposes of quality evaluation of germplasm and selection of intermediate lines in breeding programs.     

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.     

Crystallization behavior and texture of trans-containing and trans-free palm oil based confectionery fats

The objective of this study was to gain insight into the role of trans fatty acids in determining the crystallization behavior and texture of palm-based confectionery fats. Therefore, the isothermal crystallization behavior of two series, each of three fats, one trans-containing and one trans-free, was examined by pNMR, DSC, and rheology. Furthermore, the hardness of these samples was examined at three different storage times at 10 degrees C. All of the trans free samples showed a two-step crystallization at 10 degrees C which is hypothesized to be an alpha-mediated beta' crystallization for two of the samples and a fractionated crystallization in the beta' polymorph for the third, while the trans-containing fats crystallized in a single step, probably a direct beta' crystallization. The trans-containing fat series clearly crystallized faster than the trans-free fat series and also yielded higher hardness values at all storage times investigated. The presence of trans fatty acids seems to reduce the effect of compositional variations on the crystallization process. For the trans free fats, chemical composition was much more critical in determining the crystallization rate, the SFC, and the final hardness value.     

Multi-level approach for the analysis of water effects in corn flakes

The purpose of this work was to analyze the effect of water on thermal transitions, mechanical properties, and molecular mobility in corn flakes (CF), and their relationships. Commercial common (CCF) and sugar-frosted (SCF) corn flakes were studied in a water content (wc) range from 5 to 20 (% dry basis). The slope of (1)H NMR spin-spin relaxation time T 2* (determined by FID) versus temperature plot changed close to T g. Compression force showed a maximum at wc of ca. 12 and 16% (db) for SCF and CCF, respectively. (1)H NMR complemented DSC data in determining the temperature dependence of water and solid mobility, in order to assess quality of laminated corn products. The results of the present work indicate that while the compression force showed a maximum value as a function of water content, T g values determined by DSC or by spin-spin relaxation decreased progressively with increasing water content.     

Enrichment of higher molecular weight fractions in inulin

Inulin (general formulas GFn and Fm, with G = anhydroglucose and F = anhydrofructose) naturally occurs as a homologous series of oligo- and polysaccharides with different chain lengths. For reasons of growing interest in the food and pet food industries, the short chain inulins have to be separated from their long chain analogues because their properties (digestibility, prebiotic activity and health promoting potential, caloric value, sweetening power, water binding capacity, etc.) differ substantially. To study these properties in relation to the number average degree of polymerization (DPn), ultrafiltration, specific crystallization from aqueous solution, and precipitation from solvent/water mixtures were used to enrich native chicory and dahlia inulin in the higher molecular weight fractions. Depending on the membrane module used, the DPn of chicory inulin (DPn = 8.1) and dahlia inulin (DPn = 29) could be increased by ultrafiltration to a maximum value of, respectively, 22 and 43. With crystallization from aqueous solutions (25 degrees C), similar results were obtained but at a much higher yield. Finally, long chain inulin could be precipitated from aqueous solutions in the presence of high concentrations of methanol, ethanol, and acetone. Acetone demonstrated to be the best solvent system to increase the DPn, followed by ethanol and methanol. However, for safety reasons and food purposes, ethanol was evaluated to be the best choice. With ethanol, the DPn could be raised to 25 for chicory inulin and up to 40 for dahlia inulin.     

Impact of pH on the kinetics of acrylamide formation/elimination reactions in model systems

The effect of pH on acrylamide formation and elimination kinetics was studied in an equimolar (0.1 M) asparagine-glucose model system in phosphate or citrate buffer, heated at temperatures between 120 and 200 degrees C. To describe the experimental data, a simplified kinetic model was proposed and kinetic parameters were estimated by combined nonlinear regression and numerical integration on the data obtained under nonisothermal conditions. The model was subsequently validated in a more realistic potato-based matrix with varying pH. By increasing acidity, the reaction rate constants at T(ref) (160 degrees C) for both acrylamide formation and elimination can significantly be reduced, whereas the temperature dependence of both reaction rate constants increases. The introduction of a lyophilized potato matrix (20%) did not affect the acrylamide formation reaction rate constant at reference temperature (160 degrees C) as compared to the asparagine-glucose model system; the elimination rate constant at T(ref), on the contrary, was almost doubled.     

蒸发式过冷水制冰液滴蒸发结晶的模拟

蒸发式过冷水制冰系统中液滴传热传质特性研究具有重要意义。为了分析蒸发式过冷水制冰系统中液滴的热质传输特性,该文将单个液滴冷却结晶过程分为全液相区、固-液两相区和全固相区3个不同区域,建立液滴在大空间内蒸发降温结晶过程的数学模型,通过数值求解方法研究其在大空间蒸发室内降温结晶过程的温度变化特性,进一步分析液滴和空气的入口参数与液滴整个蒸发结晶特性的关系,为蒸发式过冷水制冰系统的结构优化设计和运行管理提供参考依据。     

用温度变换日数法预测包膜尿素氮素的溶出率

通过不同温度培养试验方法,根据反应速度理论法求得了包膜尿素(LP30)氮素的溶出特性值,并采用基于反应速度理论的温度变换日数法预测了包膜尿素(LP30)在自然土壤温度条件下氮素的溶出率。研究表明:包膜尿素(LP30)氮素溶出符合一级化学反应(Nt=N0[1-exp(-kt)]);溶出速率常数(k)具有温度依存性:在10℃～25℃范围内,速率常数(k)在0.0081～0.0425之间,反应活化能(Ea)为75733J mol-1;基于反应速率理论的温度变换日数法能够应用并预测自然温度条件下包膜尿素氮素的溶出率。     

动态高压微射流对乌贼墨黑色素物理性质及微观结构的影响

为改善乌贼墨黑色素在食品中的应用性能,以虎斑乌贼(Sepia pharaonis)墨囊为原材料,采用碱性蛋白酶酶解制备乌贼墨黑色素,研究不同动态高压微射流(DHPM)(0、40、80、120、160、200 MPa)均质对其物理性质的影响,并采用红外光谱、扫描电子显微镜分析其微观结构。结果表明,DHPM处理使乌贼墨黑色素聚集体解聚,浊度增加、平均粒径减小,粒度分布更加集中和细微化,同时改善了其在去离子水和生理盐水中的溶解性;在压力作用下表现为粘度、空间色度值均有所增大;差示扫描量热法(DSC)分析表明,乌贼墨黑色素在120 MPa下热变性温度为90.70℃,焓变值为0.45 J·g^-1,且该压力下其贮藏稳定性最好;红外光谱分析表明,在特定压力处理范围内,DHPM处理使乌贼墨黑色素分子间形成了较强的氢键;扫描电镜观察发现样品颗粒在120 MPa处理后颗粒尺寸最小。因此,DHPM改性技术改善了乌贼墨黑色素的物理性质和微观结构,为其在食品工业中的应用提供了理论依据。     

What determines the temperature response of soil organic matter decomposition?

The temperature dependence of litter and soil organic matter (SOM) mineralisation is important because it determines how strong the feedback from the expected warmer climate may be on the atmospheric CO₂ concentration. We have used a simple, analytical model to investigate how three different mechanism (i) the rate at which decomposers take up substrate at their surface; (ii) the rate by which substrate diffuses up to the surface of the decomposer; and (iii) the rate at which substrate is made available in the environment interact to determine the temperature response. The mechanisms are characterised by activation energies; two for the uptake rate (i) and one for each of the other two (ii, iii). The model shows that the temperature dependence is the result of the number of processes that effectively contributes to the rate of mineralisation; this result should also be valid if other processes are included. Depending upon the relative magnitude of the four activation energies, the temperature response is mainly determined by one or two of the mechanisms. In a transition zone, where all activation energies are similar and the number of contributing processes changes, there can be either a sharp increase or a sharp decrease in the temperature response when activation energies change.     

应用同步热分析仪确定小麦秸秆热解需热量

为了解决生物质热解过程需热量的定量问题,该文应用热重—差示扫描（TG/DSC）同步热分析仪对小麦秸秆进行了热解实验研究。将约5 mg的小麦秸秆粉样品装入带盖的铂铑坩锅中,放在热解炉中的DSC-cp高精度样品支架上,在流量为25 mL/min的高纯氮气吹扫下,以10 K/min的升温速率从常温升至973 K,记录生物质的热重(TG)曲线和差示扫描(DSC)曲线。通过对实验所得微分热重(DTG)曲线和DSC曲线对比分析,对小麦秸秆热解过程进行了详细的探讨。在DSC曲线上扣除水分的影响后对其积分得出热解过程需热量的规律。结果表明,要使1 kg干小麦秸秆完成从常温303 K到673 K,773 K,873 K的升温和热解,所需的总热量分别为523 kJ,558 kJ,592 kJ。     

Thermal and high-pressure inactivation kinetics of polyphenol oxidase in Victoria grape must

The inactivation kinetics of polyphenol oxidase (PPO) in freshly prepared grape must under high hydrostatic pressure (100-800 MPa) combined with moderate temperature (20-70 degrees C) was investigated. Atmospheric pressure conditions in a temperature range of 55-70 degrees C were also tested. Isothermal inactivation of PPO in grape must could be described by a biphasic model. The values of activation energy and activation volume of stable fraction were estimated as 53.34 kJ mol(-1) and -18.15 cm3 mol(-1) at a reference pressure of 600 MPa and reference temperature of 50 degrees C, respectively. Pressure and temperature were found to act synergistically, except in the high-temperature-low-pressure region where an antagonistic effect was found. A third-degree polynomial model was successfully applied to describe the temperature/pressure dependence of the inactivation rate constants of the stable PPO fraction in grape must.     

Kinetics of sucrose crystallization in whey protein films

The kinetics of sucrose crystallization in whey protein isolate (WPI) films was studied at 25 degrees C in four different relative humidity environments: 23, 33, 44, and 53%. The effects of protein matrix, crystallization inhibitors, and storage environment on the rate constants of sucrose crystallization were determined using the Avrami model of crystallization. It was found that a cross-linked, denatured whey protein (WP) matrix more effectively hindered sucrose crystallization than a protein matrix of native WP. The crystallization inhibitors tested were lactose, raffinose, modified starch (Purity 69), and polyvinylpyrrolidone (Plasdone C15). Raffinose and modified starch were determined to be the more effective inhibitors of sucrose crystallization. At lower relative humidities (23, 33, and 44%), the cross-linked protein matrix played a more important role in sucrose crystallization than the inhibitors. As relative humidity increased (53%), the crystallization inhibitors were more central to controlling sucrose crystallization in WPI films.