Crystallization Kinetics of Amorphous Lactose as a Function of Moisture Content Using Isothermal Differential Scanning Calorimetry

Isothermal differential scanning calorimetry (DSC) was used to study the crystallization kinetics of amorphous lactose at 3 moisture contents. Each sample was heated to several temperatures between Tg and Tm. After subtraction of an induction time, the Avrami equation was used to model the data and a Lauritzen-Hoffman like expression used to fit the crystallization rates between Tg and Tm. The highest Tm/Tg ratio and crystallization rate were observed for the sample containing the most moisture. Conversely the lowest Tm/Tg ratio and crystallization rate were observed for the sample containing the least moisture. Evidence for multiple transitions was seen. The Avrami equation may not be the best way to model such data.     

Crystallization and X-ray Diffraction of Crystals Formed in Water-Plasticized Amorphous Spray-dried and Freeze-dried Lactose/Protein Mixtures

ABSTRACT: Effects of proteins (whey protein isolate [WPI], Na-caseinate, and gelatin), drying method, storage relative vapor pressure (RVP), and time on lactose crystallization and crystals formed were investigated using x-ray diffraction (XRD). Crystallization was observed from increasing peak intensities of XRD patterns. Lactose in lactose/protein (5:1,3:1) mixtures crystallized in samples stored at RVP of 44.1% and above in both spray-dried and freeze-dried materials, except in freeze-dried lactose/Na-caseinate and lactose/gelatin mixtures, which showed lactose crystallization at 54.5% RVP and above. The rate of crystallization increased with increasing RVP and storage time. The rate of crystallization in spray-dried materials was higher than in freeze-dried materials, and the crystallization rate decreased with increasing protein content. Lactose crystallized mainly as α-lactose monohydrate in spray-dried lactose/WPI and lactose/gelatin mixtures. Crystals formed in freeze-dried lactose/WPI and lactose/gelatin mixtures were anhydrous β-lactose and α-lactose monohydrate crystals. Lactose crystallized as a-lactose monohydrate in both spray-dried and freeze-dried lactose/Na-caseinate mixtures. Trace amounts of anhydrous β-lactose were present in spray-dried lactose/WPI (5:1) and lactose/gelatin (5:1) mixtures. Peak intensities of XRD patterns for anhydrous β-lactose decreased with increasing protein content and storage time. The crystallization data were successfully modeled using Avrami equation at an RVP of 65.6% and above. These data are important in understanding and predicting storage stability of lactose- and protein-containing food and pharmaceutical materials.     

Crystallization Kinetics of Lactose and Sucrose Based On Isothermal Differential Scanning Calorimetry

Isothermal Differential Scanning Calorimetry (DSC) was used to study the crystallization kinetics of freeze-dried samples of lactose and sucrose at several temperatures between Tg and Tm. The sample was rapidly heated to the required temperature. After subtraction of an induction time, the Avrami equation was used to model the data and a Lauritzen-Hoffman like expression used to fit the derived rates of crystallization over the temperature range Tg相似文献   

Water Plasticization and Crystallization of Lactose in Spray-dried Lactose/Protein Mixtures

ABSTRACT: Water plasticization led to depression of the glass transition causing significant changes in the physico-chemical and crystallization properties in storage of lactose and lactose/protein (3:1) mixtures. Glass transition (Tg) and crystallization temperatures (Tcr) were determined using differential scanning calorimetry. Whey protein isolate (WPI), albumin, and gelatin increased the Tg of dry powders; when Na-caseinate was used, a decrease was observed. In the presence of proteins and water, a decrease of Tg at aw ≤ 0.23 was observed. At aw ≤ 0.33, proteins increased the Tg In the anhydrous state, Tcr decreased in the presence of proteins possibly because of browning. WPI, Na-caseinate, albumin, and gelatin delayed lactose crystallization in humidified samples, with albumin and gelatin delaying it more than WPI at all storage humidities. Temperature difference between an observed instant crystallization and glass transition (Tcr to Tg) was larger for humidified samples containing proteins than for lactose. Various proteins and water affect crystallization behavior of amorphous lactose differently in spray-dried powders. This should be considered in evaluating sugar crystallization properties in food products including dairy powders.     

Nanofiltration Concentration Effect on the Efficacy of Lactose Crystallization

Application of nanofiltration membranes to processing sweet whey and skim milk ultrafiltration permeate increased lactose crystal yield by about 10 and 8 %, respectively, at a concentration factor of 3.0. These increases were attributed to depletion of minerals, especially monovalent cations such as sodium and potassium, by the partial demineralization effect of the nanofiltration membrane. These membranes may be incorporated into current industrial processes for producing lactose from whey and milk permeates.     

Crystallization in Lactose Refining—A Review

In the dairy industry, crystallization is an important separation process used in the refining of lactose from whey solutions. In the refining operation, lactose crystals are separated from the whey solution through nucleation, growth, and/or aggregation. The rate of crystallization is determined by the combined effect of crystallizer design, processing parameters, and impurities on the kinetics of the process. This review summarizes studies on lactose crystallization, including the mechanism, theory of crystallization, and the impact of various factors affecting the crystallization kinetics. In addition, an overview of the industrial crystallization operation highlights the problems faced by the lactose manufacturer. The approaches that are beneficial to the lactose manufacturer for process optimization or improvement are summarized in this review. Over the years, much knowledge has been acquired through extensive research. However, the industrial crystallization process is still far from optimized. Therefore, future effort should focus on transferring the new knowledge and technology to the dairy industry.     

切达干酪乳清结晶分离乳糖的工艺优化

以切达干酪的乳清为原料,采用浓缩结晶的方法分离乳糖,利用响应面优化结晶工艺。通过Box-Benhnken试验设计方法,在单因素实验的基础上,以结晶乳糖得率为指标,研究了结晶时间、结晶温度以及乳清pH因素及相互作用对得率的影响,得到了最佳的结晶工艺条件:结晶温度38.4℃、结晶时间24.7 h、乳清pH 5.1,此条件下,乳糖结晶得率达到最大值47.7%。     

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.     

Rates of Crystallization of Dried Lactose-sucrose Mixtures

The isothermal crystallization kinetics of glassy lactose/sucrose mixtures were studied at several storage temperatures (close to T_g and T_m). The kinetic parameters implicit in the Avrami equation were determined. Activation energies for transport (E_D) and surface nucleation (W*) were also found and correlated to the molar composition of the lactose/sucrose mixtures. A monotonic increase in the half crystallization time (t_1/z), Avrami index (n), % crystallization per day, activation energy for transport (E_D) and surface nucleation energy (W*) and a decrease in the crystallization velocity constants (K) were related to the increase in the lactose content of lactose/sucrose mixtures.     

无定形食品物理老化过程的数值研究

为了估算无定形食品的老化时间,利用数值方法考察了升降温速率和Adam-Gibbs(AG)模型参数对连续升降温无量纲比热容的影响。结果表明,升降温速率会对计算结果产生明显影响,获得的松弛参数要给出是在何种升降温速率下获得的。AG模型参数表现出很强的相关性,如果四个模型参数同时作为自由变量可能会得到不合理结果。通过和实验数据的对照,发现本研究的分析结果对于大致估算AG模型参数有一定指导意义。     

Lactose/beta-lactoglobulin interaction during storage of model whey powders

The objective of this study was to evaluate the presence or absence of interaction between lactose and beta-lactoglobulin during storage of model whey powders at different water activities (a(w)). Model whey powders were prepared by colyophilization of lactose with increasing quantities of beta-lactoglobulin. These colyophilized beta-lactoglobulin:lactose powders, assigned as BL powders, were stored from 0.11 to 0.95 a(w). The water sorption behavior of BL powders was studied gravimetrically, and the state of lactose was investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Before storage, BL powders were amorphous. After storage, a loss of water was observed on moisture sorption isotherms of BL powders. It was related to the formation of lactose crystals, detected by DSC and SEM analysis, and to the structural collapse of the powders. Water loss due to lactose crystallization was shifted to higher a(w) with increasing beta-lactoglobulin content in BL powders. Moreover, kinetics of moisture sorption demonstrated that beta-lactoglobulin was also responsible for a slower crystallization process in BL powders. Then, the water sorption behavior of BL powders was very different from the behavior of the 2 compounds mixed after separate lyophilization. All these results pointed out interaction between lactose and beta-lactoglobulin, which appeared during lyophilization and still occurred during storage. This lactose/beta-lactoglobulin interaction stabilized model whey powders against lactose crystallization.     

Lactose: Use,measurement, and expression of results

Lactose has different uses in the dairy, food, and pharmaceutical industries. Being aware of the different forms of lactose and their concentrations can be very helpful in managing dairy product quality, properties, and manufacturing efficiency. Correct measurement and reporting of lactose concentration in milk and other dairy products will be of increased importance in the future as more value-added uses of lactose are developed and as milk lactose data are used in farm management decision making. Lactose should be reported as anhydrous lactose because lactose data will be used to make increasingly important decisions in dairy processing, dairy product labeling, and milk production in the future. Lactose also plays an important role in milk synthesis within a cow. Milk production factors and dairy cattle breed selection influence the amount of high value fat and protein produced per unit of lactose. If the off-farm value of lactose remains low, more attention may be focused on using ultrafiltration to process milk and leave 50 to 60% of the lactose and water from milk at the farm to recover the energy value of the lactose as feed and reduce the hauling cost of the high value components of milk to a dairy product manufacturing factory. Many methods exist to determine lactose concentration, but the most important methods are enzymatic assays, HPLC, and mid-infrared analysis. New, value-added uses for lactose need to be developed. Consistent and accurate methods of lactose measurement and consistent expression of lactose results will support this development process. Starting in January 2017, the USDA Federal Milk Market Laboratories began reporting lactose content of milk as anhydrous lactose and discontinued the reporting of lactose by difference.     

乳清中乳糖的酶法水解

本文研究了Aapergillur niger CWL2NU-3乳糖酶在乳清中的应用,探讨了温度、pH、金属离子、底物浓度、酶浓度及水解时间等因素对乳清中乳糖的酶法水解速度的影响,在此基础上确定了主要影响因素,通过正交试验,获得乳清中乳糖水解的最佳工艺条件(65℃、pH4.5、乳糖15%、[E]/[L]=0.03、水解时间2.5h),在此条件下乳糖水解率为91.0%。     

Crystallization Kinetics and X-ray Diffraction of Crystals Formed in Amorphous Lactose, Trehalose, and Lactose/Trehalose Mixtures

ABSTRACT: Effects of storage time and relative humidity on crystallization kinetics and crystal forms produced from freeze-dried amorphous lactose, trehalose, and a lactose/trehalose mixture were compared. Samples were exposed to 4 different relative water vapor pressure (RVP) (44.1%, 54.5%, 65.6%, 76.1%) environments at room temperature. Crystallization was observed from time-dependent loss of sorbed water and increasing intensities of peaks in X-ray diffraction patterns. The rate of crystallization increased with increasing storage humidity. Lactose crystallized as α-lactose monohydrate, β-anhydrous, and anhydrous forms of α- and β-lactose in molar ratios of 5:3 and 4:1 in lactose and lactose/trehalose systems. Trehalose seemed to crystallize as a mixture of trehalose dihydrate and anhydrate in trehalose and lactose/trehalose systems. The crystal forms in a mixture of lactose and trehalose did not seem to be affected by the component sugars, but crystallization of the component sugars was delayed. Time-dependent crystallization of lactose and trehalose in the lactose-trehalose mixture could be modeled using the Avrami equation. The results indicated that crystallization data are important in modeling of crystallization phenomena and predicting stability of lactose and trehalose-containing food and pharmaceutical materials. Keywords: crystallization, lactose, trehalose, crystal form, X-ray diffraction     

酵母乳糖酶对牛乳乳糖水解作用的研究

采用乳酸克鲁维酵母的乳糖酶(β-乳糖苷酶)对乳糖溶液、喷雾干燥脱脂奶以及全脂奶进行了试验,以确定将乳糖转化成单糖的最适条件。当牛奶中酶浓度为3u/ml时,于40℃反应2小时或4℃反应24小时,约60％的乳糖得以水解。随着乳糖浓度的增高,水解程度也有所提高。当酶浓度为10U/ml时,于40℃反应2小时,90％乳糖得以水解。用自制的乳酸克鲁维酵母的乳糖酶和加拿大lactaid Inc.生产的乳糖酶制剂lactaid水解乳糖无大的差异。     

酶法测定乳糖

介绍了酶法检测乳糖的方法，该法基于乳糖酶对乳糖的水解反应，测定所生成的葡萄糖量。本法在乳糖浓度与吸光度之间有很好的线性关系。     

Sorption Isotherm and Calorimetric Behavior of Amorphous/Crystalline Raffinose-Water Systems

ABSTRACT: The water adsorption and desorption isotherms at 27 °C of initially amorphous raffinose over a range of relative humidity of 11% to 97% have been determined. Upon adsorption, the isotherm exhibited a "quasi" plateau, and the moisture content at this plateau was found to be very close to the amount required to form the crystalline raffinose pentahydrate (R.5 H2O). Crystallization of raffinose (R.5 H2O) during water adsorption at 52% and 58% RH was indicated by differential scanning calorimetry (DSC); both thermograms showed an endothermal peak of melting corresponding to R.5H2O. The results of the crystallization kinetics at 52% and 58% RH indicated that the time to assess the stable physical state in a sugar system for a given external condition has to be properly defined and depends on the (T-T_g) value.     

Nonenzymatic Browning Kinetics in Low-moisture Food Systems as Affected by Matrix Composition and Crystallization

ABSTRACT: Nonenzymatic browning (NEB) in lactose, trehalose, and lactose/trehalose food model systems containing L-lysine and D-xylose (5% w/w) as reactants was studied at 4 different relative vapor pressure (RVP) (33.2%, 44.1%, 54.5%, 65.6%) environments at room temperature. Sorption isotherms of model systems were determined gravimetrically, and data were modeled using the Brunauer-Emmett-Teller (BET) and Guggenheim-Anderson-deBoer (GAB) models. Glass transition, T_g , was measured by differential scanning calorimetry (DSC). NEB was followed spectrophotometrically. Although the 3 model systems showed similar glass transition behavior, different crystallization properties were observed from loss of sorbed water. Mixtures of trehalose and lactose showed delayed crystallization of component sugars. The NEB rate was affected by sugar composition. At a low RVP (33.1%) environment, the NEB rate in trehalose system was higher than in the lactose/trehalose system, and the NEB rate in lactose system was the lowest. The NEB rate in different models seemed to be affected by component crystallization. The highest extent of browning in the trehalose matrix system seemed to be related to the formation of trehalose crystals in the system after crystallization at high RVP. The results indicated that the composition of the carbohydrate-based low-moisture real food systems should be considered in controlling NEB reaction.     

Corn Syrup Solids and Their Saccharide Fractions Affect Crystallization of Amorphous Sucrose

The effects of corn syrup saccharides on the glass transition (Tg) and crystallization of freeze-dried sucrose were studied using differential scanning calorimetry. Corn syrup (CS) solids were fractionated into samples with differing ranges and types of glucose polymers. Tg of the sucrose/CS additive mixtures depended on number-average molecular weight, rather than weight-average molecular weight, of CS material. Additive levels of 10% and 20% (w/w) of CS solids and their fractions interfered with crystallization of amorphous sucrose, whereas levels 50% prevented crystallization. The mechanism by which CS saccharides interfered with crystallization of amorphous sucrose depended not only on Tg but was also influenced by specific interactions between molecules.     

抗乳糖不耐受添加剂的研究

对产乳糖酶的三株乳酸菌进行协同发酵制成抗乳糖不耐受添加剂,冻干的乳糖酶在4℃贮存三个月活性基本不变,确立抗乳糖不耐受添加剂乳酸菌添加浓度为107/L。