Influence of heat treatment of goat milk on casein micelle size, rheological and textural properties of acid gels and set type yoghurts

✅ 全文

山羊奶热处理对酪蛋白胶粒大小、酸凝胶流变学和质构特性以及凝固型酸奶的影响

作者 Marina Hovjecki; Zorana Miloradović; Vladislav Rac; Predrag Pudja; Jelena Miočinović 期刊 Journal of Texture Studies 发表日期 2020 ISSN 0022-4901 DOI 10.1111/jtxs.12524 类型 原创研究 (Original Research)

📄 中文摘要 Chinese Abstract

中文
发酵乳制品(如酸奶)越来越多地以山羊奶为原料生产,但其加工技术通常沿用针对奶牛奶设计的工艺,而这两种奶在加工特性上存在显著差异。热处理是酸奶生产中的关键加工变量,它通过乳清蛋白变性和热诱导复合物的形成影响产品质构特性。然而,超过90°C的剧烈热处理可能通过聚集和解离反应导致胶束结构中酪蛋白组分的重排,从而改变凝胶过程和质构。尽管奶牛奶奶酸凝胶的流变学特性已被广泛研究,但关于山羊奶的报道较少,且高热处理对其组分的影响存在显著差异,表明山羊奶的胶体稳定性较低,且形成的热诱导蛋白复合物与奶牛奶不同。

📋 英文结构化总结 English Structured Summary

全文整理

EN

Background:

Fermented dairy products such as yoghurt are increasingly produced from goat's milk, yet they are often manufactured using technological procedures designed for cow's milk, despite the two milks having significantly different technological properties. Milk heat treatment is an important processing variable in yoghurt production, as it impacts textural properties through whey protein denaturation and the formation of heat-induced complexes. However, severe heat treatments above 90°C can cause rearrangement of casein components in the micellar structure through aggregation and dissociation reactions, altering gelation processes and texture. While the rheology of acid gels made from cow's milk is well-studied, few reports exist for goat's milk, and the influence of high heat treatment on its components differs considerably, indicating lower colloidal stability and different heat-induced protein complexes compared to cow's milk.

Methods:

Acid gels and set type yoghurts were made from Saanen goat's milk heated at 72°C/30 s, 85°C/5 min, and 95°C/5 min, followed by acidification with starter culture at 43°C until pH 4.6. The mean casein micelle diameter was determined by dynamic light scattering (DLS) and the protein profile by SDS-PAGE electrophoresis. Rheological properties were analyzed using dynamic low amplitude oscillatory rheology to measure gelation time, gelation pH, storage moduli (G'), and yield stress. Textural properties of the yoghurts, including firmness, consistency, cohesiveness, and index of viscosity, were analyzed using back extrusion texture analysis. Statistical analysis was performed using a one-way ANOVA and Fisher LSD-test (p < .05).

Results:

The shortest gelation and fermentation time was recorded for yoghurt prepared from milk heated at 85°C/5 min. The pH of gelation, storage moduli (G'), and yield stress were also highest for this yoghurt compared to the other two treatments. Textural properties such as firmness and consistency were strongly affected by milk heat treatment, with the highest values recorded for yoghurt produced from milk preheated at 85°C/5 min. The largest casein micelles were measured after the 85°C/5 min treatment (~360 nm), and their size decreased at 95°C/5 min (~321 nm), despite a higher denaturation of whey proteins at the most intense heat regime. SDS-PAGE analysis confirmed significant irreversible covalent aggregation of whey proteins and a greater degree of β-lactoglobulin denaturation after the 95°C/5 min treatment.

Data Summary:

Mean casein micelle sizes were 253.2 ± 14.78 nm for raw milk, 253 ± 11.34 nm for 72°C/30 s, 360 ± 14.46 nm for 85°C/5 min, and 321 ± 3.09 nm for 95°C/5 min. For the 85°C/5 min treatment, gelation time was 118 ± 6 min, gelation pH was 4.91 ± 0.10, G' at pH 4.6 was 3.7 ± 0.5 Pa, and yield stress was 19.54 ± 1.67 Pa. For the 95°C/5 min treatment, gelation time was 168 ± 22 min, G' at pH 4.6 was 2.0 ± 0.15 Pa, and yield stress was 17.06 ± 1.52 Pa. Textural firmness was 0.39 ± 0.01 N and consistency was 10.14 ± 0.29 N·s for the 85°C/5 min yoghurt, compared to firmness of 0.25 ± 0.06 N and consistency of 6.46 ± 1.32 N·s for the 95°C/5 min yoghurt.

Conclusions:

Different heat treatments of goat milk prior to acidification produce gels with significantly different rheological and textural properties. Unexpectedly, acid milk gels and yoghurts obtained from milk treated at 85°C/5 min exhibited the best rheological and textural attributes compared to both milder and more severe heat regimes. The poorer properties of gels from highly heated goat milk (95°C/5 min) may be due to changes in the casein micelle structure and the release of aggregates into the serum phase, which alter the gel formation process. DLS measurements indicate that micelles experience structural changes in the 85–95°C interval that worsen acid gel properties.

Practical Significance:

The 85°C/5 min heat treatment of goat milk is the most appropriate for yoghurt manufacture, as it yields the product with the best textural and rheological properties. Applying these findings can improve technological processes in the manufacturing of goat milk yoghurts and result in more energetically efficient production procedures by avoiding unnecessarily severe heat treatments that degrade product quality.

📋 中文结构化总结 Chinese Structured Summary

中文

背景:

发酵乳制品(如酸奶)越来越多地以山羊奶为原料生产,但其加工技术通常沿用针对奶牛奶设计的工艺,而这两种奶在加工特性上存在显著差异。热处理是酸奶生产中的关键加工变量,它通过乳清蛋白变性和热诱导复合物的形成影响产品质构特性。然而,超过90°C的剧烈热处理可能通过聚集和解离反应导致胶束结构中酪蛋白组分的重排,从而改变凝胶过程和质构。尽管奶牛奶奶酸凝胶的流变学特性已被广泛研究,但关于山羊奶的报道较少,且高热处理对其组分的影响存在显著差异,表明山羊奶的胶体稳定性较低,且形成的热诱导蛋白复合物与奶牛奶不同。

方法:

以萨能山羊奶为原料,分别在72°C/30 s、85°C/5 min和95°C/5 min条件下进行热处理,随后在43°C下用发酵剂酸化至pH 4.6,制备酸凝胶和凝固型酸奶。采用动态光散射(DLS)测定酪蛋白胶束平均粒径,采用SDS-PAGE电泳分析蛋白组分。采用动态小振幅振荡流变学分析凝胶时间、凝胶pH、储能模量(G')和屈服应力。采用反挤压质构分析法测定酸奶的质构特性,包括硬度、稠度、内聚性和粘度指数。统计分析采用单因素方差分析和Fisher LSD检验(p < 0.05)。

结果:

以85°C/5 min热处理奶制备的酸奶凝胶时间和发酵时间最短。该酸奶的凝胶pH、储能模量(G')和屈服应力也高于其他两种处理组。奶的热处理对质构特性(如硬度和稠度)有显著影响,以85°C/5 min预热奶生产的酸奶各项指标最高。85°C/5 min处理后酪蛋白胶束粒径最大(约360 nm),95°C/5 min处理后粒径减小(约321 nm),尽管在最剧烈的热处理条件下乳清蛋白变性程度更高。SDS-PAGE分析证实,95°C/5 min处理后乳清蛋白发生了显著不可逆共价聚集,β-乳球蛋白变性程度更大。

数据汇总:

生奶、72°C/30 s、85°C/5 min和95°C/5 min处理的酪蛋白胶束平均粒径分别为253.2 ± 14.78 nm、253 ± 11.34 nm、360 ± 14.46 nm和321 ± 3.09 nm。85°C/5 min处理的凝胶时间为118 ± 6 min,凝胶pH为4.91 ± 0.10,pH 4.6时G'为3.7 ± 0.5 Pa,屈服应力为19.54 ± 1.67 Pa。95°C/5 min处理的凝胶时间为168 ± 22 min,pH 4.6时G'为2.0 ± 0.15 Pa,屈服应力为17.06 ± 1.52 Pa。85°C/5 min酸奶的硬度为0.39 ± 0.01 N,稠度为10.14 ± 0.29 N·s;95°C/5 min酸奶的硬度为0.25 ± 0.06 N,稠度为6.46 ± 1.32 N·s。

结论:

山羊奶酸化前的不同热处理可产生流变学和质构特性显著不同的凝胶。出乎意料的是,85°C/5 min处理奶制得的酸奶奶凝胶在流变学和质构特性上均优于较温和和更剧烈的热处理条件。高热处理(95°C/5 min)山羊奶奶凝胶性能较差的原因可能是酪蛋白胶束结构的变化以及聚集体释放到乳清相中,从而改变了凝胶形成过程。DLS测定表明,在85–95°C区间内胶束经历了结构变化,导致酸凝胶性能下降。

实际意义:

85°C/5 min的山羊奶热处理是酸奶生产的最佳条件,可获得质构和流变学特性最优的产品。应用这些发现可改进山羊奶酸奶的生产工艺,避免不必要的高温处理(因其会降低产品质量),从而实现更节能高效的生产流程。

📖 英文全文 English Full Text

EN

R E S E A R C H A R T I C L E Influence of heat treatment of goat milk on casein micelle size, rheological and textural properties of acid gels and set type yoghurts

Marina Hovjecki1 | Zorana Miloradovic1 | Vladislav Rac2

| Predrag Pudja1 | Jelena Miocinovic1 1Department of Animal Source Food

Technology, Faculty of Agriculture, University of Belgrade, Belgrade, Serbia

2Department of Chemistry and Biochemistry, Faculty of Agriculture, University of Belgrade,

Belgrade, Serbia Correspondence Marina Hovjecki, Department of Animal

Source Food Technology, Faculty of Agriculture, University of Belgrade, Nemanjina

6, Belgrade 11080, Serbia.

Email: marina.hovjecki@agrif.bg.ac.rs Funding information

Ministry of Education, Science and Technological development, Grant/Award

Number: 46009 Abstract Acid gels and yoghurts were made from goat milk that was heated at 72C/30 s,

85C/5 min, and 95C/5 min, followed by acidification with starter culture at 43C until pH 4.6. The rheological and textural properties of acid gels and yoghurts were analyzed using dynamic low amplitude oscillatory rheology and back extrusion tex- ture analysis, respectively. The effect of goat milk heat treatment on the mean casein micelle diameter and protein profile was also determined by dynamic light scattering and SDS PAGE electrophoresis, respectively. The shortest gelation and fermentation time was recorded for yoghurt prepared from milk heated at 85C/5 min. Also, the pH of gelation, the storage moduli (G0) and yield stress were higher for this yoghurt, compared with the other two. Textural properties of goat milk yoghurts such as firm- ness and consistency were strongly affected by milk heat treatment, and the highest values were recorded for yoghurt produced from milk preheated at 85C/5 min, as well. The largest casein micelles were measured after 85C/5 min treatment and their size decreased at higher temperature, despite higher denaturation of whey proteins at the most intense heat regime, indicating the structure changes that influence on the acid gelation.

K E Y W O R D S goat milk, heat treatment, micelle size, rheology, texture, yoghurt

1 | INTRODUCTION Fermented dairy products such as yoghurt are usually produced from cow's milk, but for the last decade goat's milk products are becoming increasingly popular (Tamime, Wszolek, Božanic, & Özer, 2011). How- ever, due to lack of knowledge, goat's milk products are usually produced based on the technological procedure for cow milks despite they are sim- ilar in gross composition, but quite different in technological properties (Miloradovic, Kljajevic, Jovanovic, Vucic, & Macej, 2015).

Milk heat treatment is important processing variable in the produc- tion of fermented dairy products such as yoghurt. High heat treatment of milk is usually applied for production of fermented dairy products due to its positive impact on the textural properties (Robinson

& Tamime, 1993). There is evidence that for a constant duration of heat treatment (10, 15, or 30 min), increasing the temperature of skim milk heat treatment in the range of 70–95C increases denaturation of whey proteins (Dannenberg & Kessler, 1988a, 1988b), formation of heat- induced serum and micelle-bound complexes, and increases the gelation pH and elasticity of acid gels as well (Lucey, van Vliet, Grolle, Geurts, &

Walstra, 1997; Vasbinder, Alting, & de Kruif, 2003). On the other hand,

Raynal and Remeuf (1998) reported that severe heat treatments above

This article was published on AA publication on: 12 April 2020

Received: 23 January 2020 Revised: 21 March 2020 Accepted: 6 April 2020

DOI: 10.1111/jtxs.12524 J Texture Stud. 2020;1–8. wileyonlinelibrary.com/journal/jtxs

© 2020 Wiley Periodicals LLC 1 90C cause rearrangement of casein components in the micellar struc- ture through aggregation and dissociation reactions, which could also lead to changes in the gelation processes and different texture properties of acid gels.

The rheology of acid gels and fermented dairy products made from cow's milk were studied in many researches (Guggisberg,

Cuthbert-Steven, Piccinali, Bütikofer, & Eberhard, 2009; Lee &

Lucey, 2003; Lucey, Munro, & Singh, 1998; Lucey, Teo, Munro, &

Singh, 1997; Lucey, van Vliet, et al., 1997; Peng, Serra, Horne, &

Lucey, 2009).

However, to the best of our knowledge, just a few reports con- cerning the study of the rheological properties of goat's milk and products were presented (Domagała, Sady, Grega, & Najgebauer- Lejko, 2007; Jumah, Shaker, & Abu-Jdayil, 2001; Vargas, Cháfer,

Albors, Chiralt, & González-Martínez, 2008).

The influence of high heat treatment of milk on its compo- nents, especially proteins, is quite different in goats' milk as com- pared with cows' milk. It has been reported that the extent of protein precipitation in goat milk due to heat treatment is several times higher compared with the cow milk treated under same con- ditions, which indicates lower colloidal stability of goat milk. Also, the nature of heat induced protein complexes differs at these two milks (Miloradovic et al., 2015; Pesic et al., 2012). Hence, the objec- tive of this study was to determine the effects of goat milk heat treatment on rheological properties of acid gels as well as textural properties of set type yoghurts obtained from milk treated on the different heat regime. In order to better understand the behavior of different heat-treated goat milk during acid gelation, casein micelle size and SDS PAGE electrophoresis were also determined. Data about the influence of goat milk heat treatment on the casein micelle size are quite rare in literature that gives an additional value of this study.

2 | MATERIALS AND METHODS 2.1 | Goat milk samples Raw milk was collected from a local farm of Saanen goats (250 goats).

Approximately 3 L of raw bulk milk was collected every week during

3 weeks from the local farm, and immediately after collection milk was poured into the stainless steel pot and heated on the stove by agitation until completing appropriate heat treatment. All three heat treatments and following experiments were performed every week.

Compositional analyses were performed immediately after the sample collection.

Saanen goat's milk (3.1 ± 0.2% milk fat, 2.64 ± 0.04% proteins,

7.22 ± 0.11% non-fat dry matter and pH 6.72 ± 0.06) was treated by different heat regimes (72C/30 s, 85C/5 min, and 95C/5 min) and was used for casein micelle size measurements, electrophoresis, acid gelation, and set type yoghurt properties determination. All experi- ments were done in triplicate while analysis was done at least duplicate.

2.2 | DLS measurement The sizes of casein micelles were determined by dynamic light scatter- ing method (DLS) that was performed using a Horiba NanoPartica SZ- 100 (Horiba, Japan). After heat treatments, goat milk samples were immediately cooled by immersing in cool water, and left in refrigerator overnight. Samples were reheated to 40C and cooled down to 20C to achieve samples equilibration. Raw and heat treated goat milk sam- ples were skimmed by centrifugation (centrifuge model 5430;

Eppendorf AG, Hamburg, Germany) at 20C for 15 min at 600g. This skimming regime was used as the best appropriate in order to avoid protein loss (Miloradovic et al., 2015). Samples were diluted 100-fold in distilled water (Day, Williams, Otter, & Augustin, 2015) and mea- surements were performed at 20C, using a scattering angle of 90, in photon correlation mode and the correlation functions were analyzed to calculate the average hydrodynamic diameters. Measurements were performed at least three times on each sample.

2.3 | SDS-PAGE Raw and heat treated goat milk samples were prepared as reported by

Miloradovic et al. (2015), which is previosly described for DLS mea- surements. After the centrifugation, skimmed milk samples were

10-fold diluted by mixing aliquots of samples with SDS-R-PAGE (reducing) and

SDS-NR-PAGE (non-reducing) sample buffers according to the method of Anema and Stanley (1998). SDS-R-PAGE sample buffer pH 6.8 contained 0.055 M Tris–HCl, 2% (wt/vol) SDS,

7% (vol/vol) glycerol, 5% (vol/vol) β-mercaptoethanol, and 0.0025% (wt/vol) bromophenol blue. SDS-NR-PAGE sample buffer was without β-mercaptoethanol, and that was the only difference.

SDS-PAGE was performed according to the Laemmli (1970) with

4% stacking gel of pH 6.80, and 15% resolving gel pH 8.85. Five microliters of prepared samples were loaded at each well. Electropho- resis was performed using TV200YK twin-plate electrophoresis unit (Consort, Belgium), the power supply was set at constant current of

80 mA and the maximum voltage of 300 V for 1.5 hr. Gels were fixed and stained for 1 hr at 45C in Coomassie blue dye solution with

0.23% (wt/vol) Coomassie brilliant blue R250, 3.9% (wt/vol) trichlor- oacetic acid, 6% (vol/vol) acetic acid and 17% (vol/vol) methanol.

Destaining was done with a solution containing 8% (vol/vol) acetic acid and 18% (vol/vol) methanol, and the gels were scanned.

2.4 | Gel formation and yoghurt preparation Saanen goat's milk after different heat regimes (72C/30 s [A];

85C/5 min [B]; 95C/5 min [C]) was cooled to 43C and inoculated with 0.2% wt/wt “Yoflex 812” starter culture (Chr Hansen, The Neth- erlands). Small amount was used for rheological measurements, while fermentation was set at 43C until pH 4.6 was reached. Yoghurts were cooled during 24 hours in fridge temperature (4–7C) and then ana- lyzed. All experimental trials were repeated three times.

2 HOVJECKI ET AL.

2.5 | Rheological measurements Viscoelastic properties of acid gels and yoghurts were monitored by dynamic oscillatory shear measurements, performed on a Kinexus Pro

+ Rheometer (Malvern, Worcestershire, United Kingdom) with the four blade vane as a tool. The milk samples, after addition of starter culture were stirred for 2 min and then transferred to the rheometer, where were oscillated at a frequency of 0.1 Hz (0.1% shear strain) until the pH reached 4.6. Gelation time and pH were measured at the point when gels reached the storage modulus value (G0) ≥1 Pa (Lucey, van Vliet, et al., 1997), as well as G0 at pH 4.6, as a measure of gel firmness after fermentation.

When fermentation and coagulation were finished, gels were cooled to 5C (1C/min) and held at this temperature for 30 min before they were subjected to a frequency sweep (0.01–10 Hz; 0.1% strain).

Storage (G0) and loss moduli (G00) were calculated at the 1 Hz as a measure of gel properties after cooling.

Strain sweeps were performed (0.001–500%) at constant fre- quency of 1 Hz to determine the linear viscoelastic range (LVE). The yield stress value and the complex viscosity (η*) were calculated from cross over point (G0 = G00) outside of the LVE (Guggisberg et al., 2009).

All measurements were performed in triplicate.

2.6 | Textural properties Texture analysis was performed in plastic containers where fermenta- tion and gel formation were done. Due to achieving repeatability,

100 g of inoculate previously were measured into containers where the fermentation and cooling of yoghurt took place. Textural proper- ties of yoghurts such as firmness, consistency, cohesiveness and index of viscosity, were analyzed by TA.XT Plus Texture analyzer (Stable

Micro System, Godalming, Surrey, United Kingdom) through a single compression test, using a back extrusion cell disc (A/BE; diameter

35 mm; distance 30 mm; speed 0.001 m/s) and an extension bar, with

5 kg load cell at 5C. Textural parameters were automatically calcu- lated from the graph, by the Exponent Software (Stable Micro System,

Surrey, UK). Four parameters were measured: (a) firmness (N) was defined as the peak of the maximum force; (b) consistency (Ns) was taken as the area of the curve up to the point of firmness: (c) cohesiveness (N) was defined as the maximum negative force dur- ing the returning of the probe; (d) index of viscosity (Ns) was defined as the total negative area obtained when the probe returns. Six mea- surements were carried out for each sample. Experiment was per- formed in triplicate.

2.7 | Statistical analysis A one-way analysis of variance (ANOVA) was done using Statistica

10.0 software (Stat Sof. Inc., Tulsa) in order to evaluate the effects of milk heat treatment on the rheological and textural properties of goat's acid milk and yoghurts as well as casein micelle size. Mean comparisons of the parameters were performed by Fisher LSD-test, with the level of significance of .05.

3 | RESULTS AND DISCUSSION 3.1 | Mean casein micelle diameter

Results of DLS measurements showed that there were no modifi- cation of micelles size when milk was treated at 72C/30 com- pared with raw samples (~253 nm). At higher temperatures, the size of micelles increased significantly to ~360 nm and ~321 nm after 85C/5 min and 95C/5 min treatments, respectively (Table 1.).

Micelles diameter increase due to heat treatment are the result of several factors, primarily intensive formation of micelle/whey protein aggregates, and increase of micelle voluminosity caused by heat induced phosphate precipitation (Jeurnink & De Kruif, 1993;

Raynal & Remeuf, 1998). As Anema and Li (2003) reported, the majority of the changes in casein micelle size are due to the associ- ation of the denatured whey proteins with the casein micelles.

However, it is still not possible to determine whether the size changes observed are due exclusively to the association of dena- tured whey proteins with the casein micelle surface or due to the partial aggregation of casein micelles that occurs at the same time and is proportional to the levels of whey proteins that have associ- ated with the casein micelles.

Raynal and Remeuf (1998) reported that micelle size in goat milk remained unchanged after heating at 75C and increased at 85C remaining the same at 90C. Our results showed that heating at

95C/5 min led to a decrease in the micelle diameter, as compared to

85C/5 min treatment.

We assume that this phenomena probably occur because of casein dissociation after severe heating, especially of κ-casein (Singh & Creamer, 1991) which interacts with denatured whey pro- teins in the serum, or another explanation would be that κ-casein in the form of complexes with whey proteins is released from the micelle in the serum phase. Also, other studies suggested that κ-casein disso- ciated at temperatures below that of denaturation of the whey pro- teins and reached its maximum at an earlier stage than denaturation of the whey proteins (Anema,

2008b; Anema, Kim Lee, & Klostermeyer, 2007). Moreover, heat precipitated calcium phosphate

TABLE 1 Casein micelle size as affected by different heat treatments of goat milk

Heat treatment Casein micelle size (nm) Raw milk 253.2 ± 14.78a

72C/30 s 253 ± 11.34a 85C/5 min 360 ± 14.46b 95C/5 min

321 ± 3.09c Note: Values in the table represent means of three replicated trials ± SD;

Values with different letter are significantly different (p < .05).

HOVJECKI ET AL.

3 is not able to keep integrity of the native micelle, thus favoring casein dissociation (Anema & Klostermeyer, 1997), or cause the micelle to shrink (Jeurnink & De Kruif, 1993).

3.2 | SDS-PAGE analysis Observing the electrophoretogram of raw and heat-treated goat milks, we noted existence of high molecular weight disulfide-linked protein complexes in the samples treated at 85C and 95C/5 min, that could not diffuse into the gel. Significant irreversible covalent aggregation of whey proteins could be observed in samples obtained after treatments above 72C/30 s. From the Figure 1 it is evident greater degree of denaturation of β-lactoglobulin after

95C/5 min treatment.

In non-reducing conditions, significant reduction of the band intensity of major whey proteins and polymers of κ-CN were observed for samples treated above 72C/30 s treatments. Also by analysis in non-reducing conditions, it could be noted that α-lactalbumin was more heat stable than β-lactoglobulin that is in agreement with Pesic et al. (2012).

3.3 | Rheological properties Significant differences were observed among the acid gels made from goat milk treated on different heat regime considering the gelation time and the time to reach pH 4.6 (Table 2). The shortest time was recorded for the B (85C/5 min) and the longest one for the A sample (72C/30 s). The pH at gelation point for the A sample (4.67) was sig- nificant lower (p < .05) from the pH of B and C gels (4.91 ± 0.10 and

4.88 ± 0.10, respectively). Reducing the gelation time and increasing pH of gelation due to heat treatment was also found for cow milk (Lucey et al., 1998; Lucey, van Vliet, et al., 1997). In accordance with our results, Lucey, van Vliet, et al. (1997) observed an increase in pH at gelation point with increasing heat temperature up to 85C after which there was little further change. This heat induced change is consequence of the higher isoelectric point of whey proteins (5.2–5.3) that denature and form complexes with κ-casein contributing that aggregation starts earlier (Lucey, van Vliet, et al., 1997).

The significant variations (p < .05) in G0 values at the end of fer- mentation (pH 4.6) among the yoghurts were found. The highest G0 was recorded for B yoghurt (85C/5 min) while the lowest one for A sample (72/30 s). This indicates that the strength and number of

FIGURE 1 SDS PAGE patterns of raw (S) and heat treated (72, 85 and

95 corresponding to 72C/30 s, 85C/5 min and 95C/5 min heat treatments) goat milk samples prepared in reducing (R) and non- reducing (N) conditions

4 HOVJECKI ET AL. bonds in the network obtained from milk heated at 85C/5 min is much higher than in the other gels (Roefs, De Groot-Mostert, & Van

Vliet, 1990; van Vliet, van Dijk, Zoon, & Walstra, 1991).

All examined acid gels showed a significant increase in G0 after cooling probably due to swelling of casein particles and an increase in the contact area between particles (Lucey, van Vliet, et al., 1997) as well as nature of protein network. However, acid gels made from severely heated goat milk (85C/5 min and 95C/5 min) had signifi- cantly higher G0, G00, and the phase angle (tan δ) values than samples treated at lower temperature (72C/30 s).

The yield stress values were significant various (p < .05) between acid gels obtained from milks heated on different regime. The highest yield stress value for gel made from milk treated at 85C/5 min was found, indicated that the structure is less susceptible to rearrangements and fracture, compared with other two gels. For com- parison, Lucey, van Vliet, et al. (1997) found that heating of cow milk at temperatures higher than 75C resulted in an increase of the shear stress at fracture of acid gels produced, and maximum was recorded in samples obtained from milk that was heated at 85C for 15 min, after which shear stress decreased. Generally, fracture properties of gels depend on the number of bonds per cross section of the strand as well as the strength of each bond (van Vliet et al., 1991), therefore lower yield stress value recorded for acid gels obtained from

95C/5 min heated milk, indicate that this treatment could led to weakening of bonds.

Differences in the rheological properties of acid gels analyzed in this study are a consequence of different heat treatment of goat milk used.

It is known that milk heat treatment causes denaturation of whey proteins, some of which associate with casein micelles and during acidification these aggregates act as bridges between casein micelles and make strength of bonds within a protein network more stronger resulted in higher G0 (Lucey, van Vliet, et al., 1997). Moreover, the concentration of protein would be increased because of active partici- pation of denatured whey proteins in the gel structure. Both these factors are responsible for the increased G0 of acid gels made from heated milks compared to raw milk.

The most studies done for cow milk acid coagulation also show positive influence of heat treatment on the rheological properties of acid gels (Dannenberg & Kessler, 1988a, 1988b; Lee & Lucey, 2003;

Lucey, van Vliet, et al., 1997). However, rheological properties of acid gels obtained from cow milk such as G0 is much higher compared to goat milk gels because of difference between properties of compo- nents, especially proteins, as well as micelle composition, size, mineral- ization and hydration (Park, Juárez, Ramos, & Haenlein, 2007).

Additionally, as reported by Martín-Diana, Fraga, and Fontecha (2002), κ- casein in goat milk is far less glycosilated than in bovine milk. This glycosylation degree negatively correlates with the casein micelle size, which corresponds to our results, as we recorded significantly larger micelles in caprine milk, as compared to the literature data for cow milk (Day et al., 2015).

Our results showed that better rheological properties were found for acid gel obtained from goat milk heated at 85C/5 min than at

95C/5 min. Lucey, van Vliet, et al. (1997) observed a similar trend in regard to very severe heat treatments (90C/30 min) on cow milk, that resulted in reduction in the G0 of acid gels, compared with milks that were subjected to milder heat treatments. Authors consider that reason for this behavior could be very high level of whey protein denaturation and formation of large aggregates that contribute to decrease of G0 (Lucey, van Vliet, et al., 1997). However, smaller casein micelle size found in our study did not support this opinion indicating that it should be look for some other explanation.

In many studies, the higher level of whey proteins denaturation contributes to better rheological properties of acid gels obtained from cow milk (Dannenberg & Kessler, 1988a, 1988b; Lucey, van Vliet, et al., 1997; Vasbinder et al., 2003). However, in our study, as can be seen at electrophoretogram (Figure 1), the level of whey protein dena- turation after 95C/5 min treatment is higher than after 85C/5 min that also could not give explanation for lower G0.

Anema (2008a) reported that changes in acid gel properties were not dependent only to whey protein denaturation level in the milk.

Mentioned research showed that treatment temperatures higher than

70C produced acid gels with markedly higher final G0, with the final G0 increasing with treatment temperature to a maximum at about 85C, and then decreasing at more severe heat regimes. Denaturation of the whey proteins is insufficient to predict the final properties of acid gels, and the interactions of the denatured whey proteins with other pro- teins in the milk as well as the changes in the casein micelle structure are more significant for the acid gel properties than the level of whey protein denaturation (Anema, 2008a), which in the light of our results obtained for the casein micelle size better describes this phenomenon.

Moreover, internal micellar integrity and the rates of change of structure and composition with pH play a role in defining the visco- elastic properties of the resulting gels (Horne, 2003).

TABLE 2 Rheological properties of goat milk acid gels affected by different heat treatment

Parameter Yoghurt 72C/30 s 85C/5 min 95C/5 min Gelation time (min)

247 ± 13a 118 ± 6b 168 ± 22c Gelation pH 4.67 ± 0.04a

4.91 ± 0.10b 4.88 ± 0.10b Time to pH 4.6 (min) 310 ± 36a

241 ± 21b 277 ± 20c G0 at pH 4.6 (Pa) 1.12 ± 0.11a

3.7 ± 0.5b 2.0 ± 0.15c Elastic modulus, G0 at 1 Hz (Pa)

9.51 ± 1.90a 27.47 ± 9.30b 25.5 ± 1.73b Viscous modulus,

G00 at 1 Hz (Pa) 2.23 ± 0.38a 6.65 ± 2.34b 6.52 ± 0.4b

Tan delta (loss tangent) 0.235 ± 0.006a 0.241 ± 0.005b 0.256 ± 0.003b

Yield stress (Pa) 12.31 ± 2.14a 19.54 ± 1.67b 17.06 ± 1.52c

Note: Values in the table represent means of three replicated trials ± SD;

Values with different letter within the same row are significantly differ- ent (p < .05).

HOVJECKI ET AL.

5 Additionally, Raynal and Remeuf (1998) concluded that heat treatments above 90C cause rearrangement of casein components in the micellar structure through a series of aggregation and dissociation reactions which also impairs the micelles ability to form strong pro- tein/protein bonds through gelation process. Van Hooydonk, De

Koster, and Boerrigter (1987) pointed out that many physico-chemical modifications are induced by heating (changes in milk salt equilibria, micelle size and hydration), that might also interfere with processes during aggregation and gelation.

Although we recorded smaller mean micelles diameter in milks treated at 95C/5 min compared to 85C/5 min, we suggest that such high heat treatment induced changes in the casein micelle structure, so that the capacity to form strong protein chains was reduced and that led to weaker gel structure, compared to B yoghurt.

3.4 | Textural properties Yoghurt textural characteristics are an important criterion for quality assessment.

Generally, firmness describes moderate resistance of product to deformation. Consistency relates to the “firmness,” “thickness,” or

“viscosity” of a liquid or fluid semi-solid. Stirring a fluid or semi fluid food with a spoon or a finger is frequently used by consumers to give an indication of the viscosity or consistency. Cohesiveness is the ten- dency of a product to cohere or stick together. The intermolecular attractions by which the elements of a body or mass of material are held together determine its cohesiveness. It is related to the internal stickiness of a product and is usually determined by measurement of the amount of force to remove an item from the product mass (Gunasekaran

& Mehmet Ak, 2003).

However, some authors (Nishinari, Fang, & Rosenthal, 2019; Peleg, 2019) discussed the limita- tions of the instrumental texture profile analysis (TPA) and they highlighted an importance of consistency in test conditions (tempera- ture, humidity), size and shape of specimen, probe's geometries and the set deformation level that all significantly affect the TPA parame- ters' magnitudes.

In this research, firmness and consistency of yoghurts were strongly affected by goat milk heat treatment applied, while statistical difference for cohesiveness and an index of viscosity among samples were not found. Regarding firmness and consistency, yoghurt pro- duced by preheating milk at 85C/5 min had the highest values (Table 3).

Heat treatment of milk has an important impact on milk proteins, and enhances the texture of yoghurt. Presence of denatured whey proteins associated with casein micelles causes an increase in gel firm- ness, which has been well documented (Dannenberg

& Kessler, 1988a, 1988b; Lucey, Munro, & Singh, 1999; Lucey, van Vliet, et al., 1997). A relation between firmness and viscosity of yoghurt and the extent of denaturation of β-lactoglobulin during heat treatment has been reported (Dannenberg & Kessler, 1988a; Dannenberg &

Kessler, 1988b). However, our research suggests that acid gel firm- ness depends, beside the level of protein denaturation, on the micelle structure changes as well, that has been indicated by the mean micelle size measured.

Oliveira, Sodini, Remeuf, and Corrieu (2001) reported that increase of acid gel firmness depends on the total solids as well as on protein content and type. However, firmness of goat milk coagulum was about half that of cow's milk even with similar total solids con- tent, indicating that texture depends not only on the total solids con- tent, but also on the casein content as well as micelle structure between these two milk types (Vegarud et al., 1999).

In yoghurt manufacture cooling the gel after fermentation is com- plete, is considered to be an important factor in improving the texture of the final product (Robinson & Tamime, 1993), which is also indi- cated by the increased G0 values for all of our acid milk gels measured after cooling the samples.

Guggisberg et al. (2009) showed a good correlation between the sensory evaluated firmness and the yield stress values determined by vane method. Our study showed that there was a significant differ- ence between yield stress values as well as instrumentally measured firmness between samples. Also, it has been observed that in case of yoghurt prepared from milk treated at 85C for 5 min, the yield stress value correlates with the firmness results.

Textural properties of examined yoghurts were significantly lower compared to literature data obtained for cow milk yoghurts. Low casein content and other characteristics such as αs- casein proportions and micellular size are believed to be responsible for the weak texture of goat milk yoghurt (Park et al., 2007).

Choosing the right process parameters and the addition of various fortifying agents can improve textural quality of yoghurt, which has been thoroughly investigated on cow's milk. The addition of milk pro- tein isolates can significantly improve textural properties of goat's yoghurt, but obtained gel would still be less firm compared to cow milk yoghurt (Miocinovic et al., 2016). Herrero and Requena (2006) found that supplementation of goat's milk with whey protein concen- trate, followed by heat treatment, increased yoghurt firmness, adhe- siveness, fracturability and provided the product with similar values to that of yoghurt made from cow's milk. Firmness of acid cow milk gels was impacted by the pasteurization scale of milk, but the composition of milk proteins (casein/ whey protein ratio, heat-induced whey pro- tein aggregates) were highly significant as well (Nguyen et al., 2018).

TABLE 3 Textural properties of goat milk yoghurts affected by different heat treatments

Parameter Yoghurt 72C/30 s 85C/5 min 95C/5 min Firmness (N)

0.30 ± 0.04a 0.39 ± 0.01b 0.25 ± 0.06c Consistency (N s)

7.35 ± 0.89a 10.14 ± 0.29b 6.46 ± 1.32c Cohesiveness (N)

−0.13 ± 0.00a −0.20 ± 0.00b −0.13 ± 0.01a Index of viscosity (N s)

−0.18 ± 0.01a −0.24 ± 0.03b −0.21 ± 0.01a Note: Values in the table represent means of three replicated trials ± SD;

Values with different letter within the same row are significantly differ- ent (p < .05).

6 HOVJECKI ET AL.

4 | CONCLUSION The results showed that different heat treatments of goat milk prior acidification produce gels with significantly different rheological and textural properties of yoghurt. As unexpected, acid milk gels and yoghurts obtained from milk treated at 85C/5 min were character- ized by the best properties regarding rheological and textural attri- butes, compared with milder and more severe heat regime.

Also, casein micelle size of goat milk after this treatment was the largest compared to other two regimes, despite higher level of whey protein denaturation after 95C/5 min.

Poorer rheological and texture properties of gels obtained from highly heated goat milk (95C/5 min) may have been due to changes in the casein micelle structure and the release of the aggregates into the serum phase that alter the process of gel formation during acidifi- cation of heated milk, but to confirm this assumptions, further investi- gation is needed.

Our DLS measurements led to the conclusion that the micelles experience structure changes in the 85–95C interval, that cause worsening in the rheological and textural properties of acid gel, and that 85C/5 min treatment of goat milk would be the most appropri- ate in the yoghurt manufacture.

These findings would improve technological processes in the manufacturing of goat milk yoghurts as well as yield more energeti- cally efficient production procedures.

ACKNOWLEDGMENTS This study was supported with project No. 46009 financed by the

Ministry of Education, Science and Technological development of

Republic of Serbia.

AUTHOR CONTRIBUTIONS M.H. designed and performed experiment. M.H. wrote the manuscript and analyzed the data with support from Z.M. and J.M. V.R. and

M.H. conducted measurements and analyzed data about casein micelle size P.P. supervised the research. J.M. co-wrote the manu- script and conceived the original idea.

ETHICAL STATEMENTS Conflict of Interest: The authors declare that they do not have any conflict of interest.

Ethical Review: This study does not involve any human or animal testing.

ORCID Marina Hovjecki https://orcid.org/0000-0002-1594-7112

Zorana Miloradovic https://orcid.org/0000-0003-1703-4656

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📖 中文全文 Chinese Full Text

中文

山羊奶热处理对酪蛋白胶束粒径、酸凝胶及凝固型酸奶流变学与质构特性的影响

**摘要** 本研究以经72°C/30秒、85°C/5分钟和95°C/5分钟热处理的山羊奶为原料,在43°C下接种发酵剂进行酸化至pH 4.6,制备酸凝胶和酸奶。分别采用动态小振幅振荡流变仪和背压式质构分析仪测定酸凝胶和酸奶的流变学与质构特性;同时利用动态光散射法(DLS)和SDS-PAGE电泳分析热处理对山羊奶中酪蛋白胶束平均粒径及蛋白质谱的影响。结果表明:经85°C/5分钟处理的牛奶所制备的酸奶具有最短的凝乳与发酵时间,且其凝乳pH、储能模量(G0)和屈服应力均高于其他两组。山羊奶酸奶的质构特性(如硬度和稠度)显著受热处理影响,其中85°C/5分钟预处理牛奶所得酸奶的硬度和稠度值最高。经85°C/5分钟处理后,酪蛋白胶束粒径最大,而在更高温度(95°C)下尽管乳清蛋白变性程度更高,胶束尺寸反而减小,表明热处理引起的结构变化影响了酸凝胶形成过程。

**关键词**:山羊奶;热处理;胶束粒径;流变学;质构;酸奶

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### 1 引言

发酵乳制品(如酸奶)通常以牛奶为原料,但近十年来,山羊奶制品日益受到消费者欢迎(Tamime, Wszolek, Božanić, & Özer, 2011)。然而,由于技术认知不足,山羊奶制品的生产常沿用牛奶的工艺参数,尽管两者在宏观组成上相似,但在加工特性方面存在显著差异(Miloradovic, Kljajevic, Jovanovic, Vucic, & Macej, 2015)。

热处理是发酵乳制品(如酸奶)生产中的关键加工变量。通常采用高强度热处理以改善产品质构(Robinson & Tamime, 1993)。研究表明,在固定加热时间(10、15或30分钟)条件下,提高脱脂奶热处理温度(70–95°C范围)可促进乳清蛋白变性(Dannenberg & Kessler, 1988a, 1988b),形成热诱导的乳清-胶束复合物,并提升酸凝胶的凝乳pH及弹性(Lucey, van Vliet, Grolle, Geurts, & Walstra, 1997; Vasbinder, Alting, & de Kruif, 2003)。另一方面,Raynal与Remeuf(1998)指出,超过90°C的剧烈热处理会通过聚集与解离反应导致酪蛋白组分在胶束结构内重排,从而改变酸凝胶过程并影响最终凝胶的质构特性。

关于牛奶酸凝胶及发酵乳制品的流变学已有大量研究(Guggisberg et al., 2009; Lee & Lucey, 2003; Lucey et al., 1998, 1997a, 1997b; Peng et al., 2009)。然而,据我们所知,针对山羊奶及其产品流变学特性的研究报道较少(Domagała et al., 2007; Jumah, Shaker, & Abu-Jdayil, 2001; Vargas et al., 2008)。

山羊奶与牛奶在热处理对其组分(尤其是蛋白质)的影响方面存在明显差异。已有研究发现,在相同热处理条件下,山羊奶中蛋白质沉淀程度远高于牛奶,表明其胶体稳定性较低;此外,两种奶中热诱导形成的蛋白质复合物性质亦不相同(Miloradovic et al., 2015; Pesic et al., 2012)。因此,本研究旨在探究不同热处理条件对山羊奶酸凝胶流变学特性及凝固型酸奶质构特性的影响。为深入理解不同热处理山羊奶在酸化过程中的行为,还测定了酪蛋白胶束粒径并进行SDS-PAGE电泳分析。目前文献中关于热处理对山羊蛋白胶束粒径影响的数据较为匮乏,这为本研究增添了额外价值。

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### 2 材料与方法

#### 2.1 山羊奶样品 采集自本地萨能奶山羊场(约250只)的生鲜奶。每周采集约3升混合生鲜奶,共持续3周。采集后立即倒入不锈钢锅中,边搅拌边加热至目标温度完成相应热处理。所有热处理及后续实验均每周重复一次。样品采集后立即进行成分分析。

萨能山羊奶基础成分为:脂肪(3.1 ± 0.2%)、蛋白质(2.64 ± 0.04%)、非脂乳固体(7.22 ± 0.11%)、pH(6.72 ± 0.06)。分别采用三种热处理制度(72°C/30秒、85°C/5分钟、95°C/5分钟)处理,用于后续酪蛋白胶束粒径测定、电泳分析、酸凝胶制备及凝固型酸奶特性评估。所有实验设三次重复,各项测定至少双平行。

#### 2.2 DLS粒径测定 采用Horiba NanoPartica SZ-100(日本Horiba公司)动态光散射仪(DLS)测定酪蛋白胶束粒径。热处理后的山羊奶样品迅速浸入冷水冷却,并于冰箱中过夜。测试前将样品加热至40°C再降温至20°C以达到平衡。将原始及热处理后的山羊奶在20°C、600g离心15分钟脱脂(该条件可最大限度避免蛋白质损失,参见Miloradovic et al., 2015)。样品用蒸馏水稀释100倍(Day et al., 2015),在20°C下以90°散射角、光子相关模式进行测量,通过分析相关函数计算平均水动力直径。每个样品至少测定三次。

#### 2.3 SDS-PAGE电泳 参照Miloradovic等(2015)方法制备原始及热处理山羊奶样品(同DLS前处理)。离心后取脱脂奶,分别与还原型(SDS-R-PAGE)和非还原型(SDS-NR-PAGE)上样缓冲液按Anema与Stanley(1998)方法混合稀释10倍。还原型缓冲液(pH 6.8)含0.055 M Tris-HCl、2% (w/v) SDS、7% (v/v) 甘油、5% (v/v) β-巯基乙醇及0.0025% (w/v) 溴酚蓝;非还原型缓冲液仅不含β-巯基乙醇。

SDS-PAGE依据Laemmli(1970)法进行:4%浓缩胶(pH 6.80),15%分离胶(pH 8.85)。每孔上样5 μL。使用TV200YK双板电泳槽(比利时Consort公司),恒流80 mA,最大电压300 V,电泳1.5小时。凝胶于45°C下用考马斯亮蓝染液(含0.23%考马斯亮蓝R250、3.9%三氯乙酸、6%乙酸、17%甲醇)固定染色1小时;脱色液为8%乙酸与18%甲醇混合液,脱色后扫描成像。

#### 2.4 凝胶形成与酸奶制备 将经不同热处理(72°C/30秒[A]、85°C/5分钟[B]、95°C/5分钟[C])的萨能山羊奶冷却至43°C,接种0.2% (w/w) “Yoflex 812”发酵剂(荷兰Chr Hansen公司)。取少量用于流变学监测,其余在43°C下发酵至pH 4.6。发酵完成后将酸奶于4–7°C冷藏24小时,随后进行分析。所有实验设三次重复。

#### 2.5 流变学测定 使用Kinexus Pro+流变仪(英国Malvern公司)配合四叶片桨式探头,通过动态振荡剪切测量酸凝胶及酸奶的粘弹性。接种发酵剂后的牛奶搅拌2分钟,转移至流变仪中,在0.1 Hz频率、0.1%应变下振荡直至pH达4.6。凝乳时间及pH定义为储能模量G0 ≥1 Pa时的对应值(Lucey et al., 1997b),同时记录pH 4.6时的G0作为发酵终点凝胶强度的指标。

发酵结束后,将凝胶以1°C/min冷却至5°C并保温30分钟,随后进行频率扫描(0.01–10 Hz,0.1%应变)。取1 Hz下的储能模量(G0)和损耗模量(G00)作为冷却后凝胶特性的评价指标。

在1 Hz恒定频率下进行应变扫描(0.001–500%),确定线性粘弹区(LVE)。屈服应力及复数粘度(η*)由LVE外G0与G00交点计算得出(Guggisberg et al., 2009)。所有测定均设三次重复。

#### 2.6 质构特性分析 质构分析在发酵及凝胶形成的塑料容器中进行。为保证重复性,预先称取100 g接种奶于容器中完成发酵与冷却。采用TA.XT Plus质构分析仪(英国Stable Micro Systems公司),配备背压式测试单元(A/BE,直径35 mm,测试距离30 mm,速度0.001 m/s)及5 kg载荷传感器,在5°C下单次压缩测试。质构参数由Exponent软件自动从力-位移曲线计算得出,包括:(a) 硬度(N)——最大力峰值;(b) 稠度(N·s)——达硬度点前曲线下面积;(c) 内聚性(N)——探头回程过程中的最大负力;(d) 粘度指数(N·s)——探头回程总负面积。每个样品测定六次,实验设三次重复。

#### 2.7 统计分析 采用Statistica 10.0软件(美国StatSoft公司)进行单因素方差分析(ANOVA),评估热处理对山羊奶酸凝胶及酸奶流变学、质构特性及酪蛋白胶束粒径的影响。均值比较采用Fisher LSD检验,显著性水平设为p < 0.05。

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### 3 结果与讨论

#### 3.1 酪蛋白胶束平均粒径 DLS结果显示,72°C/30秒处理未引起胶束粒径变化(约253 nm),与生鲜奶无显著差异。随温度升高,胶束粒径显著增大:85°C/5分钟处理后为约360 nm,95°C/5分钟处理后为约321 nm(见表1)。

热处理导致胶束粒径增大的原因主要包括:胶束/乳清蛋白聚集体的大量形成,以及热诱导磷酸盐沉淀引起的胶束体积膨胀(Jeurnink & De Kruif, 1993; Raynal & Remeuf, 1998)。Anema与Li(2003)报道,酪蛋白胶束尺寸变化主要源于变性乳清蛋白与胶束的结合。然而,目前尚无法确定观察到的尺寸变化是否完全归因于变性乳清蛋白在胶束表面的结合,还是同时发生的胶束部分聚集所致——而后者又与结合乳清蛋白的量成正比。

Raynal与Remeuf(1998)发现,山羊奶在75°C加热后胶束粒径不变,85°C时增大,90°C时保持稳定。本研究中95°C/5分钟处理导致胶束粒径较85°C组减小。

我们认为此现象可能源于剧烈加热引发的酪蛋白解离,尤其是κ-酪蛋白(Singh & Creamer, 1991),其可与血清中变性乳清蛋白相互作用;另一种解释是κ-酪蛋白以与乳清蛋白复合物的形式从胶束释放至血清相。此外,其他研究表明,κ-酪蛋白的解离发生在乳清蛋白变性温度之前,并在乳清蛋白变性达到最大前即达峰值(Anema, 2008b; Anema, Kim Lee, & Klostermeyer, 2007)。同时,热沉淀的磷酸钙无法维持天然胶束完整性,从而促进酪蛋白解离(Anema & Klostermeyer, 1997),或导致胶束收缩(Jeurnink & De Kruif, 1993)。

**表1 不同热处理对山羊奶酪蛋白胶束粒径的影响**

| 热处理条件 | 酪蛋白胶束粒径 (nm) | |----------------|----------------------| | 生鲜奶 | 253.2 ± 14.78ᵃ | | 72°C/30秒 | 253 ± 11.34ᵃ | | 85°C/5分钟 | 360 ± 14.46ᵇ | | 95°C/5分钟 | 321 ± 3.09ᶜ |

*注:数值为三次重复试验均值±标准差;不同字母表示差异显著(p < 0.05)。*

#### 3.2 SDS-PAGE分析 观察生鲜及热处理山羊奶的电泳图谱可见,85°C和95°C/5分钟处理的样品中存在无法向凝胶内扩散的高分子量二硫键连接蛋白复合物。在72°C/30秒以上处理的样品中,可观察到显著的乳清蛋白不可逆共价聚集。图1显示,95°C/5分钟后β-乳球蛋白变性程度更高。

在非还原条件下,72°C/30秒以上处理的样品中主要乳清蛋白及κ-CN聚合物条带强度显著降低。此外,非还原电泳结果显示α-乳白蛋白的热稳定性高于β-乳球蛋白,与Pesic等(2012)结果一致。

#### 3.3 流变学特性 不同热处理山羊奶制备的酸凝胶在凝乳时间及达pH 4.6所需时间上存在显著差异(表2)。B组(85°C/5分钟)时间最短,A组(72°C/30秒)最长。A组凝乳点pH(4.67)显著低于B、C组(分别为4.91 ± 0.10和4.88 ± 0.10)。热处理缩短凝乳时间并提高凝乳pH的现象在牛奶中亦有报道(Lucey et al., 1998, 1997b)。与本研究结果一致,Lucey等(1997b)发现随热处理温度升高至85°C,凝乳点pH上升,之后变化趋缓。此变化源于乳清蛋白等电点较高(5.2–5.3),其变性后与κ-酪蛋白形成复合物,促使聚集提前发生(Lucey et al., 1997b)。

发酵终点(pH 4.6)时各酸奶G0值差异显著(p < 0.05)。B组(85°C/5分钟)G0最高,A组(72°C/30秒)最低。这表明85°C/5分钟热处理牛奶形成的凝胶网络中共价键强度与数量远高于其他凝胶(Roefs, De Groot-Mostert, & Van Vliet, 1990; van Vliet et al., 1991)。

所有酸凝胶冷却后G0均显著升高,可能源于酪蛋白颗粒膨胀及颗粒间接触面积增加(Lucey et al., 1997b),以及蛋白质网络结构的变化。然而,经剧烈热处理(85°C/5分钟和95°C/5分钟)的山羊奶制备的酸凝胶,其G0、G00及相位角(tan δ)值均显著高于低温处理组(72°C/30秒)。

不同热处理制度所得酸凝胶的屈服应力值差异显著(p < 0.05)。85°C/5分钟处理牛奶制备的凝胶屈服应力最高,表明其结构更不易发生重排与断裂,优于其他两组。作为对比,Lucey等(1997b)发现牛奶在高于75°C处理后,酸凝胶的剪切断裂应力随之增加,在85°C处理15分钟时达最大值,之后下降。一般而言,凝胶的断裂特性取决于单位横截面积内的键数量及各键强度(van Vliet et al., 1991),因此95°C/5分钟处理牛奶所得酸凝胶的屈服应力较低,说明该处理可能导致键合弱化。

本研究中酸凝胶流变学特性的差异源于山羊奶所经受的不同热处理条件。

已知热处理引起乳清蛋白变性,其中部分与酪蛋白胶束结合;在酸化过程中,这些聚集体充当胶束间的桥梁,增强蛋白质网络内键合强度,从而提高G0(Lucey et al., 1997b)。此外,变性乳清蛋白参与凝胶结构使蛋白质浓度相对增加。这两个因素共同导致热处理牛奶制备的酸凝胶G0高于生鲜奶。

多数关于牛奶酸凝固的研究也表明热处理对酸凝胶流变学具有积极影响(Dannenberg & Kessler, 1988a,b; Lee & Lucey, 2003; Lucey et al., 1997b)。然而,牛奶酸凝胶的G0远高于山羊奶凝胶,原因在于两者组分特性(尤其是蛋白质)、胶束组成、粒径、矿化程度及水合状态存在差异(Park et al., 2007)。

此外,Martín-Diana等(2002)报道,山羊奶中κ-酪蛋白的糖基化程度远低于牛奶。糖基化程度与酪蛋白胶束粒径呈负相关,这与本研究结果一致——我们测得的山羊奶胶束显著大于文献报道的牛奶胶束数据(Day et al., 2015)。

本研究发现,85°C/5分钟热处理山羊奶制备的酸凝胶流变学特性优于95°C/5分钟组。Lucey等(1997b)在牛奶中也观察到类似趋势:极剧烈热处理(90°C/30分钟)导致酸凝胶G0较温和热处理下降。作者认为此现象可能源于乳清蛋白高度变性并形成大聚集体,反而降低G0(Lucey et al., 1997b)。但本研究中测得的较小胶束粒径并不支持该观点,提示需寻找其他解释。

多项研究表明,乳清蛋白变性程度越高,牛奶酸凝胶的流变学特性越好(Dannenberg & Kessler, 1988a,b; Lucey et al., 1997b; Vasbinder et al., 2003)。然而,如图1电泳图谱所示,95°C/5分钟处理后乳清蛋白变性程度高于85°C/5分钟组,这仍无法解释G0较低的现象。

Anema(2008a)指出,酸凝胶特性的变化不仅取决于乳清蛋白变性水平。该研究表明,高于70°C的处理温度可使酸凝胶最终G0显著升高,且G0随处理温度升高至约85°C达峰值,之后在更剧烈热处理下下降。仅凭乳清蛋白变性程度不足以预测酸凝胶最终特性,变性乳清蛋白与奶中其他蛋白质的相互作用以及酪蛋白胶束结构的变化,对酸凝胶特性的影响比乳清蛋白变性程度更为关键(Anema, 2008a)。结合本研究中关于胶束粒径的结果,这一观点更能解释上述现象。

此外,胶束内部完整性及其随pH变化的结构与速率,也在决定最终凝胶粘弹性方面发挥重要作用(Horne, 2003)。

**表2 不同热处理对山羊奶酸凝胶流变学特性的影响**

| 参数 | 72°C/30秒 | 85°C/5分钟 | 95°C/5分钟 | |---------------------|-------------------|-------------------|-------------------| | 凝乳时间 (min) | 247 ± 13ᵃ | 118 ± 6ᵇ | 168 ± 22ᶜ | | 凝乳pH | 4.67 ± 0.04ᵃ | 4.91 ± 0.10ᵇ | 4.88 ± 0.10ᵇ | | 达pH 4.6时间 (min) | 310 ± 36ᵃ | 241 ± 21ᵇ | 277 ± 20ᶜ | | pH 4.6时G0 (Pa) | 1.12 ± 0.11ᵃ | 3.7 ± 0.5ᵇ | 2.0 ± 0.15ᶜ | | 弹性模量G0@1Hz (Pa) | 9.51 ± 1.90ᵃ | 27.47 ± 9.30ᵇ | 25.5 ± 1.73ᵇ | | 粘性模量G00@1Hz (Pa)| 2.23 ± 0.38ᵃ | 6.65 ± 2.34ᵇ | 6.52 ± 0.4ᵇ | | Tan δ (损耗因子) | 0.235 ± 0.006ᵃ | 0.241 ± 0.005ᵇ | 0.256 ± 0.003ᵇ | | 屈服应力 (Pa) | 12.31 ± 2.14ᵃ | 19.54 ± 1.67ᵇ | 17.06 ± 1.52ᶜ |

*注:数值为三次重复试验均值±标准差;同行不同字母表示差异显著(p < 0.05)。*

#### 3.4 质构特性 酸奶的质构特性是质量评价的重要指标。

通常,硬度描述产品对形变的适度抵抗;稠度反映液体或半固体食品的“硬度”、“厚度”或“粘度”,消费者常用勺子或手指搅拌来感知;内聚性是产品内部相互粘附的趋势,由分子间吸引力决定,通常通过测量从产品中移除探头所需的力来量化(Gunasekaran & Mehmet Ak, 2003)。然而,部分学者(Nishinari, Fang, & Rosenthal, 2019; Peleg, 2019)讨论了仪器化质构剖面分析(TPA)的局限性,并强调测试条件(温度、湿度)、样品尺寸与形状、探头几何参数及设定形变水平均显著影响TPA参数值。

本研究中,山羊奶酸奶的硬度和稠度显著受热处理影响,而内聚性与粘度指数在各组间无显著差异。就硬度和稠度而言,85°C/5分钟预处理牛奶所制酸奶数值最高(表3)。

热处理对奶蛋白有重要影响,可增强酸奶质构。变性乳清蛋白与酪蛋白胶束结合导致凝胶硬度提升,此现象已被广泛证实(Dannenberg & Kessler, 1988a,b; Lucey, Munro, & Singh, 1999; Lucey et al., 1997b)。有研究报道酸奶硬度与稠度同热处理过程中β-乳球蛋白变性程度相关(Dannenberg & Kessler, 1988a,b)。然而,本研究提示,除蛋白质变性程度外,胶束结构变化(通过平均胶束粒径反映)也影响酸凝胶硬度。

Oliveira等(2001)报道,酸凝胶硬度提升不仅取决于总固体含量,还与蛋白质含量及类型有关。然而,即使总固体含量相近,山羊奶凝乳硬度仍约为牛奶的一半,表明质构不仅依赖总固体,还与酪蛋白含量及两种奶的胶束结构差异有关(Vegarud et al., 1999)。

在酸奶生产中,发酵完成后冷却被视为改善最终产品质构的重要因素(Robinson & Tamime, 1993),这也体现为本研究中所有酸凝胶冷却后G0值的升高。

Guggisberg等(2009)发现感官评价的硬度与桨法测得的屈服应力值具有良好的相关性。本研究中,各样品间屈服应力与仪器测定的硬度均存在显著差异。值得注意的是,8°C/5分钟处理的酸奶其屈服应力值与硬度结果呈正相关。

与文献报道的牛奶酸奶相比,本研究所测山羊奶酸奶的质构特性显著较低。较低的酪蛋白含量及其他特性(如αs-酪蛋白比例和胶束尺寸)被认为是导致山羊奶酸奶质构较弱的原因(Park et al., 2007)。

选择合适的工艺参数或添加各类强化剂可改善酸奶质构,这在牛奶体系中已得到充分研究。添加乳蛋白分离物可显著提升山羊奶酸奶的质构特性,但其凝胶硬度仍低于牛奶酸奶(Miocinovic et al., 2016)。Herrero与Requena(2006)发现,向山羊奶中添加乳清蛋白浓缩物并进行热处理,可提高酸奶硬度、粘附性和破碎性,使其达到与牛奶酸奶相近的水平。牛奶酸凝胶的硬度受巴氏杀菌强度影响,但牛奶蛋白组成(酪蛋白/乳清蛋白比例、热诱导乳清蛋白聚集体)同样至关重要(Nguyen et al., 2018)。

**表3 不同热处理对山羊奶酸奶质构特性的影响**

| 参数 | 72°C/30秒 | 85°C/5分钟 | 95°C/5分钟 | |------------------|------------------|------------------|------------------| | 硬度 (N) | 0.30 ± 0.04ᵃ | 0.39 ± 0.01ᵇ | 0.25 ± 0.06ᶜ | | 稠度 (N·s) | 7.35 ± 0.89ᵃ | 10.14 ± 0.29ᵇ | 6.46 ± 1.32ᶜ | | 内聚性 (N) | −0.13 ± 0.00ᵃ | −0.20 ± 0.00ᵇ | −0.13 ± 0.01ᵃ | | 粘度指数 (N·s) | −0.18 ± 0.01ᵃ | −0.24 ± 0.03ᵇ | −0.21 ± 0.01ᵃ |

*注:数值为三次重复试验均值±标准差;同行不同字母表示差异显著(p < 0.05)。*

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### 4 结论

研究表明,酸化前对山羊奶进行不同热处理可显著改变酸奶的流变学与质构特性。出乎意料的是,经85°C/5分钟处理的牛奶所制备的酸凝胶与酸奶,在流变学与质构属性方面均优于温和或更剧烈的热处理组。

此外,尽管95°C/5分钟处理后乳清蛋白变性程度更高,但85°C/5分钟处理的山羊奶中酪蛋白胶束粒径最大。

高强度热处理(95°C/5分钟)山羊奶所制凝胶的流变学与质构性能较差,可能源于酪蛋白胶束结构改变及聚集体向血清相释放,从而干扰了酸化过程中的凝胶形成机制。但此假设仍需进一步验证。

DLS测定结果表明,在85–95°C区间内胶束发生结构变化,导致酸凝胶流变学与质构性能下降。因此,8°C/5分钟是山羊奶酸奶生产中最适宜的热处理条件。

上述发现有助于优化山羊奶酸奶的生产工艺,并推动更节能高效的生产流程发展。

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**致谢** 本研究由塞尔维亚共和国教育、科学与技术发展部资助(项目编号:46009)。

**作者贡献** M.H. 设计并执行实验,撰写论文并在Z.M.和J.M.支持下分析数据;V.R.与M.H.共同完成酪蛋白胶束粒径测定与数据分析;P.P.指导研究;J.M.参与论文撰写并提出原创构想。

**伦理声明** 利益冲突:作者声明无利益冲突。 伦理审查:本研究不涉及人体或动物实验。

**ORCID** Marina Hovjecki: https://orcid.org/0000-0002-1594-7112 Zorana Miloradovic: https://orcid.org/0000-0003-1703-4656

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**参考文献** (此处省略,保留原文引用格式)

**引用本文** Hovjecki M, Miloradovic Z, Rac V, Pudja P, Miocinovic J. Influence of heat treatment of goat milk on casein micelle size, rheological and textural properties of acid gels and set type yoghurts. J Texture Stud. 2020;1–8. https://doi.org/10.1111/jtxs.12524