A Survey of Temperature Effects on GAB Monolayer in Foods and Minimum Integral Entropies of Sorption: a Review

✅ 全文

食品中GAB单层温度效应及吸附最小积分熵综述

作者 H. Iglesias; R. Baeza; J. Chirife 期刊 Food and Bioprocess Technology 发表日期 2022 DOI 10.1007/s11947-021-02740-w 类型 原创研究 (Original Research)

📄 中文摘要 Chinese Abstract

中文
古根海姆-安德森-德博尔(GAB)等温方程被广泛用于描述食品的吸附行为,其提供的单层水分含量值通常被视为食品稳定性的最佳水分指标。该单层的物理意义与以下假设相关:生物聚合物中的每个极性基团最初吸附一个水分子。此外,水蒸气-食品平衡的热力学特性,特别是吸附的最小积分熵(MIE),已被建议作为预测脱水食品稳定性和储存寿命的标准,因为理论上它对应于吸附质与吸附剂之间形成强结合时的水分含量。

📋 英文结构化总结 English Structured Summary

全文整理

EN

Background:

The Guggenheim, Anderson, and de Boer (GAB) isotherm equation is widely used to describe the sorption behavior of foods, providing a monolayer moisture content value that is often considered an indicator of the optimum moisture for food stability. The physical meaning of this monolayer relates to the hypothesis that each polar group in a biopolymer initially adsorbs one water molecule. Additionally, the thermodynamics of water vapor-foodstuff equilibrium, specifically the minimum integral entropy (MIE) of sorption, has been suggested as a criterion to predict the stability and storage life of dehydrated foods, as it theoretically coincides with the moisture content where strong bonds between adsorbate and adsorbent occur.

Methods:

This review article surveyed literature data on GAB monolayer values and minimum integral entropies of sorption in foods. To evaluate the physical meaning of the GAB monolayer, literature data on the stoichiometry of water sorption by proteins and other biopolymers were re-analyzed to correlate the number of polar groups with the GAB monolayer. A survey of GAB monolayers at various temperatures was conducted for more than 70 different food products, selecting only articles that reported values at three or more temperatures. Finally, the relationship between the moisture content corresponding to the MIE and the GAB monolayer was studied using approximately fifty eligible articles that reported both parameters.

Results:

Re-analysis of stoichiometry data confirmed a good linear correlation between the number of polar groups and the GAB monolayer, corroborating the hypothesis that each polar group initially sorbs one molecule of water. The survey of temperature effects on GAB monolayers across 70+ food items indicated that while an increase in temperature generally produces a decrease in monolayer moisture content, an appreciable number of cases showed the monolayer remaining constant or increasing with temperature. Regarding the relationship between MIE and GAB monolayer, for 38 different food products, the regression curve was close to the 45° diagonal, suggesting GAB values matched the position of minimum integral entropy. However, for a wide variety of other products, the moisture of the MIE was located considerably above that of the GAB monolayer.

Data Summary:

A linear regression between the number of polar groups and the GAB monolayer yielded r² = 0.8431, indicating good agreement. For the 38 food products where MIE and GAB monolayer moisture contents were close, the regression was [ΔSint]min = 0.8935 × GAB value + 0.8523 with r² = 0.9089. For the 31 products where the moisture at MIE was considerably higher than the GAB monolayer, the regression was [ΔSint]min = 1.448 × GAB + 1.466 with a lower correlation coefficient of r² = 0.8024.

Conclusions:

The re-examination of data confirms Pauling’s hypothesis that each polar group initially sorbs one molecule of water. Although the decrease of GAB monolayer values with increasing temperature is the most commonly reported behavior, it cannot be taken for granted, as monolayers can also remain constant or increase with temperature due to physicochemical changes and structural modifications in the food. While the moisture at MIE coincides with the GAB monolayer in some foods, it is considerably higher in others, creating uncertainty regarding the validity of minimum entropy as a universal point of stability.

Practical Significance:

The GAB monolayer value holds high practical value for the food industry as it indicates the amount of water strongly adsorbed to specific sites, which is considered the optimum moisture content for maximizing the stability of low-moisture foods during storage. Understanding that GAB monolayers do not universally decrease with temperature, and recognizing the discrepancies between MIE and GAB values, allows for more accurate modeling of sorption isotherms and better-informed design of food dehydration operations and storage conditions.

📋 中文结构化总结 Chinese Structured Summary

中文

背景:

古根海姆-安德森-德博尔(GAB)等温方程被广泛用于描述食品的吸附行为,其提供的单层水分含量值通常被视为食品稳定性的最佳水分指标。该单层的物理意义与以下假设相关:生物聚合物中的每个极性基团最初吸附一个水分子。此外,水蒸气-食品平衡的热力学特性,特别是吸附的最小积分熵(MIE),已被建议作为预测脱水食品稳定性和储存寿命的标准,因为理论上它对应于吸附质与吸附剂之间形成强结合时的水分含量。

方法:

本综述文章调研了食品中GAB单层值和吸附最小积分熵的文献数据。为评估GAB单层的物理意义,对蛋白质及其他生物聚合物中水吸附化学计量的文献数据进行了重新分析,以将极性基团数量与GAB单层相关联。对70多种不同食品在不同温度下的GAB单层值进行了调研,仅选取报告了三个或更多温度下数值的文章。最后,利用约50篇同时报告了MIE和GAB单层两个参数的合格文献,研究了MIE对应的水分含量与GAB单层之间的关系。

结果:

对化学计量数据的重新分析证实了极性基团数量与GAB单层之间存在良好的线性相关性,支持了每个极性基团最初吸附一个水分子的假设。对70多种食品温度效应的调研表明,虽然温度升高通常会导致单层水分含量下降,但在相当数量的案例中,单层随温度保持不变或有所增加。关于MIE与GAB单层之间的关系,对于38种不同的食品,回归曲线接近45°对角线,表明GAB值与最小积分熵的位置吻合。然而,对于种类繁多的其他产品,MIE对应的水分含量明显高于GAB单层值。

数据总结:

极性基团数量与GAB单层之间的线性回归得出r² = 0.8431,表明良好的一致性。对于MIE与GAB单层水分含量接近的38种食品,回归方程为[ΔSint]min = 0.8935 × GAB值 + 0.8523,r² = 0.9089。对于MIE处水分含量显著高于GAB单层的31种产品,回归方程为[ΔSint]min = 1.448 × GAB + 1.466,相关系数较低,r² = 0.8024。

结论:

数据的重新验证证实了鲍林的假设,即每个极性基团最初吸附一个水分子。尽管GAB单层值随温度升高而下降是最常报道的行为,但这并非理所当然,因为由于食品中的物理化学变化和结构改变,单层也可能保持不变或随温度升高而增加。虽然某些食品中MIE处的水分与GAB单层吻合,但在其他食品中则明显更高,这给最小熵作为通用稳定性标准的有效性带来了不确定性。

实际意义:

GAB单层值对食品工业具有很高的实用价值,因为它指示了强吸附在特定位点的水分量,被认为是低水分食品在储存期间最大化稳定性的最佳水分含量。认识到GAB单层并非普遍随温度升高而降低,并了解MIE与GAB值之间的差异,有助于更准确地建立吸附等温线模型,并为食品脱水操作和储存条件的设计提供更充分的依据。

📖 英文全文 English Full Text

EN

Vol.:(0123456789) 1 3 https://doi.org/10.1007/s11947-021-02740-w

REVIEW ARTICLE A Survey of Temperature Effects on GAB Monolayer in Foods and Minimum Integral Entropies of Sorption: a Review

Héctor A. Iglesias1 · Rosa Baeza2   · Jorge Chirife2

Received: 12 July 2021 / Accepted: 19 November 2021

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2021

Abstract Some aspects of GAB monolayer values in foods were reviewed. Literature data on the stoichiometry of water sorption by proteins and other biopolymers were re-analyzed and a good linear correlation (r2 = 0.8431) between the number of polar groups and the GAB monolayer was obtained. This helps to corroborate the hypothesis that each polar group initially adsorbs a water molecule. A survey of GAB monolayers at various temperatures in more than 70 different food products indicated that for most of them – although not all – an increase in temperature produced a decrease in the value of moisture content (g water/100 g solids) corresponding to the monolayer. However, in an appreciable number of cases, it was observed that the monolayer remained constant or increased with temperature. The relationship between the minimum integral entropy (MIE) and the GAB monolayer was studied using literature data. For 38 different food products, the regression curve (r2 = 0.9038) between the moisture content corresponding to MIE and GAB monolayer was close to the 45° diagonal, suggesting that

GAB values matched the position of minimum integral entropy. However, for a wide variety of other products, the moisture of the MIE was located above that of the monolayer.

Keywords  GAB monolayer · Water sorption · Isotherms · Minimum integral entropies · Thermodynamic properties ·

Temperature effect Introduction A fundamental characteristic of food materials which influ- ences almost every aspect of the dehydration process and the storage stability of food products is its water sorption iso- therm. Measurement and modeling of sorption isotherms of food materials has attracted numerous researchers because of their application in relation to the stability and design of food dehydration operations. Comprehensive reviews on sorption behavior of foods have been published, and several empirical and semi-empirical equations have been proposed for the correlation of the equilibrium moisture content of food materials (Basu et al., 2006; Peleg, 2020).

Early in 1979, Boquet et al. studied the fitting abilities of various three-parameter literature isotherm equations to describe 39 food isotherms of meats, milk products, proteins, starchy foods, and vegetables. The best equation was that of Hailwood and Horrobin (1946), which was developed in attempt to interpret the water sorption isotherms of proteins.

The remarkably good ability of Hailwood-Horrobin’s equa- tion to fit experimental sorption data in foods led Boquet et al. (1979) to call it a “universal” equation to describe the sorption isotherms of water in food. Later, Boquet et al. (1980) were able to demonstrate that Hailwood-Horrobin’s equation was mathematically identical to GAB equation.

In the past, the well-known BET (Brunauer, Emmet and

Teller) sorption isotherm was the model that had the greatest application to water sorption by foods and foodstuffs (Basu et al., 2006; Iglesias & Chirife, 1976; Labuza, 1968; Timmermann et  al., 2001). One well-familiar constant obtained from BET equation was the monolayer moisture content which, as noted by Timmermann et al. (2001), was found to be a reasonable guide with respect to various aspects of

* Rosa Baeza

rosa_baeza@uca.edu.ar 1 Departamento de Industrias, Facultad de Ciencias Exactas y

Naturales, Universidad de Buenos Aires, Ciudad de Buenos

Aires, 1428 Buenos Aires, Argentina 2 Facultad de Ingeniería y Ciencias Agrarias, Pontificia

Universidad Católica Argentina (UCA), CABA, Av. Alicia

Moreau de Justo 1300 (C1107AAZ), Buenos Aires, Argentina

/ Published online: 13 January 2022 Food and Bioprocess Technology (2022) 15:717–733

1 3 interest in low-moisture foods (Iglesias & Chirife, 1982,

1984; Karel, 1973). In the past two decades, the Guggen- heim, Anderson, and de Boer (GAB) isotherm equation was widely used to describe the sorption behavior of many types of foods (Van den Berg, 1981; Basu et al., 2006; Quirijins et al., 2005; Lomauro et al., 1984). Having a reasonably small number of parameters (three), the GAB equation has been found to adequately represent the experimental data in the range of water activity of most practical interest in foods. The use of the GAB equation in foods is now almost universally used by laboratories around the world (Singh &

Singh, 1996; Quirijns et al., 2005; Peleg, 2020).

The thermodynamics of the water vapor-foodstuff equilib- rium also provides valuable information into structural mat- ters and energy requirements, but also tools to analyze the consistency of the experimental data (Iglesias et al., 1976;

Nunes & Rotstein, 1991). Rizvi and Benado (1983) have reviewed the applicability of thermodynamic properties to dehydrated foods and concluded that thermodynamic cal- culations yielded important insights regarding the structure of sorbed water.

Stability is greatly influenced by the moisture sorption characteristics of the product. The thermodynamics of water sorption in dried foodstuffs has also drawn interest because some authors suggested that it helps to understand better the stability of reduced moisture foods (Beristain et al., 2002;

Bonilla et al., 2010).

The present review is concerned with some aspects related to the GAB monolayer values and specifically the fol- lowing: its physical meaning, a survey of literature data on the effect of temperature on monolayers, and a comparison of literature data on location of minimum integral entropy (MIE) and GAB monolayer values in order to verify if both coincide at the same moisture content.

Results and Discussion The Meaning of GAB Monolayer Value

As mentioned before, the Guggenheim, Anderson and de

Boer (GAB) isotherm equation has been the most widely discussed moisture sorption model in the literature to describe the sorption behavior of foods (Basu et al., 2006;

Iglesias & Chirife, 1995; Peleg, 2020; Timmermann et al.,

2001). The GAB model’s most familiar presentation is in the form of (Eq. 1): where M is the equilibrium moisture content (g water/100 g dry solids); Mo is the monolayer water content (g (1)

퐌= 퐌퐨.퐂.퐊.퐚퐰 [(1 −퐊.퐚퐰)(1 −퐊.퐚퐰+ 퐂.퐊.퐚퐰)] water/100 g dry solids), aw is the water activity, and C and

K are constants.

Several authors reported that the monolayer value obtained from BET equation is always less than that obtained from the

GAB equation (Kaymak-Ertekin & Sultanoglu, 2001; McMinn and Magee (2003); Palou et al., 1997). Timmermann et al. (2001) analyzed the dilemma about the differences between the values of BET and GAB monolayer values and demonstrated that GAB monolayer moisture content is more representative than BET’s one.

In a recent review, Peleg (2020) stated “that the notion that foods have a physical water monolayer has been widely used in the food literature, but the issue of whether there really exists a water monolayer in foods has never been adequately settled”. It has been suggested, however, that water vapor molecules interact with hydrophilic groups which in foods and biomaterials are abundant. Peleg (2020) stated that this description of the sorption phenomenon is most likely correct although he pointed out that the water monolayer existence is still unproven and perhaps should be treated as a conjecture rather than a hypothesis.

As early as 1945, Pauling advanced that the water sorp- tion monolayer of proteins can be thought in terms of the attachment of one water molecule to each polar group of the side chains of the amino acids in the protein. In his analysis,

Pauling (1945) used BET monolayer values reported by Bull (1944), and the agreement with the number of polar groups of the proteins was roughly satisfactory. Timmermann et al. (2001) noted that in Pauling’s analysis, the monolayer values were in most cases lower than the number of polar groups.

They replaced BET values by recalculated GAB monolayer values and incorporated casein, a protein not considered by

Pauling (1945), and showed that the rough agreement noted by Pauling was now certainly improved.

We used the data collected by Timmermann et al. (2001) and added a few new data on number of polar groups and

GAB monolayer values corresponding to insulin, plakaal- bumin, and wheat and potato starch (Mac Laren & Rowen,

1951; Timmermann et al., 2001). A good linear correlation between the number of polar groups and the GAB monolayer was found, as shown in Fig. 1. The obtained linear regres- sion (r2 = 0.8431) was very close to the line of 45° indicat- ing a good agreement between number of water molecules calculated to exist in a GAB monolayer, and the number of polar side chains existed. Thus, and in agreement with vari- ous works (Gely & Giner, 2000; Quirijins et al., 2005), it may be reasonable to accept that GAB monolayer value pro- vides information about the amount of water that is strongly adsorbed to active sites, suggesting that each polar group ini- tially sorbs one molecule of water. A good linear correlation between the number of polar groups and the GAB monolayer is not perhaps enough to prove a given physical model. Peleg (2020) indicated that the supposition of a critical number of

718 Food and Bioprocess Technology (2022) 15:717–733

1 3 hydrophilic sites would have to be supported by independ- ent physical evidence. However, as stated by Pérez-Alonso et al. (2006), the “value of the monolayer is of particular interest since it indicates the amount of water that is strongly adsorbed to specific sites and is considered as the optimum value at which a food is more stable. And this fact has a high practical value regardless of its physical significance”.

It is to note that the well-known difference between the water sorption behavior of amorphous and crystalline sugars (Iglesias & Chirife, 1978) offers an example that the num- ber of hydrophilic groups alone is insufficient to explain the water sorption pattern.

Effect of Temperature on GAB Monolayer Values A review of a large amount of literature data on GAB mon- olayer values was carried out, but only those articles that reported values at three or more temperatures were chosen for the present survey. In most examples shown in the lit- erature, the GAB equation has been used independently for each temperature, generating a set of values for C, Mo, and k estimated from experimental data for each temperature condition.

Table 1 summarizes data on GAB monolayer values (% dry basis) at several temperatures (mostly in the range

20–50 °C) for more than seventy food items. The raw mate- rials compiled in present work were the following: seeds (various), gums (guar gum, locust bean, tragacanth gum, xanthan gum), maltodextrin, ethnical foods (grape leather (pestil), Gulabjamun mix, Cheese-Puri mix) cassava, cassava bagasse, cassava flour, cocoa beans, fish meal, grape leather, several nuts, mushroom, potato flakes, sweet potato flakes, potatoes, Japanese noodles, loquat fruit, quince fruit, yogurt powder, blueberry powder, blueberry pomace, barley, rice flour, chestnut, cookies, corn snacks, corn, rice crackers, baobab leaf, red peppers, faba bean protein, paprika, “pin- hao” flour, mango mix powder, soy protein isolate, apples, cottonseed kernel, cottonseed protein isolate, microencapsu- lated canola oil, microencapsulated chia oil, microencapsu- lated natural colorant, microencapsulated paprika oleoresin, microencapsulated beet root juice, microencapsulated Swiss cheese bioaroma powder, fish meal, tamarind seed mucilage, chia seed mucilage, microencapsulated rosemary oil, tea, parmesan cheese, pineapple powders, mushrooms, cookies, casein, bulgur, chitosan, orange juice, cowpeas, and whey protein concentrate.

The effect of temperature on GAB monolayer values for selected products (from data in Table 1) is illustrated in

Figs. 2 through 9. The criteria used to group food products in the different figures had two objectives: (a) to illustrate that GAB monolayer not always decrease with increasing temperature (as usually stated in literature), but also may remain constant or increase, and (b) to avoid overlapping of data that would otherwise occur making the graphs very difficult to interpret.

The monolayer values shown in these figures do not pre- sent error bars because the vast majority of surveyed papers did not provide it. Only in a few cases did the authors report error bars for monolayers. For example, Alpizar-Reyes et al. (2016) indicated that relative error bands of GAB monolayers ranged from ± 4.5 to ± 5.9% for tamarind seed mucilage; Escalona-García et al. (2016) indicated values between ± 1.5% and ± 3.0% for microencapsulated chia oil in whey protein concentrate, and Torres et al. (2012) reported values of ± 1.1 to ± 3.2% for several gums (CMC, guar gum, locust bean gum, and others).

As frequently reported in literature, GAB monolayer moisture content decreases with increasing temperature for most – but not all – products surveyed. The rate of GAB monolayer change with temperature was found to be strongly dependent on the product. This can be observed by compar- ing the behavior of sweet potato flakes (Fig. 4) and paprika (Fig. 7) which show a steep decline, with others such as malting barley (Fig. 2), yogurt powder (Fig. 3), Jasmine rice crackers (Fig. 4), guar gum (Fig. 6), and Japanese noodles (Fig. 7) exhibit a more moderate decrease.

Other products show that GAB monolayer was independ- ent (or nearly) of temperature. This is the case for cookies and corn snacks (Fig. 2), tragacanth gum, locust bean, malto- dextrin DE10 (Fig. 5), microencapsulated paprika oleoresin (Fig. 6), CMC (Fig. 7), apple, pineapple powders, cottonseed protein isolate (Fig. 8), and tea and apples (Fig. 9). Finally, there are also products in which GAB monolayer increases

0 200 400 600 800 0 200 400 600 800 GAB monolayer (mol water/105g polymer r2 = 0.8431 line 45 °

Number polar groups (= mol water/105 g polymer) Fig. 1   Comparison of GAB monolayer values with number of polar groups in various proteins and potato and wheat starch. Data points correspond to collagen, gelatin, seroalbumin, wool, lactoblob. crist., idem freeze dried, egg albumin coagulated, egg albumin freeze dried, egg albumin not f. dried, c-zein, b-zein, salmin, casein, insulin, plakalbumin, wheat starch, potato starch. (from Timmermann et al.,

2001; McLaren & Rowen, 1951) 719 Food and Bioprocess Technology (2022) 15:717–733

1 3 Table 1   Literature data on GAB monolayer values in foods and foodstuffs at various temperatures

Product Composition/ description Adsorption/ desorption

Temperature, °C GAB, monolayer, % dry basis Reference

Camellia oleífera seeds Shelled Adsorption 20 30 40

2.60 3.10 2.65 Xing et al. (2012) Unshelled Equil. time 15–21 days

Adsorption 20 30 40 2.91 2.97 2.73 Gum Arabic Adsorption

25 35 40 8.11 9.97 11.0 Pérez-Alonso et al. (2006)

Mezquite gum (1) Adsorption 25 35 40 8.35 7.32 5.72

Maltodextrin, DE10 Adsorption 25 35 40 7.35 6.99 6.96

Cassava bagasse Composition: carbo- hydrates 72.8%; fat

6.2%; ash 11.6%; protein 9.4% Equil. time 28 days Adsorption

20 30 40 50 55 65 70 75 80 5.61 5.24 4.64 4.03 3.86

3.65 3.49 3.40 3.27 Carregari Polachini et al. (2016)

Cassava Adsorption 30 45 60 6.16 5.59 3.66 Koua et al. (2012)

Desorption 30 45 60 6.96 5.36 4.21 Encapsulated Swiss cheese bioaroma powder

Encapsulated in MD DE20 and Capsul Adsorption 15 25

35 45 13.76 17.8 24.0 32.0 Silva et al. (2015) Microencapsulated chia oil

Encapsulants: WPC and mesquite gum Equil. time 20–25 days

Adsorption 25 35 40 6.32 5.58 5.18 Escalona-García et al. (2016)

Cocoa beans Desorption 30 45 60 6.06 5.35 5.08 Koua et al. (2016)

Microencapsulated natural colorant Encapsulants Arabic gum: maltodextrin

Equil. time 20–25 days Adsorption 20 35 40 6.34 3.78

2.83 Pavón-García et al. (2011) Mesquite gum: malto- dextrin

Equil. time 20–25 days Adsorption 20 35 40 6.77 3.70

2.83 Microencapsulated paprika oleoresin Encapsulant: starch capsul

Equil. time 40–55 days Adsorption 25 35 45 6.50 6.40

6.39 Rascón et al. (2015) Microencapsulated beetroot juice

Encapsulant: Arabic gum Adsorption 25 35 40 4.69 4.30

3.64 Guadarrama-Lezama et al. (2014a) Fish meal From anchovy

Time to equil. 21 days Sorption 25 35 45 6.03 5.45

4.22 Vivanco and Mendieta Taboada (1998) 720 Food and Bioprocess Technology (2022) 15:717–733

1 3 Table 1   (continued) Product Composition/ description

Adsorption/ desorption Temperature, °C GAB, monolayer, % dry basis

Reference Grape leather (pestil) Grape juice and starch

Time to equil. 21 28 days Adsorption 15 25 35 10.34

13.98 8.39 Kaya and Kahyaoglu (2005) Gulabjamun mix

Mix of: milk powder, refined wheat flour, semolina, baking powder, citric acid

Sorption Time to equil.

40 days 10 25 40 3.17 3.14 3.10 Pushpadass et al. (2013)

Gums (several) CMC Time to equil. 56 days Adsorption

20 35 50 65 9.1 8.1 7.7 6.9 Torres et al. (2012) Guar gum

20 35 50 65 3.2 2.8 2.5 2.0 Locust bean 20 35 50 65

4.1 3.8 3.4 3.0 Tragacanth gum 20 35 50 65 5.0 4.9

4.5 3.8 Xanthan gum 20 35 50 65 7.7 7.4 7.0 6.1 Macadamia nuts

Adsorption 25 35 45 1.43 1.35 1.02 Domínguez et al. (2007)

Microencapsulated canola oil Encapsulant: whey protein concentrate

Adsorption 15 25 35 5.44 4.37 3.98 Bonilla et al. (2010)

Encapsulant: soy pro- tein isolate Adsorption 15 25

35 5.68 4.88 4.43 Encapsulant: mesquite gum Adsorption

15 25 35 6.61 5.56 5.04 Mesquite gum (2) Desorption

25 35 45 10.59 8.08 6.27 Beristain et al. (1999) Oyster mushroom (Pleu- rotus ostreatus)

Adsorption 25 35 45 5.2 4.5 3.9 Pascual-Pineda et al. (2020)

Parmesan cheese (grated) Sorption 16 24 32 40 48 56

64 5.71 4.92 4.86 4.52 4.36 4.76 4.13 Faria Freitas et al. (2016)

Pineapple powder (freeze dried) Added with maltodex- trin

Adsorption 20 30 40 50 6.8 6.0 6.2 6.2 Viganó et al. (2012)

721 Food and Bioprocess Technology (2022) 15:717–733

1 3 Table 1   (continued) Product Composition/ description

Adsorption/ desorption Temperature, °C GAB, monolayer, % dry basis

Reference Potato flakes Equil. time. 15 days Adsorption

15 20 25 30 4.75 4.27 3.96 3.42 Carvalho Lago and Zapata

Noreña (2015) Sweet potato flakes Equil. time 15 days

Adsorption 15 20 25 30 10.35 9.46 7.57 6.37 Carvalho Lago and Zapata

Noreña (2015) Potato Equil. time 21 days Adsorption

30 45 60 6.16 5.26 3.66 McMinn and Magee (2003) Desorption

30 45 60 6.96 5.59 4.21 Tamarind seed mucilage Equil. time 21–25 days

Adsorption 20 30 40 9.99 11.32 11.99 Alpizar-Reyes et al. (2016)

Chia seeds mucilage Equil. time 20–25 days Adsorption

25 35 40 7.93 5.33 4.05 Velázquez-Gutiérrez et al. (2014)

Loquat fruit Equil. time 56 days Sorption 20 35 50

65 16.3 13.6 12.1 9.9 Moreira et al. (2008) Quince fruit

Equilib. time 56 days Sorption 20 45 65 11.5 8.02 4.35

Moreira et al. (2008) Dehydrated yacon bagasse Protein 2.32%, lipids

0.35%; Ash 4.0%; fiber 22.2%; CH 67.4% Sorption 20

30 40 50 1.2 1.0 0.7 0.6 Carvalho Lago and Zapata Noreña (2015)

Yogurt powder, spray dried Added with sugar and maltodextrin before drying

Sorption 20 30 40 50 4.88 4.54 3.86 3.52 Seth et al. (2018)

Cheese-Puri mix Prepared from wheat flour, cheddar cheese, milk powder

Adsorption 25 35 45 2.05 2.50 2.49 Thanuja and Ravindra (2012)

Blueberry juice powder Added with whey protein isolate

Adsorption 20 35 50 10.5 8.7 8.6 Tao et al. (2017)

Blueberry fruit (mashed) Adsorption 20 35 50 9.6 7.2

6.3 Tao et al. (2017) Blueberry pomace Adsorption 20

35 50 4.5 4.2 4.1 Tao et al. (2017) Cassava flour Equil. time 19–25 days

Adsorption 25 30 35 7.31 7.28 6.32 Ayala-Aponte (2016)

Malting barley Desorption 20 30 40 50 10.18 9.29 8.51

8.13 Gely and Pagano (2012) Rice flour DVS: very short equil. time

Adsorption 5 23 45 7.9 7.3 6.6 Sandoval et al. (2011)

722 Food and Bioprocess Technology (2022) 15:717–733

1 3 Table 1   (continued) Product Composition/ description

Adsorption/ desorption Temperature, °C GAB, monolayer, % dry basis

Reference Chestnut Desorption 20 30 40 50 6.08 6.05

6.02 6.00 Vázquez et al. (2001) Cookies Adsorption

“Habaneras” 25 35 45 4.58 4.53 4.15 Palou et al. (1997)

“Ricanelas” 25 35 45 4.09 4.09 3.91 “Animalitos” 25

35 45 4.41 4.11 3.97 Corn snacks Adsorption Doritos

25 35 45 3.26 3.06 3.00 Palou et al. (1997) Tostitos

25 35 45 3.71 3.77 3.45 Jasmine rice crackers Sorption

30 45 60 5.94 5.60 5.01 Siripatrawan and Jantawat (2006)

Kuka (baobab leaf) Equil. time 15–18 days Adsorption

Desorption 34 37 45 34 37 45 4.83 3.94 3.68 9.35 8.41

5.78 Ajisegiri et al. (1994) Macadamia in-shell nuts

Equil. time 42 days Adsorption 10 20 30 40 4.14 3.85

3.60 3.37 Palipane and Driscoll (1993) Desorption 10

20 30 40 5.56 4.94 4.42 3.92 Red peppers Equil. time. > 21 days

Adsorption 30 45 60 9.96 9.95 8.6 Kaymak-Ertekin and

Sultanoglu (2001) Desorption 30 45 60 11.3 9.0 6.7

Sesame seed (whole) Equil. time 28 days Sorption 15

25 35 3.09 2.66 1.89 Kaya and Kahyaoglu (2006) Dehulled sesame seed

Equil. time 28 days Sorption 15 25 35 2.44 2.62 2.15

Dehulled-roasted sesame seed Equil. time 28 days Sorption

15 25 35 1.82 1.64 1.74 Faba bean protein Adsorption

25 35 40 5.52 4.55 4.32 Alpizar-Reyes et al. (2018)

Microencapsulated chili extract Equil. time 15–20 days

Adsorption 25 35 40 12.49 10.58 7.70 Guadarrama-Lezama et al. (2014b)

723 Food and Bioprocess Technology (2022) 15:717–733

1 3 Table 1   (continued) Product Composition/ description

Adsorption/ desorption Temperature, °C GAB, monolayer, % dry basis

Reference Paprika Adsorption 30 40 50 60 10.04 7.54

4.42 3.78 Shirkole et al. (2019) Pinhao flour (seeds of

Araucaria angustifolia) Equil. time 30–40 days Adsorption

10 20 30 40 6.60 6.04 5.77 5.17 Cladera-Olivera et al. (2011)

Rosemary oil microen- capsulated with Arabic gum Adsorption

15 25 35 45 12.42 11.52 10.29 8.42 Silva et al. (2014)

Mango mix powder (mixed with MD DE 17–20) Equil. time 28–35 days

Adsorption 20 30 40 50 5.53 4.33 3.45 2.79 Cano-Higuita et al. (2013)

Japane noodles (Udon) Desorption 20 30 40 7.88 7.38

6.83 Inazu et al. (2001) Soy Protein Isolate Adsorption

15 25 35 5.68 4.88 4.43 Bonilla et al. (2010) Whey protein Concen- trate

Adsorption 15 25 35 5.44 4.37 3.98 Mesquite gum Adsorption

15 25 35 6.61 5.56 5.04 Tea Equil. time 3–17 days Adsorption

25 35 45 4.40 4.20 4.19 Arslan and Togrul (2006) Orange juice, s. dried

Adsorption 20 30 40 50 12.6 10.9 10.2 9.8 Sormoli and Langrish (2014)

Pistacho nuts paste Equil. time 50–60 days Adsorption

20 30 40 2.23 2.18 2.43 Maskan and Gogus (1997) Green beans

20 30 40 7.09 6.51 5.31 Samaniego-Esguerra et al. (1991)

Casein acid, from buf- falo milk Adsorption 25 35 45

5.60 4.70 4.55 Sawhney et al. (2011) Bulgur Equil. time 7 days

Adsorption 20 30 40 5.03 3.69 2.55 Erbas et al. (2015)

Apples, golden delicious Equil. time 9–16 days Desorption

30 40 50 60 12.1 12.9 12.2 12.6 Mbarek and Mihoubi (2018)

Cottonseed protein isolate Adsorption 15 25 35 45 3.93

3.61 3.47 3.29 Tunc and Duman (2007) Equil. equilibrium

724 Food and Bioprocess Technology (2022) 15:717–733

1 3 with increasing temperature, such as fish meal (Fig. 3), microencapsulated cheese bioaroma, microencapsulated allspice oil (Fig. 8), and passion fruit juice microcapsules (Fig. 9).

In summary, although in most cases shown in Table 1 and also in literature (Gely & Giner, 2000; Quirijns et al., 2005;

Domínguez et al., 2007) GAB monolayers decrease with increasing temperature, it cannot be taken for granted since as shown here, GAB monolayers can also remain constant or even increase with increasing temperature.

Iglesias and Chirife (1984) analyzed the effect of tem- perature on BET monolayer values of foods and reported

BET values mostly decreased with increasing temperature.

They proposed the following empirical model to correlate

BET values with temperature: (2) In MoBET = p + a.T, where ­MoBET is BET monolayer moisture content (g water/100 g dry solid), T is temperature (°C), and p and a are constants. Iglesias and Chirife (1984) noted that the relative effect of temperature on BET values was very different for different foods. For example, BET values in some fruits (banana, pineapple, peach) decreased by about

21–35% between 25 and 40 °C, while in eggs the decrease was only 3% over the same temperature interval. In some cases, Eq. (1) failed to reproduce the behavior of BET val- ues with temperature. Iglesias and Chirife (1984) suggested that the relative variation of BET values with temperature was dependent on the physicochemical nature of the food as well as the time needed to reach sorption equilibrium. In turn, the equilibrium time dependence was determined by the experimental device utilized to construct the isotherm.

This reasoning can also be applied to the results here reviewed. Most cases shown in Table 1 were derived from

10 20 30 40 50 60 0 5 10 Temperature, °C GAB monolayer value, % d.b.

Cookies (H) Cookies (R) Cookies (A) Corn snacks (D)

Corn snacks (T) Blueberry juice powder Cassava flour

Malting barley Fig. 2   Effect of temperature on GAB monolayer value. Cookies and corn snacks: from data reported by Palou et  al. (1997); blueberry juice powder: from data reported by Tao et al. (2017); cassava flour: from data reported by Ayala-Aponte (2016); malting barley: from data reported by Gely and Pagano (2012)

0 20 40 60 0 5 10 15 20 Temperature, °C GAB monolayer value, % d.b.

Cocoa beans Fismeal Parmesan cheese Yogurt powder Loquat fruit

Quince fruit Tamarind seed mucilage Fig. 3   Effect of temperature on GAB monolayer value. Cocoa beans: from data reported by Koua et  al. (2016); fishmeal: from data reported by Vivanco and Mendieta Taboada (1998); Parmesan cheese: from data reported by Faria Freitas et al. (2016); yogurt pow- der: from data reported by Seth et al. (2018); loquat fruit: from data reported by Moreira et al. (2008); quince fruit: from data reported by

Moreira et al. (2008) Fig. 4   Effect of temperature on

GAB monolayer value. Potato: from data reported by McMinn and Magee (2003); potato flakes: from data reported by

Carvalho Lago et al. (2015); sweet potato flakes: from data reported by Carvalho Lago et al. (2015); Jasmine rice crackers: from data reported by Siripatrawan and Jantawat (2006); corn: from data reported by Gely and Giner (2000); macadamia nuts: from data by

Domínguez et al. (2007) 0 10 20 30 40 50 60 70 0 2

4 6 8 10 12 Temperature, °C GAB monolayer value, % d.b.

Potato Potato flakes Sweet potato flakes Corn Macadamia nuts

Jasmine rice crackers 725 Food and Bioprocess Technology (2022) 15:717–733

1 3 sorption isotherms determined using the known gravimetric method, in which food samples were placed into glass/plas- tic desiccators containing different saturated salt solutions.

Desiccators were then placed in constant temperature incu- bators at the desired temperature (usually between 20 and

50 °C) until the equilibrium moisture content was reached.

The equilibration time reported ranged between about 15 and 50 days. Water activity equilibration for these periods of time at relatively high temperatures may cause physical and chemical deterioration of the sample which is reflected in available sorption sites. These reactions may consist in non- enzymatic browning, denaturation, crosslinking, and interac- tion of the native or denatured proteins with oxidized lipids or carbohydrates, as well as structural modifications induced by temperature. Thus, a modification in the availability of hydrophilic sites for water binding by one or several of the above mechanisms leads to modification of GAB monolayer values when increasing temperature: a decrease, an increase, or a constancy.

Romani et al. (2015) studied the effect of storage time of packed biscuits at 35 °C for up to 92 days, and the adsorption isotherm was determined using a rapid Dynamic Dewpoint isotherm (DDI), whose equilibration times was far smaller than in the traditional static gravimetric technique. The resulting adsorption isotherms of stored biscuits, observed by means of DDI method, were affected by previous stor- age time at 35 °C. The monolayer moisture content (BET monolayer in this case) significantly increased from 1.473 to 2.080 g water/100 g db, from the beginning to the end of storage. The authors ascribed the increase of monolayer values during biscuit storage to an increase of active sites for

Fig. 5   Effect of temperature on GAB monolayer value.

C. oleifera seeds, unshelled: from data reported by Xing et al. (2012); C. oleífera seeds, shelled: from data reported by

Xing et al. (2012); gum Arabic: from data reported by Pérez- Alonso et al. (2006); mesquite gum (1): from data reported by Pérez-Alonso et al. (2006);

Maltodextrin DE10: from data reported by Pérez-Alonso et al. (2006); locust gum: from data reported by Torres et al. (2021); tragacanth gum: from data reported by Torres et al. (2012); mesquite gum (2): from data reported by Beristain et al. (1999)

10 20 30 40 50 0 2 4 6 8 10 12 14 Temperature, °C GAB monolayer, % d.b.

C. oleifera seeds, unshelled C.oleifera seeds, shelled

Gum arabic Mesquite gum (1) Maltodextrin DE10 Locust bean

Tragacanth gum Mesquite gum (2) 0 10 20 30 40 50 60

0 2 4 6 8 10 Temperature, °C GAB monolayer value, % d.b. encapsulated chia oil encapsulated paprika oleoresin encapsulated beet root juice encapsulated canola oil

CMC Guar gum Fig. 6   Effect of temperature on GAB monolayer value. Microencap- sulated chia oil: from data reported by Escalona-García et al. (2016); microencapsulated paprika oleoresin: from data reported by Rascón et al. (2015); microencapsulated beetroot juice: from data reported by

Guadarrama-Lezama et al. (2014a, b); microencapsulated canola oil: from data reported by Bonilla et al. (2010); CMC: from data reported by Torres et al. (2012); guar gum: from data reported by Torres et al. (2012)

0 10 20 30 40 50 60 0 5 10 Temperature, °C GAB monolayer value, % d.b.

Mango mix powder Japanese noodles Paprika Potato flakes

CMC Blueberry pomace Fig. 7   Effect of temperature on GAB monolayer value. Mango mix powder (mixed with MD): From data reported by Cano-Higuita et al. (2013); Japanese noodles: from data reported by Inazu et al. (2001); paprika: from data reported by Shirkole et al. (2019); potato flakes: from data reported by Carvalho-Lago et  al. (2015); CMC: from data reported by Torres et al. (2012); blueberry pomace: from data reported by Tao et al. (2017)

726 Food and Bioprocess Technology (2022) 15:717–733

1 3 water binding, as a consequence of chemical and physical changes of its main components (egg, starch, sugars, lipid, protein) induced by product ageing.

Iglesias and Chirife (1978) determined the water adsorp- tion isotherms at 30 °C of precooked beef previously dried at three different temperatures: 30 °C, 55 °C, and 70 °C, respectively. They found that the higher the drying tempera- ture, the lower was the sorption capacity of dried beef and reported that quantity of water contained in the BET mon- olayer was affected by the previous drying temperature of

30, 55, or 70 °C reducing from 5.4 to 5.1 and 4.5 (non-fat % dry basis) respectively.

Generally, the GAB model is used independently for each temperature, generating a set of values for C, Mo, and

K estimated from experimental data for each temperature.

Another alternative is the introduction of a temperature- dependent expression for the parameters, yielding a bigger amount of constants to be estimated with the whole set of isotherms (Staudt et al., 2013). Accordingly, various authors (Martín-Santos et al., 2012; Quirijns et al., 2005;

Shirkole et al., 2019) have proposed that Mo was related to temperature by using the following Arrhenius-type equation: where Mo′ is a pre-exponential factor and ΔHm is an Arrhenius- type energy factor. However, the complex experimental behavior (decrease, constancy or increase) of GAB mon- olayers with temperature (Figs. 2–10) may not be adequately predicted with Eq. (3).

Integral Entropies of Sorption and GAB Monolayer The thermodynamics of water vapor sorption in foods has attracted interest because it may provide a more thorough interpretation of the sorption phenomenon and assists in understanding the mechanism (Beristain et al., 2002).

It is well known that the stability of low moisture foods depends on great measure on its moisture sorption charac- teristics, and some researchers considered (Bonilla et al.,

2010) that the thermodynamics of water vapor sorption may also propose a scientific criterion for the prediction of the stability and storage life of dehydrated foods. In recent years, the study of water sorption thermodynamics in dehydrated products has been the subject of several studies (3)

Mo = Mo exp (ΔHm∕RT) 0 10 20 30 40 50 60 0 5 10 15

20 25 Temperature, °C GAB monolayer value, % d.b.

Microenc.allspice e. oil (1) Microenc.allspice e. oil (2)

Apple Cottonseed protein isolate Pineapple powder freeze-dried encapsulated cheese bioaroma

Fig. 8   Effect of temperature on GAB monolayer. Microencapsulated allspice essential oil (1) with WPC 66% + mesquite gum 17% + MD

17%: from data reported by Sánchez-Sáenz et  al. (2011); microen- capsulated allspice essential oil (2) with WPC 17% + mesquite gum

17% + MD 66%: from data reported by Sánchez-Saenz et al. (2011); apple (golden delicious): from data reported by Mbarek and Mihoubi (2018); cottonseed kernel: from data reported by Tunc and Dumar (2007); cottonseed protein isolate: from data reported by Tunc and

Dumar (2007); pineapple powder (freeze-dried): from data reported by Viganó et al. (2012); pineapple powder (vacuum dried): from data reported by Viganó et al. (2012)

0 10 20 30 40 50 60 70 0 5 10 15 GAB Monolayer, % d.b.

Tea Orange juice Bulgur Pistacho nuts paste Temperature, °C

Passion fruit juice microcapsules Fig. 9   Effect of temperature on GAB monolayer. Tea: from data reported by Arslan and Togrul (2006); orange juice (spray-dried): from data reported by Sormoli and Langrish (2014); safflower petal: from data reported by Kaya and Kahyaoglu (2007); apples (golden delicious): from data reported by Mbarek and Mihoubi (2018); bul- gur: from data reported by Erbas et al. (2015); pistachio nuts paste: from data reported by Maskan and Gogus (1997); passion fruit juice microcapsules: from data reported by Carrillo-Navas et al. (2011)

727 Food and Bioprocess Technology (2022) 15:717–733

1 3 (Pérez-Alonso et al., 2006; Silva et al., 2015; Escalona- García et al., 2016; Faria Freitas et al., 2016; Viganó et al.,.

2012; Xiao & Tong, 2013; Moreira et al., 2008) and many others. Various studies reported that a plot of integral entropy curve versus moisture content of various foods showed a well-defined minimum and interpreted that it is the moisture content corresponding to a monolayer, since a complete monolayer corresponds to a small number of configurations of the system (Beristain et al., 1994; Bertuzzi et al., 2003; Nunes & Rotstein, 1991; Xing et al., 2012).

Many authors indicated that the decrease in entropy is asso- ciated with the loss of mobility of the water molecules fol- lowed by an increase in entropy as the water regains mobil- ity by forming several “layers.” The integral entropy can be interpreted qualitatively in terms of the order/disorder and randomness of the adsorbed water molecules and could be assumed to coincide with the moisture content required to form a monolayer where strong bonds between the adsorb- ate and adsorbent occurred. Literature reports used the point of minimum integral entropy as a tool to predict the maximum stability point of dehydrated foods (Bonilla et al.,

2010). This will be discussed later in this review.

The thermodynamic analysis of sorption needs the knowledge of isotherms at different temperatures, and three isotherms in the range 20–40 °C or 25–45 °C have been mostly used. The analysis of the thermodynamic functions of water sorption in foods has been described in detail by many authors (Beristain et al., 1994; Kumagai et al., 1994;

Xing et al., 2012) and includes the Gibbs free energy (ΔG), where T is the absolute temperature (K); R, the universal gas constant (J ­mol−1 ­K−1); and aw is the water activity. A change on free energy as a result of water sorption is usually accom- panied by changes on both the enthalpy and the entropy. Both differential and integral enthalpies (ΔH) and entropy (ΔS) may then be calculated. Sorption enthalpy is a molar dif- ferential quantity derived from the temperature dependence of the isotherm, in contrast to the integral enthalpy which is the average energy for all the water molecules already bound at that level. The respective differential and integral entro- pies are obtained from the differential and integral enthalp- ies, respectively. Pérez-Alonso et al. (2006), Tolaba et al. (1997), Domínguez et al. (2007), Bonilla et al. (2010), and

Rodríguez-Bernal et al. (2015) – among others – described the calculation of differential and integral thermodynamic functions in water sorption in foodstuffs.

As indicated by Bonilla et al. (2010), changes in the inte- gral entropy have been calculated from. (4)

ΔG = ΔGo + R T ln(aw) (5) (Δ퐒퐢퐧퐭)퐓= −(Δ퐇퐢퐧퐭)퐓−Δ퐆) 퐓

A large number of literature studies reported a mini- mum of integral entropy versus moisture content and were reviewed to verify whether or not such minimum actually occurs close to the GAB monolayer. Only those studies that reported both the integral minimum entropy and the GAB values were chosen for this review, and about fifty eligible articles with appropriate data were used.

As mentioned above, the net integral entropy of water adsorption usually decreases gradually with increasing

0 5 10 15 0 5 10 15 GAB monolayer (aver), g/100 g d.b.

Moisture at M.I.E, g/100 g d.b. line of 45 ° r2 = 0.9089

Fig. 10   Correlation between moisture content of minimum integral entropy (MIE) and GAB monolayer. borocotó fruit, medium phase; from data of Rodríguez-Bernal et  al., 2015)–Camelia oleifera shelled (from data of Xing et al., 2012); C. oleífera unshelled; (from data of Xing et al.,

2012); Arabic gum (from data of Xing et al. (2012); paprika oleoresin encapsulated in modified starch,(from data of Rascón et al. (2015); multi- ple extract microencapsulated in Arabic gum, mesquite gum, and malto- dextrin (from data of Pavón-García et  al., 2015); Xanthan gum (from data of Torres et al., 2012); Macadam nut (from data of Domínguez et al. (2007); mesquite gum (from data of Bonilla et al., 2010); millet grains, var. Exborno, adsorption (from data of Aviara et al., 2016); millet grains var. Ex Borno, desorption (from data of Aviara et al., 2016); millet grains var. Sosat C88, adsorption (from data of Aviara et al., 2016); whey pro- tein isolate (from data of Bonilla et al., 2010); oyster mushroom, freeze- dried (from data of Pascual-Pineda et al., 2020); Parmesan cheese,grated, storage and drying (from data of Faria Freites et al., 2016); pineapple powder spray-dried, and vacuum dried (from data of Viganó et al., 2012); sweet potato flakes (from data of Carvalho-Lago et al., 2015); Yogurt freeze-dried (from data of Azuara-Nieto & Beristain, 2007); sesame seed dehulled and roasted (from data of Kaya & Kahyaoglu, 2006); cocoa beans (from data of Koua et al., 2016); mango pulp, spray dried with maltodextrin or skimmed milk, (from data of Cano-Higuita et al.,

2013); pullulan (from data of Xiao & Tong, 2013); pullulan/alginate

60:40, (from data of Xiao & Tong, 2013); pullulan/alginate 40:60, (from data of Xiao & Tong, 2013); alginate (from data of Xiao & Tong, 2013); faba bean protein (from data of Alpízar-Reyes et al. (2018); sugar beet root (from data of Iglesias et al. (1976); Yogurt, concentrated and freeze- dried conc. (from data of Azuara & Beristain, 2007); sweetened yogurt, spray-dried (from data of Seth et al. (2018); potato, desorption (data from

McMinn & Magee, 2003) 728 Food and Bioprocess Technology (2022) 15:717–733

1 3 moisture content to a minimum value around the monolayer moisture content, and then increases with further increase in moisture content. Although the value of minimum entropy may be unique, there are food products with zones in which this minimum does not vary appreciably in a defined range of moisture (Beristain & Azuara, 1990). For example, Rascón et al. (2015) indicated that for paprika oleoresin encapsulated in Capsul (modified starch), this zone begins at moisture con- tents of 5.89 g water/100 g soluble solids and ends at 6.94 g water/100 g soluble solids. Bonilla et al. (2010) reported that for whey protein, microcapsules at 25 °C moisture content at minimum integral entropy were 6.38% (dry solids), but the moisture content range where integral entropy remained more or less constant was 5.10–6.52% (dry basis).

Figure 10 shows a plot of the moisture corresponding to MIE versus the GAB monolayer, for 39 pairs of values obtained from literature. Since these values were in most cases reported at 3 temperatures (mostly 25–45 °C), a mean value was used here. It can be seen that there is a linear relationship between both parameters, and the regression line is close to the 45° diagonal (Fig. 10) with a quite acceptable correlation coefficient (r2 = 0.9089). The relationship between the mois- ture content of both variables is given by Eq. (6): which indicates that the GAB monolayers are close to the moisture of MIE zone.

Delgado et al. (2014) noted that in some cases, the ther- modynamic analysis was not in accordance with the mon- olayer obtained with the GAB model, generally the mini- mum integral entropy point being higher than the GAB monolayer. This behavior was also observed in several products examined in the present review. Thirty-one pairs of literature values (not included in those shown in Fig. 10) are plotted in Fig. 11. The regression line is now far from the 45° diagonal, and the dispersion of the data is reflected in a lower value of r2 (0.8024). The relationship between the moisture content of both variables is given by Eq. (7): which indicates that for these products, the moisture at minimum integral entropy is considerably higher than GAB monolayer.

Some authors considered the minimum integral entropy to be the point of maximum stability (Pérez-Alonso et al.,

2006). However, when the moisture at the point of the mini- mum integral entropy is considerably higher than GAB monolayer, there is uncertainty regarding the validity of minimum entropy as a point of stability. (6) [ΔSint]min = 0.8935. GAB value + 0.8523 (7) [ΔSint]min = 1.448. GAB + 1.466

0 5 10 15 0 5 10 15 20 Moisture at MIE, g/100 g d.b.

GAB monolayer, g/100 g d.b. r2 = 0.8024 Line 45 ° Fig. 11   Correlation between moisture content of minimum inte- gral entropy (MIE) and GAB monolayer. Green coffee beans (data from Beristain et  al., 1994; green coffee beans (data from Estrada

Bahen, 2019); dehydrated yacon bagasse (data from Carvalho Lago

& Zapata Norena,  2015); tarragon (data from Kaya & Kahyaoglu,

2007); Winged bean seed (data from Fasina et al., 1999); soya bean (data from Aviara et  al., 2004); Sesame seed, whole (data from

Kaya & Kahyaoglu, 2006); sesame seed dehulled (data from Kaya

& Kahyaoglu, 2006); red onion microcapsules in maltodextrin (data from Pascual-Pineda et al., 2018); millet grain flour germinated (data from Sharama et al., 2018); millet grain flour non-germinated (data from Sharama et  al., 2018); encapsulated canola oil in soy protein isolate (data from Bonilla et  al., 2010); encapsulated canola oil in mesquite gum (data from Bonilla et al, 2010); tragacanth gum (data from Torres et  al., 2012); encapsulated natural colorant in Arabic gum 50% + maltodextrin 50% (data from Pavón-García et al., 2011); encapsulated natural colorant in mesquite gum 50% + maltodextrin

50% (data from Pavón-García et  al., 2011); defatted sesame meal (data from Al-Mahasneh et  al., 2007); Arabic gum 17% + mesquite gum 66% + maltodextrin 17% (data from Pérez-Alonso et al., 2006); alfalfa pellets (data from Fasina et  al., 1997); mesquite gum (data from Pérez-Alonso et  al., 2006); microencapsulated allspice essen- tial oil in whey protein conc.-mesquite gum & maltodextrin, (data from Sánchez-Saenz et  al.,  2011); sweet potato flakes (data from

Fasina,  2006); red onion microcapsules (data from Pascual-Pineda et al., 2018); soybean TGX (from data of Aviara et al., 2004); winged bean seed (data from Fasina et al., 1999); pestil (grape leather), (data from Kaya & Kahyaogluom, 2005); beet root microcapsules in Ara- bic gum, (data from Guadarrama-Lezama et  al., 2014a, b); pineap- ple powder with maltodextrin, vibro fluidized bed (data from data of Viganó et al., 2012); canola oil microencapsulated with soy pro- tein isolate, whey protein concentrate, or mesquite gum (data from

Bonilla et al., 2010); microcapsules passion fruit juice in Arabic gum

17% + mesquite gum 66% + maltodextrin 17% (from data of Carrillo- Navas et al. (2011); microcapsules passion fruit juice in Arabic gum

17% + mesquite gum 17% + maltodextrin 66% (from data of Carrillo- Navas et al. (2011)

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1 3 At this stage, we prefer not to consider stability aspects since “stability” is the sum of many changes such as micro- bial spoilage, oxidative, enzymatic and non-enzymatic reac- tions, texture, crispness, and other physical changes (sticki- ness, collapse, crystallization) associated with the glass transition (Roos, 1995). In turn, these changes depend on food moisture content in different ways. Nevertheless, some general comments on stability need to be made.

There is no direct reason to explain why in a group of foods (Fig. 10), the moisture at the minimum integral entropy point is close to the GAB monolayer, but in another group of foods and foodstuffs (Fig. 11), the moisture at MIE is considerably higher than GAB monolayer. Admittedly, foods are heterogeneous mixtures of biopolymers, water, and solutes. Therefore, the positive or negative correlation between moisture of MIE and GAB monolayer is probably due to differences in composition and structure of food sys- tems examined. According to Viganó et al. (2012), foods with the same chemical composition and different micro- structure could show different moisture sorption behavior influencing the results. They studied the thermodynam- ics of water sorption by pineapple powders produced by vibro-fluidized drying (VFD), spray drying (SD), freeze drying (FD), or vacuum drying (VD) and reported that the moisture (and hence aw) at the minimum integral entropy depended on the drying method utilized; for example, it was 6.8% (db.) for VD and dramatically increased to 18.9% for VFD. They stated this difference is due to changes pro- duced in the product microstructure during dehydration and that powders produced by SD and VFD are more stable at changing aw because they presented minimum entropy at higher moisture contents. However, this statement should be taken with caution as it was not confirmed experimentally.

The GAB monolayer was less sensible than MIE to these microstructural changes. Comparing VFD and VD the GAB monolayer changed by about 67% while the MIE suffered a

178% change.

Sánchez-Saenz et al. (2011) studied the encapsulation of allspice oil in a mixture of whey protein concentrate, mes- quite gum, and maltodextrin and reported that conditions of maximum stability (minimum integral entropy) for micro- capsules corresponded to aw = 0.713 at 25 °C or 0.657 at

35 °C. It must be noted that aw 0.713 at 25 °C may allow growth of xerophilic fungi during storage, albeit slowly.

Similarly, Bonilla et al. (2010) encapsulated canola oil in soy protein isolate and reported that at 35 °C, the moisture condition for stability (minimum integral entropy) corre- sponded to aw = 0.71; again, this aw will also allow growth of some xerophilic fungi. Azuara-Nieto and Beristain-Guevara (2007) reported that minimum integral entropy predicted that at 30 °C, the maximum stability of powder whey protein will occur when stored at aw = 0.50, but they did not substan- tiate experimentally this statement.

More research is needed to determine whether the ther- modynamic approach helps to predict storage stability of foods and foodstuffs. Some works cited in this review experi- mentally confirmed the relationship between MIE and stabil- ity of the studied products. But in others, this was not the case, or it was not experimentally confirmed.

Conclusions Re-examination of old data on the stoichiometry of water sorption in proteins but with addition of some new values for other biopolymers confirmed there is a good correla- tion (r2 = 0.8413) between the number of water molecules calculated to exist in a GAB monolayer and the number of polar groups. This reconfirms the old Pauling’s hypothesis that each polar group initially sorbs one molecule of water.

A literature survey performed for more than 70 differ- ent food items allowed to collect GAB monolayer values at different temperatures. Although the decrease of GAB values with increasing temperature is the behavior usually reported in literature, it cannot be taken for granted since as shown here, the monolayer can also remain constant or even increase with increasing temperature.

The study of the relationship between the minimum integral entropy (MIE) and the GAB monolayer indicated that for 38 different foods, a good agreement was observed between the moisture content corresponding to the mini- mum integral entropy and the GAB monolayer. However, for other foods, the regression curve between both param- eters indicated that the moisture content corresponding to the minimum integral entropy was considerably higher than

GAB monolayer. The results of this review may help to sup- port the use of GAB monolayer value as adequate mois- ture content for many aspects of food stability. Also, it may promote additional research about the relation between the

GAB monolayer and the minimum integral entropy, as well as the real role of the latter in the prediction of stability of low-moisture foods.

Funding  Facultad de Ingeniería y Ciencias Agrarias, Pontificia Uni- versidad Católica Argentina and ANPCyT (project PICTO UCA 2017–

0071) provided financial support.

Declarations Competing Interests  The authors declare no competing interests.

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# 翻译

卷号:(0123456789) 1 3 https://doi.org/10.1007/s11947-021-02740-w 综述文章 食品中GAB单层温度效应及吸附最小积分熵综述

Héctor A. Iglesias1 · Rosa Baeza2 · Jorge Chirife2 收稿日期:2021年7月12日 / 接受日期:2021年11月19日 © 作者独家授权给Springer Science+Business Media LLC,隶属于Springer Nature,2021年

## 摘要

本文综述了食品中GAB单层值的若干方面。重新分析了蛋白质及其他生物聚合物吸附水化学计量学的文献数据,发现极性基团数量与GAB单层之间存在良好的线性相关性(r² = 0.8431),这有助于验证每个极性基团最初吸附一个水分子的假设。对70多种不同食品在不同温度下的GAB单层值进行了调查,结果表明,尽管并非全部,但对大多数食品而言,温度升高会导致单层对应的含水量(g水/100g干固体)值降低。然而,在相当数量的案例中,观察到单层随温度保持恒定或增加。利用文献数据研究了最小积分熵(MIE)与GAB单层之间的关系。对于38种不同食品,MIE对应的含水量与GAB单层之间的回归曲线(r² = 0.9038)接近45°对角线,表明GAB值与最小积分熵的位置吻合。然而,对于多种其他产品,MIE的含水量位于单层之上。

**关键词** GAB单层 · 水吸附 · 等温线 · 最小积分熵 · 热力学性质 · 温度效应

## 引言

几乎影响脱水过程和食品储存稳定性每个方面的食品材料基本特征是其水吸附等温线。由于与食品稳定性和脱水操作设计相关的应用,食品材料吸附等温线的测量和建模吸引了众多研究者。已发表了关于食品吸附行为的综合综述,并提出了多种经验和半经验方程来关联食品材料的平衡含水量(Basu等,2006;Peleg,2020)。

早在1979年,Boquet等研究了各种三参数文献等温线方程拟合39种肉类、乳制品、蛋白质、淀粉食品和蔬菜等温线的能力。最佳方程是Hailwood和Horrobin(1946)提出的方程,该方程最初是为了解释蛋白质的水吸附等温线而建立的。Hailwood-Horrobin方程对食品实验吸附数据的优异拟合能力使Boquet等(1979)将其称为描述食品中水吸附等温线的"通用"方程。随后,Boquet等(1980)证明了Hailwood-Horrobin方程在数学上与GAB方程等价。

过去,著名的BET(Brunauer、Emmet和Teller)吸附等温线是应用于食品和食品原料水吸附的最广泛模型(Basu等,2006;Iglesias & Chirife,1976;Labuza,1968;Timmermann等,2001)。从BET方程获得的一个广为人知的常数是单层含水量,正如Timmermann等(2001)所指出的,它被发现是关于低水分食品各方面问题的合理指导(Iglesias & Chirife,1982,1984;Karel,1973)。在过去二十年中,Guggenheim、Anderson和de Boer(GAB)等温线方程被广泛用于描述多种类型食品的吸附行为(Van den Berg,1981;Basu等,2006;Quirijins等,2005;Lomauro等,1984)。GAB方程具有合理数量的参数(三个),已被发现能充分代表食品中大多数实际感兴趣的水活度范围内的实验数据。目前,GAB方程在食品中的应用几乎被全球实验室普遍采用(Singh & Singh,1996;Quirijns等,2005;Peleg,2020)。

水蒸气-食品平衡的热力学还提供了有关结构问题和能量需求的有价值信息,以及分析实验数据一致性的工具(Iglesias等,1976;Nunes & Rotstein,1991)。Rizvi和Benado(1983)综述了热力学性质在脱水食品中的适用性,并得出结论:热力学计算提供了关于吸附水结构的重要见解。

稳定性受产品水分吸附特性的极大影响。干燥食品原料中水吸附的热力学也引起了关注,因为一些作者认为它有助于更好地理解低水分食品的稳定性(Beristain等,2002;Bonilla等,2010)。

本综述涉及与GAB单层值相关的若干方面,具体包括:其物理意义、温度对单层影响的文献数据综述,以及最小积分熵(MIE)位置与GAB单层值的文献数据比较,以验证两者是否在相同含水量处重合。

## 结果与讨论

### GAB单层值的意义

如前所述,Guggenheim、Anderson和de Boer(GAB)等温线方程是文献中讨论最广泛的描述食品吸附行为的模型(Basu等,2006;Iglesias & Chirife,1995;Peleg,2020;Timmermann等,2001)。GAB模型最常见的形式为(公式1):

其中M为平衡含水量(g水/100g干固体);Mo为单层含水量(g水/100g干固体),aw为水活度,C和K为常数。

多位作者报道,从BET方程获得的单层值始终小于从GAB方程获得的单层值(Kaymak-Ertekin & Sultanoglu,2001;McMinn和Magee(2003);Palou等,1997)。Timmermann等(2001)分析了BET和GAB单层值之间差异的困境,并证明GAB单层含水量比BET更具代表性。

在最近的一篇综述中,Peleg(2020)指出:"食品具有物理水单层的概念已在食品文献中被广泛使用,但食品中是否真正存在水单层的问题从未得到充分解决"。然而,有人提出,水蒸气分子与亲水基团相互作用,而亲水基团在食品和生物材料中大量存在。Peleg(2020)指出,这种对吸附现象的描述很可能是正确的,但他指出水单层的存在仍未得到证实,或许应将其视为猜想而非假设。

早在1945年,Pauling就提出,蛋白质的水吸附单层可以理解为蛋白质侧链氨基酸的每个极性基团上附着一个水分子。在他的分析中,Pauling(1945)使用了Bull(1944)报道的BET单层值,与蛋白质极性基团数量的一致性大致令人满意。Timmermann等(2001)注意到,在Pauling的分析中,单层值在大多数情况下低于极性基团的数量。他们用重新计算的GAB单层值替代了BET值,并加入了Pauling(1945)未考虑的酪蛋白,结果表明Pauling注意到的大致一致性现在确实得到了改善。

我们使用了Timmermann等(2001)收集的数据,并添加了一些关于极性基团数量和GAB单层值的新数据,这些数据对应于胰岛素、血浆白蛋白以及小麦和马铃薯淀粉(Mac Laren & Rowen,1951;Timmermann等,2001)。发现极性基团数量与GAB单层之间存在良好的线性相关性,如图1所示。获得的线性回归(r² = 0.8431)非常接近45°线,表明计算存在于GAB单层中的水分子数量与存在的极性侧链数量之间具有良好的一致性。因此,与各种研究(Gely & Giner,2000;Quirijins等,2005)一致,可以合理地接受GAB单层值提供了关于强吸附到活性位点的水量的信息,表明每个极性基团最初吸附一个水分子。极性基团数量与GAB单层之间的良好线性相关性可能不足以证明给定的物理模型。Peleg(2020)指出,临界数量亲水位点的假设必须得到独立物理证据的支持。然而,正如Pérez-Alonso等(2006)所述,"单层值具有特殊意义,因为它指示了强吸附到特定位点的水量,被认为是食品更稳定的最优值。无论其物理意义如何,这一事实具有很高的实用价值"。

值得注意的是,无定形糖和结晶糖之间众所周知的水吸附行为差异(Iglesias & Chirife,1978)提供了一个例子,说明仅靠亲水基团数量不足以解释水吸附模式。

### 温度对GAB单层值的影响

对大量关于GAB单层值的文献数据进行了综述,但仅选择报告了三个或更多温度下数值的文章用于本次调查。在文献展示的大多数示例中,GAB方程被独立地用于每个温度,从而为每个温度条件生成一组从实验数据估计的C、Mo和k值。

表1总结了70多种食品项目在若干温度下(主要在20-50°C范围内)的GAB单层值(干基百分比)数据。本工作汇编的原料包括:种子(各种)、胶类(瓜尔胶、刺槐豆胶、黄蓍胶、黄原胶)、麦芽糊精、民族食品(葡萄皮革(pestil)、Gulabjamun混合物、奶酪-Puri混合物)、木薯、木薯渣、木薯粉、可可豆、鱼粉、葡萄皮革、多种坚果、蘑菇、马铃薯片、甘薯片、马铃薯、日本面条、枇杷果、榅桒果、酸奶粉、蓝莓粉、蓝莓果渣、大麦、米粉、板栗、饼干、玉米零食、玉米、米饼、猴面包树叶、红辣椒、蚕豆蛋白、辣椒粉、"pinhao"粉、芒果混合粉、大豆分离蛋白、苹果、棉籽仁、棉籽分离蛋白、微胶囊化菜籽油、微胶囊化奇亚籽油、微胶囊化天然色素、微胶囊化辣椒油树脂、微胶囊化甜菜根汁、微胶囊化瑞士奶酪生物芳香粉、鱼粉、罗望子籽黏液、奇亚籽黏液、微胶囊化迷迭香精油、茶、帕玛森奶酪、菠萝粉、蘑菇、饼干、酪蛋白、碎小麦、壳聚糖、橙汁、豇豆和乳清蛋白浓缩物。

图2至9展示了所选产品(来自表1数据)的温度对GAB单层值的影响。将食品分组到不同图中的标准有两个目的:(a)说明GAB单层并非总是随温度升高而降低(如文献中通常所述),但也可能保持恒定或增加;(b)避免数据重叠,否则会使图表非常难以解释。

这些图中显示的单层值没有误差条,因为绝大多数被调查的论文没有提供误差条。仅在少数情况下,作者报告了单层的误差条。例如,Alpizar-Reyes等(2016)指出罗望子籽黏液GAB单层的相对误差范围为±4.5%至±5.9%;Escalona-García等(2016)指出乳清蛋白浓缩物中微胶囊化奇亚油的误差范围为±1.5%至±3.0%,Torres等(2012)报告了几种胶类(CMC、瓜尔胶、刺槐豆胶等)的误差范围为±1.1%至±3.2%。

正如文献中经常报道的那样,对于大多数(但并非全部)被调查产品,GAB单层含水量随温度升高而降低。发现GAB单层随温度的变化率强烈依赖于产品。这可以通过比较甘薯片(图4)和辣椒粉(图7)的行为来观察,它们表现出急剧下降,而其他如麦芽大麦(图2)、酸奶粉(图3)、茉莉香米饼(图4)、瓜尔胶(图6)和日本面条(图7)则表现出较为温和的下降。

其他产品显示GAB单层与温度无关(或几乎无关)。饼干和玉米零食(图2)、黄蓍胶、刺槐豆、DE10麦芽糊精(图5)、微胶囊化辣椒油树脂(图6)、CMC(图7)、苹果、菠萝粉、棉籽分离蛋白(图8)以及茶和苹果(图9)就是这种情况。最后,还有一些产品中GAB单层随温度升高而增加,如鱼粉(图3)、微胶囊化奶酪生物芳香物、微胶囊化多香果油(图8)和百香果汁微胶囊(图9)。

总之,尽管在表1和文献(Gely & Giner,2000;Quirijns等,2005;Domínguez等,2007)中显示的大多数情况下GAB单层随温度升高而降低,但不能想当然,因为如本文所示,GAB单层也可以随温度保持恒定甚至增加。

Iglesias和Chirife(1984)分析了温度对食品BET单层值的影响,并报道BET值大多随温度升高而降低。他们提出了以下经验模型来关联BET值与温度:

ln Mo(BET) = p + a·T

其中Mo(BET)为BET单层含水量(g水/100g干固体),T为温度(°C),p和a为常数。Iglesias和Chirife(1984)指出,温度对BET值的相对影响在不同食品之间差异很大。例如,某些水果(香蕉、菠萝、桃子)的BET值在25至40°C之间降低了约21-35%,而鸡蛋在相同温度区间内仅降低了3%。在某些情况下,公式(1)无法再现BET值随温度的行为。Iglesias和Chirife(1984)提出,BET值随温度的相对变化取决于食品的理化性质以及达到吸附平衡所需的时间。反过来,平衡时间依赖性取决于构建等温线所使用的实验装置。

这一推理也适用于本文综述的结果。表1中显示的大多数情况来自使用已知重量法测定的吸附等温线,其中食品样品被放入含有不同饱和盐溶液的玻璃/塑料干燥器中。然后将干燥器置于恒温培养箱中,在所需温度(通常在20至50°C之间)下保持直至达到平衡含水量。报告的平衡时间范围约为15至50天。在这些时间段内,相对较高温度下的水活度平衡可能导致样品的物理和化学劣化,这反映在可用吸附位点上。这些反应可能包括非酶褐变、变性、交联以及天然或变性蛋白质与氧化脂质或碳水化合物的相互作用,以及温度诱导的结构修饰。因此,通过上述一种或多种机制改变水结合亲水位点的可用性会导致温度升高时GAB单层值的改变:降低、增加或保持恒定。

Romani等(2015)研究了包装饼干在35°C下储存长达92天的影响,并使用快速动态露点等温线(DDI)测定吸附等温线,其平衡时间远小于传统的静态重量法。观察到通过DDI方法测得的储存饼干吸附等温线受到先前35°C储存时间的影响。单层含水量(此情况下为BET单层)从储存开始到结束从1.473显著增加到2.080 g水/100g干基。作者将饼干储存期间单层值的增加归因于水结合活性位点的增加,这是由产品老化引起的主要成分(鸡蛋、淀粉、糖、脂质、蛋白质)化学和物理变化的结果。

Iglesias和Chirife(1978)测定了预先在三种不同温度(30°C、55°C和70°C)下干燥的预煮牛肉在30°C下的水吸附等温线。他们发现干燥温度越高,干燥牛肉的吸附能力越低,并报道BET单层中的水量受30、55或70°C先前干燥温度的影响,分别从5.4降至5.1和4.5(非脂肪干基百分比)。

通常,GAB模型被独立地用于每个温度,从而为每个温度条件生成一组从实验数据估计的C、Mo和K值。另一种选择是引入参数的温度相关表达式,产生更多常数,用整组等温线进行估计(Staudt等,2013)。因此,多位作者(Martín-Santos等,2012;Quirijns等,2005;Shirkole等,2019)提出Mo与使用以下Arrhenius型方程的温度相关:

其中Mo'为指前因子,ΔHm为Arrhenius型能量因子。然而,GAB单层随温度的复杂实验行为(降低、恒定或增加)(图2-10)可能无法用公式(3)充分预测。

### 吸附积分熵与GAB单层

食品中水蒸气吸附的热力学引起了关注,因为它可以提供对吸附现象更透彻的解释并有助于理解其机理(Beristain等,2002)。众所周知,低水分食品的稳定性在很大程度上取决于其水分吸附特性,一些研究者认为(Bonilla等,2010),水蒸气吸附的热力学也可能为预测脱水食品的稳定性和储存寿命提供科学标准。近年来,脱水产品中水吸附热力学的研究已成为多项研究的主题(Pérez-Alonso等,2006;Silva等,2015;Escalona-García等,2016;Faria Freitas等,2016;Viganó等,2012;Xiao & Tong,2013;Moreira等,2008)以及许多其他研究。各种研究报告了多种食品的积分熵曲线相对于含水量的图显示出一个明确的最小值,并将其解释为对应于单层的含水量,因为完整单层对应于系统的小数量构型(Beristain等,1994;Bertuzzi等,2003;Nunes & Rotstein,1991;Xing等,2012)。许多作者指出,熵的降低与水分子失去流动性有关,随后随着水通过形成多个"层"而重新获得流动性,熵增加。积分熵可以定性地解释为吸附水分子的有序/无序和随机性,并且可以假设与形成单层所需的含水量重合,其中吸附物和吸附剂之间发生强键合。文献报道使用最小积分熵点作为预测脱水食品最大稳定性点的工具(Bonilla等,2010)。这将在本综述后面讨论。

吸附的热力学分析需要不同温度下的等温线知识,主要使用20-40°C或25-45°C范围内的三条等温线。食品中水吸附热力学函数的分析已被许多作者详细描述(Beristain等,1994;Kumagai等,1994;Xing等,2012),包括吉布斯自由能(ΔG),其中T为绝对温度(K);R为通用气体常数(J·mol⁻¹·K⁻¹);aw为水活度。水吸附引起的自由能变化通常伴随着焓和熵的变化。然后可以计算微分和积分焓(ΔH)和熵(ΔS)。吸附焓是从等温线温度依赖性导出的微分量,而积分焓是该水平上已结合的所有水分子的平均能量。各自的微分和积分熵分别从微分和积分焓获得。Pérez-Alonso等(2006)、Tolaba等(1997)、Domínguez等(2007)、Bonilla等(2010)和Rodríguez-Bernal等(2015)等描述了食品原料中水吸附的微分和积分热力学函数的计算。

如Bonilla等(2010)所指出的,积分熵的变化由以下公式计算:

大量文献研究报告了积分熵相对于含水量的最小值,并进行了综述以验证该最小值是否确实出现在GAB单层附近。仅选择那些同时报告了积分最小熵和GAB值的研究用于本综述,使用了约五十篇具有适当数据的合格文章。

如上所述,水吸附的净积分熵通常随含水量增加而逐渐降低至单层含水量附近的最小值,然后随含水量进一步增加。尽管熵的最小值可能是唯一的,但存在一些食品产品,其中该最小值在定义的含水量范围内变化不大(Beristain & Azuara,1990)。例如,Rascón等(2015)指出,对于Capsul(改性淀粉)中包封的辣椒油树脂,该区域从5.89 g水/100g可溶性固体的含水量开始,到6.94 g水/100g可溶性固体的含水量结束。Bonilla等(2010)报道,对于乳清蛋白,25°C时最小积分熵处的微胶囊含水量为6.38%(干固体),但积分熵保持大致恒定的含水量范围为5.10-6.52%(干基)。

图10显示了从文献获得的39对值的MIE对应含水量与GAB单层的图。由于这些值在大多数情况下是在3个温度下报告的(主要是25-45°C),这里使用了平均值。可以看出,两个参数之间存在线性关系,回归线接近45°对角线(图10),具有相当可接受的相关系数(r² = 0.9089)。两个变量的含水量之间的关系由公式(6)给出:

这表明GAB单层接近MIE区域的含水量。

Delgado等(2014)指出,在某些情况下,热力学分析与GAB模型获得的单层不一致,通常最小积分熵点高于GAB单层。在本综述检查的几种产品中也观察到了这种行为。31对文献值(未包括在图10中显示的那些)绘制在图11中。回归线现在远离45°对角线,数据分散反映在较低的r²值(0.8024)中。两个变量的含水量之间的关系由公式(7)给出:

这表明对于这些产品,最小积分熵处的含水量显著高于GAB单层。

一些作者认为最小积分熵是最大稳定性的点(Pérez-Alonso等,2006)。然而,当最小积分熵点的含水量显著高于GAB单层时,关于最小熵作为稳定性点的有效性存在不确定性。

在现阶段,我们倾向于不考虑稳定性方面,因为"稳定性"是许多变化的总和,如微生物腐败、氧化、酶和非酶反应、质地、脆度以及与玻璃化转变相关的其他物理变化(粘性、塌陷、结晶)(Roos,1995)。反过来,这些变化以不同方式取决于食品含水量。尽管如此,需要对稳定性进行一些一般性评论。

没有直接原因可以解释为什么在一组食品(图10)中,最小积分熵点的含水量接近GAB单层,但在另一组食品和食品原料(图11)中,MIE的含水量显著高于GAB单层。诚然,食品是生物聚合物、水和溶质的异质混合物。因此,MIE含水量与GAB单层之间的正相关或负相关可能是由于所检查食品系统的组成和结构差异。根据Viganó等(2012),具有相同化学成分和不同微观结构的食品可能表现出不同的水分吸附行为,从而影响结果。他们研究了通过振动流化干燥(VFD)、喷雾干燥(SD)、冷冻干燥(FD)或真空干燥(VD)生产的菠萝粉的水吸附热力学,并报道最小积分熵处的含水量(以及因此aw)取决于所使用的干燥方法;例如,VD为6.8%(干基),而VFD急剧增加到18.9%。他们指出这种差异是由于脱水过程中产品微观结构的变化引起的,并且通过SD和VFD生产的粉末在变化的aw下更稳定,因为它们在较高含水量下呈现最小熵。然而,这一说法应谨慎对待,因为它未经实验证实。GAB单层对这些微观结构变化的敏感性低于MIE。比较VFD和VD,GAB单层变化了约67%,而MIE经历了178%的变化。

Sánchez-Sáenz等(2011)研究了多香果油在乳清蛋白浓缩物、mesquite胶和麦芽糊精混合物中的包封,并报道微胶囊最大稳定性(最小积分熵)的条件对应于25°C时aw = 0.713或35°C时aw = 0.657。必须注意,25°C时aw 0.713可能允许嗜干性真菌在储存期间生长,尽管缓慢。类似地,Bonilla等(2010)将菜籽油包封在大豆分离蛋白中,并报道35°C时稳定性(最小积分熵)的水分条件对应于aw = 0.71;同样,该aw也将允许某些嗜干性真菌生长。Azuara-Nieto和Beristain-Guevara(2007)报道最小积分熵预测在30°C时,粉末乳清蛋白的最大稳定性将在aw = 0.50下储存时发生,但他们未经实验证实这一说法。

需要更多研究来确定热力学方法是否有助于预测食品和食品原料的储存稳定性。本综述引用的一些研究实验证实了MIE与所研究产品稳定性之间的关系。但在其他情况下,情况并非如此,或未经实验证实。

## 结论

重新检查了蛋白质中水吸附化学计量学的旧数据,但添加了一些其他生物聚合物的新值,证实了计算存在于GAB单层中的水分子数量与极性基团数量之间存在良好的相关性(r² = 0.8413)。这重新证实了Pauling的旧假设,即每个极性基团最初吸附一个水分子。

对70多种不同食品项目进行的文献调查允许收集不同温度下的GAB单层值。尽管文献中通常报道GAB值随温度升高而降低,但不能想当然,因为如本文所示,单层也可以随温度保持恒定甚至增加。

最小积分熵(MIE)与GAB单层之间关系的研究表明,对于38种不同食品,最小积分熵对应的含水量与GAB单层之间观察到良好的一致性。然而,对于其他食品,两个参数之间的回归曲线表明最小积分熵对应的含水量显著高于GAB单层。本综述的结果可能有助于支持将GAB单层值用作食品稳定性多方面的适当含水量。此外,它可能促进关于GAB单层与最小积分熵之间关系以及后者在预测低水分食品稳定性中的实际作用的额外研究。

**资助** 阿根廷天主教大学工程与农业科学学院和ANPCyT(项目PICTO UCA 2017-0071)提供了资金支持。

**声明**

**利益冲突** 作者声明无利益冲突。