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Keywords: Recent research has shown exponentially increased thermal resistance of pathogenic bacteria at a reduced water
Food safety activity (aw) in thermal treatments. However, information on aw change as affected by food components at high
Low-moisture food temperatures is limited. The objective of this project was to quantify the influence of major food components on
Clausius-clapeyron equation aw changes in low-moisture foods at elevated temperatures. Corn starch, soy protein, coconut, and cheddar
cheese powders were selected as high-carbohydrate, high-protein, high-fat, and intermediate products. Vacuum
dried powders were equilibrated in the jars containing saturated salt solutions to different aw from 0.11 to 0.84
at 25 °C. The aw of food powders were measured from 25 to 80 °C in hermetically sealed test cells using hight-
temperature humidity sensors. For a given initial aw, high-carbohydrate product had more considerable aw
increase than high-protein, intermediate, and high-fat foods with increasing temperature. The net isosteric heat
of sorption increased from high-fat, intermediate, high-protein, to high-carbohydrate food at same moisture
content. These relationships support findings in the literature that bacterial cells are more easily inactivated in
high-carbohydrate and high-protein products than in high-fat foods. Understanding the correlation between food
components and aw change at elevated temperatures helps predict the thermal resistance of bacteria in low-
moisture foods.
∗
Corresponding author.
E-mail address: jtang@wsu.edu (J. Tang).
https://doi.org/10.1016/j.lwt.2019.108257
Received 26 April 2019; Received in revised form 8 June 2019; Accepted 10 June 2019
Available online 11 June 2019
0023-6438/ © 2019 Published by Elsevier Ltd.
Y. Jin, et al. LWT - Food Science and Technology 112 (2019) 108257
Tadapaneni, et al., 2016). We hypothesized that, because of the small macro-nutrient is not very clear. Further evaluation of qst as influenced
bacterial cell size, moisture diffusion between vegetative bacteria and by Xw and food components is required.
their micro-environment within food matrices allowed those cells to This research selected corn starch, soy protein, cheddar cheese, and
rapidly adjust their moisture content in response to aw change in the coconut milk powders, to study the food component influence on the aw
food during a thermal treatment (Syamaladevi, Tang, & Zhong, 2016). and qst in low-moisture foods at elevated temperatures. Clausius-
Thus, the influence of food components on thermal resiatnce of bac- Clapeyron equation was utilized to develop predictive models for qst as
teria, in particular vegetatives cells, in low-moisture foods is dictated influenced by Xw in four food powders.
mainly by how those components influence the water activity of the
overall food matrices at the treatment temperatures. Consequently, we 2. Material and methods
considered the aw of a food at treatment temperatures, rather than at
room temperature, as a key factor influencing the thermal inactivation 2.1. Food materials
of bacteria (Liu, Tang, Tadapeneni, Yang, & Zhu, 2018; Tadapaneni, Xu,
Yang, & Tang, 2018; Xu et al., 2019). For example, Xu et al. (2019) Four food systems were used: corn starch (Great Value™,
reported that when wheat flour at aw 0.45 at 20 °C was heated to 80 °C, Bentonville, AR), soy protein (GNC, Pittsburgh, PA), cheddar cheese
its aw increased to 0.68, and the corresponding D-value of Salmonella powder (Anthony's, Glendale, CA), and coconut milk powder (Z.
Enteritidis PT 30 was determined to be 4.9 min. But when almond flour Natural Foods, West Palm Beach, FL). The proximate composition of
at aw 0.45 at 20 °C was also heated to 80 °C, its aw became 0.54, and the food matrices was determined following standard analytical methods
corresponding D-value was 21.2min, more than four times as much as (AOAC, 2012).
in wheat flour. The significant difference in D-value for the same bac-
terium in two different flours preconditioned to the same aw at 20 °C 2.2. Equilibration of food powders
was attributed to the 0.14 aw difference at 80 °C (Xu et al., 2019). Liu
et al. (2018) established a log-linear relationship between the D-values The equilibration procedures followed Tadapaneni et al. (2017).
of both Salmonella Enteritidis PT 30 and Enterococcus faecium and the aw Food samples were dried at 25 °C under 10 kPa in a vacuum oven for
of wheat flour and silicon dioxide at elevated temperatures. Such a approximately seven days to reach the final aw of less than 0.1 at 25 °C.
relationship was further confirmed for Salmonella Enteritidis PT 30 in Dried samples were then conditioned in jars containing saturated salt
almond flour and wheat flours using two different test methods (Xu solutions for approximately ten days. The saturated salts LiCl,
et al., 2019). Thus, it is critical to quantify aw changes in different food CH3COOK, MgCl2, K2CO3, MgNO3, NaNO2, NaCl, and KCl were utilized
products at elevated temperatures as a first step for developing effective to generate relative humidities (RH) of 11.3%, 22.5%, 32.8%, 43.2%,
thermal treatments for low-aw foods, when the food is treated in a 52.9%, 65.8%, 75.3%, and 84.3% at 25 °C, respectively. Toluene solu-
closed system. tion in small open containers was placed in the 75.3% and 84.3% jars to
Tadapaneni, Yang, Carter, and Tang (2017) utilized a specially de- prevent fungal and mold growth in food samples. The aw of the samples
signed high-temperature cell to study the aw change in different food was measured by the aw meter (Aqualab, Meter Group, Inc., Pullman,
products at elevated temperatures. The high-temperature cell consisted WA) at 25 °C to verify that they were equilibrated. The Xw of samples in
of an aluminum cup and lid with a capacitance-based relative humidity the jars with different RH were measured by a halogen moisture ana-
and temperature sensor (Honeywell HumidIcon™, Morristown, NJ) lyzer (Mettler-Toledo, LLC, Columbus, OH) in two replicates.
(Tadapaneni et al., 2017). It was proven to be a reliable tool for mea-
suring the aw of food samples at high temperatures (Tadapaneni et al., 2.3. Determination of aw at elevated temperatures
2017). Tadapaneni et al. (2017) reported that the shift of aw at high
temperatures was highly dependent on food components, and the aw of The high-temperature cell (METER Group, Inc., Pullman, WA) was
food products with hydrophilic macromolecules increased with in- utilized to measure the aw of samples at elevated temperatures. The
creasing temperature. However, data on aw shift at high temperatures commercial test cell was based on the concept presented in
in different food products in the literature is limited. .Thus, it ise ne- Syamaladevi, Tadapaneni, et al. (2016) and also used in Tadapaneni
cessary to further research to quantify the influence of food component et al. (2017). Each conditioned sample was placed into the aluminum
on the aw change at elevated temperatures. cup, and then the high-temperature cell was sealed to prevent leakage.
The change of aw with temperature in a given food product can be The high-temperature cell was immersed in a glycol bath (Isotemp 5150
described by the Clausius-Clapeyron equation (Labuza, 1968; Labuza, H11, Fisher Scientific, Waltham, MA) at 25, 30, 40, 50, 60, 70, and
Kaanane, & Chen, 1985) (see Eq. (1) below). The net isosteric heat of 80 °C. The RH value at each temperature level was recorded when the
sorption (qst) is an important parameter in the Clausius-Clapeyron sample reached an equilibrium state with no RH change for a significant
equation and is unique for each food product at a specific moisture time (approximately 30 min). Two replicates were performed for each
content (Xw) (Eq. (2)). The qst equals to the total enthalpy change for the food sample. The aw of the food sample is calculated as RH value/100.
sorption process minus the specific latent heat of vaporization (Labuza
et al., 1985; Tadapaneni et al., 2017). It is a thermodynamic property in 2.4. Clausius-Clapeyron equation
evaluating the energy requirement of dehydration (Labuza et al., 1985;
Tadapaneni et al., 2017). Generally, the qst value was inversely related Data was fit into the Clausius-Clapeyron equation (Labuza, 1968):
to the Xw of a food product. For example, qst decreased from 15.2 to
a q 1 1
0 kJ/mol as Xw increased from 0.022 to 0.100 g H2O/g dry solids in ln ⎛ w1 ⎞ = − st ⎛ − ⎞
⎜ ⎟ ⎜ ⎟
almond flour (Tadapaneni et al., 2017). Also, food components can ⎝ a w2 ⎠ R ⎝ T1 T2 ⎠ (1)
affect the qst value. For example, the carbohydrate-rich wheat flour had where aw1 and aw2 are the water activity of a food sample with a certain
higher qst than protein-rich non-fat milk powder and fat-rich almond moisture content at temperatures T1 and T2 (K), R is the universal gas
flour under the same Xw (Tadapaneni et al., 2017). The qst is an im- constant: 8.314 J/(mol*K), qst is the net isosteric heat of sorption (J/
portant parameter which can provide information on understanding the mol) for the food sample.
sorbed moisture status in foods and physiochemical and micro- The net isosteric heat of sorption is different for the food sample at
biological stability kinetics at specified storage and process settings different moisture content with an empirical relation (Zuo, Rhim, &
(Tadapaneni et al., 2017). However, the mechanism of macro-nutrient Lee, 2015):
(carbohydrate, protein, fat) influence on the value of qst is seldomly
reported in previous literature. The connection between qst, Xw, and q st = a exp(−b Xw ) (2)
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Y. Jin, et al. LWT - Food Science and Technology 112 (2019) 108257
Table 1 milk powder. For example, at the same initial aw of 0.12, the Xw were
Proximate composition of food samples in g/100 g dry solids. 0.015, 0.028, 0.045, and 0.089 g H2O/g dry solids, respectively, in
Corn Soy protein Cheddar cheese Coconut milk coconut milk powder, cheddar cheese powder, soy protein, and corn
starch powder powder starch. High-carbohydrate and high-protein foods contained more hy-
drophilic macromolecules than high-fat foods (Foster, Bronlund, &
Ash < 0.1 4.5 12.1 3.1
Paterson, 2005; Labuza, 1977; Labuza & Altunakar, 2007), which ex-
Carbohydrates 98.0 < 0.1 47.6 26.3
Fat 0.9 2.4 18.4 63.8
plained the high Xw in corn starch and soy protein. At high-aw level
Protein 1.0 93.1 21.9 6.8 larger than 0.66, cheddar cheese powder showed higher Xw, for its
strong moisture absorption ability.
The moisture sorption isotherms at 25 °C of corn starch and soy
where a and b are the constants, and Xw is the moisture content g H2O/g protein powder resembled sigmoid-shaped curves. Two bending regions
dry solids. between aw 0.2 to 0.4, and 0.6 to 0.7 were found. The bends could be
Model estimations and statistical analysis in this research were the results of physical and chemical changes in samples during the
performed in Microsoft Excel (16.10, Microsoft, WA, USA). adsorption process (Labuza & Altunakar, 2007). For intermediate
cheddar cheese powder and high-fat coconut milk powder, the moisture
3. Results and discussion sorption isotherms were concaves upward. Moistures were low at low
water activities, and became high after aw 0.6, due to its surface effect
3.1. Proximate composition (moisture gain was low at low aw, the surface of crystalline components
dissolved to absorb more moisture at high aw) (Labuza & Altunakar,
The proximate composition of corn starch, soy protein, cheddar 2007).
cheese powder, and coconut powder is shown in Table 1. The corn
starch samples had 98.0 g carbohydrate/100 g dry solids and could 3.3. aw at elevated temperatures
represent the high-carbohydrate food product. The soy protein con-
tained 93.1g protein/100 g dry solids and was selected as the high- Changes of aw in corn starch of different Xw with temperature are
protein product. The coconut milk powder consisted of 63.8g fat/100 g shown in Fig. 2. The aw increased with increasing temperature at each
dry solids and could be regarded as a high-fat food. The cheddar cheese fixed Xw. For example, at the Xw of 0.110 g H2O/g dry solids, the aw
powder was the intermediate food product with 47.6 g carbohydrates, shifted from 0.23 to 0.43 as temperature increased from 25 to 80 °C.
18.4g fat, and 21.9 g protein per 100 g dry solids. Temperature influence on aw change was more significant in samples
with low and intermediate Xw. For example, the aw of corn starch with
3.2. Moisture content and aw Xw of 0.089g H2O/g dry solids increased from an initial 0.12 to 0.30
when heated from 25 to 80 °C, while the aw of corn starch with Xw of
The relationships between equilibrium aw and Xw of the conditioned 0.215 g H2O/g dry solids increased from an initial 0.84 to 0.93.
samples at 25 °C, commonly referred to as moisture sorption isotherms, Temperature dependent changes in aw for soy protein samples of
are summarized in Fig. 1. The Xw increased with increasing aw in the different Xw are shown in Fig. 3. The aw also increased with increasing
four products. Between the low-aw range of 0.12–0.53, high-carbohy- temperature. Again, aw changed more in low Xw samples. For example,
drate corn starch had the highest Xw, followed by high-protein soy the aw in soy protein samples with Xw of 0.045 g H2O/g dry solids in-
powder, intermediate cheddar cheese powder, and high-fat coconut creased from 0.12 to 0.25 as temperature increased from 25 to 80 °C,
Fig. 1. Relationships between equilibrium aw and Xw (g H2O/g dry solids) of corn starch, soy protein, cheddar cheese powder, and coconut milk powder at 25 °C
(n = 2).
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Y. Jin, et al. LWT - Food Science and Technology 112 (2019) 108257
Fig. 2. The estimated (lines) and experimental (scattered dots) aw values of corn starch at different Xw (g H2O/g dry solids) (n = 2).
while the aw in samples with Xw of 0.214 g H2O/g dry solids increased are composed mostly of hydrophilic macromolecules, it was explainable
from 0.84 to 0.86. Similar trends were also found in cheddar cheese that these two products had relatively more aw increase when heated
powder (Fig. 4). than intermediate cheddar cheese, and high-fat coconut milk powders.
The aw change for coconut milk powder, a high fat product, is The level of increase in aw mainly depends on the amount of hydro-
shown in Fig. 5. Very interestingly, the aw in coconut milk powder in- philic groups that exist in food samples (Labuza, 1977; Labuza &
creased with increasing temperature at Xw only between 0.015 and Altunakar, 2007). Carbohydrates usually consist of more hydrogen
0.021 g H2O/g dry solids and became relatively stable at higher Xw bonds per monomer than proteins (Labuza & Altunakar, 2007), so corn
range. starch had a larger aw change than soy protein as temperature in-
Temperature could affect molecular water mobility and dynamic creased. Fats are generally hydrophobic and do not contribute much to
equilibrium of vapor and absorbed phases in foods (Kapsalis, 1981; moisture sorption (Labuza & Altunakar, 2007), so coconut cheese
Labuza, 1970). Previous reports also showed that temperature influence powder had the lowest aw change among the four products.
on aw change is larger at lower to intermediate Xw of a food sample Recently published research indicated exponentially increased
(Labuza & Altunakar, 2007). Similar phenomena were reported by thermal resistance of bacteria at reduced aw determined at treatment
Tadapaneni et al. (2017) that the aw in wheat flour, non-fat milk temperature (Liu et al., 2018; Xu et al., 2019). In Xu et al. (2019), the
powder, and almond flour showed less increase at higher Xw. aw of food samples was measured at 80 °C, and the zaw-value at 80 °C for
For a given initial aw at 25 °C, high-carbohydrate corn starch had Salmonella Enteritidies PT 30 was 0.32. According to Xu et al. (2019), D-
more considerable aw increase with increasing temperature than high- value at 80 °C could be calculated for any food matrices if the aw at
protein soy powder, intermediate cheddar cheese powder, and high-fat 80 °C was given. For example, at the same initial aw of 0.53 at 25 °C, the
coconut milk powder. For example, at the same initial aw of 0.53 at aw of corn starch, soy protein, cheddar cheese powder, and coconut
25 °C, the aw increased to 0.68, 0.63, 0.58, 0.53 for corn starch, soy milk powder were 0.68, 0.63, 0.58, and 0.53 at 80 °C, respectively. The
protein, cheddar cheese powder, and coconut milk powder, respec- corresponding D-values for Salmonella Enteritidis PT 30 in corn starch,
tively, when the samples were heated to 80 °C (Figs. 2–5). The increase soy protein, cheddar cheese powder, and coconut milk powder at 80 °C
in aw is a result of . heat induced breakage of molecular bonds between were calculated to be 4.74, 6.81, 9.78, and 14.05 min, respectively. As
water molecules and hydrophilic groups (Foster et al., 2005; Labuza, the aw increased the most in high-carbohydrate corn starch, followed by
1977). As high-carbohydrate corn starch and high-protein soy powder high-protein soy powder, intermediate cheddar cheese powder, and
Fig. 3. The estimated and experimental aw values of soy protein at different Xw (g H2O/g dry solids) (n = 2).
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Y. Jin, et al. LWT - Food Science and Technology 112 (2019) 108257
Fig. 4. The estimated and experimental aw values of cheddar cheese powder at different Xw (g H2O/g dry solids) (n = 2).
The relationships between qst and Xw of the four food powders are
shown in Fig. 6, and the parameters for Eq. (2) are listed in Table 2. The
value of qst reflects the strength of bonds between water molecules and
food solids, in comparison with that among free water molecules. It is
positively related to the total enthalpy change for the sorption process
(Labuza, 1985; Labuza & Altunakar, 2007; Tadapaneni et al., 2017).
The values of qst obtained in our study were negatively correlated to Xw
in each food product. For example, the qst decreased from 7.9 to 0.5 kJ/ Fig. 6. Net isosteric heat of sorption for corn starch, soy protein, cheddar
mol as Xw increased from 0.045 to 0.214 g H2O/g dry solids in soy cheese powder, and coconut powder.
protein. The qst values were highest at the lowest Xw in the four food
products, indicating the strong attractive forces between water mole- At an identical Xw, the qst was highest in high-carbohydrate corn
cules and food molecules at the monolayer (Abdenouri, Idlimam, & starch, followed by high-protein soy powder, cheddar cheese powder,
Kouhila, 2010; Labuza, 1977; Lim, Tang, & He, 1995). More energy was and high-fat coconut powder (Fig. 6). This trend was consistent with the
required to break the bonds in low-moisture food compared to the same data for equilibrium aw and Xw data, where aw increased from corn
food product with relatively high Xw (Abdenouri et al., 2010; Labuza, starch, soy protein, cheddar cheese powder, to coconut powder at the
1977; Lim et al., 1995).
Fig. 5. The estimated and experimental aw values of coconut powder at different Xw (g H2O/g dry solids) (n = 2).
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Y. Jin, et al. LWT - Food Science and Technology 112 (2019) 108257
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Y. Jin, et al. LWT - Food Science and Technology 112 (2019) 108257
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