Food Chemistry 400 (2023) 134039

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Development of a calcium hydroxide–dye kimchi ripening indicator and its

application in kimchi packaging
Hyun-Gyu Lee , Suyeon Jeong , SeungRan Yoo *
World Institute of Kimchi, Gwangju 61755, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Intelligent packaging that provides real-time information on food quality is useful for consumers. We developed a
Intelligent packaging kimchi ripening indicator that can determine the ripeness of kimchi inside packaging and evaluated its appli­
Kimchi quality cability and limitations. The indicator was made using calcium hydroxide, which captures CO2, and four pH-
Fermentation
sensitive dyes (cresol red, bromothymol blue, bromocresol purple, and methyl red). Fourier-transform infrared
Carbon dioxide
Indicator films
spectra of the prepared powders showed shapes similar to that of calcium hydroxide, and the dyes were evenly
distributed on the calcium hydroxide surfaces. When the developed indicators were evaluated for kimchi
packaging application, the indicator made from synthesized calcium hydroxide and bromothymol blue was the
most reliable and clearly reflected useful kimchi ripening information. The indicator developed in this study is
judged to be practically usable at temperatures of 4–15 ◦ C. However, its usefulness is limited in that the seller
cannot change the packaging capacity or kimchi capacity.

1. Introduction
Food packaging protects against physical, biological, and chemical
damage from the external environment and allows food to be stored for
an extended period with efficient loading characteristics (Yildirim et al.,
2018). As the quality of life improves in modern society, consumers
expect a variety of functions beyond the conventional function of
packaging. Accordingly, intelligent packaging is being developed to
provide consumers with quality information about packaged food
(Rukchon et al., 2014). Intelligent packaging includes pH or gas sensing
technology, time–temperature indicators, and information transmission
technology using barcode labels or tag recognition (Choi & Han, 2018).
This intelligent packaging notifies consumers about changes in the food
quality status inside the packaging by showing a visual change outside
(Zajko & Klimant, 2013). The most common intelligent packaging uses
time–temperature indicators, which indirectly display information
about the food quality and its remaining shelf life by monitoring the
temperature accumulation of the product (Gao et al., 2020). However,
indirect prediction methods are at a disadvantage when attempting to
accurately predict the quality of the food. Recently, intelligent
packaging technology that uses food indicators to directly and accu­
rately monitor food quality has been actively developed (Choi & Han,
2018).
Kimchi is a traditional Korean food made by mixing and fermenting
various vegetables. The taste and quality characteristics of kimchi
depend on the ingredients and fermentation conditions (Lee et al.,
2019). Kimchi is recognized as a living food because its taste and quality
also change over time as it undergoes a complex fermentation process
involving various enzymes and microorganisms (Ko et al., 2009). Unlike
in the past, when kimchi was made and eaten at home, an increasing
number of consumers are buying kimchi at supermarkets (Kim & Yoon,
2012). However, because the taste and quality characteristics of kimchi
change during fermentation, consumers face difficulties in choosing and
purchasing kimchi. The flavor of kimchi is created by the metabolic
activity of microorganisms (Hong et al., 2016). At the beginning of
fermentation, the dominant species are microorganisms that are widely
distributed in the natural environment, but as fermentation progresses,
the microbial community is simplified to lactic acid bacteria such as
Leuconostoc sp. and Lactobacillus sp. (Lee et al., 2019). Lactic acid bac­
teria ingest the saccharides in kimchi and produce metabolites such as

Abbreviations: BP, bromocresol purple; MR, methyl red; CH, calcium hydroxide; CR, cresol red; BB, bromothymol blue; EDS, energy dispersive X-ray spectrometry;
FTIR, Fourier-transform infrared; LLDPE, linear low-density polyethylene; PE/EVOH/Ny, polyethylene/ethylene vinyl alcohol/nylon; PET, polyethylene tere­
phthalate; SEM, scanning electron microscopy; TCD, total color difference; TGA, thermogravimetric analysis.
* Corresponding author.
E-mail addresses: gtguy05@wikim.re.kr (H.-G. Lee), syjeong@wikim.re.kr (S. Jeong), sryoo@wikim.re.kr (S. Yoo).

https://doi.org/10.1016/j.foodchem.2022.134039
Received 30 March 2022; Received in revised form 24 August 2022; Accepted 24 August 2022
Available online 27 August 2022
0308-8146/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
H.-G. Lee et al.
organic acids and CO2. These metabolites lower the pH, making the
kimchi acidic (Jung et al., 2011). Thus, fermentation during distribution
acidifies kimchi. This plays an important role in the taste and quality of
the kimchi and influences consumer purchases. As the acidification of
kimchi can be confirmed by the pH and acidity, these are important
quality indices. The pH and acidity are affected by lactic acid bacteria
metabolites, and because it is continuously generated during lactic acid
bacteria fermentation, CO2 can be used as an important predictor of
kimchi quality (Moon et al., 2020).
Because food is vulnerable to environmental factors during storage
and distribution, various storage technologies have been applied to
lengthen the shelf life of food and allow wide distribution. Fermented
foods, such as kimchi, are especially affected by environmental factors
because they are naturally fermented by microorganisms. Foods affected
by environmental factors undergo changes in their physical, chemical,
and microbial characteristics and these characteristic changes serve as
quality indicators to determine whether food can be distributed. Simi­
larly, the quality of kimchi can be confirmed by changes in its physical,
chemical, and microbial characteristics. As reported by Hong Park &
Koo (1996) and Hong Park & Park (1996), the sourness (ripening) that is
correlated with consumer purchase choices can be confirmed by pH and
acidity analysis. However, because kimchi is fermented naturally, it may
be difficult to distinguish between ripening and over-ripening using the
available analytical methods (Baek et al., 2020). In addition, it is time-
consuming and expensive to perform characteristic analyses. Therefore,
it is necessary to develop intelligent packaging technology that displays
ripening information in real-time without the need for expensive quality
analysis and provides this information easily through visual
presentation.
The gas composition inside food packaging may change continuously
as various gases are generated by the food. Intelligent packaging can
detect gases (e.g., CO2, volatile compounds, and H2S) to monitor the
quality of the food in the packaging and presents this information in a
visual form (Lee et al., 2019). Fermented foods, such as kimchi,
constantly generate CO2 via their microbial metabolism, affecting their
quality. Accordingly, technology to monitor fermented food quality by
detecting CO2 that includes is continuously being developed (Choi &
Han, 2018). CO2-detecting technology includes electrochemical sensors
and colorimetric indicators. Although electrochemical sensors are
capable of sensitive and rapid CO2 detection, they are not readily used in
food packaging because of the need to damage the packaging and for an
appropriate reading device. In contrast, colorimetric indicators are
being extensively developed because they detect and display the gas
concentration inside the packaging so that it can be checked with the
naked eye without a specialized device (Lyu et al., 2019). Research into
intelligent packaging that detects CO2 and displays the ripeness of
kimchi through visual changes is being actively conducted, as outlined
below.
Many colorimetric indicators are being investigated for use in
intelligent packaging for kimchi. They work by employing a pH-
sensitive dye that reacts with CO2 to cause a decrease in pH and a cor­
responding color change. For pH-sensitive dyes, chemical dyes that are
highly reactive and show a distinct color change are the most easily used
(Baek et al., 2018). In addition, the development of colorimetric in­
dicators using natural dyes to address safety and environmental con­
cerns is also being actively studied (Zeng et al., 2019). In addition, a
study has been conducted on the development of an indicator using pH-
induced changes in the transparency of chitosan (Jung et al., 2013).
Despite these studies, a colorimetric indicator for kimchi packaging has
not yet been commercialized. For a commercialized colorimetric indi­
cator, it is necessary to have a clear color change that can be easily
identified by consumers. In addition, ripening kimchi is distributed
across various environments, and the color change of the colorimetric
indicator should correspond. Therefore, in this study, various indicator
films and indicators for kimchi packaging were developed using chem­
ical dyes with distinct color changes. The selected indicator was applied
2
Food Chemistry 400 (2023) 134039
to kimchi packaging according to the likely distribution temperature
conditions. The distribution temperatures were divided into ordinary
temperature (15 ◦ C), refrigeration temperatures (10, 7, 4, and 0 ◦ C), and
export temperature (− 2 ◦ C).
The purpose of this study was to develop a kimchi ripening indicator
applicable to kimchi packaging and to evaluate its commercialization
potential and limitations. For this purpose, calcium hydroxide (CH),
which selectively reacts with CO2, and four chemical dyes were syn­
thesized to prepare indicator films. The prepared indicator films, a
permeable polyethylene terephthalate (PET) film, and a barrier poly­
ethylene/ethylene vinyl alcohol/nylon (PE/EVOH/Ny) film were lami­
nated and attached to the kimchi packaging. Kimchi ripening and the
color change of the indicator were analyzed at the various distribution
temperatures. Based on the results of this analysis, the commercial po­
tential and limitations of the colorimetric indicator developed in this
study were evaluated.
2. Material and methods
2.1. Materials
CH with a purity of 96% was purchased from Junsei Chemical Co.,
Ltd. (Japan). Cresol red (CR) was purchased from Daejung Chemicals &
Metals Co., Ltd. (South Korea). Bromothymol blue (BB) was purchased
from Junsei Chemical Co., Ltd. (Japan). Bromocresol purple (BP) and
methyl red (MR) were purchased from Samchun Pure Chemical Co., Ltd.
(South Korea).
2.2. Synthesis of CH and dye
CH, a material that selectively reacts with CO2, was mixed with
distilled water at a ratio of 3:10 to prepare a suspension. A color-
changing dye (either CR, BB, BP, or MR) was weighed to 1/100 of the
weight of the CH and added to the prepared CH suspension. The mixture
was stirred for 20 min. The mixed suspension was dried in an oven at
80 ◦ C for 48 h to obtain a synthesized powder. The resulting powder was
then pulverized (Tube-Mill 100 pulverizer, IKA Works, Inc., Germany).
2.3. Film preparation
The indicator film was manufactured using a twin-screw extruder
(BA-19, BauTek Co., South Korea) connected to a T-die head. The
operation was carried out with a T-die and header temperature of
180 ◦ C, while zones 1–4 were set to 170 ◦ C, zone 5 was set to 140 ◦ C, and
zones 6–7 were set to 120 ◦ C. The indicator film comprised 80 wt%
linear low-density polyethylene (LLDPE; UF915, Lotte Chemical Co.,
South Korea) and 20 wt% indicator powder. The thickness of the pro­
duced films was 100 ± 5 μm. Four types of indicator films were prepared
using the four different types of powders.
2.4. Characterization of the powder and films
2.4.1. Fourier-transform infrared spectroscopy
To characterize the main functional groups and chemical bonds,
Fourier-transform infrared (FTIR) spectra were recorded using a Nicolet
iS50 FTIR instrument (Thermo Fisher Scientific Inc., USA). FTIR spectra
were recorded at a resolution of 8 cm− 1, and 32 scans were performed in
the range of 400–4000 cm− 1. Each spectrum value was calculated as the
average of three corresponding sample measurements.
2.4.2. Scanning electron microscopy and energy dispersive X-ray
spectrometer mapping
Scanning electron microscopy (SEM; Gemini 500, Zeiss, Germany)
micrographs of the powders were observed. Energy dispersive X-ray
spectrometry (EDS; Quantax FlatQUAD EDS, Bruker, USA) mapping was
carried out to characterize the composition of the powders in the SEM
H.-G. Lee et al.
Fig. 1. Fourier-transform infrared spectra of the powders and films (a: materials; b: indicator powders; c: indicator films).
(Magna FEG SEM, Tescan Orsay Holding, a.s., Czechia) with a Si drift
detector. The samples were attached to a carbon tape and coated with
platinum before observation.
2.4.3. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was carried out in an alumina
crucible with a 7-mg sample using a TGA/DSC 1 (Mettler Toledo, USA).
The analysis was performed from 25 to 600 ◦ C at a heating rate of 10 ◦ C
min− 1 under a nitrogen atmosphere.
2.5. Application of indicator film to kimchi packaging
To apply the indicator film to the kimchi packaging, it was laminated
using a barrier film (PE/EVOH/Ny, 100 μm) and a permeable film (PET,
19 μm). Before lamination, the PET film was attached to one side of the
indicator film using tape and the PE/EVOH/Ny film to the other. The
laminated indicator was attached to the kimchi packaging so that the
PET film side faced the kimchi packaging, while the PE/EVOH/Ny film
side faced outwards. The size of the final indicator was 3 × 3 cm square.
One hole, 0.98 ± 0.03 mm in diameter, was punched in the kimchi
packaging at the indicator attachment point to allow the CO2 to pass
through.
2.5.1. Preparation of kimchi packaging
Kimchi (250 g, Trechan Co., South Korea) was placed in an
aluminum pouch (14.9 × 21.9 × 5.7 cm) and sealed. The purchased
kimchi was prepared with 68.5% of the main ingredient (brined kimchi
cabbage) and 31.5% of the supplementary ingredients (red pepper
powder, radish, glutinous rice paste, onion, garlic, myeolchi-jeot, saeu-
jeot, anchovy sauce, green onion, salt, apple, and pear). The prepared
samples were stored at 15, 10, 7, 4, 0, and − 2 ◦ C. The samples stored at
15 and 10 ◦ C were analyzed daily from days 0 to 7, at 0.5-week intervals
from days 7–14, and at 2-week intervals from days 14 to 56. The samples
stored at 7 ◦ C and 4 ◦ C were analyzed at 0.5-week intervals from days
0 to 28 and at 2-week intervals from days 28 to 56. The samples stored at
0 ◦ C and − 2 ◦ C were analyzed weekly from days 0 to 56. Samples were
prepared in triplicate and photographed with a cellphone camera
(Galaxy Note 10, Samsung Electronics Co. ltd., South Korea) prior to
analysis.
2.5.2. pH and titratable acidity
The pH and titratable acidity were analyzed following Choi et al.
(2018). Kimchi was homogenized using a hand blender (HR1372,
Koninklijke Philips Electronics N.V., The Netherlands) and then filtered
through four layers of gauze. The filtrate was used as the sample for pH
and titratable acidity analysis. The filtrate (10 mL) was collected, and
the pH was measured using a digital pH meter (TitroLine Easy, SI Ana­
lytics, Xylem Inc., USA). Titratable acidity was analyzed by titrating the
filtrate with 0.1 mol/L sodium hydroxide to a pH of 8.3. The titratable
acidity was calculated as the percentage of lactic acid, according to Eq.
(1):
3
Food Chemistry 400 (2023) 134039
A × f × 0.009
Titratable acidity (%) = × 100 (1)
S
where A is the consumed 0.1 mol/L sodium hydroxide (mL), f is the
factor of sodium hydroxide (0.1 mol/L), and S is the volume of filtrate
used in the analysis (mL). The pH and titratable acidity tests were
repeated three times.
2.5.3. CO2 concentration and pressure in the kimchi packaging headspace
The CO2 in the kimchi packaging headspace was measured using a
gas analyzer (GS3 micro, Systech Illinois, USA). The pressure was
analyzed using a pressure gauge (UTK-P5000, Ultra Tec Korea, South
Korea). To measure the CO2 concentration and pressure, the top of the
kimchi packaging was pierced with a needle connected to the equip­
ment. The experiments were performed in triplicate.
2.5.4. Total color difference of the indicators
A colorimeter (CR400, Konica Minolta Inc., Japan), calibrated using
a standard white plate (L* = 94.86, a* = − 0.64, b* = 3.73), was used to
measure the color change of the indicator according to kimchi ripening.
The total color difference (TCD) was calculated using Eq. (2):
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
TCD = (ΔL* )2 + (Δa* )2 + (Δb* )2 (2)
where ΔL* indicates differences in lightness [from 0 (black) to 100
(white)], a* indicates differences in greenness–redness [from − 60
(green) to + 60 (red)], and b* indicates differences in blue­
ness–yellowness [from − 60 (blue) to + 60 (yellow)] (Baek et al., 2020).
2.6. Statistical analysis
Correlation analysis was performed using Excel 2013 (Microsoft Co.,
USA). For statistical comparisons, one-way analysis of variance and
Duncan’s multiple range comparison tests (P < 0.05) were performed
using SPSS ver. 19.0 (SPSS Inc., USA).
3. Results and discussion
3.1. Synthesis of CH and dye
CO2 is continuously generated during kimchi fermentation and ac­
cumulates inside the packaging. Therefore, CO2 is widely used as a
sensing target in intelligent packaging for determining the ripening of
kimchi (Meng et al., 2015). The dyes used in this study were pH-
sensitive substances, and as shown in Fig. S1, when the pH decreases,
the substance binds to a proton and changes color (Kahlert et al., 2016).
We attempted to change the color of the indicator selectively, only when
reacting to CO2 among the fermentation metabolites in the kimchi
packaging. CH, a material that captures CO2, and four pH-sensitive dyes
(CR, BB, BP, and MR) were reacted to produce four indicator powders.
To examine the chemical structure of the synthesized powders, FTIR
H.-G. Lee et al. Food Chemistry 400 (2023) 134039

Fig. 2. Scanning electron micrographs of the powders with corresponding energy dispersive spectroscopy mapping.

4
H.-G. Lee et al.
Fig. 3. Changes in the ripening index (pH and acidity), CO2 concentration, and headspace pressure in kimchi packaging during storage (a: pH; b: acidity; c: CO2; d:
headspace pressure).
analysis was performed, and the results are shown in Fig. 1. In the FTIR
spectrum of CH, a narrow OH stretching peak was observed at 3642
cm− 1. In addition, small peaks at 1464 and 873 cm− 1 indicated the CO
vibration peaks of carbonate groups (Khachani et al., 2014). Khachani
et al. (2014) reported that the carbonate was produced by the reaction of
atmospheric CO2 with CH. CR, BB, and BP are sulfonphthalein dyes that
contain sulfonic acid in their molecular structures. The sulfonic acid
peaks of CR, BB, and BP were observed at 1339 cm− 1 (Zou et al., 2013).
MR is a type of azo dye with an azo group in its molecular structure. The
MR spectrum measured in this study showed a strong characteristic
N–– N stretching peak near 1395 cm− 1 (Hassan et al., 2019). The FTIR
spectra of the powders prepared by combining CH and the dyes were
similar to those of CH. A narrow OH stretching peak was observed at
3642 cm− 1, and the CO vibration peaks of the carbonate groups were
also observed at 1464 and 873 cm− 1. The CO vibration peaks found in
the indicator powders were presumed to be caused by CO2 in the at­
mosphere during the synthesis and measurement processes.
SEM analysis was performed to visually examine the bonding shapes
of the indicator powders, and the results are shown in Fig. S2. CH, BB,
and BP were distributed in regular, angular shapes. In addition, the
surface exhibited a smooth appearance. CR showed small, agglomerated
crystals, and MR showed cylindrical agglomerated crystals. All four
powders showed similar shapes, with small particles attached to the
surfaces of large angular particles. As all four indicator powders had
similar shapes, it was assumed that the large particles were CH and the
small particles attached to them were the dyes.
EDS mapping analysis was performed to examine the particle dis­
tribution more accurately, as shown in Fig. 2. The EDS mapping images
show the distribution of the cation elements in the powder. In the EDS
mapping images of the raw materials (CH, CR, BB, BP, and MR), the
elements contained in each material were measured. In contrast,
although not all the elements of the particles were measured in the EDS
mapping analysis of the synthesized powders, the distribution of the
5
Food Chemistry 400 (2023) 134039
indicator powders could be confirmed. The distribution of Ca was easily
identified in all four powders, clearly showing the shape of the large
particles. In the images of the CH + CR and CH + BB powders, all the
cation elements constituting CR and BB were measurable. However,
they did not show the colors as strongly as Ca. In the images of the CH +
BP and CH + MR indicator powders, Br, S, and N, which are elements of
BP and MR, were not measured. It is thought that measurement was
limited because the weight of the dye was extremely low compared to
that of the CH in the indicator powders. C, which is also a component of
BP and MR, was measured, confirming that the dye was distributed
throughout the indicator powder. EDS mapping analysis confirmed that
the large angular particles were CH, and the small particles attached to
them were the dyes.
3.2. Film preparation
To manufacture a powdery material into a film, it needs to be mixed
and melted with LLDPE. The most significant variable in the
manufacturing process is the temperature. To melt LLDPE, a high tem­
perature must be applied. However, applying this high temperature
must not affect the color change performance of the functional indicator
powder via a decomposition reaction. Therefore, it is necessary to
analyze the decomposition temperature of the powder, and the
manufacturing process must be carried out within a temperature range
that does not affect the indicator powder. TGA analysis was performed
to analyze the decomposition temperatures of the indicator powders,
and the results are shown in Fig. S3. The decomposition of CR, BB, BP,
and MR started at 280, 220, 240, and 190 ◦ C, respectively. In addition,
the powders synthesized with CH and the four dyes were decomposed by
an exothermic reaction at 350 ◦ C. Based on these results, the film-
making process was carried out at temperatures below 180 ◦ C.
The FTIR spectra of the prepared films were measured to examine
their chemical structures, and the results are shown in Fig. 1. All films
H.-G. Lee et al.
Fig. 4. Changes in the total color difference of the CO2 indicator during storage (a: CH + CR indicator; b: CH + BB indicator; c: CH + BP indicator; d: CH + MR
indicator). BP, bromocresol purple; MR, methyl red; CH, calcium hydroxide; CR, cresol red; BB, bromothymol blue.
showed common peaks at 2918, 2851, 1468, and 718 cm− 1. These peaks
correspond to CH2 asymmetrical stretching, symmetrical stretching,
bending deformation, and rocking deformation, respectively, which are
chemical characteristics of PE (Rajandas et al., 2012). In contrast, a
narrow OH stretching peak was generated at 3642 cm− 1 after mixing in
the indicator powder. This peak shows the chemical characteristics of
the CH. The main peaks of each raw material appeared in the FTIR
spectra of the film prepared by melting and mixing the indicator powder
and LLDPE. It was found that the indicator powder and LLDPE exist as
separate phases in a physical bond (Fasihnia et al., 2018). Lee et al.
(2020) reported that the FTIR peak of a film made by melting and mixing
a powder and LLDPE showed the peak characteristics of each raw ma­
terial, similar to the results of this study.
3.3. Application of the films to kimchi packaging
3.3.1. Evaluation of kimchi ripening
The flavor of kimchi differs owing to the presence of lactic acid
bacteria derived from various ingredients. The major lactic acid bacteria
that affect the flavor of kimchi are Leuconostoc mesenteroides, Lactoba­
cillus sakei, and Weissella koreensis, which decompose sugars during
growth to produce metabolites such as lactic acid, acetic acid, and CO2
(Kim et al., 2020). As these metabolites acidify the kimchi, affecting the
flavor, the degree of acidification can predict the degree of ripening and
the quality of the kimchi. The pH and acidity are known analytical
indices used to determine the degree of acidification of kimchi (Lee &
Yoo, 2017). As the lactic acid bacteria that acidify kimchi are strongly
influenced by temperature, the temperature is an important factor in
kimchi ripening and quality. Therefore, it is important to maintain a
constant temperature from when the kimchi is produced in the factory
until it reaches the consumer. During the distribution stage, many
technological developments and regulations are being developed to
6
Food Chemistry 400 (2023) 134039
provide consumers with high-quality products through low-temperature
management (Han, 2018).
In this study, changes in pH and acidity were measured when kimchi
was stored for 56 days at ordinary temperature (15 ◦ C), refrigeration
temperatures (0, 4, 7, and 10 ◦ C), and export temperature (− 2 ◦ C). The
results are presented in Fig. 3. According to Meng et al. (2015), the
kimchi ripening process is divided into two stages. During the first
ripening stage, acidification proceeds rapidly, and the slope of the pH or
acidity curve is steep. The second ripening stage corresponds to the
second half of fermentation, when there is little change in the pH or
acidity, which shows a gently curved slope. A similar pattern was
observed in this study. At all temperatures, the pH and acidity showed
significant changes as ripening progressed (P < 0.05). The higher the
temperature, the faster the acidification of kimchi during the early
stages. At lower temperatures, the changes in pH and acidity were lower
at the start, and the onset of the first (rapid acidification) stage was
delayed. In other words, it was confirmed in this study that the
fermentation of kimchi is greatly affected by temperature, and the
higher the temperature, the faster fermentation proceeds. Hong et al.
(2016) reported that kimchi ripens slowly at low and rapidly at high
temperatures, which is consistent with the results of this study.
3.3.2. CO2 concentration and pressure in the headspace of the kimchi
packaging
CO2 is a fermentation metabolite of lactic acid bacteria that con­
tributes to the acidification of kimchi, affecting the pH and acidity.
Therefore, CO2 is an important sensing material for this indicator.
Moreover, CO2 accumulates in the packaging, causing volume expansion
and a pressure increase in the packaging. Because an increase in pressure
can damage the packaging, it is necessary to properly control the con­
centration of CO2 in the packaging (Jaisan et al., 2019). The changes in
the CO2 concentration and pressure in the packaging during the storage
H.-G. Lee et al.
Fig. 5. Photographs of the indicators attached to the outside of the kimchi packaging (a: CH + CR indicator; b: CH + BB indicator; c: CH + BP indicator; d: CH + MR
indicator). BP, bromocresol purple; MR, methyl red; CH, calcium hydroxide; CR, cresol red; BB, bromothymol blue. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
of kimchi in this study are shown in Fig. 3. The CO2 concentration
pattern in the kimchi packaging appeared similar to that of acidity.
Although there were some decreases, most samples showed significant
increases during storage (P < 0.05). In addition, the higher the storage
temperature, the faster the CO2 increased.
The pressure in the kimchi packaging (Fig. 3) showed a significant
increase in the kimchi stored at 15 ◦ C on day 14 (P < 0.05) and in the
kimchi stored at 10 ◦ C on day 28 (P < 0.05). In the kimchi stored at 15 ◦ C
and 10 ◦ C, the increased pressure decreased again, showing no signifi­
cant difference from the initial pressure. Contrary to previous reports
(Lee et al., 2001), the results of this study did not show an increase in
pressure as the CO2 increased. This is because the CO2, which should
have accumulated in the packaging, instead passed through the hole in
the packaging, where it reacted with the indicator. This suppression of
the pressure increase by CO2 permeation shows potential as an appli­
cable method to solve the problem of kimchi packaging damage.
3.3.3. Color changes of the indicator in the kimchi packaging
To analyze the color change performance of the developed indicator,
a storage experiment was conducted after attaching the indicator to the
outside of the kimchi packaging. The results are shown in Figs. 4 and 5.
In all samples, the higher the storage temperature, the steeper the slope
of the TCD curve (Fig. 4). In other words, the higher the storage tem­
perature, the faster the color of the indicator changed. This supports the
results for CO2, pH, and acidity discussed above. The CO2 generated
during kimchi storage reacts with CH through the Eqs. (3)–(8) (Han
et al., 2011).
Ca(OH)2 hCa2+ + 2OH −
CO2 + OH − hHCO−3
HCO−3 + OH − hH2 O + CO2−3
HCO−3 hH + + CO2−3
Ca2+ + CO2−3 hCaCO3
H + + H2 OhH3 O+
Hydronium ions (H3O ) generated during the reaction between CO2
+
and CH react with the basic form of the pH-sensitive dye to form a
protonated acidic form, causing a color change (Puligundla et al., 2012).
As shown in Fig. S1, the dye reacts, and a color change appears. The
higher the temperature, the faster the CO2 production rate; thus, the
value of TCD increases rapidly. It is difficult to maintain a constant
temperature during distribution. Therefore, it is important to accurately
Food Chemistry 400 (2023) 134039
determine the ripeness of the kimchi despite the color change effect of
the indicator changing speed according to the temperature. The effect of
temperature on TCD was examined at an acidity of 0.8%, which is the
optimal ripening stage for kimchi (Lee et al., 2019). For all four in­
dicators, the lower the temperature, the higher the TCD value corre­
sponding to an acidity of 0.8%. This is owing to the difference between
the permeation rate of the CO2 and the rate of kimchi ripening. To
change the color of the indicator, the CO2 produced by fermentation
must pass through the PET film-lamination layer to react with the in­
dicator. For CO2 to permeate through PET, a basic permeation time is
required, which depends on the pressure. At high temperatures, kimchi
ripening proceeds faster than the CO2 permeation time. Therefore, when
the kimchi acidity reached 0.8%, a low TCD value was still observed. In
contrast, although kimchi ripening proceeds slowly at low temperatures,
the small amounts of CO2 generated from the beginning of fermentation
penetrate the film and react slightly with the indicator, resulting in a
relatively high TCD value when the acidity reaches 0.8%%. Preferably,
the TCD value should not differ depending on the temperature, and the
CH + BB indicator showed the smallest difference in this study.
Fig. 5 shows a photograph of the indicator attached to the outside of
the packaging. Unlike TCD, which is a mechanical measurement value
that can detect minute changes, the color of a photograph can be
observed intuitively with the human eye. In this study, the initial colors
of the CH + CR, CH + BB, CH + BP, and CH + MR indicators were
purple, blue, navy blue, and yellow, respectively. As the kimchi storage
period increased, the indicator colors changed to yellow, yellow-green,
gray, and red, respectively. The four dyes used in this study are pH-
sensitive substances, and their color changes in response to changes in
(3)
pH. CR is a vivid violet when the pH is higher than 8.8 and yellow when
the pH is lower than 7.2 (Kahlert et al., 2016), while BB is blue when the
(4)
pH is higher than 8.0 and yellow when the pH is lower than 6.0 (Li et al.,
2018). The color of BP changes to purple when the pH is higher than 6.8
(5)
and yellow when the pH is lower than 5.2 (Kari et al., 2021), and that of
MR changes to yellow when the pH is higher than 6.2 and red when the
(6)
pH is lower than 4.4 (Kahlert et al., 2016). This is similar to the results of
the present study. It was confirmed that the colors of the indicators
(7)
changed according to changes in the pH, but the most important target is
an obvious color change that occurs at an acidity of 0.8%, the optimal
(8)
ripening point of kimchi. The color changes of the CH + CR and CH + BB
indicators at 15, 10, 7, and 4 ◦ C were first displayed when the acidity
reached 0.8%, and the color changed vividly as fermentation continued.
In the case of the CH + BP and CH + MR indicators, the color only
changed after the optimal ripening time. It was assumed that these late
changes occurred because the discoloration pH ranges of BP and MR
were lower than those of CR and BB. Combining the TCD results and
indicator color changes, the CH + BB indicator most accurately
7
H.-G. Lee et al. Food Chemistry 400 (2023) 134039

Table 1
Correlation coefficients between kimchi quality characteristics and indicators.
Temperature pH vs indicator TCD Acidity vs indicator TCD CO2 vs indicator TCD
(℃)
Indicator Indicator Indicator Indicator Indicator Indicator Indicator Indicator Indicator Indicator Indicator Indicator
(CH + (CH + (CH + (CH + (CH + (CH + (CH + (CH + (CH + (CH + (CH + (CH +
CR) BB) BP) MR) CR) BB) BP) MR) CR) BB) BP) MR)

15 − 0.86 − 0.83 − 0.71 − 0.71 0.66 0.82 0.85 0.85 0.75 0.82 0.82 0.84
10 − 0.95 − 0.97 − 0.70 − 0.75 0.84 0.87 0.84 0.86 0.90 0.92 0.86 0.88
7 − 0.92 − 0.95 − 0.84 − 0.84 0.78 0.82 0.83 0.82 0.85 0.86 0.91 0.91
4 − 0.98 − 0.98 − 0.92 − 0.90 0.91 0.94 0.96 0.94 0.88 0.91 0.95 0.92
0 − 0.93 − 0.88 − 0.89 − 0.99 0.92 0.92 0.94 0.99 0.94 0.94 0.92 0.98
− 2 − 0.64 − 0.62 − 0.96 − 0.85 0.74 0.74 0.97 0.85 0.67 0.63 0.83 0.82

TCD, total color difference; BP, bromocresol purple; MR, methyl red; CH, calcium hydroxide; CR, cresol red; BB, bromothymol blue.

represented the degree of kimchi ripening. However, to obtain similar
results to this study in actual distribution, distribution should be per­
formed within a temperature range of 4 to 15 ◦ C, and the same pack­
aging capacity and amount of kimchi should be used as were used in this
study. In addition, it was limited to kimchi cabbage because it affects the
composition of lactic acid bacteria depending on the main ingredient of
kimchi.
3.3.4. Correlating colorimetric indicator response with kimchi ripening
Correlation analysis was performed on the ripening index (pH and
acidity) of kimchi, the CO2 concentration, and the color change of the
indicator (TCD). The results of the correlation analysis are presented in
Table 1. The pH and TCD data displayed a strong correlation of ≥ 0.9 at
4 ◦ C. Most of the correlations between acidity and TCD showed high
values ≥ 0.8, with some exceptions. In particular, they showed strong
correlations ≥ 0.9 at 4 ◦ C and 0 ◦ C. CH + CR and CH + BB showed low
correlation coefficients between the kimchi ripening index and the TCD
of the indicator at − 2 ◦ C, and CH + BP and CH + MR showed low
correlation coefficients between these variables at 10 and 15 ◦ C. This is
because the pH range of CR and BB discoloration is relatively high, while
the pH range of BP and MR discoloration is relatively low. When the
indicator discoloration pH range is high, it only takes a short time for the
CO2 reactions to lower the pH enough to induce a change, which is more
suitable at high temperatures at which kimchi ripens rapidly. Baek et al.
(2018) prepared a three-step indicator using BB with a high pH discol­
oration range and MR with a low pH discoloration range. They reported
the same phenomenon as observed in this study and illustrated the
possibility of creating more reliable and improved products by applying
the indicators developed in this study simultaneously. The correlation
between CO2 and TCD was similar to that between CO2 and acidity;
these strong correlations demonstrate that CO2 affects kimchi
acidification.
that the pressure did not increase could play a role in solving a chronic
problem in kimchi packaging. The color change analysis of the in­
dicators confirmed that the CH + BB indicator, which clearly indicates
the optimal ripening period with a strong color change, has the highest
commercialization potential. However, the color change rate of all the
indicators differed depending on the temperature, and it was necessary
to use a certain packaging capacity and kimchi capacity. This is owing to
the difference between the permeation rate of the CO2 and the rate of
fermentation. The indicator developed in this study relies on discolor­
ation through a reaction between CO2 and CH. Therefore, the amount of
CO2 that permeates the packaging is an important factor in the discol­
oration of the indicator. As the amount of CO2 that permeates the
packaging is affected by the packaging capacity, kimchi capacity, and
storage temperature, these factors that affect the rate of kimchi ripening
should not be changed. To improve this, a valve that discharges CO2 at a
certain pressure is required, or additional research into a discoloration
method involving direct contact with the kimchi is needed.
CRediT authorship contribution statement
Hyun-Gyu Lee: Conceptualization, Investigation, Writing – original
draft, Writing – review & editing. Suyeon Jeong: Visualization, Writing
– review & editing. SeungRan Yoo: Conceptualization, Writing – review
& editing, Supervision, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability

4. Conclusion
Data will be made available on request.

In this study, a kimchi ripening indicator was developed to display

Acknowledgements
kimchi ripening inside the packaging for observation outside of it. The
practical applicability and limitations of the indicators were evaluated.
This study was supported by research grants (KE2202-2-1&KE2201-
The indicators were made using CH, which captures CO2 and four pH-
2-1) from the World Institute of Kimchi, and a High Value-added Food
sensitive dyes. Through FTIR spectrum analysis, OH peaks were
Technology Development Program (321047-03-2-SB010), Ministry of
observed in all samples owing to the synthesis of CH and the dye, and
Agriculture, Food and Rural Affairs, Republic of Korea.
OH peaks were also confirmed in the LLDPE-based films. SEM and EDS
mapping confirmed that the dye was attached to the CH surface and
evenly spread across it. These results show that CH and the dye were Appendix A. Supplementary data
attached to each other, so that changes in the CH would directly affect
the dye. To verify the color change performance of the indicators, after Supplementary data to this article can be found online at https://doi.
attaching the indicators to the outside of kimchi packaging, they were org/10.1016/j.foodchem.2022.134039.
stored at an ordinary temperature (15 ◦ C), refrigeration temperatures (0,
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