The International Conference on Food and Applied Bioscience 2018 proceeding book
1
Department of Packaging and Materials Technology, Faculty of Agro-Industry,
Kasetsart University, Thailand,
2
Department of Fishery Products, Faculty of Fisheries, Kasetsart University, Thailand,
*Corrsponding author(s), e-mail: panuwat.s@ku.ac.th
Abstract:
Fish spoilage indicator (FSI) is a member of diagnostic packaging (DP) as a subclass
of intelligent packaging (IP). It uses metabolites to monitor the status of fish freshness and
spoilage. Total volatile basic nitrogen (TVB-N) is responsible for a smell of spoiled fish and
can be employed as metabolite during fish spoilage. Turmeric (Curcuma longa) is
commonly used for sensing pH, carbon dioxide and ammonia during food spoilage with a
pH transition from 7.8 (yellow) to 9.2 (brown). Cellophane, a well-known regenerated
cellulose, water insoluble natural polymer. Containing of numerous capillaries but no pore
made cellophane good adsorb substance during its swell. This present work aimed at
investigating the effects of dye concentration and mixed solvent on immobilization of
turmeric into cellophane film via an adsorption technique and at assessing a color transition
of turmeric-immobilized cellophane (TIC) film on pH buffer and targeted metabolite from
fish spoilage. A stock solution of 1% w/v turmeric was dissolved in an absolute ethanol.
Commercial cellophane film size 1.53.0 cm2 was immersed in turmeric solutions with
concentrations of 0.005 0.01 and 0.02% w/v in different mixed solvent ratios (ethanol
:deionized water) 1:9 5:5 and 9:1 for 0 4 and 8 h. Unbound turmeric was washed with
deionized water and dried at room temperature. The color transition of turmeric solution and
TIC film in different pH buffer have been revealed as absorption spectra and total color
difference (TCD) values. The optimal mixed solvent ratio of ethanol and deionized water
was 1:9 (1E). The turmeric concentration 0.02% w/v enabled to sense pH change. The color
transition of TIC film were yellow-orange-brown at pH 7.0–9.0 and red-brown-orange at pH
10.0–13.0. TIC film is ability to sense pH change from yellow to brown within a few
seconds after exposure to a vapor of 1% ammonia solution in the headspace. A 0.02% TIC
film turned from yellow to brown within 1 min after expos to ammonia vapor concentration
of 0.01–0.10 M and color intensity increased and reached equilibrium within 30 min.
Furthermore, Turmeric-immobilized cellophane film is potentially used for monitoring
packed fish during storage.
The International Conference on Food and Applied Bioscience 2018 proceeding book
1. Introduction
All fresh seafood is very perishable products and the microbial growth is the main
cause of quality deterioration.1 A fraction of the initial microbial of fish, known as specific
spoilage organisms (SSOs), which grow up in appropriate storage conditions (e.g.,
atmosphere, temperature). When the microorganisms reach high populations, several
metabolites or chemical spoilage indices (CSIs) are produced and responsible for the off-
flavors/odors which results in their organoleptic rejection.1–3
Turmeric or curcumin is the well-known natural dye obtained from curcuma, the
rhizome of Curcuma longa L. Zingiberaceae. Curcumin is an orange-yellow crystal powder
which melts at 183°C and dissolves in alcohol and glacial acetic acid. The pH transition
interval is between pH 7.8 (yellow) and pH 9.2 (brown).4 Curcumin contains two ferulic acid
molecules connected by a methylene bridge at the carbon atoms of the carboxyl groups
(Figure 1). Curcumin can persist in tautomeric diketo and keto–enol forms. In aqueous
solution the enol form predominates and corresponds to deprotonation of the three hydroxyl
groups. The most common applications of curcumin are as an ingredient in dietary
supplement, in cosmetics, flavoring for foods, coloring material and widely used in
biological actions and medicinal applications.6–8
Cellophane or regenerated cellulose films is a well-known hydrophilic and water
insoluble natural polymer. Their property is related to its crystallinity and the inter-molecular
hydrogen bonding between its hydroxyl groups.9–10 The regenerated cellulose films are
obtained by casting or extruding cellulose solutions and then transferring to the coagulation
bath for regeneration. They are attractively used for different applications, such as green
packaging, printable labels, biomedical materials, electronic devices, and optical products.11
Intelligent packaging is a packaging system (or material) that uses either internal
(e.g., metabolites) or external (e.g., temperature, gas, humidity) package environment as
“information” to monitor a status of product quality to enhance product safety, biosecurity,
and/or convenience or capability of tracking a product for automatic product identification
and traceability.12,13 Fish spoilage indicator (FSI) is a member of diagnostic packaging (DP)
as a subclass of intelligent packaging (IP). Fish spoilage indicator is defined as “a packaging
system (or material) which uses metabolites as “information” to monitor the status of fish
freshness and spoilage”.14 Recently, researchers have developed the intelligent packaging to
monitor the target metabolites from fish and seafood spoilage. For example, pH dye-based
indicator,15, 16 Natural dye-based indicator,17–19 polymer based indicator14,20,21 and bio-based
indicator for monitoring either volatile amines or biogenic amines have been developed.
In order to further develop a novel colorimetric fish spoilage indicator, turmeric and
cellophane film were used to investigate the effect of dye concentrations on pH transition of
turmeric solution and the effect of mixed solvent on immobilization of turmeric into
cellophane film and to assess the color transition of turmeric-based cellophane film on pH
and target metabolite from fish spoilage. A color change of turmeric solution in different pH
buffer was determined by using the UV-Visible spectrophotometer at lambda range of 300–
700 nm. A dynamic change in the solution expressed as total color difference (TCD, ∆E)
was measured using the CIE L*, a*, b* Chroma system. The color transition of turmeric
immobilized-cellophane (TIC) film was observed by photography.
The International Conference on Food and Applied Bioscience 2018 proceeding book
Figure 1 Chemical structure of keto-enol form of curcuma, in aqueous solution correspond to deprotonation of
the three hydroxyl groups of curcumin with the enolic (a) and phenolic (b and c) protons highlighte.
Where L* is the brightness difference between initiation and each time interval, a* is the
redness-greenness difference between initiation and each time interval, and b* is the
yellowness-blueness difference between initiation and each time interval.
The International Conference on Food and Applied Bioscience 2018 proceeding book
The International Conference on Food and Applied Bioscience 2018 proceeding book
to 550 nm. Moreover, a new brown shifted (pH 9.0) to dark orange (pH 13.0) leading to
maximum lambda appeared at 431–459 nm and 520–550 nm (Figure 4). Pourreza and
Golmohammadi stated that at pH 3.0–7.0 curcumin acts as a potent H-atom donor because of
its keto form and above pH 8.0, the enol form predominates, and it acts mainly as an electron
donor. At pH 13.0, curcumin is completely deprotonated to form the highly negatively
charged species Cur3-. From their research study, it showed that the absorption intensity of
curcumin nanoparticle in the pH range of 7.0–9.5 initially decreased at lambda 423 nm with
a color change from yellow to red, and new red shifted absorption bands in the pH range of
10.0–13.0 appeared at lambda 460 nm with a color change from red to brown.
Focusing on color span of turmeric, the pH buffer range of 7.8–9.2 were prepared from the
primary salt based borax. The color transition in pH buffer range of 7.8–8.0 was yellow, pH
buffer range of 8.2–8.6 was orange and pH buffer range of 8.8–9.2 was brown. The color
transition of turmeric solution was shifted from acidic from (yellow, pH 6.0–7.8) to basic
form (brown, pH 9.2), resulting in maximum lambda shifting from 420–423 nm to 550–560
nm (Figure 5). The effect of higher concentrations of turmeric in buffer solution shows the
better intensity of color for all pH ranges.
The total color different (TCD) values in pH buffer solution 7.0–9.0 were 1.33–19.1,
3.71–23.89 and 4.63–39.00 at concentration of turmeric 0.005 0.01 and 0.02%w/v,
respectively. In the pH buffer based borax (pH range of 7.8–9.2), TCD values were 5.74–
15.58, 13.18–27.51 and 18.11–44.99 at concentration of turmeric 0.005 0.01 and 0.02% w/v,
respectively (Figure 6). It is generally known that TCD values greater than 5 can be easily
detected by the unaided eye, and TCD greater than 12 indicates a completely different color
space. Then, the effect of higher concentrations of turmeric shows the better intensity of
color in buffer solution pH range of 8.0–13.0 and 7.8–9.2 and we noticed that 0.02% w/v of
turmeric was ability to sense pH change and showed a clearer color transition in different
pH buffer solution, in turn, wider color span at narrower pH range.
Figure 2 A 1% Turmeric solution in absolute ethanol 10E (a), in mixed ethanol and deionized water 5E (b) and
in deionized water 0E (c)
The International Conference on Food and Applied Bioscience 2018 proceeding book
Figure 3 Absorbance spectra of 0.01% Turmeric in different solution of ethanol and deionized water 5E and
10E
Figure 4 Absorption spectra of turmeric solution with concentration of 0.005% w/v (a), 0.01% w/v (b)and
0.02% w/v (c) in different pH buffer prepared from different primary salts (pH 7.0–13.0)
Figure 5 Absorption spectra of turmeric solution with concentration of 0.005% w/v (a), 0.01% w/v (b) and
0.02% w/v (c) in different pH buffer prepared from primary salt based borax (pH 7.8–9.2).
The International Conference on Food and Applied Bioscience 2018 proceeding book
Figure 6 Total color difference of turmeric solution in different pH buffer solution prepared from different
primary salts pH 7.0–13.0 (a) and from primary salt based borax pH 7.8–9.2 (b)
The International Conference on Food and Applied Bioscience 2018 proceeding book
Table 1 Total color difference of turmeric solution before absorption and turmeric
immobilized-cellophane film after absorption (mixed solution 1E)
conc. time solution before absorption film after absorption
(%w/v) (hr) a* b* TCD a* b* TCD
0.005 0 8.565 -22.970 8.565 -22.970
4 8.275 -22.453 0.768 1.755 -5.178 19.052
8 8.220 -21.833 1.193 1.868 -5.208 18.988
0.010 0 11.375 -35.118 11.375 -35.118
4 11.088 -34.813 0.732 3.855 -10.695 25.557
8 11.310 -34.285 0.897 4.025 -10.900 25.333
0.020 0 11.278 -45.813 11.518 -45.268
4 10.905 -45.518 0.507 7.450 -22.335 23.328
8 10.928 -45.165 1.015 7.450 -22.468 23.199
The International Conference on Food and Applied Bioscience 2018 proceeding book
Figure 7 Color transition of turmeric 0.02%w/v (0.02T) immobilized-cellophane (TIC) film in pH buffer
solution 7.0–13.0 and 7.8–9.2.
Figure 8 Color transition of turmeric immobilized-cellophane (TIC) film after exposed to head space of 1%
ammonia solution
4. Conclusions
The results presented in this study indicate that color of turmeric in absolute ethanol
was brighter than that of turmeric in deionized water-based solvent. The concentration of
0.02%w/v (0.02T) as ability to sense pH change and showed a clearer color transition in
different pH buffer solution. However, the swelling degree of cellophane was decreased
when the ratio of ethanol increased. Then turmeric was able to absorb into the cellophane
structure only in mixed solvent ethanol and deionized water 1:9 (1E). After exposure to
ammonia vapor, TIC film (0.02T) turned from yellow to brown within 1 min. The color
intensity of TIC film increased with time and reached equilibrium within 30 min. Hence,
TIC film is potentially used for monitoring packed fish during storage.
The International Conference on Food and Applied Bioscience 2018 proceeding book
Acknowledgements
Financial support from the Center of Advanced Studies for Agriculture and Food
(CASAF), Kasetsart University.
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