Natural pH indicator from tapioca starch/

curcumin film
Cite as: AIP Conference Proceedings 2279, 070002 (2020); https://doi.org/10.1063/5.0023184
Published Online: 26 October 2020

N. Petchana, N. Phoopiam and L. Thiraphattaraphun

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© 2020 Author(s).
 Natural pH Indicator from Tapioca Starch/Curcumin Film
N. Petchana, N. Phoopiam and L. Thiraphattaraphuna)

Division of Packaging Technology, Faculty of Agro-Industry, Chiang Mai University, Chiang Mai, 50100, Thailand
a)
Corresponding author: linda.t@cmu.ac.th

Abstract. An intelligent packaging film based on natural product was prepared from tapioca starch and curcumin.
Curcumin was extracted from turmeric using a Soxhlet extractor. The visual color changes of curcumin solution were
investigated at different pH values (pH 5-11). It can be seen that the color changes of curcumin solution changed from
yellow to reddish-brown as the pH values changed from 7 to 8. Additionally, curcumin was added into the tapioca starch
and prepared as a bio-film by a solution casting technique. The visual color changes and color parameters (CIELab color
system) of tapioca starch/curcumin film at different pH values (pH 5-11) were observed. The color of tapioca
starch/curcumin film changed from yellow to dark orange color as the pH values increased. Moreover, the addition
curcumin to the tapioca starch film can increase contact angle and elongation at break. As a result of a change in film
colors, the tapioca starch/curcumin film could be applied as a natural pH indicator for monitoring food spoilage based on
the pH changes. Moreover, an environmentally friendly indicator film was also achieved.

INTRODUCTION
A pH indicator is one type of intelligent packaging. This indicator can be presented the visual color changes
based on the pH changes. The total volatile basic nitrogen (TVBN) such as ammonia, dimethylamine and
trimethylamine, can be used to indicate freshness of fish [1] and shrimp [1, 2]. The pH increased as TVBN increased
during fish [1] and shrimp [1, 2] spoilage from microorganism. Normally, a pH indicator consists of solid support
material and dye or pigment. Curcumin [(1E,6E)-1,7bis(4-hydroxy-3-methoxyphenyl)hepta-1,6-diene-3,5dione] was
extracted from turmeric by solvent extraction [1, 3]. It is a natural pigment and non-toxic [1, 4]. The chemical
structure of curcumin as keto–enol tautomerism [5] is shown in Fig. 1. The keto form exhibits in acidic and neutral
pH mediums (the pH range of 3-7), while the enol form presents in alkaline pH medium [4, 5].

H
O O
OMe O O
MeO OMe
MeO

OH
HO OH
HO
(a) (b)

FIGURE 1. The chemical structure of curcumin as keto–enol tautomerism; (a) keto form [5] and (b) enol form [5].

The solid support materials with curcumin pigment have been produced by bacterial cellulose membrane [1], tara
gum/polyvinyl alcohol [2], gelatin [3] and paper [4]. However, there are no reports on starch as a solid support
material with curcumin pigment. Thus, starch is an alternative solid support material, due to abundantly available,
low cost and biodegradable.

The Second Materials Research Society of Thailand International Conference

AIP Conf. Proc. 2279, 070002-1–070002-6; https://doi.org/10.1063/5.0023184
Published by AIP Publishing. 978-0-7354-4009-8/$30.00

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 The objective of this work was to prepare a natural pH indicator film using tapioca starch as a solid support and
curcumin as a pH indicator. In addition, the properties of tapioca/curcumin indicator film were also evaluated.

PREPARATIONS OF CURCUMIN AND TAPIOCA STARCH/CURCUMIN FILM

Materials; tapioca starch was purchased from Thai Flour Industry Company Limited, Thailand. Turmeric powder
was purchased from Cheevarom Company Limited, Thailand. Glycerol (food grade) was purchased from Srichand
United Dispensary Company Limited, Thailand. Moreover, Ethanol (95%), Mg(NO3)2 and other chemicals used for
preparing the buffer solutions were analytical grade.
Extraction of curcumin; curcumin was extracted from the dried turmeric powder with 95% ethanol at a mass:
volume ratio of 1:13 using a Soxhlet extractor. The curcumin extraction was carrier at 80 ºC for 72 h. The curcumin
extract solution was concentrated using a rotary evaporator and dried in a hot air oven at temperature 80 ºC for 48 h.
Finally, the dried curcumin was ground with a mortar and kept in a desiccator.
Preparation of tapioca starch/curcumin film; the tapioca starch was dispersed in distilled water (3% w/v) at 75 ºC
with stirring at 600 rpm by an overhead stirrer for 30 min. Glycerol (25% v/w of starch) was added and stirred for 30
min. The tapioca starch solution was poured into an acrylic plate and dried in a hot air oven at 40 ºC for 14 h. The
tapioca starch/curcumin preparation, the tapioca starch dispersed in distilled water was prepared similar to previous
mention, then, glycerol (25% v/w of starch) and curcumin powder (0.04% w/v) were added and stirred at 600 rpm
for 30 min at 75 ºC (curcumin was dissolved in 95% ethanol with a weight:volume ratio of 1:125 before use). The
tapioca starch/curcumin film was formed by pouring the tapioca starch/curcumin solution into an acrylic plate and
dried in a hot air oven at 40 ºC for 14 h.

CHARACTERIZATION TECHNIQUES
UV-vis analysis; curcumin powder was dissolved in 95% ethanol at a weight:volume ratio of 1:1000. The UV-
vis spectrum of curcumin solution was performed by a UV spectrophotometer (V730- Jasco, Japan). The absorbance
was measured at wavelengths from 300 to 600 nm and the absorption peak was reported.
Color changes of curcumin solution at different pH values; curcumin powder was dissolved in 95% ethanol at a
weight:volume ratio of 1:1000. The curcumin solution was poured into buffers (The pH values of 5, 6, 7, 8, 9, 10
and 11) with a volume:volume ratio of 1:2. The curcumin solution and buffer were stirred for 10 min and left at
room temperature. The color changes of curcumin solution were observed from the visual color changes.
Film thickness; the film thickness was measured using a micrometer (GT-313-A, Mitutoyo Mfg Company
Limited, Japan) at ten random positions of each film with five replicates. The average value was calculated and
reported.
Color changes and color parameters of films at different pH values; the tapioca starch/curcumin film was
immersed in the buffers at pH values of 5, 6, 7, 8, 9, 10 and 11. Then, the film samples were dried at room
temperature for 24 h. The color changes were investigated by the visual color changes. In addition, the color
parameters of tapioca starch film and tapioca starch/curcumin film (not immersed and immersed in the buffer
solutions) were also evaluated. The CIELab color system was used, L* = 100 (white) to 0 (black), a* = –a (green)
and +a (red) and b* = –b (blue) and +b (yellow). The color parameters of film samples were measured by using a
Hunter Lab ColorQuest XE Spectrophotometer. The measurement was carried out in four replicates.
Contact angle; the contact angle of tapioca starch film and tapioca starch/curcumin film was determined using a
drop shape analyzer (DSA 30E, Krüss, Germany) with a sessile-drop method. A drop of distilled water was applied
on the film surface. The contact angle was measured from five replicates.
Water solubility and water vapor transmission rate; the film sample was cut into 20 mm x 20 mm and dried at
105 ℃ for 24 h to determine the initial dry weight. The dried film was immersed in 50 ml of distilled water and
shake with a mechanical stirrer (WNB22, Memmert GmbH, Co. KG, Germany) at room temperature for 24 h. The
solution and non-dissolved film were filtered through Whatman No. 1 filter paper. The solid residue was dried at
105 ℃ for 24 h to determine the final dry weight. The measurement was performed in triplicate. The percentage of
water solubility (%WS) was calculated as: 100 x (initial dry weight – final dry weight)/initial dry weight. A
desiccant method was used to determine the water vapor transmission rate (WVTR), at 23±2 °C and 50±5% relative
humidity (saturated Mg(NO3)2 solution). The film sample was sealed over a metal cup containing desiccant and
weighted until constant weight. The test was carried out in four replicates. The WVTR was calculated as follows:
(G/t)/A, where; G/t = slope of the straight line (g/h) and A = test area (m2).

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 Tensile properties; the film sample was conditioned under 50±5% relative humidity (saturated Mg(NO3)2
solution) at 23±2 ℃ for 48 h prior to test. Moreover, the film sample was cut into 150 mm x 15 mm. A tensile tester
(Instron Model 5565 H159, England) was used to measure tensile strength and elongation at break of film. The
measurement was performed using initial grip distance of 100 mm, cross-head speed of 5 mm/min and load cell of 5
kN. The average values from ten samples were taken and reported.

RESULTS AND DISCUSSION

A yellowish brown curcumin extract solution (in 95% ethanol as a solvent) was obtained by extracting the
turmeric powder, as shown in Fig. 2 (a). Furthermore, a dark brown curcumin powder was achieved from an
evaporation of curcumin extract solution, as shown in Fig. 2 (b).

(a) (b)

FIGURE 2. Curcumin extracted from turmeric powder; (a) curcumin extract solution (in 95% ethanol as a solvent) and (b)
curcumin powder.

In this work, the curcumin extract solution is not further purified. A dark color of concentrated curcumin extract
is known as oleo-resin [6]. It may be contained oils and resins, which are presented in turmeric [6]. Therefore, a dark
brown curcumin powder was revealed rather than yellowish powder as a commercial curcumin.
The spectrum of curcumin solution at wavelengths from 300 to 600 nm exhibited a single peak. Moreover, the
absorption peak of curcumin solution presented at 421 nm. This is attributed to the phenolic compounds and
unsaturated bonds in curcumin [2]. In addition, the absorption peak of curcumin revealed in the visible region (at
410-430 nm [3]. Therefore, in this work, curcumin can be achieved from dried turmeric extraction.
The color of curcumin solution (curcumin powder:95% ethanol=1:1000 (w:v) and the color changes of curcumin
solution at the pH values of 5, 6, 7, 8, 9, 10 and 11 were investigated by the visual color changes, as shown in Fig. 3.

(a) (b) (c) (d)

(e) (f) (g) (h)

FIGURE 3. Colors of (a) curcumin solution (curcumin powder:95% ethanol=1:1000 (w:v)) and color changes of curcumin
solution at the pH values of (b) 5, (c) 6, (d) 7, (e) 8, (f) 9, (g) 10 and (h) 11.

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 It can be seen that the color of curcumin solution was yellow. Additionally, at pH 5-7, a yellow curcumin
solution was achieved. While a reddish-brown curcumin solution was presented at pH 8-11. Therefore, the color
changes of curcumin solution changed from yellow to reddish-brown as the pH values changed from 7 to 8.
The average thicknesses of tapioca starch film and tapioca starch/curcumin film were 0.089±0.013 mm and
0.089±0.014 mm, respectively. In addition, the colors and color parameters of tapioca starch film and tapioca
starch/curcumin film are presented in Fig. 4 and Table 1, respectively.

(a) (b)
FIGURE 4. Colors of films; (a) tapioca starch film and (b) tapioca starch/curcumin film.

TABLE 1. Color parameters of tapioca starch film and tapioca starch/curcumin film.

Film L* a* b*
Tapioca starch 96.79±0.04 0.13±0.01 1.55±0.08
Tapioca starch/curcumin 87.65±0.18 -1.61±0.42 113.37±0.61

At different pH values of 5, 6, 7, 8, 9, 10 and 11, color changes of tapioca starch/curcumin film are shown in Fig.
5. It can be seen that a yellow color of tapioca starch/curcumin film turn to a dark orange color as pH values
increased. Furthermore, a clearly dark orange color of tapioca starch/curcumin film can be seen at pH values of 10
and 11.

(a) (b) (c) (d)

(e) (f) (g)

FIGURE 5. Color changes of tapioca starch/curcumin film at the pH values of (a) 5, (b) 6, (c) 7, (d) 8, (e) 9, (f) 10 and (g) 11.

In Table 2, the color parameters of tapioca starch/curcumin film at different pH values, the a* values of tapioca
starch/curcumin film also highly increased as pH values increased to 10 and 11. This represented that more red color
intensity would be presented in tapioca starch/curcumin film at pH values of 10 and 11. Moreover, b* values of
tapioca starch/curcumin film highly decreased as pH values increased to 10 and 11. It indicated that less yellow
color of tapioca starch/curcumin film would be achieved at high pH values of 10 and 11.

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 TABLE 2. Color parameters of tapioca starch/curcumin film at pH 5-11.

pH L* a* b*
5 82.86±0.40 5.82±1.03 112.35±0.76
6 83.58±0.46 4.75±0.81 111.37±1.36
7 83.64±1.26 4.67±2.27 109.48±3.46
8 82.61±0.47 5.26±0.82 100.50±1.69
9 80.52±0.76 9.29±1.00 100.12±0.35
10 69.82±0.50 24.79±0.91 85.22±1.06
11 65.95±1.28 28.86±1.31 90.39±0.81

However, a dark orange color can be seen in curcumin solution at the pH values of 8-9 as shown in Fig. 2, while
a light orange color can be seen in the tapioca starch/curcumin film at the pH values of 8-9. Therefore, the curcumin
content adding to the tapioca starch film also could be affected to intensity of color changes.
The contact angles of tapioca starch film and tapioca starch/curcumin film are presented in Fig. 6. It can be seen
that contact angles of tapioca starch film and tapioca starch/curcumin film are 83.2°±4.6° and 97.1°±5.8°,
respectively. Therefore, curcumin can be reduced the wettability on tapioca starch film surface, due to a
hydrophobic polyphenol compound of curcumin [4].

(a) (b)

FIGURE 6. Water drop shape on (a) tapioca starch film and (b) tapioca starch/curcumin film.

Table 3 exhibited the water solubility (WS) and water vapor transmission rate (WVTR) of tapioca starch film
and tapioca starch/curcumin film. The addition of curcumin into the tapioca starch film can be reduced the WS. Due
to the nature of curcumin, it is low water solubility [2, 3]. However, the incorporation of curcumin with content of
0.04% w/v into tapioca starch film does not change WVTR of tapioca starch/curcumin film as compared with only
tapioca starch film. Therefore, the curcumin content of 0.04 % w/v in the tapioca starch film might be not enough to
block or retard the water vapor mobility.

TABLE 3. Water solubility and water vapor transmission of tapioca starch film and tapioca starch/curcumin film.

Film WS WVTR
(%) (g/h.m2)
Tapioca starch 76.36±5.32 1.4775±0.0944
Tapioca starch/ curcumin 62.60±2.12 1.3111±0.0888

The tensile properties of tapioca starch film and tapioca starch/curcumin film are shown in Table 4. The tapioca
starch/curcumin film exhibited lower tensile strength than the tapioca starch film. However, the tapioca
starch/curcumin film showed higher elongation at break than the tapioca starch film. Therefore, curcumin could be
acted as a plasticizer.

TABLE 4. Tensile strength and elongation at break of tapioca starch film and tapioca starch/curcumin film.

Film Tensile strength Elongation at break

(MPa) (%)
Tapioca starch 1.69±0.76 62.54±17.29
Tapioca starch/curcumin 0.93±0.09 126.38±24.87

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 CONCLUSIONS
A dark brown curcumin powder was achieved from an evaporation of curcumin extract. The color changes of
curcumin solution changed from yellow to reddish-brown as the pH values changed from 7 to 8. A pH indicator can
be prepared by adding curcumin into the tapioca starch. It can be seen that a yellow color of tapioca starch/curcumin
film turn to a dark orange color as the pH values increased. Curcumin can be reduced the wettability and water
solubility of tapioca starch film. Moreover, curcumin also acted as a plasticizer.

ACKNOWLEDGMENT
The authors would like to thank Faculty of Agro-Industry, Chiang Mai University, Thailand, for supporting
some chemicals in this work.

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2. Q. Ma, L. Du and L. Wang, Sensor Actuat. B Chem. 244, 759-766 (2017).
3. Y. S. Musso, P. R. Salgado and A. N. Mauri, Food Hydrocoll. 66, 8-15 (2017).
4. N. Pourreza and H. Golmohammadi, Talanta 131, 136-141 (2015).
5. S. Wanninger, V. Lorenz, A. Subhan and F. T. Edelmann, Chem. Soc. Rev. 44, 4986-5002 (2015).
6. A.P. Damant, “Food Colourants,” in Handbook of Textile and Industrial Dyeing, edited by M. Clark
(Woodhead Publishing Limited, Cambridge, 2011), p. 278.

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