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 27th IAPRI Symposium on Packaging 2015

Effect of Dispersants on Particle Size

and Size Dispersion of a Nanosemiconductor,
and pH on Color Transition of a Novel TiO2-based,
UVA-activated, Oxygen Bio-indicator
Surachai Khankaew1, Waraporn Boonsupthip2,3,
Chanassa Nandhivajrin1 and Panuwat Suppakul1,3*
1
Department of Packaging and Materials Technology, Faculty of Agro Industry,
Kasetsart University, Bangkok, Thailand
2
Department of Food Science and Technology, Faculty Agro-Industry,
Kasetsart University, Bangkok, Thailand
3
Center for Advanced Studies in Agriculture and Food (CASAF),
Kasetsart University, Bangkok, Thailand
*
Corresponding author name. Email: panuwat.s@ku.ac.th

Abstract: A colorimetric oxygen indicator is in a subclass of diagnostic packaging which being

as is a member of intelligent packaging. It can react with a concentration of oxygen in a headspace of
the package and the results of this reaction can be applied to monitoring of food and provide
information for customers. The colorimetric oxygen indicators particularly are non-toxic and in-pack
activated i.e. they are located inside the package. They offer a simple possibility to monitor the
integrity of the packaging. Titanium dioxide is the most used as a semiconductor (SC) in UV-activated
oxygen indicator. However, the aggregation behavior of SC can affect color changing of UV-activated
oxygen indicators. This work was to investigate the effect of food grade dispersants on the particle
size and size distribution of the nano semiconductor ( nSC) on color transition of a novel TiO 2-based,
UVA-activated, oxygen bio-indicator. This colorimetric indicator consisted of a bio-redox dye
(anthraquinone derivative-anthraquinone β-sulfonate, AQS), a sacrificial electron donor
(SED=glycerol:sorbitol), a nano-semiconductor (nSC=TiO2) and tree of bio-based surfactant (i.e.
polyethylene-b-polyethylene glycol (PE-b-PEG), Tween 60® (poly sorbate 60, Tw60) and sodium
lauryl sulphate (SLS) as dispersants. The indicator label with a thickness approximately 106.67 µm
was fabricated by using casting techniques. Upon exposure to 3 min of UVA light (12.90 mWcm-2), the
indicator label was readily photoactivated, and the leuco-AQS (colorless) changed to AQS (yellowish).
Indicator label recovered to its original color in approximately 10 h under ambient conditions (~25 C,
~65%RH, 21%O2), but did not recover its original color in the absence of O2. The total color
differences (TCD), the photoactivation rate and the times of color changing of each dispersant were
investigated as well as the effect of pH on the color transition, the particle size and size distribution of
nSC in indicator solution, which has been characterized by dynamic light scattering (DLS) is also
reported.

Keywords: oxygen indicator, surfactant, particle size, TiO2, intelligent packaging

1 Introduction

Currently, the detection of oxygen gas in food packages, whether it be packed using modified
atmosphere packaging (MAP) or vacuum packaging (VP) methods is important [1]. Oxygen gas
significantly affects the quality of food products via enzyme catalyzed reactions, browning reactions,
lipid oxidation, and protein decomposition, as well as microbial growth [2]. In order to measure or
detect the oxygen concentration, the use of oxygen indicators in food packages was increasingly
interesting because the level of oxygen in a headspace of food package increased due to poor sealing,
package leakage and/or gas permeability of package materials.
Oxygen indicator is in a subset of diagnostic packaging which is a member of intelligent packaging
[3], it works as leak indicator by monitoring the oxygen concentration in a headspace of food package
and giving information [3], [4] by change in color. Oxygen indicator is the most common indicator
used for MAPed [5]. The MAP is flushed with inert gas (i.e. carbon dioxide and/or nitrogen) before
packing in order to remove oxygen gas from one that contains 21% (i.e. in ambient air) to one that is
largely free of oxygen (i.e. <0.1-1% [6], [7]). After an inert gases was flushed into a food package,
the residual oxygen concentration in the package headspace is often still significantly more than 2%,
depending on the properties of food, poor sealing, the permeability of oxygen through the package
material [6] and efficiency of the packaging equipment [7]. To certify a very low oxygen
concentration, an oxygen scavenger can be added to the food package combined with an oxygen
indicator [6], this method has been shown typically to extend the shelf-life of food more than 3-4
times that in air [8].

The most typical Oxygen indicators are colorimetric light-activated, redox dye-based oxygen indicators
[6] which use a semiconductor photosensitiser (SC), coupled with a redox dye (Dox), a sacrificial
electron donor (SED), and an encapsulated polymer in the form of an intelligent ink [9], [8], [10]. In
this system, the semiconductor, usually TiO2, absorbs UV-light (≥energy bandgab, Ebg) in an
activation process, creating electron-holes in order to react rapidly with the sacrificial electron donor,
leaving the photogenerated electrons to react the redox dye (usually methylene blue, MB) and
generating a different color from blue to colorless as a reduced form (Dred) of the MB [9]. Obviously in
the absence of oxygen, such as VP or MAPed packages, the UV-activated indicator remains bleached
and will only revert back to the original blue color again upon exposure to oxygen in air [11].

The novel features of this typical oxygen indicator ink/film include: UVA-activated, irreversible, re-
useable, easily handled, non-toxic, printable, very inexpensive and a long shelf-life [11]. UPM Raflatac
Ltd creates a UV-activated oxygen sensitive label based on later technology, to detect leaking of MAP
food packages [12]. Subsequent work, colloidal TiO2 was used in oxygen indicator ink, showed that
the ink could be printed onto flat substrates such as paper of plastic film using an inkjet printer [13].
Hence, the key compositions (i.e. redox dyes, semiconductor powder particles and sacrificial electron
donors) are chosen so that they readily disperse in water containing a polymer which act as a
encapsulated polymer binder when this oxygen indicator is used as printing ink or dries to form an
indicator film [9].

Moreover, oxygen indicators should therefore not only be discussed on the basis of their technological
or scientific, but also on their general contributions towards a more sustainable world which are
influenced from packaging technology [14] According to the definition from the EU, intelligent
packaging contains a component which enables monitoring the condition of food packaged or the
environment surrounding the food during transport and storage. The system provides the user with
reliable and correct information on the conditions of the food, the environment and/or the integrity of
package. Intelligent packaging is an extension of the communication function of traditional food
packaging, and communicates information to the consumer based on its ability to sense, detect, or
record changes in the product or its environment, [15], [16]. However, the conventional oxygen
indicator is normally used by packing it with a food product, therefore it should not only be non-toxic
but also not release any components to the packaging materials and the food product [17]. These can
be protected by using a hydrophobic polymer such as polypropylene [18], [19].

In order to develop a non-toxic oxygen indicator, a novel TiO2-based, UVA-activated, oxygen bio-
indicator which anthaquinone derivative was introduced as a bio-redox dye, TiO2 as a semiconductor,
food grade glycerol:sorbitol and methyl cellulose as a sacrificial electron donor and an encapsulated
polymer, respectively. The food grade dispersing agents, i.e. polyethylene-b-polyethylene glycol (PE-
b-PEG), Tween 60® (poly sorbate 60, Tw60) and sodium lauryl sulphate (SLS), were used as
dispersants, to investigate the particle size and size distribution of TiO 2 and the effects on color
transition in activation and recovery processes of the indicator. This novel oxygen bio-indicator, which
is not only different in the original color but also the color transition compared with other research in
the published domains and commercials.
2 Methods

2.1 Materials and chemicals

Sodium Anthraquinone-2-sulfonate (C14H7NaO5S), (AQS) and titanium (IV) oxide, TiO2 (anatase) were
used as a redox dye and a nano-semiconductor (nSC) in this research, these were purchased from
Sigma-Aldrich (Gillingham, UK). Glycerol (C3H8O3) was used as a sacrificial electron donor (SED), it
was purchased from Ajax Finechem (NSW, Australia). Polyethylene-b-poly (ethylene glycol) (PE-b-
PEG) which is Mw= 575, Tween 60® (poly sorbate 60, Tw60) and sodium lauryl sulphate (SLS) was
purchased from Ajax Finechem (NSW, Australia), were used as a bio-surfactant. Acetic acid (C2H4O2)
and sodium hydroxide (NaOH) were purchased from Merck (Germany) and Ajax Finechem (Australia),
respectively, these were used to adjust pH of bio-colorimetric solutions. The polymer, methylcellulose
(MC) (Methocel®, Dow Chemical, USA) was used as a bio-based polymer and distilled water and
served as a solvent. Vacuum bag packaging, linear low-density polyethylene (nylon/LLDPE, thickness:
150 µm), was purchased from BangkokBestpack (Bangkok, Thailand), it was used to prepare the
oxygen free condition. All of the chemicals were used without further purification, unless specified,
and at the highest purity available.

2.2 Thin film oxygen bio-indicator preparation

The oxygen bio-indicator solution was used to make the indicator films, comprised: 15 mg of AQS, 50
mg of a bio-surfactant, 25 mg of TiO2, 500 mg of glycerol (G) and 5 g of distilled water. All
components were mixed together and stirred for 5 min, followed by 2 min with an ultrasound probe
(Sonics Vibra-Cell VCX130, Sonics and Materials, Inc., Newtown, USA), to disperse the usually
aggregated TiO2 particles thorough the various components. In order to produce the final oxygen bio-
indicator polymeric solution, 5 g of 10wt% methylcellulose (MC) aqueous solution was added into the
mixture, and then stirred magnetically for 10 min. The composition of the AQS/bio-
surfactants/TiO2/G/MC film can be summarized as follows: 3/10/5/100/100 pphr where pphr is part
per hundred resin.

A novel oxygen bio-indicator film was prepared from this solution by degassing and immediately
pouring 7.5 g of polymeric oxygen bio-indicator onto the Petri dish, and drying in laboratory conditions
for 24-30 h to produce a dry film with an average thickness of ca. 0.110 ± 0.009 cm. After finishing, it
was peeled out of the dish and cut into a small circle (ø1.5 cm). The final oxygen bio-indicator film on
the glass disk proved stable for over 3 months in the dark and ambient conditions. The novel oxygen
bio-indicator films are colorless and translucent.

2.3 Photoactivation, recovery processes and color response measurement

Oxygen bio-indicator films were packed and sealed with a vacuum packaging method using clear
polyamide laminated with nylon/LLDPE, a vacuum packaging film was used as an oxygen barrier layer.
The indicator packaged was tested by placing on coated paper prior to be exposed to UVA light with
intensity of 12.90 mWcm-2. Experiments were recorded before photoactivation (original color) and
after each time interval (5, 10, 15, 30, 60, 120, 180, 300, 600, 900 and 1500 s) by a chroma meter
spectrodensitometer (SpectroDens, Techkon®, Königstein, Germany) in L*, a*, b* color mode.

The color recovery step tested after being irradiated to maximum of a total color difference (TCD)
value and opened the label film indicator to react with oxygen in ambient air (20.9% oxygen). The L*,
a*, b* value were recorded before (colored) and after opening the vacuum package indicator, which
were measured at each time interval from 5, 10, 15, 30, 60, 120, 180, 240, 300 and 600 min. For
total color measurement, the main plot was then demonstrated, and the change in delta E (∆E* ab) or
the total color difference (TCD) was expressed as follows (1):
Used (L*1, a*1, b*1) and (L*2, a*2, b*2), two colors in L*, a*, b* mode.

(1)

Where ∆L* is the brightness difference between initiation (L*1) and each time interval (L*2), ∆a* is the
redness-greenness difference between initiation (a*1) and each time interval (a*1), and ∆b* is the
yellowness–blueness difference between initiation (b*1) and each time interval (b*1) [20].

2.4 Bio-indicator solution with different pH and absorption spectra measurement

A stock of bio-indicator solution was prepared as follows: 0.3 g of a redox dye (AQS), 1.0 g of a bio-
surfactant, 0.5 g of a semiconductor (TiO2), 10.0 g of a sacrificial electron donor (glycerol) and
deionized water 100 g, these were mixed together and stirred for 15 min, and followed by 30 min of
sonication from an ultrasonic probe for 5 min to ensure though mixing and dispersion of various
components.

In order to make the different pH of indicator solution, it was adjusted to pH values of 2, 4, 6, 8 and
10 by using solution A (i.e. 0.2 M of H3BO3 and 0.05 M of C6H10O8) and solution B (i.e. 0.1 M of
Na3PO4•12H2O) [21]. After that, an oxygen bio-indicator solution was suspended in a quartz cuvette
and sealed plastic topper. The boundary of the cuvette and topper was dipped into a sealing wax to
prevent oxygen leak into the solution. A photoactivation was carried out using a UVA light (irradiance
of 12.90 mWcm-2) from 11W BLB Sylvania Lynx light source. In order to determine the effect of pH on
color transition of the indicator solution, the absorption spectra were measured before and after
photoactivation by using a visible-spectrophotometer (CM7300A, Konica Minolta, Japan).

2.5 Particle size and size dispersion of a nanosemiconductor measurement

A stock of bio-indicator solution was prepared as follows: 0.3 g of a redox dye (AQS), 1.0 g of a bio-
surfactant, 0.5 g of a semiconductor (TiO2), 10.0 g of a sacrificial electron donor (glycerol) and
deionized water 100 g, these were mixed together and stirred for 15 min, and followed by 30 min of
sonication from an ultrasonic probe for 5 min to ensure though mixing and dispersion of various
components.

3 Results and discussions

3.1 Initial reactions of oxygen bio-indicator

Normally, the typical oxygen indicator works on the ultra-band gab (Ebg) illumination of semiconductor
particles (SC, such as TiO2) creates electron-hole pairs (process 1 in Fig. 1), the photogenerated
holes of which rapidly oxidize irreversibly the sacrificial electron donor (SED, such as glycerol) present,
and the photogenerated electrons reduce the redox dye (such as methylene blue, MB), Dox (MB) to a
different color as a reduced form (leuco-MB, colorless), which is oxygen sensitive and remains in its
Dred in the absence of oxygen, but critically, this indicator has its original color restored upon
exposure to oxygen in air [8], [6]. However, this oxygen bio-indicator works in contrast. During the
photoactivation process the SED (glycerol) reacts rapidly and irreversibly with the photogenerated
holes, whereby it is oxidized, leaving the photogenerated electrons on the SC (TiO2), as process 2a in
Fig 1, to increase the color value of redox dye, Dox (leuco-anthraquinone, LAQS) to its colored,
reduced from, Dred (anthraquinone, AQS), as process 2b in Fig. 1. AQS is oxygen sensitive, so that
after UV activation, the UV activated oxygen bio-indicator film remains in its colorless form in the
absence of oxygen, but crucially, this indicator has its original color restored upon exposure to oxygen
in air (via the oxidation step 2 in Fig. 2).
 hυ> Ebg
nSC process 1 nSC*

process 2b
AQS SED
process 2a

nSC-
O2
LAQS SEDOX
Process 3

OH

Figure 1: Schematic reaction of the key processes in an oxygen bio-indicator, comprising: (process 1)
the UVA-light driven reduction of LAQS to AQS (photoactivation), (process 2a) the SED leaving the
photogenerated electrons to react with a redox dye, thereby generating a differently color (process
2b) and its subsequent re-oxidation by oxygen (if present) (recovery, process 3).

From this mechanism, the oxygen bio-indicator is well addressed by anthraquinone derivative which is
an organic redox dye [22], that is readily reduced by photogenerated conductance band electrons on
TiO2 semiconductor particles, and changed from LAQS (colorless) to its AQS form (yellowish) via the
following reaction:

2TiO2(e-) + H+ + LAQS 2TiO2 + AQS

(2)

At present, oxygen bio-indicators do not have color, the reduction process occurs via a concerted two
electron-transfer step or via the intermediate formation of a semi-reduced LAQS radical, and its
subsequent disproportionation, as found in homogeneous solution, for example in the reduction of
methylene blue by reduction agent [8], [11].

3.2 Photoactivation and color response of the oxygen bio-indicator films

The results in Fig. 2, illustrate the change in apparent TCD values between the before and after
photoactivation process, of oxygen bio-indicator film (under vacuum package). It can be seen that the
films are increased in TCD value and color shade, from colorless and translucent to a just discernible
yellowish, upon exposure to > 5 s UVA photoactivation (12.90 mWcm-2) as the colorless (LAQS) is
generated to color (AQS), via process 2b in Fig.1. The results showed that all samples yielded an
increase in TCD value during these samples were exposed by UV-activation. This could be immediately
distinct after > 5 s and then the highest value of TCD was reached at a minimum of 600 s (10 min).
The highest TCD values of all samples used 10 pphr of PE-b-PEG (blue line), SLS (red line) and Tw60
(green line) as surfactants which were 46.72, 41.95 and 39.94 of 300 s, respectively. From Fig. 2, it
demonstrates that TCD values were attended to a decrease in their values after reaching the
maximum.

The initial rate of photoactivation for an oxygen bio-indicator film was studied as a of irradiation time,
as shown in inserted diagram of Fig. 4, it was found that the rate of film photoactivation, using a
series of indicators film prepared with the following different type of food grade surfactants content:
10 pphr. The highest initial rate was 0.97 of PE-b-PEG, as same as the highest TCD value.
 50

40
50

Initial Rate (TCD L*a*b*)

30 40
TCD (L*a*b*)

y = -0.0041x2 + 0.9661x
30
y = -0.0039x2 + 0.8964x
20 y = -0.0033x2 + 0.7847x
20

10
10
0
0 20 40 60 80 100 120
Time / s
0
0 200 400 600 800 1000 1200 1400
Time / s

Figure 2: The change in TCD values as a function of irradiation time, during a photoactivation
(12.90 mWcm-2 UVA-light intensity) under oxygen free condition, insert plot illustrated the initial rate
profiles from the normalized TCD values vs irradiation time. The blue, red and green lines are the
oxygen bio-indicator film which used PE-b-PEG, SLS and Tw60 as surfactants, respectively.

The oxygen bio-indicator was activated to a maximum TCD (L*a*b*), under oxygen free conditions,
following exposure to oxygen in ambient air (20.9% oxygen). The results showed that all samples
yielded to decrease immediately in TCD value after these samples were exposed to oxygen in ambient
air and the change in the TCD value pre- and post- UVA photoactivation was recorded, as illustrated in
Figure 3. The results show that the photoactivation process affected all samples, these increased in
TCD values to colored, yellowish. Upon 300 s exposure time with UVA intensity 12.90 mWcm-2. In
contrast, the recovery process (as the photogenerated AQS reacts with oxygen in ambient air), all of
samples were continuously decreased in TCD value close to steady state in colorless of > 10 h
(normally 24 h [23]). The TCD value of oxygen bio-indicator film when exposed to the air in ambient
conditions at room temperature showed that TCD values were reduced corresponding to exposure
time. In this research, the oxygen bio-indicator of PE-b-PEG, Tw60 and SLS (as show in blue, green
and red lines in Figure 3) as dispersants, presented the fast samples to fade from yellowish (AQS) to
colorless (LAQS), the TCD values of these were 3.15, 3.53 and 5.11 at 1800 s (i.e. 30 h) oxygen
exposure, respectively, it was closed to steady state of color. However, the initial rates (at 600 s) of
TCD values revealed differences, the fastest and lowest of the initial rate in recovery process were
used PE-b-PEG and Tw60, respectively, as in inserted plot of Figure 3.
 45
35
30
y = 0.0666x
25 y = 0.0648x

TCD (L*a*b*)
20 y = 0.0626x
30
15
TCD (L*a*b*)

10
5
0
15 0 100 200 300 400 500 600
Exposure Time / min

0
0 300 600 900 1200 1500 1800
Exposure Time / min

Figure 3: The change in TCD values as a function of recovery time of activated oxygen bio-indicator
films and after exposed to oxygen in ambient air, the insert plot illustrated the initial rate profiles from
the normalized TCD values vs recovery time. The blue, red and green lines are the oxygen bio-
indicator film which used PE-b-PEG, SLS and Tw60 as surfactants, respectively.

3.3 Particle size and size distribution of a semiconductor

Normally, TiO2 is usually aggregated particles [24] and preferred over the bulk (i.e. microcrystalline)
[25], thus ensuring effective photocatalytic reactions and clear of indicator films by small amounts of
the semiconductor (SC) [9]. In this experiment, the SC was used at 5 pphr with the ultrasound
method and dispersants to disperse.

The particle size of a nano photocatalyst semiconductor, TiO2, was investigated by using dynamic light
scattering (DLS) method. Table 1 revealed the average size of TiO2 particles of oxygen bio-indicator
solution (AQS/bio-surfactants/TiO2/glycerol) which using SLS, PE-b-PEG and Tw60 as surfactants were
189.90 ±2.89, 1678.67 ± 125.17 and 663.90 ± 10.95 nm, respectively.

Table 1: Particle size of a semiconductor, TiO2, in oxygen bio-indicator solution.

Dispersants Temp / °C Z-Average /d.nm S.D.

SLS 25.0 189.90 2.89
PE-b-PEG 25.0 1678.67 125.17
Tw60 25.0 663.90 10.95

From Table 1, the effectiveness dispersant to decreased the size of agregated TiO2 particles was
sodium luaryl sulphate (SLS), the particle size range was around 80 – 500 nm with around 17%
intensity peak, and the polyethylene-b-polyethylene glycol (PE-b-PEG) was the biggest of TiO2
particles, it was shown that the particle size range around 700 – 2500 nm with around 22% of
intensity peak, as shown in Figure 4.
 Figure 4: The size distribution of a nano TiO2 in oxygen bio-indicator solutions
used different surfactants.

3.4 Effect of pH on color of an oxygen bio-indicator

Light absorption spectra of the oxygen bio-indicator solution on which different pH were recorded, as
shown in Figure 5. When UVA-irradiation time was more than 300 s, the solutions were changed
from colorless to yellowish. However, the shades of colors were different, depending on the pH from 2
to 11, the solutions were changed from light green, greenish yellow, yellow, yellowish orange and
finally orange, respectively. According to the report of Galagan and Su, it was found that a reduction
in sodium anthraquinone-2-sulphonate by sodium hydrosulphite in water led to a bright yellow
compound and it was responsible for red color in the alkaline media [26].

The maximum absorbance (λ-max) of the indicator solutions were changed and shifted when
activated with UVA-light, upon the pH of the indicator solutions. Normally, the original indicator
solution was around 375 nm, after activation process, the maximum lambdas were continuously
shifted from 430 to 510 nm of the pH from 2 to 11, respectively (Figure 5). The inserted
photographs in Figure 5 also revealed the color shades of the indicator solutions which different pH.
 1.0 Non-
activated
0.9 UVA-activation 2
Process 1 and 2
0.8 3

Before pH 2 3 4 5 6 7 8 9 10 11 4
0.7
5
0.6
Abs

6
0.5
7
0.4
8

0.3
9

0.2 10

0.1 11
375 425 475 525 575 625 675 725
Wavelength / nm

Figure 5: Absorption spectra of oxygen bio-indicator solutions used PE-b-PEG as a dispersant

which different pH, before and after photoactivation process (under oxygen free condition) and the
photographs reveal color shades of the indicator solutions in cuvette cell.

As shown in Figure 6. An initial photoactivation rate of an oxygen bio-indicator solution was studied
as a function of pH, the maximum TCD values increased as increasing pH values. The indicator
solution with pH=10 led to the highest TCD values.

35
maximum TCD / activation time (300 s)

y = 0.0934x2 + 0.919x + 10.591

30 R² = 0.9701

25

20

15

10

0
2 3 4 5 6 7 8 9 10 11
PH of oxygen bio-indicator

Figure 6: The change in maximum TCD values (300 s UVA activation time) of oxygen bio-indicator
solutions used PE-b-PEG as a dispersant which different pH.
4 Conclusions
A novel UVA-activated oxygen bio-indicator consisting of AQS/bio-dispersant/TiO2/glycerol was
fabricated using methylene cellulose as a bio polymer. The oxygen bio-indicator film with thickness
ca. 0.110 ±0.009 cm is translucent and colorless (LAQS). In this study, the effectiveness dispersant
on photoactivation process was polyethylene-b-polyethylene glycol (PE-b-PEG), it was activated
(under oxygen free condition) from oxidized form (colorless, LAQS) to reduced form (yellowish, AQS),
maximized TCD in 300 s by UVA-light (12.90 mWcm-2 intensity) and recovered in around 30 h in
ambient conditions (~27 ˚C, ~60 %RH, ~21 %oxygen). However, PE-b-PEG was shown to be the
biggest of the average particle size and the effectiveness dispersant to decreased the agregated TiO2
particle size was sodium luaryl sulphate (SLS) which was around 189.90 ±2.89 nm. The color shades
and initial rates of indicator solutions were different depending on the pH, it could appear greenish-
yellow at low pH (pH<7) and gradually change to yellowish and orange at higher pH (pH > 7), these
appeared in λ-max from 430 to 510 nm, respectively.

5 Acknowledgements
This work was financially supported by the Thailand research fund through the Royal Golden Jubilee
(RGJ.) Ph.D. Program (grant no. PHD/2554/0054) is acknowledged.

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