Food Control 25 (2012) 328e333

Contents lists available at SciVerse ScienceDirect

Food Control
journal homepage: www.elsevier.com/locate/foodcont

Review

Carbon dioxide sensors for intelligent food packaging applications

Pradeep Puligundla, Junho Jung, Sanghoon Ko*
Department of Food Science and Technology, Sejong University, 98 Gunja-dong, Gwangjin-gu, Seoul 143-747, South Korea

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 30 June 2011
Received in revised form
12 October 2011
Accepted 18 October 2011

Recently, the demand for safe and high quality foods, as well as changes in consumer preferences have led
to the development of innovative and novel approaches in food packaging technology. One such development is the smart or intelligent food packaging technology. Intelligent packaging has enabled to monitor
and communicate information about food quality. This technology also helps to trace a products history
through the critical points in the food supply chain. In general, occurrence of elevated CO2 gas level is the
prime indicator of food spoilage in packed foods and also its maintenance at optimal levels is essential to
avoid spoilage in foods packed under modied-atmosphere packaging (MAP) conditions. Hence, a CO2
sensor incorporated into food package can efciently monitor product quality until it reaches the
consumer. Although much progress has been made so far in the development of sensors monitoring CO2,
most of them are not versatile for food packaging applications and suffers from limitations such as high
equipment cost, bulkiness, and energy input requirement, including safety concerns. Therefore, the
development of efcient CO2 sensors that can intelligently monitors the gas concentration changes inside
a food package and specic to food packaging applications is essential. In the present review, progress on
the development of different types of CO2 sensors such as optical sensors, polymer opal lms, polymer
hydrogels, etc., which can be readily applicable to food packaging applications, is discussed.
Crown Copyright 2011 Published by Elsevier Ltd. All rights reserved.

Keywords:
Carbon dioxide sensor
Intelligent food packaging
Optical sensors
Polymer opal lms
Polymer hydrogels

Contents
1.

2.

3.
4.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
1.1.
Novel food packaging techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
1.2.
Carbon dioxide (CO2) as a direct indicator of food quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
1.3.
Driving force for innovation in food quality monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
CO2 sensors for intelligent food packaging applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
2.1.
Conventional CO2 sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
2.2.
Innovative optical CO2 sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
2.2.1.
Wet optical CO2 indicators (pH-based) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
2.2.2.
Principle in pH dye-based indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
2.2.3.
Fluorescent CO2 sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
2.2.4.
Dry optical CO2 sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
2.2.5.
Solegel-based optical CO2 sensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
2.2.6.
Photonic crystal sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Polymer opal films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Polymer hydrogel-based CO2 sensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
2.2.7.
Color changing metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Safety & regulatory aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332

* Corresponding author. Tel.: 82 2 3408 3260; fax: 82 2 3408 4319.

E-mail address: sanghoonko@sejong.ac.kr (S. Ko).
0956-7135/$ e see front matter Crown Copyright 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodcont.2011.10.043

P. Puligundla et al. / Food Control 25 (2012) 328e333

1. Introduction
1.1. Novel food packaging techniques
Conventionally, a food package helps protect food from environmental inuences, such as moisture, light, oxygen, microbes,
mechanical stresses and dust. These factors lead to or enhance the
deterioration of food or drink. An ideal food packaging material
should be inert, not to allow the transfer, i.e. must have a perfect
barrier property, and recyclable. Food package makes distribution
easier. Apart from these, there are other important functions of
packaging, including containment, convenience, marketing, and
communication. However, in recent years, the area of active and
intelligent packaging is becoming increasingly signicant.
According to the denitions of the European Actipak project,
the active packaging changes the condition of the packed food to
extend shelf life or to improve safety or sensory properties, while
maintaining the quality of the packaged food. And, the intelligent
packaging systems monitor the condition of packaged foods to give
information about the quality of the packaged food during transport and storage (Ahvenainen, 2003). Active food packaging plays
a dynamic role in food preservation and allows packages to interact
with food and the environment. Active packaging technique
enables the regulation of various aspects that may play a role in
determining the shelf life of packaged foods, such as physiological
(e.g., respiration of fresh fruit and vegetables), chemical (e.g., lipid
oxidation), and physical (e.g., dehydration) processes as well as
microbiological aspects. Other developments in packaging technologies include odor absorbers, ethylene removers, and carbon
dioxide emitters/absorbers.
On the other hand, intelligent packaging systems attached as
labels, incorporated into, or printed onto a food packaging material
offer enhanced possibilities to monitor product quality, trace the
critical points, and provide product information like product
history (Han, Ho, & Rodrigues, 2005). The commonly used intelligent visual indicators are time/temperature indicators and leak
detectors, and these are indirect indicators, based on polymerization rate, diffusion, chemical or enzymatic reaction. However, the
direct indicators are preferred because of their ability to provide
more precise and targeted information on quality attributes
(Gontard, 2004).
1.2. Carbon dioxide (CO2) as a direct indicator of food quality
To decrease microbial growth rate and subsequent spoilage,
food products are often packed under modied-atmosphere packaging (MAP) conditions. The carbon dioxide (CO2) gas can be solely
(100%) or in different combinations with other gases such as
nitrogen (N2) and oxygen (O2) is typically used (as ush gas) for
creating protective atmosphere surrounding the food inside of
a pack with an aim to exclude or minimize the oxygen content,
thereby the shelf life of food can be extended through inhibiting the
aerobic spoilage microbes. And also, oxygen has been suggested to
be a major factor for deterioration of meat quality through lipid
oxidation (Andersen & Skibsted, 1991). Carbon dioxide is considered as an active packaging gas because high levels reduce the
metabolic rates of microbes even if oxygen is present (Wayne,
2000). Depending on the type of food and the delivery stage of
food item, the composition of protective atmosphere varies (Mills,
1998). The quality of MAP-packed food ultimately depends on the
integrity of package and, therefore, leakage detection is the
essential part of MAP technology (Bltzingslwen et al., 2002).
In modied-atmosphere food packages, freshness and safety of
food can be assessed by determination of CO2 concentrations
(Smolander, Hurme, & Ahvenainen, 1997). A decrease in its original

329

concentration could be a sign of leakage in a package (Neethirajan,

Jayas, & Sadistap, 2009). Conventionally, package headspace gas
analysis is generally carried out at various points of the food supply
chain by using electrochemical fuel cell for oxygen analysis, and by
infrared absorption spectrometry for carbon dioxide content
measurement, to ensure package integrity. However, in this
method, the food packs are sampled destructively by inserting
needle probe for gas collection (Smolander et al., 1997). A major
disadvantage with this method is, if a package fails the leak test,
a large number of packages before and after the tested one will have
to be considered failed and need to be destroyed or repacked (Mills,
1998); sometimes may include food products of an entire batch
also. Moreover, apart from destructive and time consuming nature
of conventional method, trained technician and expensive analytical equipment is required to monitor the equality.
Under normal atmosphere packing conditions, when the food
within a sealed container starts to spoil, several by-products are
formed and they accumulate inside. Therefore, theoretically it is
possible to detect spoilage by detecting one or more of these byproducts. Production of heat, acidity, pressure, and carbon
dioxide is commonly observed as by-products in food spoilage.
Ideally, a spoilage detector should be useable with as many
different food products as possible, without requiring different
detectors for each different type of food material. As the small
amounts of heat evolve during deterioration process, heat detection is not likely to be practical. And also, pH of the various foods
varies widely and, therefore impractical. Pressure detection is also
impractical.
Limited amount of published work is available regarding food
spoilage indicators. Based on volatile compounds produced in
microbial spoilage, indicators have been fabricated on a trial basis.
A myoglobin-based indicator for modied-atmosphere-packed
poultry meat has been developed, which can indicate spoilage by
detecting presence of hydrogen sulde (H2S) formed upon spoilage
(Smolander et al., 2002). For monitoring sh spoilage, Pacquit et al.
(2006, 2007) developed a colorimetric dye-based sensor that
detects the presence of total volatile basic nitrogen (TVB-N),
a product of spoilage. Knowledge about the quality-indicating
metabolites is an essential prerequisite for the development of
food spoilage indicators. Under non-MAP or nitrogen-ushing
conditions, aerobic and facultative anaerobic microbes thrive
during storage of the food products and often resulted in the
formation of lactic and acetic acids by lactic acid bacteria (LAB).
However, carbon dioxide is generally known to be produced during
any kind of bacterial, mold growth on foods. Therefore, to indicate
deterioration of foods, simply detection of CO2 levels is the ideal
way, and such detectors would have to operate without interference of the other properties of food, such as pH, salt content
(corrosiveness), pressure or vacuum etc (Eaton, Kilgore, &
Livingston, 1977). A correlation between CO2 concentration and
the growth of microorganisms was made in pea or tomato soup that
is packaged aseptically either in air or in a mixture of 5% oxygen and
nitrogen (Mattila & Ahvenainen, 1989; Mattila, Tawast, &
Ahvenainen, 1990); bromothymol blue, the pH-sensitive dye was
used as indicator for detecting the formation of CO2.
1.3. Driving force for innovation in food quality monitoring
The prime driving force is the growing consumer demand for
mildly preserved, minimally processed, easily prepared and readyto-eat fresher foods (Nopwinyuwong, Trevanich, & Suppakul, 2010).
Also, the innovations are fueled by globalization of food business
and, therefore, food products are needed to be kept fresh over long
distances and time. Conventional packaging techniques are inadequate to meet this requirement. In addition, consumers complaints

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P. Puligundla et al. / Food Control 25 (2012) 328e333

over the reduction in shelf life of foods and an increase in the risk of
food-borne illnesses from microorganisms reporting around the
world in recent years are also an important issue. Food traceability
throughout the food supply chain is increasingly becoming
a necessary task, mandatory in European Union (EU) since 2005
(Giraud & Halawany, 2006). In the light of the above, to maintain
safety and freshness and to evaluate real-time freshness of food
products, there is a constant need to develop a cost-effective,
accurate, rapid, reliable, non-invasive and non-destructive
methods or devices. Therefore, in order to achieve these goals,
a measurable technology, visually or instrumentally, should be
developed which provide in-situ information about the gas
composition and, therefore, information on food quality of packaged foods through any point of food supply chain until reaching
the consumer.
Indicator should be very inexpensive, and not add signicantly
to the overall cost of the package. It should be non-toxic, and have
non-water soluble nature. The sensor components should have
approval for use in food-contact materials. Also, it should not
require an expensive instrumentation for analysis and should be
able to check it even by an untrained person. It also should exhibit
an irreversible response toward analytes.
2. CO2 sensors for intelligent food packaging applications
2.1. Conventional CO2 sensors
Broadly, the CO2 sensors can be divided into two types, optical
and electrochemical, based on the type of transducer. The electrochemical CO2 sensors are further sub-categorized into potentiometric, amperometric, and conductometric types. Non Distributive
Infra Red (NDIR) and Severinghaus-type sensors are used conventionally, commercially for gaseous and dissolved CO2 detection,
respectively. However, the NDIR instrument is expensive, large in
volume, vulnerable to contamination, and water vapor interference
despite its high precision. Furthermore, the process requires the
destruction of a sealed package for gas analysis, and not suitable for
routine sample analysis. Therefore, compact and cheap sensors are
in high demand.
Severinghaus CO2 sensor consists of a bicarbonate solution lled
glass electrode covered by a thin CO2 permeable membrane. The
membrane is impermeable to water and electrolytes. The sensor
functions on principle that in an aqueous solution, CO2 forms
carbonic acid, which is then dissociates into a bicarbonate anion
and a proton (Dieckmann & Buchholz, 1999). The proton-induced
pH change in electrolyte solution can be measured by a pH probe.
A CO2 sensor principle that slightly differs from Severinghaus
concept was presented by Varlan and Sansen (1997). The concept is
based on conductivity change as a result of the reaction of carbon
dioxide and bicarbonate solution inside a cavity covered with a gas
permeable membrane. This kind of sensors can measure CO2
concentrations between 0 and 11 kPa with a very fast response
time. The advantage with this kind of sensors is that the use of
a separate reference electrode is not required. Unfortunately,
however, keeping the cavities clean is a major concern.
Electrochemical potentiometric CO2 sensors using solid electrolytes are one among promising methods because of their
compact structure, ability of continuous monitoring, high selectivity, and low cost (Hong, Kim, Jung, & Park, 2005). However, they
require power for signal generation, and often require above 400  C
operating temperature and, therefore, are not suited for food
packaging applications. The environmental factors such as
temperature and humidity can affect the sensors performance,
especially in the case of metal oxide sensors, by cross-sensitivity
reactions.

2.2. Innovative optical CO2 sensors

The concept of on-pack, continuous gas composition indicating
optical sensors are attractive and have been developed, tested by
many researchers for monitoring MAP package integrity. Optical CO2
sensors can be classied into two types, namely, the sensors which
function based on the color (colorimetric) change of a pH indicator
dye, such as thymol blue, phenol red, cresol red, etc. (Kawabata,
Kamichika, Imasaka, & Ishibashi, 1989; Mills, Chang, & McMurray,
1992, Mills, Lepre, & Wild, 1997); and those based on the CO2induced uorescence change of a luminescent dye (Marazuela,
Moleno-Bondi, & Orellana, 1995; Mills & Chang, 1993) such as
ruthenium (II) complexes and 1-hydroxypyrene trisulfonate.
2.2.1. Wet optical CO2 indicators (pH-based)
All wet optical sensors function on the principle of Severinghaus
carbon dioxide electrode, and therefore diffusion of CO2 from the
test medium (gaseous or aqueous) through a thin (ca. 10 mm) gas
permeable membrane, and a quick establishment of equilibrium
with the entrapped aqueous layer, which contains pH-sensitive
dye, usually occurs in a typical wet optical sensor for CO2 (Mills,
2009). The detection process involves mixing of gas to be tested
with a chemical reagent/dye which results in a color change/shift of
the chemicals. This change of color can be measured and compared
to a standard. The usefulness of colorimetric analysis for CO2
measurement has been shown (Hauser & Liang, 1997; Mills &
Monaf, 1996; Uttamial & Walt, 1995). Tufex GS pouches that
contain a visible CO2 indicator were developed by Sealed Air
Limited. The pouches can be used to identify machine faults and gas
supply problems, to indicate non-integrity of the package, and to
check the presence of desired gas mixture in modied-atmosphere
packaging. A reversible CO2 indicator comprising ve indicator
strips for use in modied-atmosphere packages was fabricated and
patented by Balderson and Whitwood (1995); the strips are coated
with CO2-sensitive indicator material, for instance, anion of an
indicator and a lipophilic organic quaternary cation (Mills &
McMurray, 1991), and each strip is designed in such a way that
changes their color when the CO2 level is below a certain limit (e.g.,
25%, 20% or 15%). A mixed pH dye-based, on-package colorimetric
indicator was developed for real-time monitoring of intermediatemoisture dessert spoilage (Nopwinyuwong et al., 2010). This indicator responds through visible color change to carbon dioxide (CO2)
as a spoilage metabolite; and the change correlates well with
microbial growth patterns in dessert samples.
To sense ripeness of fermented vegetable foods such as kimchi
several physical properties such as color, volume, turbidity;
chemical properties such as pH, acidity, CO2, sugars, salts, etc., and
microbiological properties have been tested (Mheen & Kwon, 1984).
However, commercial packed kimchi products generally undergo
a continuous natural fermentation process even during storage and
distribution. So, the ripeness/over-ripeness cannot be detected by
general testing methods without destroying the packaging materials (Hong & Park, 1999). Therefore, a sensor which can monitor
the CO2 gas continuously, and indicate levels through exhibiting
different colors accordingly, non-destructively, has been under
development. Changes in CO2 concentration within the kimchi
package showed a sigmoid increase during fermentation. A color
indicating sachet responding to CO2 levels has been developed for
application to kimchi packaging (Hong & Park, 1997). However, the
technique suffered from disadvantages of inconvenience, handling
difculty and safety concerns for commercial products. The same
research group had developed a color indicator lm consisting of
polypropylene (PP) resin, Ca(OH)2 as a CO2 absorbent and bromocresol purple or methyl red indicators, and the lm was attached
to the lid.

P. Puligundla et al. / Food Control 25 (2012) 328e333

Majority of colorimetric CO2 optical indicators are solventbased (i.e. non-aqueous) systems, incorporating a phase transfer agent (PTA) to solubilize the usually lipophilic dye and base
(Mills et al., 1992). However, poor shelf life stability of such
systems is a major drawback when stored under dark and/or
ambient conditions (Mills & Monaf, 1996; Weigl & Wolfbeis,
1995). Thus, the dye in such indicators changes irreversibly to
its acidied form, rendering the indicator ineffective in short
time. Therefore, usually an inert atmosphere is used in packaging, but with additional cost to production. Interestingly,
water-based CO2 indicators have shown markedly greater lifetimes, than their solvent-based counterparts. A water-based ink
containing base-sodium hydrogen carbonate and plasticizerglycerol, having improved operational lifetimes, quick response
and recovery times (2 min), reversible color change on all
tested surfaces, and works under ambient condition has been
reported (Mills & Skinner, 2010). However, sensitivity to
humidity and temperature is needed to be addressed before
realizing potential usage for intelligent food packaging applications. But, luckily, a xed temperature (chilled, 4  C) and
unchanged % RH is usually maintained for MAP food packages
and, therefore, water-based CO2 sensors could be used.
The sensitivity of CO2 sensor is linked to the equilibrium
constant (pKA) of the pH indicator used and to the nature of
surrounding buffer (Mills & Chang, 1994). An aqueous bicarbonate
buffer usually contained in rst generation optical carbon dioxide
sensors. The aqueous buffer containing sensors have been replaced
by quaternary ammonium hydroxide containing solid sensor
membranes (Mills et al., 1992). Earlier, colorimetric leak indicators
in the form of sachets and tablets have been used for sensors
development in food packaging technology. Latest approaches, for
more compatible with industrial demand, would consist of printable sensor membranes on the packaging material and should
provide information about analytes at any given stage in the
packaging and delivery process.
2.2.2. Principle in pH dye-based indicators
The carbon dioxide gas dissolves in the aqueous buffer or
hydrophilic lter layer in strip or membrane type sensor and forms
carbonic acid.

CO2 g4CO2 aq
CO2 aq H2 O4H2 CO3
The two hydrogen atoms from the formed carbonic acid
(diprotic) may dissociate to form hydrogen ions (H) and bicarbonate ions (HCO3) with pKa of 6.36 at 25  C (Mook & de Vries,
2000).

H2 CO3 4HCO
3 H

Then, a hydrogen ion, as a proton, combines with a water

molecule to form a hydronium ion, H3O

H H2 O/H3 O
Hydronium ions react with the basic (dissociated) form (In) of
the indicator dye, resulting in an acid (protonated) form (HIn)
which in turn produces a color change of the indicator containing
solution or label.

H In /HIn
There are certain drawbacks are associated with use of
pH-based sensors that CO2 levels cannot be measured directly, but
in its ionic form and, therefore, the pH-value measurement could

331

be impaired by other volatile acid or basic gases produced during

spoilage. And also, maintenance costs are very high.
2.2.3. Fluorescent CO2 sensors
Similar to the colorimetric method except that a uorescent dye
is used to generate its own radiative energy at a different wavelength to that of the excitation wavelength. The generated excitation spectra will depend on the sample gas concentration. CO2
measuring instrumentation also fabricated using this principle
(Choi & Hawkings, 1995a,b; Wolfbeis & Weis, 1998).
A printable oxygen and carbon dioxide sensors formulations
have been developed for application in food packaging (McEvoy
et al., 2003); the oxygen was measured by detecting the degree
of quenching of a uorescent ruthenium complex entrapped in
a solegel matrix. For monitoring CO2 gas, a uorescence-based and
pH-sensitive 8-hydroxypyrene-1, 3, 6-trisulfonic acid (HPTS) indicator dye encapsulated in organically modied silica (ORMOSIL)
glass matrix was used. In the context of in-situ monitoring of
analytes, issues such as cross-reactivity, robustness, and humidity
interference need to be addressed before realizing the full potential.
2.2.4. Dry optical CO2 sensors
A novel plastic lm incorporated with uorescent dye HPTS was
used to sense CO2 gas with a 0e90% response and recovery times of
the lm when exposed to an alternating atmosphere of air and 5%
CO2 are typically 4.3 and 7.1 s, respectively (Mills & Chang, 1993).
Phase transfer agent (PTA) such as tetraoctyl ammonium hydroxide
(TOAH) plays vital role in the fabrication of solid, dry CO2 sensors.
PTA agent in its general form, QOH, can be used to dissolve the
anionic form (D) of a colorimetric pH indicator dye, such as
m-cresol purple (MCP), in a hydrophobic solvent, such as toluene,
that is mutually compatible with that of a water-insoluble polymer,
such as ethyl cellulose (EC) or poly vinyl butyral (PVB) (Mills, 2009).
Thus, it was found that mixing of pH-sensitive, hydrophilic indicator dye anion with phase transfer agent result in formation of ion
pairs, QD, which can be dissolved in hydrophobic solvents.
Therefore, a color-based dry CO2 sensor comprises a pH-sensitive
dye/phase transfer agent/polymer/solvent, which could be cast,
by printing, spin-coating, to generate a range of thin, colored plastic
lms containing a pH-sensitive dye in its deprotonated anionic
form, i.e. as QD. Carbon dioxide levels in dry and humid gases can
be determined by using these types of solid dry sensors. The sensor
sensitivity toward CO2 decreased with increase of temperature.
Also, acidic and oxidizing gases have a marked and irreversible
deleterious effect on the response features. A luminescence
intensity-based dry optical sensor lm was designed using the
luminescent dye, HPTS, the phase transfer agent, TOAH, the polymer, EC, and the plasticizer, tributyl phosphate (TBP) (Mills &
Chang, 1993).
2.2.5. Solegel-based optical CO2 sensor
An optical solegel-based CO2 sensor strip was fabricated using
a uorescent pH indicator, 1-hydroxypyrene-3, 6, 8-trisulfonate
(HPTS) (Bltzingslwen et al., 2002). The sensor exhibited a fast
and reversible response to carbon dioxide over a wide range of
concentrations (0e100% CO2) with sufcient resolution (2%). The
dye was immobilized in hydrophobic organically modied silica
matrix. Cetyltrimethylammonium hydroxide (CTA-OH), a quaternary ammonium base, was used as an ion-pairing agent for a polar
pH indicator in a non-polar gas permeable membrane, and also it
functions as internal buffer. The Dual Luminophore Referencing
(DLR) sensing method, an internal ratiometric method, is used for
measuring the uorescence. In which, the analyte-sensitive uorescence intensity signal is converted into the phase domain by
co-immobilizing an inert long-lifetime reference luminophore

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P. Puligundla et al. / Food Control 25 (2012) 328e333

having similar spectral characteristics. Ruthenium complex and

HPTS dye are the excellent candidates for a DLR-type CO2 sensor
because their excitation and emission wavelengths are well
matched. Oxygen cross-sensitivity is minimal and compatible with
established optical oxygen sensor technology.
2.2.6. Photonic crystal sensors
2.2.6.1. Polymer opal lms. Color changing polymer opal lms have
been developed by various research groups and were initially
developed at the University of Southampton in the United Kingdom
and the Deutsches Kunststoff-Institut (DKI) in Darmstadt, Germany.
The polymer opals are a type of photonic crystal consisting of a 3D
lattice of plastic spheres but have a large contrast in their components optical properties. This causes a range of frequencies to occur
and, therefore, causes variations in the light that is reected from
these regions, also called photonic band gaps. Tiny carbon nanoparticles can be wedged between the crystalline spheres. Thus,
incident light cannot reect at the interfaces between the crystalline spheres and the surrounding materials, but scattering of light
can occur. Due to a high surface to volume ratio of nanoparticles, an
intense color is generally observed in produced opal lms. The color
depends on manner of arrangement of the spheres and the placement of the nanoparticles. Stretching of exible lms will cause
orientation of the lattice structure and changes to the distance
between the spheres. This will cause a change in color to appear.
2.2.6.2. Polymer hydrogel-based CO2 sensor. In response to external
stimuli, polymer hydrogels can exhibit large reversible change in
their volume, and thus regarded as suitable materials for chemical
sensors. These kinds of sensors are best suited for food packaging
applications due to the fact that they dont require sophisticated
and expensive detection systems. They offer fast response times,
and are robust. Also, sensors have a long lifetime (>6 months)
without degradation of response time or reproducibility. Volume
change in hydrogel is exerted by Donnan potential between the
analyte ions and their receptor which is covalently bound to the
hydrogel building block (Shin, Braun, & Lee, 2010). In order to
compensate the local ion inhomogeneity, there is inux of water
molecules to the hydrogel. Color change of sensor is observed due
to volume change in periodic structure, known as photonic crystal.
These hydrogels are imprinted with photonic crystal; such color is
often called structural color. Relatively simple optical detection
techniques are possible using hydrogel photonic crystal sensor, for
a wide variety of analytes such as protons (Debord & Lyon, 2000;
Xu, Goponenko, & Asher, 2008), metal ions, glucose, and volatile
organic compounds (VOC). Therefore, a proton-based photonic
crystal CO2 gas sensor could be fabricated for use in food packaging.
2.2.7. Color changing metals
Recently, a research group identied the color changing nature
of modied rhodium metal to different gases. The modied
rhodium changes to yellow in the presence of nitrogen, deep blue in
the presence of oxygen, and brown in the presence of carbon
monoxide. According to head of the team, the gases bind to the
compounds central metal without disrupting the exact placement
of each individual atom in the compounds crystalline lattice in an
unprecedented way (Queens University, 2011, July 21). This
discovery could form the basis for development of early warning
system if failure of MAP system occurs. However, this metal usage
in food systems could be subject to food safety clearance.
3. Safety & regulatory aspects
Indicators or sensors are intended to be placed inside the
package exposing to headspace atmosphere and, therefore, safety

criteria have to be fullled. Often, packaging materials are in direct

contact with food inside the pack, so the embedded or attached
indicators to these packing materials must be suitable for direct
food contact applications. A major role by nanotechnologies is expected in fullling the additional safety considerations and existing
gap in knowledge (Danielli, Gontard, Syropoulos, Zonderwan Van
Den Beuken, & Toback, 2008).
For innovative food packaging technologies to be successful,
they must comply with strict regulations. Most of the active and
intelligent agents are considered as food-contact material constituents, not as additives, and, therefore, food packaging systems
must comply with the existing food-contact materials regulations.
According to the EU framework directive, all the food-contact
materials shall not be hazardous to human health and shall not
affect the composition or sensory character of the packed foodstuff
in an unacceptable way (De Kruijf et al., 2002).
4. Conclusions
It can be concluded that the optical carbon dioxide gas sensors
are suitable for food package indicator applications. Especially, dry
optical sensors containing pH-sensitive dye indicators are better
suited for CO2 monitoring and/or as spoilage indicators in food
packaging application. However, issues such as humidity interference, lifetime, cost, safety, and proton generation during other
oxidative reactions have to take into consideration before realizing
the complete potential of pH-based sensors. Water-based, CO2
indicator inks can be used potentially in food package applications.
Although they are relatively less sensitive toward CO2 than their
solvent-based counterparts, posses more stable shelf life and quick
response/recovery time. On the other hand, photonic crystal
sensors are promising due to low cost, long lifetime, suitability to
wide variety of analytes, and effective indication with quick
response time. However, there is still more research efforts are
necessary for the development of food application-specic sensors.
Acknowledgments
This research was supported by the Agriculture Research Center
program of the Ministry for Food, Agriculture, Forestry and Fisheries, Korea.
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