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Procedia Engineering 53 (2013) 197 – 202

Malaysian Technical Universities Conference on Engineering & Technology 2012, MUCET 2012
Part 3 - Civil and Chemical Engineering

Development of Interdigitated Electrode Molecular Imprinted Polymer

Sensor for Monitoring Alpha Pinene Emissions from Mango Fruit
Huzein Fahmi Hawariª*,
a
Nurul Maisyarah
a
fa, Supri. A.
Samsudinª, AlibYeon Md Shakaff
b
Ghani , Mohd Noor Ahmad , Yufridin Wahab , Uda Hashimm
a
Centre of Excellence for Advanced Sensor Technology (CEASTech),
University Malaysia Perlis, Malaysia
b
IInstitute Nanotechnology Electronic Engineering,
University Malaysia Perlis
Malaysia

Abstract

Alpha Pinene is a type of terpene hydrocarbons commonly emitted in substantial amounts by plants such as mango. Using
Interdigitated Electrode (IDE) structure, a sensor for detecting Alpha Pinene volatile by using molecular imprinted polymer (MIP) was
fabricated. The MIP membrane contained methacrylic acid, which formed specific cavities originated by target molecule. The use of
Polyethylene Terephthalate (PET) as a substrate The IDE MIP sensor is
capable to detect Alpha Pinene contained gas. The sensor characteristics were strongly influenced by the composition ratio of cross-linker,
functional monomer and template molecule. The remained molecule on MIP can be removed by immersing thus the sensor can be used
repeatedly. By determining Alpha Pinene volatile released during pre-matured until matured period, one could use this as a data point as
potential non destructive solution to discriminate the mango ripeness stage hence improving the quality of harvest.

© 2013
© 2013 The Authors.
The Authors. Published
Published by Elsevier
by Elsevier Ltd. Ltd.
Selection
Selection and/or peer-review
and peer-review under responsibility
under responsibility ofManagement
of the Research the Research
& Management & Innovation
Innovation Centre, Centre, Universiti Malaysia
Universiti Malaysia
Perlis.
Perlis
Keywords: Electronic Nose, Gas Sensor, Molecular Imprinted Polymer, Interdigitated Electrode, Alpha Pinene.

1. Introduction

One of the distinctive volatile organic compounds emitted by odoriferous fruit or plant is Alpha Pinene. Alpha Pinene is
a type of terpene hydrocarbon with the molecular formula, C10H16. It is found in many species of plants, notably pine,
mango and also even in the essential oil of rosemary. Mango for example, terpene hydrocarbons are found to be the major
class of compounds in, with contents of 16-90%, with Alpha Pinene is among the major compound identified [1]. For a
- - - - -caryophyllene are found to be released at
higher levels of most volatiles [2]. Utilizing information about Alpha pinene emission as biomarker, we then can utilize this
information to detect maturity stage of a mango.

* Corresponding author. E-mail address:huzeinfahmi@gmail.com

1877-7058 © 2013 The Authors. Published by Elsevier Ltd.

Selection and peer-review under responsibility of the Research Management & Innovation Centre, Universiti Malaysia Perlis
doi:10.1016/j.proeng.2013.02.026
198 Huzein Fahmi Hawari et al. / Procedia Engineering 53 (2013) 197 – 202

Molecular Imprinting Polymer (MIP) is an established method targeted for the production of polymeric artificial
receptors of specific molecular recognition. Apart from inexpensive and are highly stable, molecular imprinting has also
been used to produce a large variety of materials which have selective adsorption properties for specific molecules, [3, 4, 5].
The technique of Molecular Imprinting Polymer (MIP) was built upon a simple concept of molding
rally described as a plastic cast or mold of a molecule of interest, wherein detection

selective.

Fig. 1. Structure of -pinene used for molecular imprinting

Basic concept of Molecular Imprint Polymer (MIP) was illustrated in Figure 2 below where it involves pre-
arrangement of functional monomer and template. This is then followed by polymerization by using cross-linker at certain
temperature that will yield the MIP complex. -pinene template from the polymer matrix will then leave cavity
that is only selective to template molecule. The imprinting molecule was used as a template to form a receptor site with

functionality.

Fig. 2. Basic Concept of MIP

The MIPs possess several advantages over the conventional immunosorbent (IS) such as high selectivity and affinity,
high stability and the ease of preparation [6]. Due to the highly cross-linked nature, MIPs are intrinsically stable and robust,
facilitating their application of acids, bases, or metal ions. It is said to be a synthetic polymer that design to selectively bind
a certain molecule. Covalent interactions, non-covalent interactions and metal ion coordination can be exploited to organize
the functional monomers around the template. The synthesis technique of MIPs is simple, cheap and the polymers obtained
exhibit high selectivity, excellent mechanical strength, and durability to heat, acid and base conditions [7].
Interdigitated Electrodes (IDE) are made up by two overlapping metal comb structure. Each metal comb shall act as one
electrode. The MIP is then deposited on the free opposite side and has direct contact to the comb electrode. In order to
identify the capacitance, C value of a simple parallel plate capacitor structure the capacitance is given by
 Huzein Fahmi Hawari et al. / Procedia Engineering 53 (2013) 197 – 202 199

0 r A
C (1)
d

where r is the dielectric constant of the material between the plates, 0 is the dielectric constant for a vacuum, A is the area
and d the distance between the plates. Thus, with no change of geometry any modification of its capacitance value would
indicate modification of the dielectric constant [8, 9].
This paper describes the development of a sensor using MIP on IDE platform to method for monitoring alpha pinene
from mango fruit. The proposed sensor is simple, low in cost and high selectivity.

2. Materials and Methods

2.1 Materials

-pinene, Methacrylic Acid (MAA), Ethylene Glycol Dimethacrylate Acid (EGDMA), 2-Aminoethanethiol (AET) were
purchased from Acros Organics, Belgium. Tetrahydrofuran (THF) was purchase from Fisher Scientific, U.K. PET is
purchased from Sigma Aldrich, USA.

2.2 Mango Fruit Material

Maturity. Fresh Harumanis mango were sorted from a batch of single harvest by the by classified by trained personnel
located in Bukit Temiang, Perlis, Malaysia.

2.3 Interdigitated Electrode (IDE)

In this research, gold IDE with dimensions of 5mm x 10mm x 2 μm is fabricated and used as a sensor. The IDE is
fabricated through sputtering machine (DCRF Sputtering Brand Nanomaster, USA) with thickness profile of up to 292A
resolution. PET is selected as the substrate for this research due to its flexibility and in the same time, provides a low cost
solution which makes it attractive and feasible for agriculture application. The IDE are made up by two overlapping metal
comb structure where each metal comb shall act as one electrode. For this research, an eight finger metal mask was used to
sputter the gold IDE. Figure 3 illustrates a scanning electron microscopy (SEM) image obtained with both the spacing
between the mask fingers and their widths were equal to 500 micron.

Fig. 3. Surface morphology of IDE using SEM.

The MIP is then deposited on the free opposite side and has direct contact to the comb electrode.
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2.4 Preparation of MIP Solution

One mmol template alpha pinene was added to 5 mmol functional monomer (MAA) and stirred together with 0.01g
initiator AIBN. The mixture was dissolved in 10ml THF. 20 mmol EGDMA was added to the mixture and stirrer for 5
minutes. In this research, EGDMA was used with the ratio of 20:1 (EGDMA:template)[10]. The mixture was purged with
nitrogen for 3 minutes to remove oxygen. Non-Imprinted polymer (NIP) was prepared and treated as the same manner as
MIP for control purpose.

2.5 Polymerization and Removal of Templates

2μl of solution were coated on IDE using spin coating method. All coated IDE were then polymerized under UV light at
room temperature for 6hours. The remained molecule on MIP can be removed by immersing it with mixture of methanol
and acetic acid for extraction of templates thus allowing the possibility for the sensor to be used repeatedly.

2.6 IDE measurement

In this work, capacitance measurement was done by using Novocontrol dielectric analyzer with Windeta software. The
tested frequency range was from 0.1 kHz to 1 kHz, with an alternating potential voltage of 100 mV. [11].

2.7 Online Alpha Pinene monitoring on Harumanis Mango

Emanates of Alpha Pinene from Harumanis mango are successfully monitored online by IDE-MIP sensor through the
setup in figure 4. For this purpose, fresh Harumanis mango are put in seal glass desiccators 60 minutes where the volatile
are then pull in towards the gas chamber using micro pump. The capacitance change of the IDE-MIP sensor which is in
correspondence with Alpha Pinene analytes deposited over the layers is then recorded. Prior to each test, the glass desiccator

Fig 4: Schematic Diagram of Online Monitoring for IDE testing

3. Result and Discussion

3.1 IDE-MIP Capacitance Measurements

To confirm the sensor selectivity, the IDE-MIP sensors were first exposed to alpha pinene gas together with Non-
imprinted polymer (NIP) sensor on similar IDE platform. Same molar ratio of MAA and EGDMA were used in these MIP
and NIP samples with only the quantity of target molecular were different. Fig. 5 shows the selective property of IDE-MIP
sensor and IDE-NIP sensor when exposed to alpha pinene volatile. First, both sensors are exposed with nitrogen gas as
baseline measurement. Then, both sensors are exposed to alpha pinene volatile from time stamp 60s to 120s. A capacitance
increase of approximately of 0.08 pikofarad was recorded for IDE-MIP Alpha Pinene sensor prior to exposure and while
 Huzein Fahmi Hawari et al. / Procedia Engineering 53 (2013) 197 – 202 201

only a small increase of approximately 0.02 pikofarad for the NIP- modified electrode. Since the only difference is the
target molecular which is alpha pinene therefore, the result proved that the sensor response was originated by the adsorption
of alpha pinene to the cavity of MIP.

Fig. 5. Sensor response of both a non imprinted control polymer and IDE-MIP with Alpha Pinene as a template.

3.2 Online Alpha Pinene monitoring on Harumanis Mango

The IDE-MIP sensor was then exposed to an actual ripe Harumanis mango to monitor the emission of Alpha Pinene. At
the start, as shown in Fig. 5, capacitance response is along the baseline indicating the emission of alpha pinene is gradually
slowly increasing until it reach time 30 mins. However, when it reach time 40 mins, the IDE-MIP sensor then start to
increase fast within the next 20 minutes indicate significant emanate of alpha pinene concentration. Thus, in this research, it
was confirmed that the sensor for alpha pinene gas can be fabricated in a unified way. This result suggested that the sensor
fabrication process and can be applied to other type of terpene hydrocarbons which are also emitted by mango.

Fig. 6. IDE-MIP sensor response to a ripe Harumanis mango.

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4. Conclusion

In this research, a sensor to detect alpha pinene emission from mango was successfully implemented by using MIP as the
sensing materials. When exposed to alpha pinene gas, the IDE-MIP sensor was able to exhibit a specific sensitivity and
selectivity responses towards alpha pinene only compared to NIP. Since fruits released volatile compound during pre-
matured until matured period, one could use these volatiles act as a maturity marker to determine the optimal harvest
maturity of the fruit. The IDE-MIP sensor was then capable of monitor emission alpha pinene from odoriferous such as
mango. Furthermore, with low cost, flexible substrate and simple to fabricate, this could provide an exciting alternative for
agriculture to determine quality of harvest. Having the IDE coated with molecularly imprinted materials to detect alpha
pinene represent one of the first attempts to create an array of sensor to obtain time-resolved trend lines for the emanation of
terpenes from plants such as mango directly from the bin without any requirement of sample pretreatment and preparation.
Additional efforts is currently in progress to explore more mango volatiles and array combination in order to further
enhance the IDE MIP sensor selectivity in detecting mango ripeness.

Acknowledgements

We wish to thank Ministry of Higher Education Malaysia for their financial support (FRGS 9003-00250) of Huzein
Fahmi Hawari and Nurul Maisyarah Samsudin during their studies. The authors would also like to thanks Perlis Agriculture
department for their technical advice and support on Harumanis Mango.

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