Sensors and Actuators B 247 (2017) 98–107
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Sensors and Actuators B: Chemical
jo u r nal homep age: www.elsevier.com/locate/snb
Determination of hydrogen peroxide and triacetone triperoxide
(TATP) with a silver nanoparticles—based turn-on colorimetric sensor
Ays ¸ em Üzer, Selen Durmazel, Erol Erc ¸ a˘ g
1
, Res ¸ at Apak
∗
Istanbul University, Faculty of Engineering, Chem. Dept., 34320, Istanbul, Turkey
a r t i c l e i n f o
Article history:
Received 7 December 2016
Received in revised form 27 February 2017
Accepted 2 March 2017
Available online 6 March 2017
Keywords:
Hydrogen peroxide
Triacetone triperoxide (TATP)
Silver nanoparticles
Colorimetry
Explosive
Sensor
a b s t r a c t
Hydrogen peroxide (H
2
O
2
) is a synthetic precursor and degradation product of peroxide-based explosives,
such as TATP. We developed a colorimetric sensor that is selective, sensitive, cost-efficient and easy-to-use
in conventional laboratories for the naked eye detection of hydrogen peroxide and for indirect determina-
tion of peroxide-based explosives (which are devoid of chromogenic/fluorogenic functional groups). We
were able to partly oxidize zero-valent silver nanoparticles (Ag
0
NPs) by H
2
O
2
to Ag
+
under special condi-
tions, and thus devise an indirect method for trace H
2
O
2
quantification by measuring the absorbance of
the blue-colored diimine of TMB (3,3
′
,5,5
′
- tetramethylbenzidine) at 655 nm, arising from TMB oxidation
with Ag
+
. TATP was acid-hydrolyzed to H
2
O
2
by an acidic cation-exchanger (Amberlyst-15) for potential
field use. The limit of detection (LOD) of the sensor was 20 nM for H
2
O
2
and 0.31 mg L
-1
for TATP. Com-
mon soil ions did not interfere, and TATP was analyzed in synthetic mixtures of other energetic materials.
The responses of detergents, sweeteners, acetylsalicylic acid (aspirin) and paracetamol-based painkiller
drugs, used as camouflage material in passenger belongings, were also examined. The developed method
was statistically validated against the standard analytical methods of titanium(IV) oxysulfate (TiOSO
4
)
for H
2
O
2
and GC–MS for TATP using t- and F- tests.
© 2017 Elsevier B.V. All rights reserved.
1. Introduction
Hydrogen peroxide is a dual-function redox compound (i.e. that
may act as both an oxidant and reductant) finding wide use in
nutrition, pharmaceutical, textile and clinical industries. H
2
O
2
is
a potent bleaching and disinfecting agent in water treatment, and
may play key roles in atmospheric phenomena and biochemical
processes [1–5]. Because it is a product of biochemical reactions
catalyzed by oxidase enzymes (such as catalase, glucose oxidase,
horseradish peroxidase, etc.), H
2
O
2
can be associated with a great
many diseases such as diabetes, cancer, and aging [6,7]. Since
peroxo-oxygen is unstable that may undergo disproportionation,
H
2
O
2
is also used as a precursor for synthesis of homemade explo-
sives (TATP, HMTD, etc.) classified under peroxide-based energetic
materials [8–13]. In the late 1970
′
s and early 1980
′
s, peroxide-
based explosives (TATP and HMTD) confiscated by the Israeli police
were commonly used in terrorist attacks for their simple synthesis,
accessibility of raw chemicals used for synthesis, and high explosive
potential [14–16]. The determination of peroxide explosives has
∗
Corresponding author.
E-mail address: rapak@istanbul.edu.tr (R. Apak).
1
The researcher was an academic staff member of Istanbul University at the
initiation of the work.
gained importance in recent years due to some historical terrorist
actions such as 2005 London Subway bombing, 2009 failed terrorist
attempt in a Northwest Airways flight, and Paris suicide bomb-
ing in 2015 [14]. Peroxide explosives lack spectroscopically active
functional groups such as nitro substituents and aromatic rings,
and therefore may elude common spectral detection techniques
employed at check points of mass transport. TATP easily sublimes
at room temperature, and does not leave post-blast residues unlike
common nitro-explosives [17,18]. TATP may yield similar colored
products as H
2
O
2
with the use of chromogenic reagents (such
as titanyl oxalate) on microfluidic paper-based analytical devices,
though at a much weaker color intensity [19]. Colorimetric deter-
mination of TATP is greatly facilitated when it is hydrolyzed to
H
2
O
2
. Thus, hydrogen peroxide, which is a synthetic precursor and
degradation product of TATP and HMTD, is accepted as a note-
worthy compound for determination of peroxide-based explosives
[20–23]. Considering all these facts, trace H
2
O
2
determination has
become essential for both industrial and academic purposes. Rela-
tively older assay methods such as titrimetry, spectrophotometry,
fluorometry [24,25] for H
2
O
2
and colorimetry [26], spectroscopy
[27–30], fluorometry [31,32], and chromatography [33,34] for TATP
have started to be replaced by recently improved nanoparticle-
based hydrogen peroxide sensors. Accordingly, nanosensors were
designed for H
2
O
2
detection using metals like copper (Cu) [35], gold
http://dx.doi.org/10.1016/j.snb.2017.03.012
0925-4005/© 2017 Elsevier B.V. All rights reserved.