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FULL PAPER
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2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1
www.MaterialsViews.com
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Ying Wang, Anthony La, Yu Ding, Yixin Liu, and Yu Lei*
1. Introduction
One pressing concern in anti-terrorism and homeland security
is explosive detection. Most high explosives are nitro-substituted
organic compounds. Typically, nitroaromatics, such as 2,4,6-trin-
itrotoluene (TNT) and 2,4-dinitrotoluene (2,4-DNT), are the pri-
mary military explosives and also the principle components in
the unexploded landmines worldwide.
[1]
Nitramines and nitrate
esters (e.g., 3,5-trinitroperhydro-1,3,5-triazine (RDX) and pen-
taerythritol tetranitrate (PETN)), are main components of highly
energetic plastic explosives, such as C-4 (91% RDX) and Semtex
(40–76% PETN). As nitro explosives are extremely sensitive to
shock, friction and impact, and therefore, detection methods
that permit contact-free analysis are desirable. Moreover, the
demands of detecting hidden explosives in transportation hubs
and buried explosives in warzones also have led to an intense
interest in the low cost and ultrasensitive
explosive detection techniques.
Compared to the detection in solution
and solid phases, the detection of nitro
explosives in vapor phase is more chal-
lenging since most of them have substan-
tially low volatility (Table S1, Supporting
Information). Although current nitro-
explosive vapor detection heavily relies on
ion mobility spectrometry (IMS)
[2]
and gas
chromatography coupled with mass spec-
trometry (GC-MS),
[3]
their sophisticated
protocols, poor portability and high-cost
have restricted their broad applications.
Thus, it is in great demand to develop
innovative sensing systems that are cheap,
easy to use, highly sensitive and selective
for a broad spectrum of nitro-explosives.
The stability of energetic materials is
often assessed by their trigger linkage,
which is generally the C-NO
2
(or N-NO
2
and O-NO
2
) bond in nitro explosives, and
consequently, a high nitro substitution has
become their most important character and renders nitro explo-
sives electrophilic, which could quench fluorophores through
photoinduced electron transfer.
[4]
Fluorescent conjugated poly-
mers have been considered as the leading structures in explo-
sive detection due to their efficient exciton migration along the
polymer chains, which could result in fluorescence quenching
over long range by a single quencher-binding, or called “molec-
ular wire” signal amplification.
[5–8]
It has been reported that by
spin-casting pentiptycene derived poly(phenylenethynylene)
(PPE) into an ultrathin film, the trace detection of particulate
TNT at 10–100 femtograms level can be realized, and its com-
mercialized product, FidoXT, has been applied in war zones of
Afghanistan and Iraq.
[9]
Nevertheless, fluorescence quenching based methods have
been mainly limited to nitroaromatic (e.g., TNT, 2,4-DNT)
vapors, and extension of these methods to vapor detection of
nitramine and nitrate ester explosives is still remaining a chal-
lenge, largely owing to their ultra-low volatility (e.g., the satura-
tion vapor concentrations for HMX, RDX, and PETN are 0.1,
5 and 7 ppt, respectively),
[10]
unfavorable reduction potential,
[11]
and the lacking of conjugated electrons to engage in π -stacking.
Recently, Andrew and Swager have reported a fluorescence
turn-on explosive sensor for nitramines and nitrate esters
through their photolytic cleavage products.
[12]
This system is
one of a few examples to detect nanogram particulate RDX and
Novel Signal-Amplifying Fluorescent Nanofibers for Naked-
Eye-Based Ultrasensitive Detection of Buried Explosives
and Explosive Vapors
A novel electrospun fluorescent nanofiberous membrane with a function like
“molecular wires” was developed via electrospinning for the detection of
ultra-trace nitro explosive vapors and buried explosives by naked eye under
UV excitation. The high binding affinity between the electron-deficient nitro
explosives and the sensing film results in a rapid, dramatic quenching in its
fluorescence emission. A wide spectrum of nitro explosives, in particular,
TNT, Tetryl, RDX, PETN and HMX could be “visually” detected at their sub-
equilibrium vapors (less than 10 ppb, 74 ppt, 5 ppt, 7 ppt and 0.1 ppt, respec-
tively) released from 1 ng explosives residues. Such outstanding sensing
performance could be attributed to the proposed “sandwich-like” conforma-
tion between pyrene and phenyl pendants of PS which may allow efficient
long-range energy migration similar to “molecular wire”, thus achieving
amplified fluorescence quenching. Its application for the detection of buried
explosives in soil by naked eye was also demonstrated, indicating its potential
application for landmine mapping. To the best of our knowledge, this is the
first report about the detection of buried explosives without the use of any
advanced analytical instrumentation.
DOI: 10.1002/adfm.201200047
Y. Wang, A. La, Y. Ding, Y. Liu, Prof. Y. Lei
Department of Chemical
Materials and Biomolecular Engineering
University of Connecticut
Storrs, CT, 06269-3222, USA, 191 Auditorium Road,
U3222, Storrs, CT 06269, USA
E-mail: ylei@engr.uconn.edu
Adv. Funct. Mater. 2012,
DOI: 10.1002/adfm.201200047