Detection of hydrogen peroxide using dioxazaborocanes: elucidation of the sensing mechanism at the molecular level by NMR and XPS measurements

Article abstract of DOI:10.1039/d0nj00038h

A fluorescent dioxazaborocane was synthesised and characterized, in order to study its turn-off sensing process for hydrogen peroxide detection. The exposure of the dioxazaborocane to diluted vapours of H₂O₂ led to a strong non reversible quenching of the fluorescence. Both NMR and XPS analyses were carried out before and after exposure of dioxazaborocane to H₂O₂ vapours. They unequivocally show that the boron atom is oxidised in the film with cleavage of the N-B dative bond. Identification of products such as phenol and boric acid by NMR, supported by consistent XPS data, enabled the whole reaction sequence that explains the fluorescence quenching of dioxazaborocane upon H₂O₂ exposure to be described accurately. Direct hydrolysis of dioxazaborocane to diol, without oxidation, was only marginally observed.

Full text of DOI:10.1039/d0nj00038h

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Detection of hydrogen peroxide using
dioxazaborocanes: elucidation of the sensing
mechanism at the molecular level by NMR
and XPS measurements†
Cite this:DOI: 10.1039/d0nj00038h
a
a
a
b
Thomas Caron, Pascal Palmas, Celine Frenois, Christophe Methivier,
´
´
´
a
b
c
a
Eric Pasquinet,* Claire-Marie Pradier,
Françoise Serein-Spirau, Lionel Hairault
a
and Pierre Montmeat
´
A fluorescent dioxazaborocane was synthesised and characterized, in order to study its turn-off sensing
process for hydrogen peroxide detection. The exposure of the dioxazaborocane to diluted vapours of H
led to a strong non reversible quenching of the fluorescence. Both NMR and XPS analyses were carried out
before and after exposure of dioxazaborocane to H vapours. They unequivocally show that the boron
2 2
O
Received 3rd January 2020,
Accepted 20th February 2020
2 2
O
atom is oxidised in the film with cleavage of the N–B dative bond. Identification of products such as phenol
and boric acid by NMR, supported by consistent XPS data, enabled the whole reaction sequence that
DOI: 10.1039/d0nj00038h
2 2
explains the fluorescence quenching of dioxazaborocane upon H O exposure to be described accurately.
rsc.li/njc
Direct hydrolysis of dioxazaborocane to diol, without oxidation, was only marginally observed.
15,16
response, excellent sensitivity (pptv range for
to be integrated into portable devices.
) and opportunity
Introduction
The reliable and sensitive detection of hidden explosives in
Our group has already disclosed films of dioxazaborocane 2
3
3
luggage, cars, or aircraft is currently a major issue for law as efficient sensors for this purpose. The detection concept
enforcement agencies facing the continuous threat of sudden that was conceived for 2 took advantage of two different properties.
terrorist attacks. In this context, the detection of peroxide- (i) Boron compounds are known to react with hydrogen peroxides
34
based explosives (PBEs) in particular triacetone triperoxide through an oxidation process. In solution, this reaction is readily
(
(
TATP) has now evolved as a crucial need. Hydrogen peroxide used for alcohol and phenol synthesis, but it is believed that the
HP), as both a precursor and a decomposition product of such process may also occur at the solid/gas interface, and (ii) the
1
,2
explosives, is also an important target. As a matter of fact, presence of a nitrogen atom in the side chain usually quenches
detection of HP after UV exposure may constitute a useful the anthracene ring fluorescence via photoinduced electron
3
5
indirect sensing method for PBEs.
Among the various strategies that have been described for
PBE and HP vapour sensing, numerous studies concern solid N–B bond and does not interact with the anthracene chromo-
transfer (PET).
3
,4
In 2, the lone pair of the nitrogen atom is involved in the
5
–32
state gas sensors.
In particular, Table 1 summarises the major detection This has been shown in studies dedicated to boronic acid detec-
methods and their limit of detection. tion in solution through a fluorescence turn-on process, in which
They, in particular, include optical and fluorimetric methods, the formation of compound 2 was postulated as a complex in
phore, thus resulting in a high fluorescence of the compound.
36
that have drawn increasing attention in recent years due to fast solution, though it was not isolated or characterised.
We thought that, using a somewhat reverse turn-off process,
upon hydrogen peroxide vapour exposure, a deboronation
reaction would release the N lone electron pair so that the
anthracene fluorescence would be quenched (Fig. 1).
a
b
c
CEA-DAM Le Ripault BP 16, F-37260 Monts, France.
E-mail: eric.pasquinet@cea.fr; Fax: +33 247345142
Sorbonne Univ., CNRS, LRS, UMR 7197, LRC n1 1 CEA-UPMC-CNRS, 4 Pl Jussieu,
Case Courrier 178, F-75005 Paris, France
In this work, we report the synthesis and characterisation of
Institut Charles Gerhardt, UMR CNRS 5253, Equipe AM2N, Ecole Nationale
Sup ´e rieure de Chimie de Montpellier, 8, Rue de l’Ecole Normale,
2, as well as our efforts to obtain the most accurate picture of
the chemical reactions that result in its excellent hydrogen peroxide
sensing properties in the solid state. Understanding what really
occurs at the solid/gas interface is complicated due to technical
3
4296 Montpellier Cedex 05, France
†
Electronic supplementary information (ESI) available. See DOI: 10.1039/
d0nj00038h
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Table 1 Detection of peroxide vapours with solid state gas sensors
Ref.
5
Detection method
Sensitive coumpound
Organic core structure
Limit of detection for HP
Optical waveguide
Fluorescence quenching
Fluorescence turn-on
Colorimetric
Fluorescence quenching
Fluorescence quenching
Fluorescence turn-on
Colorimetric
Fluorescence quenching
Fluorescence quenching
Impedance spectroscopy
Fluorescence turn-on
Fluorescence quenching
Calorimetry
40 ppbv
100 ppbv
3 ppbv
200 pptv
0.1 pptv
4 pptv
10
12
14
15
16
17
18
19
20
22
23
24
25
28
29
EuVO
Boronate based polymer
TiO
4
2
Multi-formyl phenols
Dioxaborolane
Dioxaborolane
Dioxaborolane
Pyrenyl borate
Borate ester polymer
ZnO
Boronate quinoline chromophore
Polymer–titanium complex
7 ppbv
2.9 ppbv
TATP: 0.5 ppmv
1.6 ppbv
100 ppmv
150 pptv
200 pptv
2% v
MnO
2
Transistor
Resistivity
Phthalocyanines
Single-walled carbon nanotubes
0.64 ppbv
25 ppmv
(30 mL) were introduced into a Dean–Stark apparatus. The
mixture was refluxed for 5 h and then cooled to room tempera-
ture before filtration and washing with toluene.
All NMR measurements were performed at 21 1C on a Bruker
Avance 400 MHz spectrometer. We used a standard Bruker
1
13
11
5
mm BBFO+ probe for H, C and B experiments. Samples
were prepared using quartz tubes, in order to reduce the wide
1
1
line B contribution of the borosilicate. Despite this, a residual
response, probably coming from the probe itself, was observed.
It was suppressed from the spectra afterwards by a simple
1
13
baseline correction. H and C experiments were calibrated accord-
ing to the solvent signal used as a secondary internal reference
1
13
1
(
CDCl
3
H: 7.27 ppm; C: 77.2 ppm; MeOD H: 3.31 ppm;
1
3
11
C: 49.2 ppm in respect with TMS, 0 ppm). For B chemical shifts,
the rather sharp signal of phenylboronic acid (C –B(OH)
(d = 28.4 ppm) with respect to BF –Et
d = 0 ppm) was used as an external secondary reference.
XP spectra were collected on a SPECS GmbH PHOIBOS
6
H
5
2
)
2
O
Fig. 1 Molecular structure of dioxazaborocane 2.
43
solution in ethanol-d
(
6
3
issues, including the small amount of molecules that are involved
at the film surface. That is why indirect proofs of concepts have 100-1D delay line detector photoelectron spectrometer, using
7
20,21
been used in related studies, such as IR or UV spectroscopy
a monochromatised Al Ka (1486.6 eV) radiation source with
37
after reaction in solution. Electrochemistry can also be applied in 250 W electron beam power. The samples were analysed under
À8
case of the detection of HP with boronate in liquid media. Direct ultra-high vacuum conditions (1 Â 10 Pa). After recording a
attempts to address the deboronation reaction on borate-ester- broad range spectrum (pass energy 100 eV), high-resolution
based sensing materials have been reported in only very few papers, spectra were recorded for the B1s, N1s, C1s, O1s core XPS levels
21
17,18
using IR and absorption spectroscopy.
Herein, we focused on (pass energy 20 eV). Spectrum processing was carried out using
such direct approaches and exclusively studied solid/gas reactions, the Casa XPS software package.
monitored by XPS and NMR analyses.
IR spectra were recorded on an ATR PerkinElmer 100
This allowed us not only to evidence the deboronation spectrophotometer.
process on dioxazaborocane 2, but also to unequivocally deter-
mine the whole sensing mechanism.
Melting points were measured with a TA Instruments Q100
DSC (heating rate: 10 1C min ).
À1
High-resolution mass spectra (HRMS) were obtained using
impact ionisation (EI) with PFTBA as internal standard. Spectra
were recorded on the Accu-TOF GC JEOL.
The X-ray data collection of the single crystals was
performed at 173 K on an Oxford-Diffraction GEMINI-S single
Experimental section
Synthesis and characterisation
Dioxazaborocane 2 was obtained as presented in Scheme 2. crystal diffractometer, using graphite-monochromatised Mo Ka
3
8
Diol 1 was obtained as described elsewhere. The chemical radiation (l = 0.71073 Å).
reactants were purchased (Aldrich) and used without further
The three-dimensional structures were solved by ab initio
purification. Phenylboronic acid (120 mg, 1 mmol) and toluene methods, such as those implemented in the charge-flipping
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algorithm. The structural refinements were performed with
Paper
3
9
4
0
the CRYSTALS package
on Fobs using reflections with
I 4 2s(I). CCDC 1543590 contains the supplementary crystal-
lographic data for this paper.†
Film deposition
Dioxazaborocane 2 was deposited on the entire surface of a
glass substrate (microscope slide 75 mm  25 mm  1 mm) by
spin coating (Braive Instrument spin coater – 600 rpm for 60 s)
À1
from a chloroform solution (5 mg mL ). The absorption
intensity at 373 nm, measured using a PerkinElmer Lambda
35 spectrometer, was between 0.2 and 0.4.
Detection tests
Chemical gas detections were performed on water and HP
(
30%) using a fluorescent laboratory prototype. A more detailed
4
1
1
Fig. 2 Evolution of the H NMR spectrum of 2 in CDCl
3
as a function of
description of the instrument was given previously. The
hydrogen peroxide concentration was evaluated by a commercial
detector (Polytron 7000-Dr ¨a ger): 50 ppmv. Dioxazaborocane film
time of exposure to HP. Small peaks indicated by a star correspond to
product degradation not directly due to HP.
s
has been used as sensing materials on the microscope slide acting
as transducer and substrate. The prototype line was connected to
the generation cell; equilibrated at the vapour pressure of com-
pound. The sensor response was expressed as a percentage of
fluorescence inhibition.
4
2b
influence, it seems that the B–N bond length is more sensitive
to substitution on the N atom.
3
NMR characterisation of 2 was performed using CDCl as
solvent. The H spectrum is displayed in Fig. 2 and partial
1
assignment is given therein. NMR data of 2 in the same solvent
Sensing mechanism study
3
6c
1
had been already reported,
but the H information on
For the sensing mechanism comprehension, a specific setup
was used to generate HP vapours and exposed powder of
dioxazaborocane. A dynamic method based on evaporation
was chosen to produce HP vapours at controlled and constant
concentrations, over a long period of time (19 h, 48 h). Fine
powder of 2 (130 mg) was thus exposed at 100 ppmv of HP. For
NMR characterisation after exposure, 10 mg of 2 were sampled
methylene moieties was missing, seemingly due to large broad-
ening. The same broadening effect was observed here, but the
peaks were readily detectable. Hence, chemical shifts [d = 4.62
(
s, 2 H), 4.21 (s, 4 H), 2.96 (s, 4 H) ppm] were measured for
methylene protons and [d = 8.51 (s, 1 H), 8.02 (m, 6 H), 7.50
m, 7 H) ppm] in the aromatic region, some of which were
(
significantly different from those of diol 1. In compensation,
and diluted in 4 mL of CDCl or MeOD. All of the experiments 13
36c
3
C chemical shifts of methylene carbons were given
were carried out at between 15 1C and 23 1C.
and agree well with present values d = 63.0, 56.4, 51.9 ppm
1
1
(
spectrum not shown). Turning to the B spectrum, a single
line was observed at 14 ppm. Such a chemical shift is char-
Results and discussion
Synthesis and characterisation of dioxazaborocane 2
3
acteristic of a sp hybridisation and thus with the formation of
a N - B dative bond, in agreement with XRD data. The slight
Dioxazaborocane 2 was obtained in a 64% yield as fluorescent difference with the published value of 15.9 ppm certainly
crystals (250 mg). results from a different referencing, as the reported phenylboronic
The product was fully characterised and suitable crystals for acid chemical shift was 32.27 ppm instead of 29.6 ppm in our
XRD studies were obtained after recrystallisation in toluene. case. Moreover, chemical shift values lying within the same range
42b–44
Complete data are available in ESI,† S1 and S2.
The molecular structure is shown in Fig. 1.
[12–13 ppm] were also reported for similar systems.
Hydrogen peroxide sensing
The crystallographic structure confirms the tetrahedral geo-
metry of the boron atom and the presence of a dative B–N bond. Fig. 3 presents the fluorescence intensity shift of a thin film of 2
The B–N and B–O bond lengths lie within the ranges of 1.767– upon exposure to water vapours for 10 minutes, then to hydro-
1.745 and 1.431–1.443 Å, respectively (the asymmetric unit gen peroxide vapours for 10 minutes. While the signal
contains 2 molecules). These values are in agreement with those remained almost unchanged in the presence of water (less than
42
reported for already known N-substituted dioxazaborocanes.
5% fluorescence decrease), 64% of the fluorescence 2 was
The B–N bond is, however, somewhat lengthier than for the other quenched by HP vapours. This highlighted the potential inter-
related compounds (typically 1.70–1.72 Å for the latter). The B–N est of 2 as a sensing material for HP and peroxide-based
43
bond is even shorter for N–H dioxazaborocanes. Since it has explosives. In our test conditions and based on our fluorescent
4
1
been shown that substitution on the B atom was of little laboratory prototype performances, we can estimate the limit
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of detection around 4 ppmv (see ESI† S3 for details). Otherwise, amount of pure 1. An increase in the existing peaks was
the response of films of 2 was clearly irreversible, suggesting observed, accompanied by a line broadening and a slight
that a chemical reaction occurred between HP and 2. This chemical shift displacement. This procedure gives stronger
would be consistent with the postulated concept and this evidence than a simple comparison with a spectrum of the
prompted us to investigate the detection mechanism resulting pure compound in the same solvent, because environmental
in the fluorescence quenching of 2 in greater depth.
effects on chemical shifts and line width can be different from
the real sample. It must be noticed that a separate OH proton
signal from 1 at 2.3 ppm was not detected. This is due to an
exchange with a water proton in the presence of 2 and phenol
Sensing mechanism: NMR and XPS experiments
Our detection turn-off concept was based on the oxidation of
the boron atom of the fluorescent compound 2, which would
lead to the non-fluorescent diol 1. Both NMR and XPS experi-
ments were designed to obtain the most accurate picture of
what was happening at the surface of 2 during exposure to
hydrogen peroxide vapours. Our aim was not only to prove the
oxidation of the boron atom, but also to identify the molecular
species that were generated in the whole process.
(
vide supra) that leads to a large broadening and collapse at an
intermediate chemical shift. Second, the increasing quantity of
was accompanied by the appearance and gradual growth of
1
three other multiplets in the aromatic region. These peaks were
clearly assigned to free phenol following the same procedure as
described above (addition of phenol). Conversely, phenylboronic
acid was also added to the sample to demonstrate the absence of
this compound in 2 before and after exposure to HP. Additional
smaller contributions (marked by a star) were also detected as
two symmetrical doublets in the aromatic region. A dramatic
Similar molecular approaches are very scarce in the litera-
1
9,21
ture for the detection of peroxide
1
Fig. 3 displays the H spectrum of 2 after being exposed to
HP vapours. There were several modifications in the spectrum,
which increased as a function of exposure time. This is one key
to the demonstration, as it showed without ambiguity what
changes were related to the detection process and not to a
possible degradation of the product. First, several peaks grew
together as a function of exposure time with chemical shifts
close to those originating from 1, suggesting a quite similar
structure. Due to the fact that the lines were broader and
originally present in 2 as weak contributions, we initially
thought of a possible equilibrium between the bicyclic coordi-
nated tetrahedral boron species with a possible ‘‘open’’ form,
bearing an 8-membered ring and lacking the N - B dative
bond, as suggested in ref. 43 However, the interpretation of the
entire set of NMR observations led us to the conclusion that
these growing peaks were due to diol 1, a weak proportion of
which was initially present in 2, and that they increased with
exposure time. This assignment was confirmed by comparison
with a second spectrum acquired after addition of a small
1
increase in their intensity was observed when a H experiment
was performed on the same sample a few days later. They were
consequently attributed to a ‘‘natural’’ degradation of 2 that
occurred at least when dissolved in an organic solvent and, in
any case, independent from the HP treatment.
13
These results were further confirmed by C NMR but, finally,
the elucidation of the whole detection mechanism required
11
B NMR measurements and the use of a different solvent.
1
1
The B spectrum in CDCl of 2 acquired after exposure to
3
HP still contained only one line at 14 ppm, which was assigned
to compound 2 itself (see ESI,† S4). Phenylboronic acid was
thus missing both in the starting material and after reacting
with HP, as this compound gives a rather sharp line at
1
2
9.6 ppm. This is in accordance with the H NMR observations.
A different situation was seen using MeOD as solvent, in
which 2 was completely dissociated into 1 and phenylboronic
1
acid. This was obvious from the H spectrum first, and further
1
1
confirmed by the observation of a single B signal at 28.4 ppm
Fig. 4). This was also in accordance with the fact that MeOH
(
solutions of 2 were not fluorescent.
Of course, this line was still present after exposure to HP and
came from residual 2 that had not reacted. It turned out that
such a complete dissociation of 2 made MeOD inappropriate to
follow any transformation into 1 occurring during HP exposure.
1
1
However, a new B component was revealed at 18.8 ppm,
whose intensity (relative to phenylboronic acid) increased as a
44
function of time. This chemical shift is compatible with boric acid,
a product that was not soluble in CDCl . This assignment was again
3
confirmed by addition of boric acid (also in Fig. 4), thus ruling out
other hypotheses (‘‘open’’ 8-membered ring, intermediate 3). All
of these features were also observed using DMSO as the solvent
(not shown).
In the conclusions of the NMR study, it is demonstrated that
2, upon exposure to HP vapours, produces diol 1, boric acid and
phenol.
XPS experiments were also carried out to get additional
information on the chemical processes involved, especially at
Fig. 3 Fluorescence quenching of a film of 2 upon successive exposures
to water and hydrogen peroxide vapours.
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11
Fig. 4 Evolution of B NMR spectra of 2 in MeOD as a function of
exposure to HP vapours. The spectrum at the top was recorded (for
3
assignment purpose) after the addition of a small amount of B(OH) to
the NMR sample (t = 19 h).
Fig. 5 Evolution of N1s and B1s X-ray photoelectron spectra of 2 as a
function of exposure to HP vapours.
the surface. Fig. 5 shows the high-resolution XPS spectra
recorded for the N1s and B1s region for dioxazaborocane 2 just
synthesised (spectrum a), after having been exposed to H
h (spectrum b) and for 48 hours (spectrum c).
The narrow and symmetric peak observed before any expo-
2 2
O for
2
sure and centred at 400.5 eV is in agreement with the chemistry
of the nitrogen atom of a dioxazaborocane structure, bound to
3
3
carbon atoms and one boron atom (sp hybridisation). In the
B 1s region, a peak is observed at 190.5 eV, which is a
fingerprint of an electron-rich B atom. This is easily explained
by the electron transfer of a doublet from the N atom, thus
constituting a bond between the N and the B atom of the
molecule (N–B dative bond), as schematised in Scheme 1
Scheme 1 Sensing concept: fluorescence turn-off upon hydrogen per-
oxide exposure to dioxazaborocane 2.
(tetrahedral geometry of the boron atom). This is in perfect
agreement with the XRD and NMR data.
After exposure to hydrogen peroxide vapours, XPS spectra
undergo significant changes. After 2 h, the N1s peak of dioxa-
zaborocane 2 is much broader, with two new contributions in
addition to that at 400.5 eV. The one at higher binding energy
(BE), ca. 402.2 eV, suggests a positive charge on the N atom,
while that at lower BE, ca. 398.8 eV, bears testimony to an
additional negative charge on the nitrogen atom. After a 48 h
exposure, the N1s peak is dominated by the contribution at Scheme 2 Synthesis of dioxazaborocane 2.
402.2 eV.
Simultaneously, the B1s peak also changes, displaying, after
exposure for 2 h, a new contribution at 191.8 eV, which shows a peaks at 192 and 193.4 eV. The latter contribution is compatible
45
lower negative charge on the boron atom. After 48 h, the pristine with the formation of boric acid, B(OH)
3
,
while the former is
contribution at 190.4 eV has almost disappeared to the benefit of indicative of an intermediate species. Phenylboronic acid, as a
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In order to explain the changes in the electronic states of the
N atom, diol 1 was in turn analysed by XPS in its pristine form
and after 2 hours of exposure to hydrogen peroxide. The N1s
spectra obtained are presented in Fig. 6, showing a very inter-
esting evolution. The narrow N 1s peak observed for the diol is
indeed characteristic of a nitrogen atom bound to three carbon
atoms, and still bearing an electron doublet, while, after
2 2
exposure to H O , a new contribution appears at 402.2 eV,
typical of an ammonium type nitrogen (see Scheme 3). The
latter contribution is at exactly the same binding energy as that
of dioxazaborocane 2 after 48 h under H O . These data are
2
2
strong suggestions that exposure of 2 to H O induces a
2
2
strong alteration of the chemical bonds on a fraction of the
compound, in particular a breaking of the N–B dative bond,
together with an oxidation (in the electronic sense) of the
Fig. 6 Evolution of N1s X-ray photoelectron spectra of 1 before and after
exposure to HP vapours.
nitrogen atom. A longer exposure to H
nation of the N atom due to the acidic nature of hydrogen
hydrolysis product, could be a possibility B1s was reported to peroxide.
2 2
O leads to the proto-
4
6
be at 192 eV, but a control experiment showed that hydrolysis
To summarise the situation, XPS data are in strong agree-
only marginally occurred when 2 was subjected to water ment with a substantial chemical reactivity of dioxazaborocane
vapours (recording of XPS spectra before and after exposure 2 upon exposure to H O . It results into a mixture of diol 1, its
2
+
2
for 2 h indicated only around 10% formation of phenylboronic protonated form 1.H , boric acid, another boron-containing
acid. This is consistent with the very small response of films compound (maybe intermediate 3) and traces of unreacted
of 2 upon exposure to water, see Fig. 2). Moreover, phenyl- dioxazaborocane 2.
boronic acid was never observed in the NMR experiments. The
It is noteworthy that XPS data, focusing only on surface
rearrangement product 3 would also be expected to give a peak layers (5–10 nm), were found both consistent and complemen-
around 192 eV, however, we were unable either to isolate this tary with NMR data, which probe the entire samples. These XPS
product for XPS identification, or to confirm its formation by and NMR data, as well as detection results, strongly support the
1
1
B NMR.
mechanism depicted in Scheme 3. Upon exposure to vapours of
Scheme 3 Chemical transformations of dioxazaborocane 2 upon exposure to vapours of aqueous hydrogen peroxide, as supported by selected NMR
and XPS assignments (all chemical shifts in CDCl unless otherwise stated).
3
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aqueous hydrogen peroxide, fluorescent dioxazaborocane 2 is 11 A. Fang, PhD thesis, University of California, USA, 2004.
mainly oxidised to the expected intermediate 3 through a 12 J. Sanchez and W. Trogler, J. Mater. Chem., 2008, 18,
3
4
commonly accepted mechanism, followed by hydrolysis to
5134–5141.
get a mixture of non-fluorescent diol 1, boric acid and phenol. 13 (a) M. L. Grone, US Pat., McAfee & Taft, 2010/0144050, 2010;
+
Part of 1 is protonated with excess HP to 1.H . Another pathway,
leading to the same ultimate products, also occurs but to a
lesser extent. In this case, hydrolysis is the first reaction, thus
producing diol 1 and phenylboronic acid. The latter is then
(b) R. Deans, A. Rose, K. Bardon, L. Hancock and T. Swager,
WO 2008/073173, Nomadics Inc., 2008; (c) R. Deans,
A. Rose, B. O’Dell and M. La Grone, WO 2008/121124,
Nomadics Inc., 2008.
4
7
oxidised and hydrolysed to boric acid and phenol.
14 P. Marks, B. Radaram, M. Levine and I. A. Levitsky, Chem.
Commun., 2015, 51, 7061–7064.
1
1
1
1
1
2
2
2
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and J. Cheng, Chem. Commun., 2015, 51, 10868–10870.
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Conclusions
In the context of detection of hidden peroxide explosives, a
dioxazaborocane compound as an efficient hydrogen peroxide
(HP) sensing material was synthesised and characterised.
When exposed to diluted vapours of HP, the fluorescence of a
thin film of this material strongly decreased. NMR and XPS
studies on dioxazaborocane after exposure to HP vapours
showed that the N–B dative bond is cleaved with oxidation of
the boron atom. Identification of phenol and boric acid as end
products allowed us to accurately describe the whole reaction
sequence that explains the fluorescence quenching of dioxaza-
borocane upon HP exposure.
1 L. Zang, J. Han and M. Xu, US Pat., 2014/0193923 A1, Univ.
Utah Research Foundation, 2014.
2 G. H. Shahkhatuni, V. M. Aroutiounian, V. M. Arakelyan,
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3 B. P. Garreffi, M. Guo, N. Tokranova, N. C. Cady,
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