A dialdehyde-diboronate-functionalized AIE luminogen: Design, synthesis and application in the detection of hydrogen peroxide

Article abstract of DOI:10.1039/c6cc05116b

A dialdehyde-diboronate-functionalized tetraphenylethene (TPE-DABF) was reported as a H₂O₂-specific AIE luminogen. TPE-DABF, bearing multiple reductive units (aldehyde, boronate and fructose) in one molecule, afforded an excellent H<

Full text of DOI:10.1039/c6cc05116b

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DOI: 10.1039/C6CC05116B
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Received 00th January
20xx,
Dialdehyde-Diboronate-Functionalized AIE Luminogen:
Design, Synthesis and Application for Detection of
Hydrogen Peroxide
Guang-Jian Liu, Zi Long, Hai-juan Lv, Cui-yun Li and Guo-wen Xing＊
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A dialdehyde-diboronate-functionalized tetraphenylethene (TPE-DABF) was reported as a H2O2–specific AIE luminogen.
TPE-DABF, bearing multiple reductive units (aldehyde, boronate and fructose) in one molecule, afforded an excellent H2O2
selectivity over other ROS in biological buffer, and can be used for sensitive detection of glucose under neutral conditions.
The aggregation-induced emission (AIE) effect1
opposite to conventional aggregation-caused quenching (ACQ)
,which is
is also an intramolecular charge transfer (ICT) probe upon
reacting with H2O2, since the oxidation product TPE-DAP
(Scheme 1) contains both electron-withdrawing (aldehyde) and
electron-donating (phenoic hydroxyl) groups in its TPE core.
Remarkably, the multiple reductive units (aldehyde, boronate,
double bond and D-fructose) in TPE-DABF should be helpful
to increase H2O2-selectivity via the different oxidation reactions
with various ROS (Scheme 1).
phenomenon, features with fluorescence increasing caused by
restriction of intramolecular motions.2 Various AIE luminogens
(AIEgens) have been created and successfully used in the field
of
optoelectronic
devices,3
luminescent
sensors,4
mechanofluorochromic materials,5 etc. Notably, based on
electrostatic interaction, coordination binding or chemical
reactions between AIEgens and analytes, many new analytic
methods utilizing AIE effect have been established for the
enzyme assays,6 screening of inhibitors,7 detection of ionic
species,8 biomolecules9 and volatile/explosive organic
compounds.10
To explore our attractive ideas, we prepared the probe TPE-
DABA in six steps according to the synthetic route shown in
Scheme
tolylethene (
bromophenyl)(
Crafts reaction of 4-bromobenzoyl chloride (
bromination and Korublum reaction of , the dialdehyde-
dibromo-functionalized TPE ( ) was obtained. Then palladium-
catalyzed Miyaura borylation reaction25 of
proceeded
smoothly to furnish bis(pinacolato)diboron TPE . Finally,
treatment of with NaIO4 and HCl in the mixture of THF and
S1.
) was synthesized by McMurry reaction of (4-
-tolyl)methanone ( ), following the Friedel-
). After the
Firstly,
1,2-bis(4-bromophenyl)-1,2-di-p-
3
p
2
Over last decade, it has been found that the AIEgen sensing
systems have the advantages of easy fabrication, facile
functionalization, high signal-to-noise ratio and strong
photobleaching resistance.11 However, fewer literatures12 were
reported using AIE probes for the detection of reactive oxygen
species (ROS). Hydrogen peroxide (H2O2), one of the most
important ROS, plays an important physiological and
pathological role in human health and aging.13-14 Although
many fluorescent probes for H2O2 sensing have been
illustrated,15-21 it still remains a great challenge to design a
AIEgen for detection of H2O2 over other ROS.
1
3
5
5
6
6
water gave the desired deprotected product TPE-DABA, which
was characterized precisely by NMR and high resolution mass
spectroscopy (Fig. S1 in supporting information).
We carried out the pH titration experiments of probe TPE-
DABA and its precusor
6 at various pH values in Britton-
Inspired by the previous findings that sugar-bearing AIE
molecules have nearly no luminescence in aqueous solution22
and aromatic boronic acids could rapidly and reversibly interact
with carbohydrates to form boronate complex,23 herein, we
reported a unique sugar-boronic acid complex (TPE-DABF,
Scheme 1) as a new AIEgen for highly selective detection of
H2O2.
TPE-DABF, a complex of D-fructose and dialdehyde-
diboronic acid-functionalized tetraphenylethene (TPE-DABA,
Scheme 1), not only has lower background fluorescence due to
its better water solubility, but also becomes more reactive to
H2O2 for the boronic ester formation.24 In addition, TPE-DABF
Department of Chemistry, Beijing Normal University, Beijing 100875, China. E‐mail:
gwxing@bnu.edu.cn
Electronic supplementary information (ESI) available: Detailed experimental
procedures. See DOI: 10.1039/x0xx00000x
Scheme 1 Design of AIEgens for specific detection of H2O2 over
various ROS.
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DOI: 10.1039/C6CC05116B
Figure 2. (a) Fluorescence spectra of the TPE-DABF complex (TPE-
DABA, 50 μM; D-fructose, 30 mM) upon titration of H2O2. (b) Plot of
the relative fluorescence intensity
concentration of H2O2. Inset: linearity of the ratio of fluorescence
intensity ( I0) at 576 nm. ex = 430 nm.
(I/I0) at 576 nm versus the
I
/

To verify the chemospecific H2O2-triggered transformation of
arylboronates to phenols, we extracted the detection systems
with EtOAc and analyzed the extracts by ESI mass
spectrometry. The high abundance of the ion at m/z 419.33 in
the mass spectrum (Fig. S6) indicated that only the boronate
moiety in the TPE-DABF complex was oxidized into phenol by
H2O2 and the aldehyde moiety remained unchanged. Moreover,
we amplified the same reaction in an Erlenmeyer flask and the
obtained product was identified with NMR and HRMS spectra,
which further indicated the formation of TPE-DAP. As a result,
the oxidative product TPE-DAP with electron donor-acceptor
structure showed longer-wavelength emission. In addition, the
Figure 1. (a) Fluorescence spectra of probe TPE-DABA (50 μM) in the
presence of different concentrations of D-fructose in 0.1 M PBS buffer
containing 2 vol% DMSO (pH = 7.4, ex = 380 nm). (b) Plot of the
relative fluorescence intensity (I0
/I) at 510 nm versus the concentration
of D-fructose. Inset: linearity of the ratio of fluorescence intensity (I0/I)
at 510 nm. (c) Photographs of the solutions of TPE-DABA and different
concentrations of D-fructose in 0.1 M PBS buffers containing 2 vol%
DMSO (pH = 7.4) under UV illumination.
Robinson buffers. As depicted in Fig. S2-S3, the fluorescence
intensities of TPE-DABA and
6 were strong under neutral and
acid conditions, but decreased dramatically in alkaline medium.
Gradual raising the pH from 8 to 12 resulted in a significant
decline of the fluorescence emission, indicating that TPE-
relative fluorescence intensity I (in the presence of H2O2)/I0 (in
DABA and
6 were transformed into borate salts and became
the absence of H2O2) of TPE-DABF complex with different
concentrations of H2O2 at pH 7.4 over time was summarized in
Fig. S7. Notable fluorescence changes could be observed within
60 min in most cases, therefore 60 min of reaction time was
selected in the following experiments.
As shown in Fig 2a, the fluorescence emission of TPE-
DABF was gradually switched on in the presence of H2O2. A
32-fold fluorescence enhancement at 576 nm was observed
after TPE-DABF was incubated with 300 μM H2O2 for 60 min.
Moreover, the fluorescence intensity ratio at 576 nm was
linearly related to the concentration of added H2O2 in the range
of 60-300 μM (Fig 2b) and the detection limit of our probe was
soluble in the buffers with high pH values. This pH effect was
fully consistent with the fact that the boron atom of arylboronic
acid could be ionized by OH- in alkaline aqueous solutions.9b
Based on our long-standing interests and studies in the
synthesis of complex glycosides and fluorescent detection of
oligosaccharides,26 next, we tested whether the initial strong
fluorescence intensity of TPE-DABA under physiological pH
conditions could be decreased by binding with sugars through
increasing its solubility. Considering that arylboronic acid has a
high binding constant with D-fructose,23 we evaluated the
fluorescence responses of TPE-DABA to D-fructose under
physiological conditions (0.1 M PBS buffer solutions, pH 7.4).
As anticipated, the fluorescence intensity of TPE-DABA
decreased gradually upon the addition of D-fructose as shown
in Fig. 1, suggesting that the boronic acid TPE-DABA indeed
interacted with the diol groups of D-fructose to form TPE-
DABA-fructose boronate complex (TPE-DABF). In addition,
determined to be
3.2 μM, indicating that the AIEgen TPE-
DABF could sensitively detect micromolar changes of H2O2
concentration.
As illustrated in Scheme 1, the detection mechanism of our
AIEgen probes TPE-DABA/TPE-DABF was deeply
investigated. The existence state, especially, the size of AIEgen
probes upon addition of D-fructose and H2O2 sequentially was
the relative fluorescence intensity at 510 nm (I0/I) changed
linearly with the concentration of D-fructose in the range of 4-
16 mM (Fig. 1b). Due to the good solubility of the sugar-
bearing complex TPE-DABF, the fluorescence intensity could
be neglected when the concentration of D-fructose reached 30
mM.
Then, we turned our attention to investigate the optical
properties of the resulting complex TPE-DABF formed by
TPE-DABA (50 μM) and D-fructose (30 mM) towards H2O2 in
0.1 M phosphate buffer solution at pH 7.4. To our delight, a red
shift in the absorption spectrum and excitation spectrum of the
complex TPE-DABF was observed when H2O2 was added to
the mixture (Fig. S4-S5 in supporting information). Meanwhile,
the maximum fluorescence band of the solution of TPE-DBAF
and H2O2 was red-shifted to 576 nm compared with that of
TPE-DABA. The red shifts upon addition of H2O2 may be
ascribed to the ICT effect caused by the electron-donating and
electron-withdrawing units in the oxidative product TPE-DAP.
Figure 3. Fluorescence microscopy image of (a1) TPE-DABA (50 μM);
(b1) TPE-DABF; (c1) TPE-DABF and H2O2 (250 μM); DLS data of
(a2) TPE-DABA (50 μM); (b2) TPE-DABF; (c2) TPE-DABF and H2O2
(250 μM). TPE-DABF complex was formed with 50 μM TPE-DABA
and 30 mM D-fructose in situ
.
2 | J. Name., 2012, 00, 1‐4
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U/mL GOD and 250 μM glucose) sequentially; these photographs were
measured by fluorescence microscopy and dynamic light
scattering (DLS). It can be seen that probe TPE-DABA was
immiscible with water and showed a strong fluorescence in 0.1
M PBS buffer solution (Fig. 3a). The average diameter of the
particles measured by DLS was about 6000 nm, which was in
accordance with the results obtained by fluorescence
microscopy. The aggregate formation restricted the
intramolecular rotations of the phenyl rings in TPE-DABA,
resulting fluorescence “on” at pH 7.4 buffer solution. Owing to
the high affinity binding interaction between boronic acid and
D-fructose, when D-fructose was added into the solution of
TPE-DABA, the suspension became nearly non-fluorescent
with concomitant decreasing of the average diameter of the
aggregates (Fig. 3b). The results reflected that the
intramolecular motions were activated as a radiationless
relaxation channel due to the good solubility of the formed
TPE-DABF complex. As has been discussed, the addition of
H2O2 to the solution caused the complex recover its emission
(Fig. 3c). This is likely because the hydrophobic property of the
oxidation product TPE-DAP induced the formation of
aggregates as was borne out by the DLS experiment. Taken
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taken under UV illumination at 365 nm.
DOI: 10.1039/C6CC05116B
together, these data provided further evidence for the dual AIE
and ICT mechanism of the detection system to decipher the
significant “on-off-on” signal responses as have been observed
in the detection process (Scheme 1).
Furthermore, the selectivity of TPE-DABF complex towards
other reactive oxygen species at several time points was
investigated in pH 7.4 buffer solution. Due to the multiple
reductive units (aldehyde, boronate, double bond and D-
fructose) in TPE-DABF, even though previous literatures23a,27
have reported aryl boronic esters can be oxidized into phenols
by peroxynitrite (ONOO-), hypochlorite (ClO-) and superoxide
-
(O2 ) , our probe shows a >20-fold higher fluorescence response
to H2O2 over other ROS, such as hydroxyl radicals (•OH),
hypochlorite (ClO-), peroxynitrite (ONOO-), tert-butyl
-
hydroperoxide (TBHP), superoxide (O2 ), peroxyl radicals
-
-
(ROO•), nitrite (NO2 ) and nitrate (NO3 ) (Fig. 4). As illustrated
in Scheme 1, we think that only H2O2 could oxidize boronates
to phenols selectively and other ROS may either not react with
TPE-DABF or react with other reductive units simultaneously.
As a result, the incorporation of multiple reductive units into
the detecting system was crucial to the good selectivity of TPE-
DABF to H2O2 over other ROS.
Finally, TPE-DABF was employed for sensitive glucose
detection by monitoring the produced hydrogen peroxide in the
enzymatic reaction28 between glucose and glucose oxidase
(GOD). Different concentrations of glucose and 1 U/mL GOD
were added to the TPE-DABF solution under neutral conditions
and the mixture was shaken at 37 ºC for 1 h. As expected,
remarkable increasing in the fluorescence of solution was
observed upon excitation at 430 nm (Fig. 5a and Fig. S8). The
relative fluorescence intensity at 576 nm was increased linearly
with the glucose concentration at 50-300 μM, which is
indicative of powerful glucose detection (Fig. 5b). Notably, the
control experiments indicated that glucose or concomitant
product glucolactone could not induce the fluorescence
enhancement under the same conditions. More importantly, the
changes of the solution before and after addition of H2O2 or its
alternatives can be easily distinguished with naked eyes under
UV illumination as shown Fig. 5c.
Figure 4. Fluorescence responses of TPE-DABP complex (TPE-DABA
,
50 μM; D-fructose, 30 mM) to various reactive oxygen species (ROS)
in PBS buffer containing 2 vol% DMSO at pH 7.4. Data shown are for
250 μM of all ROS reagents. Bars represent relative responses at 15
(red), 30 (green), 45 (blue) and 60 (pink) min after addition of each
ROS. Fluorescence intensity was collected at 576 nm (λex = 430 nm).
In summary, a novel dialdehyde-diboronic acid-functionalized
tetraphenylethene derivative (TPE-DABA) was designed and
synthesized. Based on the H2O2-mediated boronate-to-phenol
reaction, we have successfully developed a highly H2O2-specific
AIEgen TPE-DABF. Due to dual AIE and ICT mechanisms, TPE-
DABA displayed an “on-off-on” response companying with
concomitant bathochromic shift when treated with D-fructose and
hydrogen peroxide sequentially. In addition, TPE-DABF was also
used for detection of glucose under neutral conditions by sensing the
generated H2O2 from the GOD catalyzed oxidation reactions. We
believe that the methodology presented in this study should have
potential applications to detect substrates related to H2O2 generation,
and provide a basis for further development of AIEgens for detection
of other reactive oxygen species.
Figure 5. (a) Fluorescence spectra of the aqueous mixture containing
TPE-DABF (probe TPE-DABA, 50 μM; D-fructose, 30 mM), GOD (1
U/mL) and different concentrations of glucose. (b) Plot of the relative
The project was financially supported by the National
Natural Science Foundation of China (21272027).
fluorescence intensity (
glucose. Inset: linearity of the ratio of fluorescence intensity (
I
/
I0) at 576 nm versus the concentrations of
I0) at
Notes and references
I
/
576 nm. The data were collected in PBS buffer solution containing 2
vol% DMSO (0.1 M PBS, pH 7.4) with excitation at 430 nm. (c)
Photographs of the solutions of TPE-DABA (50 μM) before and after
addition of D-fructose (30 mM) and H2O2 (250 μM) or its alternative (1
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