A smart ratiometric red fluorescent chemodosimeter for fluoride based on anthraquinone nosylate

Article abstract of DOI:10.1039/c7nj01575e

The present work reports a smart design of a chemodosimeter, namely 4-(6,11-dihydro-6,11-dioxo-1H-anthra[1,2-d]imidazol-2-yl)phenyl-4-nitrobenzenesulfonate (AH), which recognises F^- specifically through a naked eye colour change from light yell

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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A smart ratiometric red fluorescent chemodosimeter for fluoride
based on anthraquinone nosylate
Shweta,aAjit Kumar,b Neeraj,a Sharad Kumar Asthana,a and K. K. Upadhyay*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The present work reports an smart design of a chemodosimeter viz: 4-(6,11-dihydro-6,11-dioxo-1H-anthra[1,2-d]imidazol-
2-yl)phenyl-4-nitrobenzenesulfonate (AH) which recognises F- specifically through naked eye colour change from light
yellow to light orange and remarkable ratiometric fluorescence from green to red from the matrix of a large number of
similar anions in acetonitrile solution. The sensing mechanism was worked out as fluoride triggered deprotonation of
imidazole accompanied with deprotection of nosylate group (p-nitrobenzene sulfonate group). The AH was fully
characterized through single crystal X-ray diffraction studies alongwith FT-IR, 1H & 13C NMR and ESI-MS. The detection limit
calculated through fluorescent titration was found to be 3.45×10-10 M. The theoretical calculations at density functional
level were in consonance with experimental observations. AH also showed its practical applicability in the form of test
paper strips.
www.rsc.org/
are based upon colorimetric changes/fluorescent quenching
[10]. Only a few on the line of fluorescence enhancement have
Introduction
been reported, hitherto [11]
.
The design and synthesis of new molecular probes have
received portentous attention in the light of their applications
in the field of chemical analysis, bio imaging, molecular
electronics etc [1]. Among these, the optical ones transform
probe analyte interaction into an optical signal visible to naked
eye [2]. Ions play vital role in the physiology and biochemistry
of living beings besides their crucial roles in the environment.
A number of ion specific optical chemosensors have been
reported in the literature. Normally anion sensing is more
challenging than cations due to their varying shapes and sizes.
At the same time the stability constant of an anion sensor
ensemble is lower than that of cation one and a few of them
has complex pH dependence [3]. In recent years a number of
probes based upon hydrogen bonding and electrostatic
Taking into consideration these points we designed a
ratiometric fluorescent probe for fluoride in the form of
Anthraquinoneimidazolylphenyl-p-nitrobenzenesulfonate (AH)
(Scheme 1)
.
interactions have been designed and synthesised [4], [5]
.
Among the anions, fluoride has attracted attention of
researchers due to its diverse array of biological, medical and
technological processes. Its role in dental health, osteoporosis,
acute gastric and kidney problems and in bone diseases are
well documented in the literature [6, 7, 8]. The fluoride is also
known to get release upon the hydrolysis of sarin, a chemical
warfare agent [9]. The majority of reported fluoride sensors
Scheme 1: Structure of AH and its sensing effect with fluoride
The ratiometric probes allow the measurement of emission
intensities at two different wavelengths which provide an in-
built correction for environmental effects [12]. Here we have
coupled the chemodosimetric approach with ratiometric
strategy. The result was quite promising in the form of high
selectivity and rapid response time. The design of the present
chemodosimeter is based upon following considerations; (i)
the benzimidazole system has been utilized as the constituent
of chemosensors due to its facile deprotonation tendency [13]
(ii) the benzene sulfonate moiety is quite prone towards
nucleophilic attack, hence can play well as one of the
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constituent
of
chemodosimeter
[14]
(iii)
the 133.605, 130.754, 130.677, 129.266, 128.796, 127.318,
anthraimidazoledione unit coupled with group having ability of 126.780, 125.657, 123.037, 121.578; ESI-MS: m/z calculated
protection/deprotection concept has rarely been reported in for C27H15N3O7S; [M] = 525.1; found [M+H]+ = 526.2
the literature hitherto [15]. Present design also incorporates
the Intramolecular charge transfer (ICT) concept with
anthraimidazolylphenyl as the donor and p-nitrobenzene
sulfonate as acceptor units. Till now only a few ICT designs
have successfully been utilized for the anion due to feeble
colour changes upon their interaction with analyte [15, 16]
.
Experimental Section
The synthesis of AH involves two steps as shown in Scheme 2
.
Synthesis of AHOH
1, 2-diaminoanthraquinone (2 mmol) was dissolved in 15
mL of methanol. To this solution, mmol of 4-
2
hydroxybenzaldehyde in methanol (15 mL) was added.
Catalytic amount of trifluoro acetic acid was added to the
reaction mixture and put under reflux for ~ 12 hours. The
reaction mixture was finally cooled at room temperature and
the resulting brick red precipitate was filtered and washed
several times with ethanol (2 ml at a time). The resulting
product was dried in vacuum and used further without
Scheme 2: Synthetic approach of AH
Results and discussion
X-ray crystallographic studies
The structure of AH was confirmed through its single
crystal X-ray analysis. The asymmetric unit of AH crystallizes
into a monoclinic lattice with space group C2/c. An ORTEP view
of the same is shown in (Fig. 1) while crystal data and
structural refinement details are listed in Table S1; ESI.
1
purification. AHOH was characterized by FT-IR, H NMR & 13C
NMR (Fig S1-S3; ESI)
.
Spectroscopic characterization data of AHOH
Yield: 95%; IR/cm-1: 3347, 1661, 1607, 1586, 1546, 1492, 147
1, 1443, 1371, 1327, 1282, 1241, 1168, 1010, 845, 718, 634,
520; 1H NMR (500 MHz, DMSO-d6, TMS): δ ppm = 12.885 (s, -
NH, 1H), 10.224 (s, -OH, 1H), 8.240 - 8.223 (d, Ar-H, 2H), 8.162
(d, Ar-H, 2H), 7.997 (d, Ar-H, 2H), 7.880 - 7.866 (d, Ar-H, 2H),
6.905 - 6.888 (d, Ar-H, 2H); 13C NMR (125 MHz, DMSO-d6,
TMS): δ ppm = 183.720, 182.846, 160.789, 158.638, 134.939,
134.757, 133.663, 133.567, 130.562, 127.951, 127.279,
126.732, 121.539, 120.224, 116.126.
Synthesis of AH
Fig.1 Crystal structure of AH showing an ORTEP view
The 4-Nitrobenzenesulfonyl chloride (1.2 mmol) in 10 mL
dry dichloromethane was added to a suspension of AHOH (1.2
mmol) and triethylamine (3.9 mmol) in 40 mL dry
dichloromethane. The reaction mixture was stirred at room
temperature overnight. The resulting golden yellow precipitate
was filtered and dried in air. The yellow single crystal of AH
were obtained on slow evaporation of its saturated solution in
A
weak intermolecular supramolecular interaction
involving O(6) [O(6)….O(6) = 2.938 Å] atoms of AH was seen.
The O(6) of anthraquinone moiety of AH undergoes
intramolecular [O(6)….H―N(3) = 2.857 Å] and intermolecular
[O(6)….H―N(3) = 3.059 Å] hydrogen bonding interaction
resulting into a nice supramolecular self-assembly (Fig 2 a &
b). The selected important bond lengths and angles for AH are
1
DMSO. AH was characterized by FT-IR, HNMR, 13CNMR, ESI-
presented in Table S2 ESI
.
MS (Fig S4-S7; ESI) and Single crystal XRD studies.
Spectroscopic characterization data of AH
Yield: 90%; IR/cm-1: 3345, 3106, 1666, 1646, 1583, 1539, 1489,
1475, 1383, 1331, 1293, 1202, 1179, 1149, 1090, 1011, 868,
768, 717, 636, 563; 1H NMR (500 MHz, DMSO-d6, TMS): δ ppm
= 13.312 (s, -NH, 1H), 8.458 - 8.412 (m, Ar-H, 4H), 8.193 - 8.179
(m, Ar-H, 4H), 8.101 - 8.046 (m, Ar-H, 2H), 7.907 - 7.891 (m, Ar-
H, 2H), 7.280 - 7.264 (d, Ar-H, 2H); 13C NMR (125 MHz, DMSO-
d6, TMS): δ ppm = 183.605, 182.962, 155.740, 151.708,
150.806, 147.293, 142.925, 139.863, 134.978, 134.853,
(a)
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sensing for F-. The 5 µM solution of AH in acetonitrile showed
an emission band at ~ 510 nm upon its excitation at ~ 425 nm.
After gradual addition of fluoride (upto 100 eq.) a new band at
~ 592 nm was observed with the shift of ~ 82 nm. The emitted
colour of fluorescence under UV light changed from green to
orange red at this juncture (Fig. 4). The same could be
understood as a two-step process, the first stage involves
reversible abstraction of a proton from AH through F- leading
to formation of the resonance stabilized anionic form of AH i.e.
A-. The next attack of fluoride over A- leads to deprotection of
nosylate resulting into the collapse of A- into A1 and p-
nitrobenzene sulphonic acid. Our this proposal is well
supported through 1HNMR (Fig. 8) and mass spectral studies
(Fig. S16; ESI). The emission intensity ratio, I592/I510, increases
with the increase in the fluoride concentrations which allows
(b)
Fig. 2 (a) Intermolecular and Intramolecular hydrogen bonding interaction in
AH; (b) The supramolecular architecture of AH
UV-visible studies
Anion binding studies of AH (10 μM) towards a number of
-
anions viz. F-, Cl-, Br-, I- HSO4 , HPO42-, H2PO4 , BzO-, AcO-, PF6 ,
-
-
-
-
ClO4 , BF4 as their tetrabutylammonium salts were performed
in acetonitrile. Only F- responded through light orange colour
while rest of the anions were remained silent towards naked
eye response (Fig S8; ESI). The same was also translated in the
form of corresponding absorption changes (Fig. 3a) and has
also been represented in the form of bar graph (Fig S9; ESI)
.
the detection of fluoride ions ratiometrically (Fig. 5)
.
The time response through UV-visible study depicted in Fig
S10; ESI indicated that AH was quite efficient against fluoride
as the naked eye response was observed within one minute.
Additionally, the visual responses of AHOH (precursor of AH)
were also monitored against a number of anions mentioned
above including fluoride also. The corresponding responses
were not of much interest as the same were not selective
against any particular anion. (Fig.S11, ESI).
The absorption spectra of free AH (10 µM) exhibit a
characteristic π-π* transition of the chromophore at ~ 395 nm
[17]. Upon concomitant addition of fluoride ion (TBA salt), a
new band at ~ 470 nm which is the charge transfer (CT) band
appeared with its gradual increment and simultaneous
disappearance of band at ~ 395 nm (Fig.3 a). After addition of Fig 4: Emission titration profile of AH (5 μM) with fluoride (0 - 100 equiv.) in
acetonitrile; λex = 425 nm; [Inset] Change in intensity of AH at ~ 510 nm and
~ 592 nm as function of F‒ ion concentration
~ 40 eq of fluoride, ~ 75 nm red shifted full fledge peak at
~ 470 nm with corresponding instantaneous colour change
from light yellow to light orange was observed. Two clear
isosbestic points at ~ 340 nm and ~ 422 nm confirmed the
interaction of AH with F- at chemical level.
Fig 5: Ratiometric calibration curve I592/I510 of AH (5 μM) as a function of the
concentration of F-. Inset: fluorescent photograph of 1-AH (10 μM) and
(2−7) AH + F−: with fluoride added as (2) 10 eq., (3) 30 eq., (4) 50 eq., (5) 80
eq., (6) 100 eq., (7) 150 eq.
Fig. 3 (a) Absorption spectral changes of AH (10 µM) upon addition of
increasing equivalents of F- ions (0 – 40 equiv.) in acetonitrile. Inset: the
Similar studies were also repeated in acetonitrile with
photographs showed the colour change of AH in the presence of F- ions; (b)
other anions also as their TBA salts, viz. Cl-, Br-, I-, HSO4 , HPO4
-
2-
Change in absorption intensity of AH at ~ 395 nm and ~ 470 nm as function
, H2PO4 , BzO-, AcO-, PF6 , ClO4, BF4 . As expected none of the
anions caused the change in emission pattern (Fig S12; ESI)
and the corresponding bar graph along with the optical
responses of different anions in acetonitrile under the UV light
have been shown in Fig S13; ESI. To check the practical ability
of chemosensor AH as fluoride selective fluorescent sensor,
-
-
-
of F- ion concentration.
Fluorescence studies
Having seen the selectivity of AH towards F- ion in
absorption mode, the emission property of the same was also
investigated to explore the possibility of yet another mode of
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we carried out competitive experiments in the presence of
above mentioned anions. To the mixture of AH (5 μM) and
fluoride (10 equiv.) in acetonitrile, the respective anions were
added separately and corresponding spectra were recorded
after one minute. The results have been represented in the
form of bar graph Fig S14; ESI. This study clearly establishes a
high selectivity of AH towards F‒.
Fig 7: (a) Naked eye colour change of AH in presence of S2- ion with respect
The detection limit (LOD) from fluorescence titration data
was worked out as 3.45 x 10−10 M (R2 = 0.9998) (Fig. 6 a). The to time and its corresponding absorption spectra; (b) Optical response
(under UV light) of AH in presence of S2- ion with respect to time and its
time dependent fluorescence change of AH upon addition of
corresponding emission spectra
fluoride ion was virtually completed within one minute (Fig. 6
The most probable reason for the above changes caused by
S2- and F- ion can be understood in terms of HSAB theory (Hard
b). Since the present study involves chemodosimeter approach
involving dissociation of the sensor AH. Hence calculation of
Soft Acid Base). According to this theory, hard acids prefer
hard bases; soft acids prefer soft bases.
S2- is a soft base and H+
binding constant/stoichiometry could not be done [18].
is hard acid and thus the formation of HS- according to
equation (1) is less favoured, hence backward reaction
dominates.
(1)
Thus, the instant colour change with S2- is the result of
partial deprotonation of imidazole proton which persists for
certain time period and finally reverts back to the parent
moiety giving original colour. On the other hand, F- is hard
base and prefers hard acid H+ resulting into the formation of
HF; hence the forward reaction dominates (equation2).
Fig6: (a) Calibration curve for the determination of detection limit of AH
with fluoride; (b) Reaction time profile of AH with F-
Response of AH with Sulphide (S2-) ion
(2)
Thus, the colour change was long lasting with F- ion.
Probes
based
on
deprotection
of
Consequently, we can say that AH is distinctly selective only
for F- ion.
dinitro/nitrobenzenesulfonyl
(DNBS/NBS) protected
fluorophores responded mainly for thiols [19] and only a few
of them could detect F- with significant interferences from
sulphide [20]. Surprisingly, AH also gave response towards S2-
similar to that of F-, but reverts back to the original state after
10 minutes. To study the interference of S2-, we performed the
UV-visible, fluorescence and optical response studies of AH
towards S2-. Upon the addition of ~ 40 equiv. of S2- to AH (10
μM), instant colour change from light yellow to light orange
occurred which eventually reverted back to original colour
after 10 minutes. The emission spectrum of AH (5 μM) with S2-
also exhibited similar pattern as that in absorption mode. The
absorption and emission spectra of the same have been
represented in the Fig 7 (a) & (b). Relative time response
studies were also performed for F- and S2- ions through UV-
1H NMR Studies
The mechanistic aspect of fluoride sensing by AH was
further confirmed through 1H NMR study in DMSO-d6. The
study showed that addition of 1 equiv. of F‒ (as its TBA salt) to
the 5 mM solution of AH led cessation of nosylate group
resulting to the bifurcation of nosylate protons and the
complete deprotonation of -NH proton resulting into vanishing
of peak at 13.312 δ ppm. Before the addition of fluoride, the
nosylate protons were observed in the range of 8.458 - 8.428 δ
ppm (single red star in Fig:8) while upon addition of F‒,
bifurcation along with [14, 21] upfield shifting in the range of
8.452 - 8.434 δ ppm and 8.396 - 8.379 δ ppm was observed
(two separate red stars in Fig:8). For comparison, the
interaction of fluoride with AHOH have also been shown (Fig.
visible as shown in Fig S15; ESI
.
8).
4 | J. Name., 2012, 00, 1-3
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Fig. 8: Partial 1H NMR spectra of AH, AH + F- and AHOH + F- in a DMSO-d6
solution
The mass spectrometric studies also fortified our above
notion of chemodosimetric path of AH towards F‒. The
molecular ion peak of corresponding product A1 was observed
clearly in the spectrum. The corresponding mass spectra of AH
and A1 have been shown in ESI; Fig S7 and S16 respectively.
Density Functional Theory Calculations
Fig 10: HOMO and LUMO distributions of AH and A1
Mechanistic aspect of sensing of fluoride by AH
On the basis of above studies the chemodosimetric
approach employing the dual nature of fluoride viz. basic and
nucleophilic nature resulting into deprotonation accompanied
with deprotection of AH as shown in Scheme 3 was proposed.
AH as such showed green fluorescence in acetonitrile under
UV light. The first F- ion, acting as a base, led to the acid-base
reaction resulting into the deprotonation of -H from imidazole
nitrogen generating A-. The negative charge developed on the
nitrogen atom of imidazole was in resonance with both 9 and
10 quinone carbonyls (only one structure has been shown i.e.
resonance with 9 quinone carbonyl). Another F- ion behaving
as a nucleophile, attacked on A- causing the deprotection of
nosylate group resulting into the formation of highly
fluorescent dianionic form A1 which showed red fluorescence
in acetonitrile under UV light.
In order to further investigate the electronic structure and
the observed spectroscopic properties of AH and its
deprotected–deprotonated π-conjugated, A1, DFT geometry
optimizations followed by TD-DFT calculations were carried
out using the Gaussian 09 software package at the B3LYP/6-
311G** level [22]. The corresponding optimized geometries of
AH and A1 have been shown in Fig. 9.
Fig 9: Optimized structures of AH and its corresponding deprotonated–
deprotected π-conjugated A1
The spatial distributions of frontier orbitals and orbital
energies of HOMO and LUMO of AH and A1 were also
determined. As it can be seen, the HOMO is delocalized over
the phenyl ring and the neighbouring imidazole moiety and
LUMO is completely localized over 4-nitrbenzenesulfonyl i.e.
nosylate group only, thus, presenting AH as a good example of
an ICT (Fig. 10). A comparison of electron density distribution
in HOMO and LUMO of AH and A1 clearly indicates a greater
extent of conjugation and strengthening of ICT in latter than
the previous one. The decrease in HOMO-LUMO gap upon
interaction with fluoride is in coherence with bathochromic
shift (~ 75 nm) in the UV-vis. band of AH as mentioned earlier.
Thus TD-DFT helped in getting insight of the electronic
transitions involved and matched well with the experimental
absorption wavelengths. Some selected transitions have been
mentioned in Table S3; ESI.
Scheme 3: The mechanism involved in the sensing of fluoride by AH
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Practical Application
To enrich the practical application of AH we performed the
detection of fluoride by AH through test paper strip. For this
we prepared two test strips and dipped first one into AH
solution (10 μM in acetonitrile) and the second one in AH+F-
solution (in acetonitrile) for a minute. Then the strips were
allowed to dry at room temperature. As shown in Fig. 11,
paper strip dipped in AH was light yellow and emitted green
fluorescence while the one dipped in AH+F- showed dark
yellow and red fluorescent when seen under visible and UV
light respectively.
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Fig. 11: Chromo-fluorogenic response of test paper strips with AH and AH+F-
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Conclusion
Thus, we have presented a new kind of chemodosimeter
AH which specifically detects F- both in absorption and
ratiometric
emission
mode
through
deprotonation
accompanied with deprotection process which was well
1
supported from H NMR study. The DFT study supported the
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Acknowledgements
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Shweta acknowledges UGC, New Delhi for JRF/SRF [19-
12/2010 (i) EU-IV]. AK thanks SERB, New Delhi for the Young
Scientist award [YSS/2015/000057]. Neeraj acknowledges the
UPE-JRF fellowship [chem./2012-13/154]. SKA thanks the CSIR,
New Delhi for JRF/SRF [09/013(0475)/2012-EMR-I].
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GRAPHICAL ABSTRACT
A smart ratiometric red fluorescent chemodosimeter (AH) has been explored for
specific detection of F- with a lowest detection limit of 3.45×10-10 M. The sensing mechanism
was worked out as fluoride triggered deprotonation of imidazole accompanied with
deprotection of nosylate group.