Novel coumarin-based fluorescent probe for selective detection of bisulfite anion in water

Article abstract of DOI:10.1002/cjoc.201090035

Coumarins and its analogues have been widely used as chromophore in design of fluorescent probe, while less coumarin-based fluorescent probe was reported for detection of anion in water. In this article, coumarin-based fluorescent probes with salicylaldehyde functionality as recognition unit have been developed for selective detection of bisulfite anions in water. Four novel fluorescent probes were synthesized from 4-haloresorcinol in three steps. The chemoprobe exhibited selective response to bisulfite over other anions. Moreover, the detection mechanism was studied. Upon bisulfite added, the fluorescent intensity of the probes was enhanced highly due to the nucleophilic addition reaction of formyl group with bisulfite anion.

Full text of DOI:10.1002/cjoc.201090035

FULL PAPER
Novel Coumarin-based Fluorescent Probe for Selective
Detection of Bisulfite Anion in Water
Chen, Kangyu(陈康裕)
Guo, Yuan*(郭媛)
Lu, Zhenhuan(陆振欢)
Yang, Bingqin(杨秉勤)
Shi, Zhen(史真)
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education),
College of Chemistry and Materials Science, Northwest University, Xi'an, Shaanxi 710069, China
Coumarins and its analogues have been widely used as chromophore in design of fluorescent probe, while less
coumarin-based fluorescent probe was reported for detection of anion in water. In this article, coumarin-based fluo-
rescent probes with salicylaldehyde functionality as recognition unit have been developed for selective detection of
bisulfite anions in water. Four novel fluorescent probes were synthesized from 4-haloresorcinol in three steps. The
chemoprobe exhibited selective response to bisulfite over other anions. Moreover, the detection mechanism was
studied. Upon bisulfite added, the fluorescent intensity of the probes was enhanced highly due to the nucleophilic
addition reaction of formyl group with bisulfite anion.
Keywords coumarin-based fluorescent probe, bisulfite anion, selective detection, synthesis
Introduction
in many countries. Therefore, the development of a sen-
sitive, selective and low cost method for the determina-
tion of bisulfite is of great importance for food quality
assurance and quality control. Many analytical tech-
niques are available for the determination of bisulfite,
As an important group of organic heterocycles,
coumarin derivatives are found to possess versatile bio-
logical activities and can be found in many natural or
synthetic drug molecules. Besides, their unique photo-
chemical and photophysical properties make them use-
ful in a variety of applications such as optical bright-
16
17
such as spectrophotometry, spectrofluorimetry, che-
18
19
miluminescence measurements,
phosphorimetry,
20
21
chromatography,
electrochemical
and enzymatic
1
2
3
eners, fluorescent whiteners, fluorescence indicators
22
techniques. But some of them are not selective, some
need cumbersome pretreatment and some are not sensi-
tive enough to determine low concentration of bisulfite.
Salicylaldehyde is a popular reaction counterpart for
nucleophilic addition reactions owing to its activated
carbonyl by phenolic hydroxyl group through an inter-
4
and organic nonlinear optical materials. Their appro-
priate excitation and emission maxima, which are long
enough to minimize the background fluorescence of
cellular components and biological fluids, made them
widely used in in vivo measurements. Their Stokes
shifts are large enough to avoid overlap of the excitation
and emission spectra, and the high enough fluorescence
quantum yields make ion detection possible at low
23
molecular hydrogen bond. It is usually applied to the
enantioselective recognition of homocysteine or cys-
24
teine and cyanide. We now expect that it could also be
5
probe concentration. By integration of recognition unit
with the coumarin chromophore, the resulting cou-
marin-based fluorescent probe has been extensively
useful in the detection of bisulfite.
In this paper, four novel coumarin-based fluorescent
probes have been developed for highly selective detec-
tion of bisulfite anions in water. The chemoprobes have
shown a selective response to bisulfite over other anions
via nucleophilic addition reactions. The probes were
weakly fluorescent compounds in weakly acidic aque-
ous. Upon addition of the probes to bisulfite anion in
pH-buffered aqueous solution at room temperature,
fluorescence intensity of the detected solution increased
dramaticlly (Scheme 1). The probes showed high selec-
tivity toward bisulfite anions in water.
＋
＋
2＋
used in metal ion detection such as Na , K , Ca ,
2
＋
2＋
2＋
2＋
2＋
2＋
6-14
Mg , Fe , Cu , Zn , Hg , Pb and so on.
However, less coumarin-based fluorescent probe was
reported for detection of anion in water.
Bisulfite has been widely used as a preservative for
foods, beverages and pharmaceutical products. It acts as
15
antimicrobial agent, enzyme inhibitor and antioxidant.
However, due to the reported harmful effects towards
people, the threshold levels of bisulfite and sulfur diox-
ide in food and medicine have been rigorous controlled
*
E-mail: yuanorganic@gmail.com; Tel.: 0086-029-81739198; Fax: 0086-029-88303606
Received July 17, 2009; revised October 21, 2009; accepted December 9, 2009.
Project supported by the National Natural Science Foundation of China (No. 20802056), the Natural Science Foundation of Shaanxi Province (No.
SJ08B15), the China Postdoctoral Science Foundation (No. 20070421139), the Special Foundation of the Education Committee of Shaanxi Province
(
No. 09JK750) and the Northwest University Graduate Cross-discipline Funds (No. 09YJC21).
Chin. J. Chem. 2010, 28, 55— 60 © 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
55

Chen et al.
FULL PAPER
Scheme 1
Scheme 2
Experimental
Apparatus
Elemental analyses were performed with a Vario
EL-III instrument (Germany). Infrared (IR) spectra in
－
1
cm were recorded on a Bruker EQUIOX-55 spec-
trometer (Germany). Proton magnetic resonance spectra
1
(
H NMR) were recorded at 400 MHz on a Varian
INOVA-400 spectrometer (USA), and chemical shifts
were reported relative to internal Me Si. The
4
fluorescence spectra and relative fluorescence intensity
were measured with a Sanco CRT-970 spectro-
fluorimeter (Shanghai, China) with a 10 mm quartz cu-
vette. The excitation and emission wavelength band-
passes were both set at 5 nm. Unless specific noted, the
sensitivity of the spectrofluorimeter was set at “1”. The
2
,4-Dihydroxy-5-fluorobenzaldehyde (1b): Crystal
－
6
－1
1
concentration of the probe was 1×10 mol•L in wa-
ribbon, yield 62%. H NMR (CDCl
phenyl), 7.36 (s, 1H, phenyl), 9.98 (s, 1H, formyl); IR
3
) δ: 6.53 (s, 1H,
ter.
(
KBr) ν: 3087, 2924, 1644, 1515, 1443, 1287, 1132
Reagents
－
1
＋
cm ; MS m/z: 155 (M ). Anal. calcd for C
7
H
5
FO
3
: C
－
1
A stock solution of sodium bisulfite (0.01 mol•L )
was prepared daily by dissolving 52 mg of sodium bi-
sulfite in 50.0 mL water. Standard test solution were
prepared by dilution of the stock solution. A 0.2 mol•
5
3.86, H 3.23; found C 53.72, H 3.24.
,4-Dihydroxy-5-chlorobenzaldehyde (1c): Crystal
2
1
ribbon, yield 58%. H NMR (CDCl
phenyl), 7.51 (s, 1H, phenyl), 9.69 (s, 1H, formyl); IR
3
) δ: 6.62 (s, 1H,
－
1
L
2 4
NaH PO citric buffer solution (pH 5.0) was em-
(
KBr) ν: 3145, 2895, 1640, 1513, 1432, 1245, 1152
ployed.
－1
＋
cm ; MS m/z: 173 (M ). Anal. calcd for C
7
H
5
ClO
3
: C
All the regents were of analytical-reagent grade, and
distilled water was used throughout.
4
8.72, H 2.92; found C 48.67, H 2.93.
,4-Dihydroxy-5-bromobenzaldehyde (1d): Crystal
2
1
ribbon, yield 55%. H NMR (CDCl
phenyl), 7.65 (s, 1H, phenyl), 9.69 (s, 1H, formyl); IR
3
) δ: 6.62 (s, 1H,
Synthesis
This kind of probe has a coumarin groups as fluo-
rescent signal unit and a salicylaldehyde functionality as
a recognition or reaction unit. The four probes were
synthesized from 4-haloresorcinol as a starting material
in three steps as Scheme 2.
(
KBr) ν: 3189, 2878, 1639, 1511, 1415, 1234, 1190
－1
＋
cm ; MS m/z: 217 (M ). Anal. calcd for C
7
H
5
BrO
3
: C
3
8.74, H 2.23; found C 38.67, H 2.24.
Synthesis of 2a— 2d A solution of 6.6 mmol of 2,
-dihydroxybenzaldehyde, 4.0 mmol of diethyl malo-
4
Synthesis of 1a— 1d 0.1 mol of 4-haloresorcinol
was dissolved in 70 mL of dry diethyl ether and 0.2 mol
of finely powder zinc cyanide was added with stirring.
The suspension was cooled on ice. A strong stream of
hydrogen chloride gas was blown into the solution with
vigorous stirring in the first 30 min. The addition of hy-
drogen chloride gas was continued for another 1 h. The
mixture was stirred for an additional hour on ice. Then
the diethyl ether was distilled off to get a solid. The
solid was treated with 100 mL of ice water and heated
to 80 ℃ in water bath. Upon cooling, the product
crystallized in shiny plates from the solution. They were
removed by filtration, then washed with ice water three
times and dried.
nate and 0.1 mL of piperidine in 10 mL of ethanol was
heated under reflux with stirring for 2 h while a yellow
precipitate formed. After cooling, the solid was col-
lected, washed with ethanol, and dried.
Ethyl 7-hydroxycoumarin-3-carboxylate (2a): Yel-
1
low power, yield 74%. H NMR (400 MHz, DMSO-d
6
)
δ: 1.29 (t, J＝7.6 Hz, 3H, CH
3
), 4.26 (q, J＝7.2 Hz, 2H,
CH
2
), 6.73 (s, 1H, Ar-H), 6.84 (d, J＝8.4 Hz, 1H, Ar-H),
7
1
1
.76 (d, J＝8.6 Hz, 1H, Ar-H), 8.69 (s, 1H, Ar-H),
1.10 (s, 1H, OH); IR (KBr) ν: 3060, 2984, 1741, 1627,
－1
＋
565, 1520, 1430, 1237 cm ; MS m/z: 234 (M ). Anal.
calcd for C12
.29.
Ethyl
H
10
O
5
: C 61.54, H 4.30; found C 61.42, H
4
6-fluoro-7-hydroxycoumarin-3-carboxylate
5
6
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 55— 60

Novel Coumarin-based Fluorescent Probe
1
(
2b): Yellow power, yield 69%. H NMR (400 MHz,
Ethyl 6-bromo-7-hydroxy-8-formylcoumarin-3-car-
boxylate (3d): Yellow power, yield 48%. H NMR (400
1
DMSO-d
7
6
) δ: 1.29 (t, J＝6.8 Hz, 3H, CH
3
), 4.27 (q, J＝
.2 Hz, 2H, CH
2
), 6.90 (s, 1H, Ar-H), 8.16 (s, 1H,
MHz, DMSO-d
6
) δ: 1.29 (t, J＝6.8 Hz, 3H, CH
3
), 4.28
Ar-H), 8.66 (s, 1H, Ar-H), 11.95 (s, 1H, OH); IR (KBr)
(q, J＝6.4 Hz, 2H, CH
2
), 8.08 (s, 1H, Ar-H), 8.68 (s, 1H,
ν: 3558, 3059, 2998, 1741, 1627, 1574, 1522, 1439,
Ar-H), 10.34 (s, 1H, formyl); IR (KBr) ν: 3512, 3067,
－
1
＋
－1
1
C
247 cm ; MS m/z: 252 (M ). Anal. calcd for
1740, 1701, 1648, 1599, 1426, 1377, 1236 cm ; MS
＋
12
H
9
FO
5
: C 57.15, H 3.60; found C 57.24, H 3.59.
m/z: 340 (M ). Anal. calcd for C13
H
9
BrO
6
: C 45.17, H
Ethyl
6-chloro-7-hydroxycoumarin-3-carboxylate
2.66; found C 45.20, H 2.67.
1
(
2c): Yellow power, yield 71%. H NMR (400 MHz,
DMSO-d
.0 Hz, 2H, CH
Ar-H), 8.66 (s, 1H, Ar-H), 11.91 (s, 1H, OH); IR (KBr)
Procedure
6
) δ: 1.29 (t, J＝7.0 Hz, 3H, CH
3
), 4.27 (q, J＝
7
2
), 6.90 (s, 1H, Ar-H), 8.02 (s, 1H,
The bisulfite recognition reaction was performed in
10 mL volumetric tube. To a test tube containing 1 mL
－
5
－1
ν: 3060, 2984, 1741, 1627, 1574, 1522, 1439, 1247
probe (1×10 mol•L ), 1.0 mL of buffer solution (pH
5.0) was added and the solution was diluted to 5.0 mL
with water. Then different concentrations of bisulfite
was added and the solution was diluted to 10 mL with
water. The fluorescence was measured with the excita-
tion and emission wavelengths at 404 and 458 nm, re-
spectively.
－
1
＋
cm ; MS m/z: 268 (M ). Anal. calcd for C12
H
9
ClO
5
: C
5
3.65, H 3.38; found C 53.55, H 3.39.
Ethyl 6-bromo-7-hydroxycoumarin-3-carboxylate
2d): Yellow power, yield 68%. H NMR (400 MHz,
1
(
DMSO-d
6
) δ: 1.29 (t, J＝7.6 Hz, 3H, CH
3
), 4.27 (q, J＝
7
2
.2 Hz, 2H, CH ), 6.88 (s, 1H, Ar-H), 8.16 (s, 1H,
Ar-H), 8.86 (s, 1H, Ar-H), 11.95 (s, 1H, OH); IR (KBr)
ν: 3060, 2984, 1697, 1627, 1587, 1507, 1420, 1225
Results and discussion
－
1
＋
cm ; MS m/z: 312 (M ). Anal. calcd for C12
H
9
BrO
5
: C
Choice of the probe
4
6.03, H 2.90; found C 46.12, H 2.91.
Synthesis of 3a— 3d A solution of 14 mmol of
-hydroxycoumarin-3-carboxylate and 21 mmol of
In our search for fluorescence probes suitable for se-
lective detection of bisulfite, we prepared four coumarin
derivatives with salicylaldehyde functionality and de-
termined the fluorescence quantum yields of the probes
and their bisulfite adducts in pH-buffered aqueous solu-
tions. Fluorescence quantum yields were determined by
comparing the emission and absorption intensity of the
probe with that of a fluorescence standard. Fluorescence
quantum yields used for the reference is the quinine
7
hexamethylenetetramine in 20 mL of trifluoroacetic acid
was heated to reflux for 20 h. 40 mL of water was added
to the solution, the mixture was warmed at 60 ℃, and
then stirred for an additional 30 min. Upon cooling on
ice, a yellow solids were precipitated out from the solu-
tion, which were collected by filtration and washed
three times with water to give the desired product as a
yellow solid.
－
1
－4
sulfate in 0.1 mol•L sulfuric acid (less than 10 mol•
－
1
Ethyl
7-hydroxy-8-formylcoumarin-3-carboxylate
L ) with a known quantum yield of 0.546 excited at
365 nm.
1
(
3a): Yellow power, yield 56%. H NMR (400 MHz,
DMSO-d
6
) δ: 1.29 (t, J＝6.8 Hz, 3H, CH
3
), 4.28 (q, J＝
As shown in Table 1, upon addition of excess bi-
sufite anion, the fluorescence quantum yield of the sys-
tem obviously increased. We select 3b as a model in the
further investigations because of its sensitive response
to bisulfite.
6.8 Hz, 2H, CH
2
), 7.01 (d, J＝9.2 Hz, 1H, Ar-H), 8.06
(
1
1
d, J＝8.4 Hz, 1H, Ar-H), 8.75 (s, 1H, Ar-H), 10.40 (s,
H, formyl); IR (KBr) ν: 3431, 3045, 1742, 1700, 1659,
595, 1480, 1445, 1304, 1236 cm ; MS m/z: 262 (M ).
－
1
＋
Anal. calcd for C13
9.62, H 3.83.
Ethyl 6-fluoro-7-hydroxy-8-formylcoumarin-3-car-
10 6
H O : C 59.55, H 3.84; found C
a
5
Table 1 Fluorescence parameters of the probes
λ
max/nm
1
boxylate (3b): Yellow power, yield 54%. H NMR (400
Dye
φ
0
φ
Absorption
Emission
452
MHz, DMSO-d
6
) δ: 1.28 (t, J＝6.8 Hz, 3H, CH
3
), 4.27
3
a
402
404
407
408
0.018
0.023
0.022
0.016
0.33
0.62
0.52
0.26
(
q, J＝6.4 Hz, 2H, CH
2
), 8.08 (s, 1H, Ar-H), 8.68 (s, 1H,
Ar-H), 10.37 (s, 1H, formyl); IR (KBr) ν: 3431, 3050,
1
3b
458
－
1
743, 1700, 1662, 1585, 1480, 1407, 1268 cm ; MS
3c
459
＋
m/z: 280 (M ). Anal. calcd for C13
H
9
FO
6
: C 55.72, H
3
d
460
3
.24; found C 55.80, H 3.25.
Ethyl 6-chloro-7-hydroxy-8-formyl-coumarin-3-car-
a
φ
0
and φ were the fluorescence quantum yields of the probes and
1
their bisulfite adducts, respectively. The mixture absorption and
emission wavelength were the mixture wavelength of the bisulfite
adducts. Determination condition: pH 5.0, reaction time 5 min.
boxylate (3c): Yellow power, yield 53%. H NMR (400
MHz, DMSO-d
6
) δ: 1.30 (t, J＝7.2 Hz, 3H, CH
3
), 4.30
(
q, J＝7.2 Hz, 2H, CH
2
), 8.36 (s, 1H, Ar-H), 8.78 (s, 1H,
Ar-H), 10.33 (s, 1H, formyl); IR (KBr) ν: 3037, 3047,
1
Nucleophilic addition reaction for detection of bisul-
fite anion
－
1
763, 1703, 1647, 1595, 1466, 1426, 1288, 1236 cm ;
＋
MS m/z: 296 (M ). Anal. calcd for C13
H
9
ClO
6
: C 52.63,
Bisulfite is assumed to be detectable owing to the
nucleophilic addition reaction of formyl functional
H 3.06; found C 52.71, H 3.07.
Chin. J. Chem. 2010, 28, 55— 60
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
57

Chen et al.
FULL PAPER
group with bisulfite anion. In order to analyze the reac-
tion pathway and obtain the fluorescence enhancing
mechanism of the probe, the product of addition reac-
tion of the probe 3b with bisulfite was prepared. The
synthetic route of the intermediate was shown in
1
Scheme 3. We monitored H NMR spectra of the inter-
mediate and compared it with that of the probe 3b itself.
The aldehyde proton at around δ 10.3 was dramatically
shifted (Figure 1). The intermediate was also character-
ized by mass spectrometry. The intermediate has a
＋
＋
“
M ” of 383, while the probe has a “M ” of 280.
According to the above experimental data, the possible
reaction mechanism of the coumarin-based fluorescent
probe for selective detection of bisulfite in water is nu-
cleophilic addition reaction of formyl functional group
of the probe with bisulfite anion.
Figure 2 Effect of pH on the fluorescent intensity of the probe
addition reaction system by bisulfite. Bisulfite concentration: (a)
－
1
blank and (b) 100 µmol•L in phosphate buffer.
Scheme 3
ditions was fast. Therefore, five minutes reaction time
was selected in the following experiment.
1
Figure 1 H NMR spectral change of (a) probe 3b and (b) the
adduct of 3b with bisulfite.
Figure 3 Effect of reaction time on the fluorescent intensity of
the probe addition reaction system by bisulfite. Bisulfite concen-
－
1
Effect of pH on detection
tration: (a) blank and (b) 100 µmol•L . Detection condition:
pH＝5.0.
The effect of the detection pH on the fluorescence
properties of the system was investigated in the range
Spectral characteristics
2
.0—8.0 and the results are shown in Figure 2. In order
to get different pH, phosphate buffers were used. It is
obvious that the fluorescent signal of the probe in-
creased slightly with the pH increasing, while the fluo-
rescence signal of the probe solution containing bisulfite
anion increased sharply from pH 2.0 to 5.0 and de-
creased when pH was above 5.0. The adduct of alde-
hyde and bisulfite was instability both in acid and alka-
line solution. It is appropriate for the adduct to exist at
Aromatic aldehyde and its bisulfite adduct have dif-
ferent spectral characteristics, because the conversion of
the aldehyde into the bisulfite adduct can bring about a
2
5
change in the electron withdrawing effect. Figure 4
depicts the spectrophotometric changes of probe 3b
－
3
－1
upon mixing with bisulfite anion (10 mol•L ) in
phosphate buffer. With excess bisulfite anion, the ab-
sorption band changed from 399 to 404 nm, while the
absorbance nearly not changed. Furthermore, the probe
3b was mixed with different concentrations of bisulfite
anion, and the changes of fluorescence spectra are
shown in Figure 5. Upon addition of an increasing con-
centration of bisulfite anion, the fluorescence emission
intensity of the probe at 458 nm gradually increased.
2
5
2 4 2 4
pH 5.0. Therefore pH 5.0 (NaH PO /Na HPO ) was
selected for the determination system.
Effect of reaction time
The effect of the reaction time on the fluorescence
emission of the system was studied and the results are
shown in Figure 3. It can be seen that the fluorescence
signal of the system increased gradually with increasing
the reaction time, and the complete nucleophilic addi-
tion of the bisufite under the selected reaction con-
Selectivity study
To evaluate the selectivity of the probe for bisulfite,
we monitored the fluorescence intensities for various
5
8
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 55— 60

Novel Coumarin-based Fluorescent Probe
－
1
Figure 6 Fluorescence spectra of the probe (1 µmol•L ) upon
－
1
addition of 1000 equiv of various anions. From left to right: only
Figure 4 Absorption spectra of the probe 2b (10 µmol•L )
－
2－
－
－
－
－
－
－
－
－
1
the probe, F , S , AcO , ClO
4
, Br , Cl , I , NO
3
, SCN ,
after incubation with 1000 µmol•L sodium bisulfite in water
buffered at pH 5.0. 1, probe 2b only; 2, probe 2b with bisulfite.
2－
CO3
.
－
1
tion (c) range of 0.8—200 µmol•L with a correlation
coefficient of r＝0.9982 (n＝9). The linear regression
equation was determined to be F － F
0
＝ 1.9336 ＋
1
.2134c (n＝9, r＝0.9982). According to IUPAC rec-
ommendations, the detection limit was calculated from
three times the standard deviation of the blank signal
－
1
(
3σ) as 0.37 µmol•L and the relative standard devia-
－
6
－1
tion was 3.3% for 1.0×10 mol•L bisulfite solution
with eleven repeated measurements.
－
1
Figure 5 Fluorescence spectra of the probe (1 µmol•L ) upon
addition of varying concentration of NaHSO . λ ＝380 nm, the
3
ex
excitation and emission wavelength bandpasses were both set at
－
1
1
2
3
0 nm. The concentration of bisulfite a to s (µmol•L ): 0, 5, 10,
0, 30, 40, 60, 80, 100, 150, 200, 300, 400, 600, 800, 1000, 2000,
000, 4000.
anions upon addition of 1000 equiv. guests in phosphate
buffer solution at room temperature. The probe’s fluo-
rescence intensity was highly enhanced by bisulfite.
Figure 7 Calibration graph for bisulfite anion. Working condi-
tions: pH 5.0, reaction time was 5 min.
－
2－
－
－
However, other anions such as F , S , AcO , ClO ,
Sample analysis
4
－
－
－
－
3
－
2－
Br , Cl , I , NO , SCN and CO3 did not cause
To investigate the feasibility of probe 3b in real
samples, the content of the bisulfite in granulated sugar
was examined. A sample solution of granulated sugar
was prepared by dissolving 10.0 g of sugar in water and
diluting with water to 50 mL. This solution was diluted
appropriately with water and was analyzed by the pro-
posed method. The recoveries were good enough for
practical use and all determination values are listed in
Table 2. The bisulfite content in granulated sugar sam-
ple was 28.3 and 19.9 mg/kg, respectively.
any significant changes in the fluorescence emission
intensity (Figure 6).
The fluorescence profiles at 458 nm of the probe
showed a remarkably higher selectivity for bisulfite
over the other anions in water.
Analytical characteristics of 3b for bisulfite anion
Under the optimal conditions given above, the cali-
bration graph for bisulfite was constructed (Figure 7).
The graph was linear between the bisulfite concentra-
Chin. J. Chem. 2010, 28, 55— 60
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
59

Chen et al.
FULL PAPER
Table 2 Results for detection of bisulfite in granulated sugar
sample
1423.
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10 Ma, Y. M.; Luo, W.; Quinn, P. J. J. Med. Chem. 2004, 47,
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2
Granulated Bisulfite content/ Added/
Found/ Recovery/
－
－
1
－
1
1
sugar
(µmol•L )
(µmol•L ) (µmol•L )
%
6
4
6
3.94
5.81
2.43
2.89
98.3
96.7
97.2
96.3
Sample 1
5.45
4
2
.5
1
2
Sample 2
3.82
3
4
14
9
(
6
Conclusion
In summary, we have developed four chemoprobes
based on coumarin with aldehyde functionality as detec-
tion units. The probes selectively reacted with bisulfite
via nucleophilic addition reaction in water. Its fluores-
cence intensity increased dramaticlly due to nucleo-
philic addition reaction functionality. The probes
showed high selectivity toward bisulfite over other ani-
ons in water at room temperature. Further study showed
that the probe is feasible in the determination of bisul-
fite in real sample.
1
5
6
(
2
1
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