An optical material for the detection of trace S2O3 2? in milk based on a copper complex

Article abstract of DOI:10.1007/s10534-017-0017-y

A novel S₂O₃ ^2? luminescent sensor (Cu²⁺-p-CPIP) was developed and the presence of S₂O₃ ^2? caused an obvious fluorescence enhancement at 420?nm upon excitation at 330?nm, which c

Full text of DOI:10.1007/s10534-017-0017-y

Biometals
DOI 10.1007/s10534-017-0017-y
22
An optical material for the detection of trace S O3 in milk
2
based on a copper complex
.
.
.
Qingming Wang Huifang Sun Weilin Sha Juan Chen Liuyue Gu
.
.
.
Dong Wang Xinhui Tang
Received: 8 April 2017 / Accepted: 9 April 2017
Ó Springer Science+Business Media New York 2017
2
-
2-
Abstract A novel S O
2
luminescent sensor
rapid and sensitive colorimetric detection of S O
2
in
3
3
2
Cu -p-CPIP) was developed and the presence of
?
(
aqueous solution.
2
-
S2O3 caused an obvious fluorescence enhancement
at 420 nm upon excitation at 330 nm, which could be
distinguished with the naked eye under a UV lamp.
Remarkably, the compound exhibited excellent selec-
2
-
Keywords Chemodosimeter Á S O
Á 1,10-
2
3
Phenanthroline-5,6-dione Á Copper complex
2
-
tive and sensitive response to S O3
over other
common anions with a micromolar limit of detection
0.442 lM) in DMSO/H O (v/v, 1:1) buffer. The
2
Abbreviation
p-CPIP 2-(4-Chlorophenyl)imidazo[4,5-f]1,10-
phenanthroline
(
2
2
?
absorbance intensity and the color of Cu -p-CPIP
solution changed gradually with the increase of
2
-
S2O3
concentration. The proposed method was
2
-
applied to the determination of S O3
in milk
samples and the recoveries were 97.5–105%. The
2
Introduction
2
preparation of Cu -p-CPIP exhibited the quick,
?
-
Many anions such as sulphate, phosphate, CN and
simple and facile advantages. The results showed that
2
Cu -p-CPIP can be a good candidate for simple,
?
carboxylate are vital for biological functions (Beer and
2-
3
Gale 2012; Yoon et al. 2006) while S O
2
is excep-
tionally hazardous. Thiosulfate, distributed in the blood
and urine has been used as a reliable index for
confirmation of sulfur poisoning (Kage et al.
Q. Wang (&) Á H. Sun Á W. Sha Á J. Chen Á
L. Gu Á D. Wang Á X. Tang (&)
1997, 1998; Maseda et al. 2017). So far, many methods
School of Pharmacy, Jiangsu Provincial Key Laboratory
of Coastal Wetland Bioresources and Environmental
Protection, Yancheng Teachers’ University,
Yancheng 224051, Jiangsu, People’s Republic of China
e-mail: wangqm@yctu.edu.cn
have been used to detect thiosulfate, such as absorption
spectrometry, highperformance liquid chromatography
(HPLC) (Imanari et al. 1982; Kawanishi et al. 1984;
Shea and Howell 1984), gas chromatography–mass
spectrometry (GC–MS) (Kohler and Guillarme 2014;
Meyer et al. 2014) and so on. However, these methods
are time-consuming, require highly trained personne,
sophisticated instrumentation, poor specificity, espe-
cially not suitable to real-time monitoring (Jin et al.
X. Tang
e-mail: xinhuitang@sina.com
Q. Wang
State Key Laboratory of Coordination Chemistry, Nanjing
University, Nanjing 210093, People’s Republic of China
123

Biometals
2
016). So it is meaningfully to develop a simple and an
CrCl Á6H O, CoCl Á6H O, MnCl Á4H O, FeCl Á6H O,
3
2
2
2
2
2
3
2
2-
inexpensive method to detect S O
2
with desirable for
NiCl Á6H O, CuCl Á2H O, CdCl Á6H O, ZnCl , SrCl,
3
2
2
2
2
2
2
2
real-time monitoring of milk samples.
SnCl , AlCl , Hg(NO ) , AgNO and the salts solutions
2 3 3 2 3
Fluorescence is the release of energy in the form of
light when molecules or moieties, named fluo-
rophores, are excited with a high-energy light source
of anions such as Na PO , Na CO , NaAC, NaBr,
3 4 2 3
Na C O ÁH O, NaCl, NaF, NaI, NaNO , NaNO ,
2
2
4
2
3
2
NaH PO , Na HPO , Na P O , Na B O , Na SO ,
2
2
4
2
4
2
2
7
4
7
2
4
(
Lakowicz 2006; Coble et al. 2014; Carstea et al.
016). With the development of analytical techniques,
NaClO , NaCN, NaSCN, NaHCO , NaHSO were
4 3 4
2
purchased from Shanghai Experiment Reagent Co.,
Ltd (Shanghai, China). All other chemicals used were of
analytical grade. Deionized water was used to prepare all
aqueous solutions.
fluorescence spectroscopy has become a powerful tool
for sensing because of its simplicity, sensitivity and
fast response times (Yu et al. 2016; Reynolds 2003;
Hudson et al. 2007; Henderson et al. 2009; Yang et al.
2
015; Murphy et al. 2011; Chong et al. 2013). A
Instruments
number of devices have been used to discriminate
anions through various investigational techniques. Up
1
13
H-NMR and C-NMR spectra were recorded on a
2
-
-
to now, fluorescent sensors for SO3 /HSO3 have
been developed (Tan et al. 2014; Xie et al. 2013; Wang
et al. 2013; Chen et al. 2013; Xie et al. 2012; Ding et al.
Bruker DRX400 spectrometer with DMSO as the
internal standard. Electrospray ionization mass spectra
TM
(ESI–MS) was analyzed by using a Triple TOF 5600
?
2
017; Yin et al. 2017). For example, a coumarinhemi-
system with an ion spray source in thepositive-ionmode.
Elemental analyses (EAs) was carried out with a VARI-
-1)
cyanine dye was constructed and the detection limit
7
was 3.8 9 10 M (Sun et al. 2013). A coumarin-
-
ELelementalanalyzer. IRspectra(4000–400 cm was
based fluorescent probe was synthesized with detec-
recorded using a Shimadzu Fourier transform IR-8300
spectrometer in KBr disks. UV–Vis spectra were
recorded on a Hewlett Packard HP-8453 spectropho-
tometer. Fluorescence spectral data were obtained by
means of a RF-5301 fluorescence spectrophotometer.
-
tion limit and response time were 5 9 10 M and
6
6
0 min respectively (Chen et al. 2012). A coumarin-
-
based fluo-rescent probe with 2 9 10 M detection
6
limit and its reaction timewas 10 min was reported
(
Yang et al. 2012). However, there are hardly any
2
-
2?
Preparation of copper complex (Cu -p-CPIP)
report about the detection of S O
2
by fluorescence
3
sensor. So it is very urgent and necessary to develop a
2
-
simple and convenient way to detect S O
2
by
Synthesis of 2-(4-Chlorophenyl)imidazo[4,5-f]1,10-
3
fluorescence method.
phenanthroline (p-CPIP)
In this paper, a novel copper(II) complex based on
-(4-Chlorophenyl)imidazo[4,5-f]1,10-phenanthroline
2
The p-CPIP was prepared followed by the reported
procedure with some modification (Zhao et al. 2014;
Dickeson and Summers 1970; Amouyal et al. 1990). As
shown in Scheme 1, a mixture of 4-chlorobenzalde-
hyde (0.14 g, 1 mmol), 1,10-phenanthroline-5,6-dione
(0.21 g, 1 mmol) and glacial acetic acid (10 mL) was
refluxed for about 3 h, then cooled to room temperature
and diluted with water (40 mL). Dropwise addition of
concentrated aqueous ammonia gave yellow precipi-
tates, which were collected and washed with water. The
crude products were recrystallized from CH CH OH/
2-
(
p-CPIP) was developed to probe S O
2
via the
3
luminescence method. With the incremental addition of
2-
S2O3 , the characteristic emission at 420 nm was
enhanced gradually. The response showed high selec-
2
3
-
tivity for S O
2
compared with other common anions,
2-
metals ions and could be used to probe S O3
2
.
Experimental details
3
2
Materials
H O (V:V = 1:1). The products were obtained, and
2
then dried at50 °C invacuo. Yield0.23 g, 73.5%. Anal.
calc. for C H ClN Á 0.4H O: C, 67.52, H, 3.52, N,
Phenanthrolinedione, 4-chlorobenzaldehyde and ammo-
nium acetate were purchased from Aladdin Chemical
Co., Ltd. (Shanghai, China). The salts solutions of metal
ions such as NaCl, KCl, MgCl Á6H O, CaCl , BaCl ,
1
9
11
4
2
16.58%, 14.49%, found: C, 67.57; H, 3.39; N, 14.58%.
-1
FT-IR (KBr, cm , s strong, m medium, w weak):
3420 m, m(N–H); 2986 m, m(C–H); 1622 s m(C=N).
2
2
2
2
1
23

Biometals
Scheme 1 Synthesis of p-
CPIP
1
-
10equiv. of anions such as NO , H PO , HPO4
-
2-
2-
-
H-NMR (400 MHz, DMSO), d (ppm): 7.224–8.754
,
,
2
2-
2
4
1
3
2-
3-
2-
2-
(
m, 10H). C-NMR (75 MHz, DMSO), d (ppm):
P2O7 , PO4 , SO , C O , B O , CO
4 2 4 4 7 3
-
-
-
-
-
-
-
-
1
1
1
1
58.617, 158.217, 155.104, 148.221, 144.236, 141.125,
38.198, 136.227, 131.008, 128.148, 126.100, 125.698,
24.102, 121.351, 117.612, 114.106, 113.763, 112.871,
11.240. Exact mass for p-CPIP: 330.07, ESI–MS
ClO4 , NO3 , SCN , AC , F , Cl , Br , I , CN ,
-
HCO , HSO and 10equiv. of metal ions Na , K ,
-
?
?
3
4
2
?
2?
2?
3?
2?
2?
3?
Mg , Ca , Ba , Cr , Co , Mn , Fe , Ni
2?
,
2
?
2?
2?
?
2?
3?
2?
?
Cu , Cd , Zn , Sr , Sn , Al , Hg , Ag were
added to the resulting solution, fluorescence spectrum
was used to record the effect on the addition of
different anions and metal ions.
?
?
(
positive mode) [p-CPIP ? H ] (m/z, 331.1250).
2
Preparation of Cu -p-CPIP
?
-
4
A solution of p-CPIP (2.0 mL, 1.0 9 10 M) was
placed in a quartz cell (10.0 mm width) and 8 lL
Cu (1.0 9 10 M)was added, then the Cu -p-
Titration experiments
2
?
-1
2?
2?
The titration experiments of Cu -p-CPIP were
CPIP solution in DMSO/H O (V:V = 1:1) was
2
carried out in DMSO/H O (V:V = 1:1) solution
2
2
-
obtained. The species was characterized by ESI–MS
spectrum and UV–vis spectrum.
system. The S O
2
solutions were introduced in
3
portions and the changes of fluorescence intensity
were recorded at room temperature (kex = 330 nm).
The limit of detection (LOD) was calculated based on
the standard deviation of the response (SD) and the
slop of the calibration curve (S) at levels approximat-
ing the LOD according to the formula: LOD = 3
(SD)/S.
Preparation of anions and metal ions solution
0
.1 mmol of anions Na PO , Na CO , NaAC, NaBr,
3 4 2 3
Na C O ÁH O, NaCl, NaF, NaI, NaNO , NaNO ,
2
2
4
2
3
2
NaH PO , Na HPO , Na P O , Na B O , Na SO ,
2
2
4
2
4
2
2
7
2
4
7
4
NaClO , NaCN, NaSCN, NaHCO , NaHSO were
4
3
4
dissolved in double distilled water (10 mL), respec-
-
tively, to afford 1.0 9 10 M aqueous solution.
2
Result and Discussion
?
Solutions of Na , K , Mg , Ca , Ba , Cr
?
2?
2?
2?
3?
,
2
?
2?
3?
2?
2?
2?
2?
Co , Mn , Fe , Ni , Cu , Cd , Zn , SrCl,
2?
Characterization of Cu -p-CPIP system
2
?
3?
2?
?
Sn , Al , Hg , Ag were prepared from their
chloride salts or nitrate and were dissolved in double
ESI–MS spectrum was measured to characterize the
2?
speciesof Cu -p-CPIP system. As shown in Fig. 1, a
main species were observed clearly. The one observed
-
2
distilled water to afford 1.0 9 10
M aqueous
solution, respectively. The stock solutions were then
diluted to desired concentration with suitable solvent
when needed. p-CPIP (313.0 mg) was dissolved in
DMSO (1.0 mL) to afford the stock solution with the
2
?
as m/z 381.1121 may be assigned to [Cu(p-CPIP)2]
(m/z = 381.55). Therefore, the stoichiometric ratio of
2
?
2?
Cu
to p-CPIP is 1:2. Cu
coordinated by two molecules of p-CPIP.
was unsaturated
-
2
concentration of 1.0 9 10 M, respectively.
Also, the titration experiment by UV–vis was used
2
?
Fluorescence studies with various anions and metal
ions
to further confirmed the stoichiometric ratio of Cu to
p-CPIP (Han et al. 2012). The absorption spectrum of
the p-CPIP showed a main low energy bands at
330 nm. Moreover, the UV–vis absorption titrations
A solution of p-CPIP (2.0 mL) was placed in a quartz
2
?
2?
cell (10.0 mm width) and Cu
was added, then
were carried out by gradual addition of Cu to the
123

Biometals
Fig. 1 ESI–MS spectrum
2?
of Cu -p-CPIP solution
solution of p-CPIP. As shown in Fig. 2, two new
absorption peaks at 282 and 305 nm appear and
gradually increase, which implies the formation of Cu
complex of the ligand. In addition, as shown in the
inset of Fig. 2, the p-CPIP easily formed a 2:1
2
?
complex with Cu
.
2
?
Selectivity of Cu -p-CPIP over anions
2
The binding activity of probe Cu -p-CPIP with
?
-
different anions, such as NO , H PO , Na HPO ,
-
2
2
4
2
4
2-
2
-
3-
2-
2-
2-
P2O7 , PO4 , SO , C O , B O , CO
3
,
4
-
2
4
4
7
-
-
-
-
-
-
-
-
ClO4 , NO3 , SCN , AC , F , Cl , Br , I , CN ,
-
-
HCO3 , HSO4 , was investigated respectively by
fluorescence. From Fig. 3, it could be observed that
2
Cu -p-CPIP had no obvious fluorescence intensity
2?
Fig. 3 Fluorescence (kex = 330 nm) responses of Cu -p-
CPIP respectively upon the addition of several anions in
DMSO/H O (v/v = 1/1) at emission slit 5 nm. Inset a color
?
2
-
change with addition of other ions except S O
2
.
3
2
2
However, with the addition of S O , a dramatic
-
2-
3
change photograph for S
2
O
and the other anions under
2
3
illumination with a 365 nm UV lamp
fluorescence intensity enhancement at 420 nm was
Fig. 2 Absorption titration of p-CPIP (2 mL, 0.1 mM) with
2?
Fig. 4 Fluorescence intensity of Cu -p-CPIP and its com-
2?
Cu
temperature. Inset shows absorption vs. [Cu ]/[p-CPIP]
k = 282 nm)
(0–0.45 mM) in DMSO/H
2
O (v:v = 1:1) at room
2-
plexation with S
DMSO/H O (v/v, 1:1). (kex = 330 nm, kem = 420 nm, slit
widths: 5/5 nm)
O
2 3
in the presence of various anions in
2?
2
(
1
23

Biometals
appeared. Remarkably, an obviously blue emission of
the solution can be easily visualized by the naked eye
under a UV lamp at 365 nm (Fig. 3 inset). Further-
more, the competitive experiments were performed for
the moderate increase in the intensity of fluorescence
2
-
can be observed, which indicates that HPO
-
and
for
4
2-
H PO
2
may slightly compete with S O
2
4
3
2
?
binding with Cu -p-CPIP. Nevertheless, the overall
2?
results reveal that the Cu -p-CPIP could effectively
2
?
2-
Cu -p-CPIP (1 lM) in the presence of S O
2
3
2
-
(
2.5 lM) mixed with other interfering anions
10 lM) to evaluate the response, and the coexist in
recognize the S O
2
.
3
(
2
3
-
selectivity of the sensor. As shown in Fig. 4, the
UV–Vis spectra for S O
2
titration
competitive anions shows the weaker anions except
2
-
-
HPO4 , H PO , do not significantly interfere with
In addition, Fig. 5 showed the change on the UV–vis
2?
2
4
2
the intensity of emission Cu -p-CPIP-S O
-
tem, while for the presence of HPO4 and H PO
?
2-
sys-
-
spectra of the Cu -p-CPIP (1.0 lM) upon addition
2
3
2
2-
2-
,
of S O
2
in DMSO/H O (v/v, 1:1). As the S O
2 2 3
2
4
3
2?
Fig. 5 Absorbance spectra of Cu -p-CPIP (10 lM) in
2-
Fig. 7 Fluorescence intensity at 420 nm changes on incremen-
tal addition of S O
2 3
DMSO/H
0
2
O (v/v, 1:1) in the presence of S
O
2 3
(0 to 35 lM,
–3.5 equiv). Inset the colorimetric responses of Cu -p-CPIP
2-
2?
2-
2 3
toward S O
2
?
2?
Fig. 8 Fluorescence intensity of Cu -p-CPIP and its com-
Fig. 6 Fluorescence spectra of sensor Cu -p-CPIP (1.0 lM)
2
-
2-
on addition of different amount of S
1
incremental addition of S
2
O
3
in DMSO/H
:1). Inset Fluorescence intensity at 420 nm changes on
2
O (v/v,
plexation with S
DMSO/H O (v/v, 1:1). (kex = 330 nm, kem = 420 nm, slit
widths: 5 nm/5 nm)
2
O
3
in the presence of various metal ions in
2
2
3
-
2
O
(0–2.5 lM)
123

Biometals
Table 1 Determination of
in milk samples
2-
2-
3
Sample
S O
2 3
added (lM)
2
S O
found (lM)
Recovery (%)
RSD (n = 3) (%)
2
3
-
S
2
O
1
2
3
4
0.04
0.2
0.8
1.4
0.042
0.21
0.78
1.42
105
105
97.5
101
0.82
1.1
2.2
1.8
concentration increased, the absorption peaks at 282
and 306 nm were disappeared and a new absorption
peaks at 345 nm emerged and gradually decreased.
The results indicated the formation of a new species.
experiments were performed in milk samples obtained
from the local supermarket F = -3.06869 ?
2
-
2-
156.19113 [S O ] and the recoveries of S O
2 3
2
3
were in range of 97.5–105%. The results revealed the
2
designed method was reliable and Cu -p-CPIP could
?
2
Fluorescence spectra of Cu -p-CPIP with
?
2-
be applied for the detection of S O in real samples,
2
3
2-
S2O3
as shown in Table 1.
2
?
The fluorescence properties of Cu -p-CPIP (1.0 lM)
2
-
for the titration of S O
2
were studied in DMSO/H O
2
Conclusions
3
2
v/v, 1:1) system. As shown in Fig. 6, the probe Cu -
?
(
2
-
2?
p-CPIP shows no fluorescence emission at 420 nm
when it is excited at 330 nm. With gradual increase in
A novel S O
luminescent sensor(Cu -p-CPIP)
was developed and showed a remarkable colorimetric
2
3
2
-
2-
the S O
concentration (0.25–2.5 lM), the emission
intensity of the probe Cu -p-CPIP increases contin-
selectivity to S O
2 3
over common anions and
2
3
2
?
generated color change from bright yellow to orange
uously. It is noteworthy that the fluorescence changes
-
in DMSO/H O (v/v, 1:1) the naked eye. It could be
2
2
induced by S O
2
exhibits good linear relationships
serve as an effective probe for colorimetric detection
2-
3
2
Fig. 7), which means that the probe Cu -p-CPIP is
?
(
of S O
with a detection limit as low as 0.442 lM
2
3
2
suitable for quantitative detection of S O . The limit
-
using the fluorescence spectra and the color change
from colorless to light blue. Combining its simple and
fast synthetic method and high sensitivity and selec-
2
3
of detection calculated according to the formula
-
(LOD) = 3(SD)/S] is 4.42 9 10 M, the low limit
7
[
2
?
of detection indicates that the probe Cu -p-CPIP may
2-
tivity to S O , we expect that the sensor will act as a
2
3
2
-
2-
be an efficient fluorogenic chemosensor for S O
2
practical tool for S O
2 3
detection.
3
recognition.
Acknowledgments This work was financially supported by
the National Natural Science Foundation for Young Scientists of
China (21301150, 21571154), the Post-Doctoral Foundation of
Jiangsu Provincial (1501032B), the Six Taleng Peak Project in
Jiangsu Province (SWYY-063) and sponsored by Qing Lan
Project of Jiangsu Provices.
2
Selectivity of Cu -p-CPIP over metal ions
?
2?
In order to confirmthe unique selectivity of probe Cu -
2
3
-
p-CPIP as the chemosensor for S O , competitive
2
experiments were performed in the presence of a wide
?
rangeofmetal ionssuchasNa , K , Mg , Ca , Ba
?
2?
2?
2?
,
3?
2?
2?
3?
2?
2?
2?
2?
?
Cr , Co , Mn , Fe , Ni , Cu , Cd , Zn , Sr ,
References
2?
3?
2?
?
Sn , Al , Hg , Ag . It is evident from Fig. 8 that the
addition of these metal ions had almost no effect on the
fluorescence emission enhancement to the selective
Amouyal E, Homsi A, Chambron JC, Sauvage JP (1990) Syn-
thesis and study of a mixed-ligand ruthenium (II) complex
0
in its ground and excited states: bis (2,2 -bipyr-
0
2?
0
recognition of probe Cu -p-CPIP.
idine)(dipyrido [3, 2-a: 2 ,3 -c] phenazine-N 4N 5) ruthe-
nium(II). J Chem Soci Dalton Trans 6:1841–1845
Beer PD, Gale PA (2012) Anion recognition and sensing: the
state of the art and future perspectives. Angew Chem Int Ed
Analysis of real samples(Wu et al. 2016)
4
0(3):486–516
Carstea EM, Bridgeman J, Baker A, Reynolds DM (2016)
Fluorescence spectroscopy for wastewater monitoring: a
review. Water Res 95:205–219
2
To verify the application value of Cu -p-CPIP, we
?
2
-
analyzed S2O3
in real samples. Recovery
1
23

Biometals
Chen S, Hou P, Wang JX, Song XZ (2012) A highly sulfite-
selective ratiometric fluorescent probe based on ESIPT.
RSC Adv 2:10869–10873
Chen B, Ding Y, Li X, Zhu W, Hill JP, Ariga K, Xie Y (2013)
Steric hindrance-enforced distortion as a general strategy
for the design of fluorescence ‘‘turn-on’’ cyanide probes.
Chem Commun 49(86):10136–10138
Chong SS, Aziz AR, Harun SW (2013) Fibre optic sensors for
selected wastewater characteristics. Sensors 13(7):8640–8668
Coble PG, Lead J, Baker A, Reynolds DM, Spencer RG (2014)
Aquatic organic matter fluorescence. Cambridge Univer-
sity Press, Cambridge
(2017) Liquid chromatography-tandem mass spectrometry
method for the determination of thiosulfate in human blood
and urine as an indicator of hydrogen sulfide poisoning.
Leg Med 24:67–74
Meyer MR, Helfer AG, Maurer HH (2014) Current position of
high-resolution MS for drug quantification in clinical &
forensic toxicology. Bioanalysis 6(17):2275–2284
Murphy KR, Hambly A, Singh S, Henderson RK, Baker A,
Stuetz R, Khan SJ (2011) Organic matter fluorescence in
municipal water recycling schemes: toward a unified
PARAFAC model. Environ Sci Technol 45(7):2909–2916
Reynolds DM (2003) Rapid and direct determination of tryp-
tophan in water using synchronous fluorescence spec-
troscopy. Water Res 37(13):3055–3060
Dickeson JE, Summers LA (1970) Derivatives of 1,
1
2
0-Phenanthroline-5, 6-quinone. Aust
3(5):1023–1027
J
Chem
Shea M, Howell S (1984) High-performance liquid chromato-
graphic measurement of exogenous thiosulfate in urine and
plasma. Anal Biochem 140:589–594
Ding YB, Zhu WH, Xie YS (2017) Development of ion
chemosensors based onporphyrin analogues. Chem Rev
1
17(4):2203–2256
Han H, Lu LP, Wang QM, Zhu ML, Yuan CX, Xing S, Fu XQ
2012) Synthesis and evaluation of oxovanadium(IV)
complexes of Schiff-base condensates from 5-substituted-
-hydroxybenzaldehyde and 2-substituted-benzenamine as
Sun YQ, Liu J, Zhang JY, Yang T, Guo W (2013) Fluorescent
2
probe for biological gas SO derivatives bisulfite and sul-
fite. Chem Commun 49:2637–2639
(
Tan L, Lin W, Zhu S, Yuan L, Zheng K (2014) A coumarin-
quinolinium-based fluorescent probe for ratiometric sens-
ing of sulfite in living cells. Org Biomol Chem
12(26):4637–4643
2
selective inhibitors of protein tyrosine phosphatase 1B.
Dalton Trans 41(36):11116–11124
Henderson RK, Baker A, Murphy KR, Hambly A, Stuetz RM,
Khan SJ (2009) Fluorescence as a potential monitoring tool
Wang T, Douglass EF Jr, Fitzgerald KJ, Spiegel DA (2013) A
‘‘turn-on’’ fluorescent sensor for methylglyoxal. J Am
Chem Soc 135(33):12429–12433
for recycled water systems:
3(4):863–881
a review. Water Res
4
Wu X, Gong XJ, Dong WJ, Ma J, Chao JB, Li CZ, Wang L,
Dong C (2016) A novel fluorescein-based colorimetric
Hudson N, Baker A, Reynolds D (2007) Fluorescence analysis
of dissolved organic matter in natural, waste and polluted
waters-a review. River Res Appl 23(6):631–649
Imanari T, Ogata S, Tanabe S, Toida T, Kawanishi T, Ichikawa
M (1982) Determination of thiocyanate, thiosulfate, sulfite
and nitrite by high performance liquid chromatography
coupled with electrochemical detection. Chem Pharm Bull
2?
probe for Cu detection. RSC Adv 6(64):59677–59683
Xie YS, Ding YB, Li X, Wang C, Hill JP, Ariga K, Zhang WB,
Zhu WH (2012) Selective, sensitive and reversible ‘‘turn-
0
on’’ fluorescent cyanide probes based on 2,2 -dipyridy-
laminoanthracene-Cu
48(94):11513–11515
2?
ensembles. Chem Commun
3
0:374–375
Xie Y, Wei P, Li X, Hong T, Zhang K, Furuta H (2013)
Macrocycle contraction and expansion of a dihydrosap-
phyrin isomer. J Am Chem Soc 135(51):19119–19122
Yang YT, Huo FJ, Zhang JJ, Xie ZH, Chao JB, Yin CX, Tong
HB, Liu DS, Jin S, Cheng FQ, Yan XX (2012) A novel
coumarin-based fluorescent probe for selective detection of
bissulfite anions in water and sugar samples. Sens Actua-
tors B-Chem 166–167:665–670
Jin S, Hyodoh H, Matoba K, Feng F, Hayakawa A, Okuda K,
Shimizu K, Haga S, Ozaki M, Terazawa K (2016) Devel-
opment for the measurement of serum thiosulfate using
LC–MS/MS in forensic diagnosis of H2S poisoning. Leg
Med 22:18–22
Kage S, Takekawa K, Kurosaki K, Imamura T, Kudo K (1997)
The usefulness of thiosulfate as an indicator of hydrogen
sulfide poisoning: three cases. Int
10(4):220–222
Kage S, Kudo K, Ikeda N (1998) Determination of sulfide,
thiosulfate and polysulfides in biological materials for
diagnosis of sulfide poisoning. Jpn J Forensic Toxicol
J
Legal Med
Yang L, Hur J, Zhuang W (2015) Occurrence and behaviors of
fluorescence EEM-PARAFAC components in drinking
water and waste water treatment systems and their appli-
cations: a review. Environ Sci Pollut Res 22(9):6500–6510
Yin CX, Li XQ, Yue YK, Chao JB, Zhang YB, Huo FJ (2017) A
new fluorescent material and its application in sulfite and
bisulfite bioimaging. Sens Actuators B Chem 246:615–622
Yoon J, Kim SK, Singh NJ, Kim KS (2006) Imidazolium
receptors for the recognition of anions. Chem Soc Rev
35(4):355–360
1
1
6(3):179–189
Kawanishi T, Togawa T, Ishigami A, Tanabe S, Imanari T
1984) Determination of thiosulfate in human urine and
(
plasma by high performance liquid chromatography with a
dual electrochemical detector. Bunseki Kagaku
3
3:295–300
Yu TT, Sun P, Hu Y, Ji YJ, Zhou HP, Zhang BW, Tian YP, Wu
JY (2016) A novel and simple fluorescence probe for
detecting main group magnesium ion in HeLa cells and
Arabidopsis. Biosens Bioelectron 86:677–682
Zhao XF, Ouyang Y, Liu YZ, Su QJ, Tian H, Xie CZ, Xu JY
(2014) Two polypyridyl copper(II) complexes: synthesis,
crystal structure and interaction with DNA and serum
protein in vitro. New J Chem 38:955–965
Kohler I, Guillarme D (2014) Multi-target screening of bio-
logical samples using LC–MS/MS: focus on chromato-
graphic innovations. Bioanalysis 6(9):1255–1273
Lakowicz J (2006) Principles of fluorescence spectroscopy.
Springer, New York
Maseda C, Hayakawa A, Okuda K, Asari M, Tanaka H, Yamada
H, Jin S, Horioka K, Matoba K, Shiono H, Matsubara K
123