Nanomolar colorimetric quantitative detection of Fe3 + and PPi with high selectivity

Article abstract of DOI:10.1016/j.saa.2016.02.001

A novel rhodamine and 8-hydroxyquinoline-based derivative was synthesized, which is shown to act as a colorimetric chemosensor for Fe^{3 +} in aqueous solution with high selectivity over various environmentally and biologically relevant metal ions and anions with a distinct color change from colorless to pink in very fast response time (< 1 min). Fe^{3 +} can be detected quantitatively in the concentration range from 6.7 to 16 μM and the detection limit (LOD) on UV-vis response of the sensor can be as low as 15 nM. The 'in situ' prepared Fe^{3 +} complex (1 Fe) showed high selectivity toward PPi against many common anions, and sensitivity (the LOD can be as low as 71 nM). In addition, both the chemosensor and the 'in situ' prepared Fe^{3 +} complex are reusable for the detection of Fe^{3 +} and PPi respectively.

Full text of DOI:10.1016/j.saa.2016.02.001

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 159 (2016) 249–253
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Nanomolar colorimetric quantitative detection of Fe3+ and PPi with
high selectivity
a,b
b
b
b
b
a,
Zhanxian Li , Haixia Li , Caixia Shi , Mingming Yu , Liuhe Wei , Zhonghai Ni ⁎
a
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu Province, China
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel rhodamine and 8-hydroxyquinoline-based derivative was synthesized, which is shown to act as a color-
imetric chemosensor for Fe in aqueous solution with high selectivity over various environmentally and biolog-
Received 3 December 2015
Received in revised form 29 January 2016
Accepted 5 February 2016
Available online 6 February 2016
3+
ically relevant metal ions and anions with a distinct color change from colorless to pink in very fast response time
3+
(
b1 min). Fe can be detected quantitatively in the concentration range from 6.7 to 16 μM and the detection
3
+
limit (LOD) on UV–vis response of the sensor can be as low as 15 nM. The ‘in situ’ prepared Fe
complex
(
1⋅Fe) showed high selectivity toward PPi against many common anions, and sensitivity (the LOD can be as
Keywords:
3
+
low as 71 nM). In addition, both the chemosensor and the ‘in situ’ prepared Fe complex are reusable for the
detection of Fe and PPi respectively.
Colorimetric sensor
Quantitative detection
3
+
3
+
Fe
PPi
Naked-eye detection
© 2016 Elsevier B.V. All rights reserved.
1
. Introduction
Rhodamine derivatives are extensively employed in fluorescent and
colorimetric chemosensors in solution because of their high absorption
coefficient, high fluorescence quantum yield and long-wavelength ab-
sorption and emission [17–22]. On the other hand, as prototypical
fluorophores, 8-hydroxyquinoline (8-HQ)-based derivatives have
been widely used in fluorescence detection and imaging of metal ions,
because metal binding to 8-HQ can block the excited-state intramolec-
ular proton transfer channel and restore the fluorescence [23–29]. The
chemical sensors, in which rhodamine and 8-HQ moieties simulta-
neously existed, are very rare [30–32].
In recent years, great achievement has been achieved in the develop-
ment of artificial optical chemosensors toward environmentally and
biologically important analytes such as metal ions and anions. As an
essential element in the human body, Fe3 plays an important role in
many biological processes such as oxygen metabolism to DNA. In addi-
tion, the trivalent form of iron provides the oxygen-carrying capacity of
heme, acts as a cofactor in many enzymatic reactions, and is indispens-
able for most organisms. As a result, both its deficiency and excess result
in various pathological disorders [1,2]. On the other hand, pyrophos-
+
In this paper, based on rhodamine and 8-HQ, selective colorimetric
chemosensor 1 (Scheme 1) was synthesized. Compound 1 can quantita-
tively detect Fe3 with great color change in aqueous solution. The de-
4
−
phate P
tions and involved in DNA replication catalyzed by DNA polymerase
3–5]. Therefore, it is significant to develop optical chemosensors
2
O
7
(PPi) is the product of ATP hydrolysis under cellular condi-
+
[
tection limit on UV–vis response of the sensor can be as low as 15 nM.
3
+
3+
toward Fe and PPi.
The ‘in situ’ prepared Fe
complex (1⋅Fe) showed high selectivity
In general, fluorescent sensors depend on emission intensity or posi-
tion power and detector sensitivity [6–8], to contrast, color changes
based on absorption properties of the ground state are more suitable
for direct observation with the naked eye [9], and considerable efforts
have been devoted to designing colorimetric chemosensors toward
and sensitivity toward PPi.
2. Experimental
2.1. Methods and materials
3
+
Fe [10–13] and PPi [14–16] in solution during the past few decades,
but the reported colorimetric sensors toward Fe3 and PPi are very
rare, and as a result, it is still challenging to prepare colorimetric sensors
for Fe3 and PPi.
+
Acryloyl chloride (analytical grade) and Rhodamine (95%) were pur-
chased from Sigma Aldrich Inc., USA. SeO (99%) was obtained from the
2
+
Aladdin Reagent Co., Ltd., China. 1,4-Dioxane (analytical grade) was
purchased from Tianjin Kermel Chemical Reagent Co., Ltd., China, hy-
drazine hydrate (analytical grade) from Tianjin Jiangtian Chemical
Technology Co., Ltd., China, methanol and ethanol (gas chromatography
grade) from Tianjin Siyou Fine Chemicals Co., Ltd., China. Other reagents
⁎
Corresponding author.
E-mail address: nizhonghai@cumt.edu.cn (Z. Ni).
http://dx.doi.org/10.1016/j.saa.2016.02.001
386-1425/© 2016 Elsevier B.V. All rights reserved.
1

250
Z. Li et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 159 (2016) 249–253
Scheme 1. Synthesis route of chemosensor 1.
were of analytical grade and provided by Tianjin FengChuan chemical
reagent Technology Co., Ltd., China. All chemicals and solvents
were used without further purification. Compounds 4, 3, 2 and 1 were
synthesized by following Scheme 1 and modified reported methods
NMR: δ
(d, 1H), 7.84 (m, 1H), 7.78 (d, 1H), 6.64 (d, 2H), and 6.27 (t, 1H).
NMR: δ (100 MHz, DMSO-d ): 193.75, 164.68, 152.43, 147.76, 140.62,
138.84, 134.62, 131.27, 129.86, 127.87, 126.86, 123.42, 118.31.
H 6 4
(400 MHz, DMSO-d , Me Si): 9.98 (s, 1H), 8.70 (d, 1H), 8.07
13
C
C
6
[33,34].
2.5. Synthesis of compound 2
2
.2. Measurements
Compound 2 was synthesized from rhodamine B via a procedure we
1H NMR and 13C NMR spectra were recorded on a Bruker 400 NMR
have reported [33]. Rhodamine B (1.0039 g, 2.76 mmol) and 80% hydra-
zine hydrate (4 mL) were dissolved in 30 mL methanol. The mixture
was refluxed under stirring for 6 h in argon atmosphere. After distilla-
tion in vacuum, the residue was recrystallized with methanol to give
the final product 2 in a yield of 76.9%.
spectrometer. Chemical shifts are reported in parts per million using
tetramethylsilane (TMS) as the internal standard. Mass spectra were
obtained on high resolution mass spectrometer (IonSpec4.7 Tesla
FTMS-MALDI/DHB).
All spectral characterizations were carried out in HPLC-grade solvents
at 20 °C within a 10 mm quartz cell. UV–vis absorption spectra were
measured with a TU-1901 double-beam UV–vis spectrophotometer.
2.6. Synthesis of compound 1
The mixture of compound 3 (0.1215 g, 0.27 mmol), compound 2
(0.0630 g, 0.30 mmol), and 3.8 mL ethanol was refluxed under stirring
for 12 h in argon atmosphere. The crude residue was obtained after dis-
tillation in vacuum. The final product 1 was obtained by column chro-
matography (mesh chromatography silica, 1:1 dichloromethane/light
2
.3. Synthesis of compound 4
A mixture of 8-hydroxy-2-methylquinoline (2.4032 g, 15 mmol) and
triethylamine (1.5 mL) was dissolved in 20 mL toluene and the mixture
was stirred at 0 °C. After stirring for 30 min, 4 mL acryloyl chloride was
slowly added dropwise and the reaction mixture was stirred for 12 h at
petroleum) in a yield of 84.7%. Characterization of probe 1: HRMS (EI)
1
calcd. for C41
(400 MHz, CDCl
7.53 (m, 3H), 7.40 (m, 1H), 7.27 (m, 1H), 7.15 (m, 2H), 6.57 (m, 2H),
H
40
N
5
O
4
[M + H], 666.3080; found, 666.3098. H NMR:
2
0 °C. The mixture was filtered and evaporated to generate the crude
residue. The final product 4 was obtained by column chromatography
mesh chromatography silica, 1:4 ethyl acetate/light petroleum) in
δ
H
3 4
, Me Si): 8.69 (s, 1H), 8.12 (m, 2H), 8.05 (m, 3H),
1
3
(
6.52 (d, 2H), 6.26 (q, 2H), 3.34 (t, 8H), and 1.18 (q, 12H). C NMR: δ
(100 MHz, CDCl ): 165.35, 153.13, 152.62, 152.16, 152.10, 149.07,
C
1
a yield of 47.3%. Characterization of compound 4: H NMR: δ
H
3
(
7
(
400 MHz, DMSO-d
.47 (d, 1H), 6.59 (d, 2H), 6.20 (t, 1H), and 3.36 (s, 3H). C NMR: δ
100 MHz, DMSO-d
6
, Me
4
Si): 8.31 (d, 1H), 7.86 (d, 1H), 7.55 (m, 2H),
146.01, 137.52, 135.83, 133.83, 128.59, 128.40, 128.38, 128.06, 127.86,
123.97, 123.63, 118.81, 117.70, 110.02, 108.07, 105.61, 98.04, 66.13,
44.33, 29.06, 22.62, 12.62.
13
C
6
): 164.71, 159.47, 146.76, 140.37, 136.69, 133.92,
1
28.23, 127.90, 126.32, 125.85, 123.30, 121.95, 25.72.
3. Results and discussion
2
.4. Synthesis of compound 3
3.1. Synthesis of sensor 1
A mixture of SeO
2
(0.3240 g, 2.9 mmol), compound 4 (0.4638 g,
2
.2 mmol), and 10 mL 1,4-dioxane was refluxed under stirring for 4 h
In this work, the sensor 1 was synthesized via four-step synthetic
in argon atmosphere. The mixture was filtered and evaporated to gener-
ate the crude product. The final product 3 was obtained by column chro-
procedure starting from 2-methy-8-hydroxyquinoline. The reaction of
compound 8-hydroxy-2-methylquinoline with acryloyl chloride in tol-
uene gave the product 4 in a 47.3% yield. Compound 4 reacted with
matography (mesh chromatography silica, 1:15 ethyl acetate/light
1
petroleum) in a yield of 71.6%. Characterization of compound 3:
H
2
SeO in 1,4-dioxane and gave compound 3 in a 71.6% yield. The sensor

Z. Li et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 159 (2016) 249–253
251
−
5
Fig. 2. Absorption (up) spectra change of compound 1 (1.0 × 10 M, water/ethanol =
7
(
:3, v/v) and photographs of compound 1 (1.0 × 10− M, water/ethanol = 7:3, v/v)
5
−
4
down) in daylight with the presence of different metal ions (1.5 × 10 M). The metal
ions are none, Fe , Al , Ca , Cd , Co , Cu , Hg , K , Mg , Mn2+, Na , Ni
3
+
3+
2+
2+
2+
2+
2+
+
2+
+
2+
,
−
5
Fig. 1. Absorption (up) spectra change of compound 1 (1.0 × 10 M, water/ethanol =
2+
2+
3+
Pb , Zn , and Cr
.
−
5
7
(
1
3
:3, v/v) and photographs of compound 1 (1.0 × 10
M, water/ethanol = 7:3, v/v)
3
+
down) in daylight in the presence of Fe (the concentrations from left to right are 0,
−
4
−4
−4
−4
−4
−3
with Fe3+ concentration, implying that Fe3+ can be quantitatively de-
× 10
× 10
M, 3 × 10
M, 5 × 10
M, 7 × 10
M, 9 × 10
M, 1 × 10
M,
−
3
−3
M, 5 × 10
M) at different concentrations. Absorption spectra response of
tected in a wider concentration range. From this linear calibration
−
5
compound 1 (1.0 × 10
M, water/ethanol = 7:3, v/v) at 563 nm as a linear
3+
graph, the detection limit of probe 1 for Fe
is found to be about
dependence with the concentration of Fe3+ (inset of Fig. 1 up). A represents the
absorbance at 563 nm.
1
5 nM based on signal-to-noise ratio (S/N) = 3 [35–37], which is
much lower than the average concentration of iron in intake water
0.3 mg/L, about 5 μM) and the max concentration of iron in industrial
circulating water (0.5 mg/L, about 9 μM). These results led us to con-
(
1
was obtained in an 84.7% yield by the reaction of compound 3 with
compound 2 in methanol. The chemical structures were confirmed by
HRMS, H, and C NMR.
3
+
1
13
clude that 1 could be an effective colorimetric chemosensor for Fe
.
Job plots indicated that sensor 1 chelated Fe3 with 1:1 stoichiometry
+
(
Fig. S2 in the Supporting Information). The proposed sensing
3
+
3
.2. Fe colorimetric sensing properties of 1 in aqueous solution
mechanism was shown in Scheme 2.
To evaluate the selectivity of probe 1 for Fe3+, various species in-
cluding environmentally and biologically relevant metal ions and an-
ions were tested. As shown in Fig. 2 and green bars of Figs. 3 and 4,
To investigate the changes in absorption spectrum of 1 upon expo-
sure to Fe , UV–vis titration experiments were conducted with Fe
in aqueous solution of 1 (1.0 × 10
3
+
3+
−
5
3+
M, water/ethanol = 7:3, v/v)
only the introduction of Fe to the sensor 1 solution induced a signif-
(
Fig. 1). As is evident from inspection of Fig. 1, sensor 1 exhibits no ab-
icant enhancement in the absorption at 563 nm and a great color change
from colorless to pink. In the same condition, other tested species men-
tioned above did not induce any UV–vis spectroscopic change to
the sensor 1 solution except PPi, indicating that compound 1 as a
chemosensor have high selectivity toward Fe3 over many common
metal ions and anions.
sorption at 563 nm in aqueous solution in the absence of Fe(NO )
(
absorption peak at 563 nm was observed with the solution color chang-
ing from colorless to pink, implying that compound 1 can be a naked-
eye sensor toward Fe . Fig. S1 (Supporting Information) indicates
the relationship between the absorption peak intensity at 563 nm and
the concentration of Fe3 . In the concentration range of 6.7 μM and
3 3
3
+
3+
Fe ). However, upon addition of Fe , a significant increase in the
+
3
+
To further assess its utility as a Fe3+-selective colorimetric sensor, its
+
3+
UV–vis spectrum response to Fe
in the presence of other species
1
6 μM, the absorption at 563 nm of 1 is in good linear relationship
mentioned above (red bars of Figs. 3 and 4) was also tested. The results
Scheme 2. Possible sensing mechanism of chemosensor 1 toward Fe3+ and PPi.

252
Z. Li et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 159 (2016) 249–253
3
+
3
.3. Colorimetric sensing properties of the ‘in situ’ prepared Fe complex
(1⋅Fe) toward PPi
4 2 7
As we have mentioned above, addition of Na P O water solution
3
+
can result in the absorption and color of the ‘in situ’ prepared Fe com-
plex (1⋅Fe) signals identical to those of compound 1 only. That is, the
complex 1⋅Fe can detect PPi colorimetricly.
To investigate the changes in absorption spectrum of the complex
1
⋅Fe upon exposure to PPi, UV–vis titration experiments were conduct-
ed. As shown in up of Fig. 5, upon addition of Na water solution,
4 2 7
P O
absorbance at 563 nm decreased and absorption signals the same as
those of compound 1 only were restored with the solution color chang-
ing from pink to colorless gradually, implying that Fe3 is removed
from the complex 1⋅Fe by PPi, and the complex 1⋅Fe can detect PPi. In
concentration range of 6 and 18 μM, the absorbance at 563 nm is in
good linear relationship with PPi concentration (inset of Fig. 5 up), im-
plying that PPi can be quantitatively detected in a wider concentration
range. The LOD value from the UV–vis titration experiment can be as
low as 71 nM.
+
−
5
Fig. 3. Absorption spectra response of compound 1 (1.0 × 10 M, water/ethanol = 7:3, v/v)
at 563 nm in the presence of different metal ions (1.0 × 10− M) (green bars) and absorption
5
To examine the selectivity and anti-disturbance capacity toward PPi,
further experiments were carried out. Upon addition of different anions,
only PPi can induce absorbance at 563 nm of the complex 1⋅Fe decreas-
−
5
spectra response of the mixture of compound 1 (1.0 × 10 M, water/ethanol = 7:3, v/v)
3
+
−5
M) after addition of other metal ions (1.0 × 10−5 M). A and A
and Fe (1.0 × 10
0
−
−
−
represent the absorbance at 563 nm. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
ing (red bars of Fig. 6), other representative anions, such as F , Cl , Br ,
−
−
−
−
−
−
2−
2− 2−
−
I , H
2
PO
4
, CH
3
COO , HSO
4
, NO
3
, SCN , SO
4
, HPO
4
, S , NO
2
,
2
−
−
−
−
2−
2−
−
SO
, HSO , ClO , N , SiO , S O , and ClO showed almost no ef-
3 3 4 3 3 2 3 3
demonstrated that all of the selected species have no interference in the
except PPi. This result strongly indicates that
compound 1 showed remarkable anti-disturbance toward Fe
fects on the UV–vis and color behavior of the complex 1⋅Fe, implying
high selectivity of the complex 1⋅Fe toward PPi. The competition exper-
3
+
detection of Fe
3
+
3
+
over
iments were conducted in the presence of Fe
and PPi mixed with
−
−
−
−
−
−
−
−
−
common metal ions and anions.
many anions (F , Cl , Br , I , H
2
PO
4
, CH
3
COO , HSO
, ClO , N , SiO , S O , and
4 3 3 2 3
ClO ) respectively (green bars and down of Fig. 6). No significant ab-
3
4
, NO
3
, SCN ,
Experiments to explore the counterion effect on the Fe3+-selective
properties of sensor 1 were also performed (Fig. S3 in the Supporting
Information). Chloride and sulfate had similar influence as nitrate
when it comes to ferric salts, demonstrating that the anions do not
coordinate the metal ions while chemosensor 1 reacts with Fe3 . This
indicates that compound 1 as a colorimetric sensor has a much wider
application range in sensing Fe3 ions.
2
−
2− 2−
−
2−
−
−
−
2−
2−
SO
4
, HPO
4
, S , NO
2
, SO
3
, HSO
3
−
sorption spectra and color change were found by comparison with
that without the other anions, which revealed strong anti-disturbance
capacity of the complex 1⋅Fe toward PPi over other common anions.
+
+
Fig. 5. Absorption (up) spectra change of the ‘in situ’ prepared complex 1⋅Fe
Fig. 4. Absorption spectra response of compound 1 (1.0 × 10− M, water/ethanol = 7:3, v/v)
5
(1.0 × 10
complex 1⋅Fe (1.0 × 10
presence of PPi (the concentrations from left to right are 0, 0.17
0.33 × 10
−5
M, water/ethanol = 7:3, v/v) and photographs of the ‘in situ’ prepared
−
5
at 563 nm in the presence of different anions (0.1 M) (red bars) and absorption spectra
response of the mixture of compound 1 (1.0 × 10 M, water/ethanol = 7:3, v/v) and
M, water/ethanol = 7:3, v/v) (down) in daylight in the
−
5
−5
×
10
M,
M,
M,
3
+
4−
−5
−5
−5
−5
−5
−5
−5
Fe after addition of different anions (0.1 M), and the anions from 1 to 21 are P
2
O
, SO
7
,
M, 0.5 × 10
M, 0.67 × 10
M, 0.83 × 10
M, 1 × 10
M, 1.83 × 10
F
−, Cl , Br , I , H
HSO
−
−
−
2
PO
−
, CH
3
COO , HSO
−
−
, NO
−
, SCN , SO
−
2−
, HPO
2− 2−
, S , NO
−
2−
,
1.17 × 10
−5
M, 1.33 × 10
M, 1.5 × 10
−5
M, 1.67 × 10
−5
−
−
−
2−
2−
−
−5
−5
−5
3
, ClO
4
, N
3
, SiO
3
, S
O
2 3
, and ClO
3
. A and A
0
represent the absorbance at 563 nm.
2 × 10 M, 2.17 × 10 M, 2.33 × 10 M). Inset: absorption spectra response of the
(For interpretation of the references to color in this figure legend, the reader is referred
‘in situ’ prepared complex 1⋅Fe at 563 nm as a linear dependence with the
to the web version of this article.)
concentration of PPi.

Z. Li et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 159 (2016) 249–253
253
high selectivity over various environmentally and biologically relevant
metal ions and anions with a distinct color change from colorless to
pink in very fast response time (b1 min). The chemosensor can detect
3
+
Fe quantitatively in the concentration range from 6.7 to 16 μM and
the LOD can be as low as 15 nM. The ‘in situ’ prepared complex 1⋅Fe
showed high selectivity and sensitivity (the LOD can be as low as
7
1 nM) toward PPi. In addition, both the chemosensor and the ‘in situ’
3
+
3+
prepared Fe complex are reusable for the detection of Fe and PPi
respectively.
Acknowledgments
This work was supported by “the Fundamental Research Funds for
the Central Universities (2015XKZD08)”.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.saa.2016.02.001.
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Fig. 6. Absorption spectra response of the ‘in situ’ prepared complex 1⋅Fe (1.0 × 10− M,
water/ethanol = 7:3, v/v) at 563 nm in the presence of different anions (0.1 M) (red
bars) and absorption spectra response of the ‘in situ’ prepared complex 1⋅Fe
5
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[
3
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3
+
3+
3+
−
3+
−
3+
−
3+
−
3+
−
3+
−
3+
−
3+
2 4 3 4
and I ; Fe , PPi and H PO ; Fe , PPi and CH COO ; Fe , PPi and HSO ; Fe , PPi
−
; Fe3+, PPi and SCN ; Fe3+, PPi and SO
−
2−
; Fe3+, PPi and HPO
2−
; Fe3+, PPi and
and NO
3
4
4
2
−
3+
−
3+
2−
3+
−
3+
−
S
; Fe , PPi and NO
2
; Fe , PPi and SO
3
3+
; Fe , PPi and HSO
3
; Fe , PPi and ClO
4
;
3
+
−
3+
2−
2−
3+
−
Fe , PPi and N
3
3 2 3 3
; Fe , PPi and SiO ; Fe , PPi and S O ; Fe , PPi and ClO .
[
[
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3
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3
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As we have mentioned above, addition of Na water solution
4 2 7
P O
3
+
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can result in the absorption and color of the ‘in situ’ prepared Fe com-
plex (1⋅Fe) signals identical to those of compound 1 only. That is, the
complex 1⋅Fe can detect PPi colorimetricly.
The reusability of material is very important for incorporating them
into a sensing device or directly using them as a reusable tool, which re-
quires that the sensing behavior should be reversible. The reversibility
study of sensing Fe (5 × 10 M) was carried out for compound 1.
A 0.1 M Na water solution was added to the compound 1
1.0 × 10 M, water/ethanol = 7:3, v/v). Absorption and color signal
identical to those of compound 1 (1.0 × 10 M, water/ethanol = 7:3,
v/v) only were restored (Fig. 5), demonstrating that Fe3 is removed
from the ‘in situ’ prepared complex 1⋅Fe by PPi, and the binding con-
2
[
[
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3
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P O
[
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−
5
(
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−
5
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[
[
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3
+
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stant of Fe
with PPi is larger than that with compound 1. That is,
3
+
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the binding of compound 1 and Fe is really chemically reversible. Fur-
thermore, after addition of ferric salt solution to the ‘in situ’ prepared
complex 1⋅Fe mixed with PPi, the absorption signal identical to that
of the ‘in situ’ prepared complex 1⋅Fe was obtained (Fig. S4 in the
Supporting Information). Such results indicate that both compound 1
[
[
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of Fe3+ and PPi respectively.
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[
[
[
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4
. Conclusion
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3
+
chemosensor for Fe
and further for PPi has been developed with
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