6 Sensors and Actuators B 181 (2013) 749–755

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

A new photoresponsive coumarin-derived Schiff base: Chemosensor selectively

for Al3+ and Fe3+ and fluorescence “turn-on” under room light
Lingyun Wang ∗ , Huihui Li, Derong Cao
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China

a r t i c l e i n f o a b s t r a c t

Article history: A novel coumarin Schiff base compound (L) prepared from 4-(diethylamino)salicylaldehyde and 6-
Received 19 November 2012 amino-7-hydroxycoumarin was synthesized and evaluated as a chemoselective Fe3+ and Al3+ sensor
Received in revised form 29 January 2013 utilizing “turn-on” fluorescence enhancement. There were 7-fold and 4-fold fluorescence enhancement
Accepted 29 January 2013
of L at em,max = 488 nm upon the addition of 1 equiv. of Al3+ and Fe3+ , respectively. Other metal ions, such
Available online 9 February 2013
as K+ , Li+ , Na+ , Cu+ , Mg2+ , Ca2+ , Ba2+ , Cu2+ , Fe2+ , Hg2+ , Ni2+ , Sb3+ , Sn2+ , Zn2+ , Ce3+ , Cr3+ , Pr3+ , Sm3+ and Sn4+
had no such significant effect on the fluorescence of L, whereas In3+ and Ga3+ induced slightly fluorescence
Keywords:
enhancement of L. In addition, rapid photoresponse through fluorescence “turn-on” signaling displayed L
Coumarin Schiff base
Fluorescence “turn-on”
via intramolecular O H· · ·N CH interaction in photoisomerized product (L ) has been described, where
Chemosensor showed 130-fold and 65-fold fluorescence enhancement at em,max = 488 and 516 nm, respectively. The
Detection results indicated L was less reactive or inert toward metal ions.
Photoisomer © 2013 Elsevier B.V. All rights reserved.

1. Introduction electron transfer, intramolecular charge transfer, metal-ligand

The development of fluorescent probes for metal ions detection
is an attractive field because sensors based on ion-induced changes
in fluorescence show simplicity, high sensitivity and instanta-
neous response. The essential role of iron in human and animal
health became apparent. Fe3+ provides the oxygen-carrying capac-
ity of heme and acts as a cofactor in many enzymatic reactions
involved in the mitochondrial respiratory chain. However, high
levels of Fe3+ ions within the body can be toxic because of its
ability to promote oxidation of lipids, proteins and other cellular
components and have been associated with increased incidence
of certain cancers and dysfunction of organs, such as heart, pan-
creas and liver. Meanwhile, Al3+ is also an essential nutrient for
humans and the iron binding protein is known to be the main car-
rier of Al3+ in plasma. In addition, widespread use of Al3+ in food
additives, aluminum-based pharmaceuticals and storage/cooking
utensils has been implicated as a causative factor of Alzheimer’s
disease and associated with damage to the central nervous system
in humans. Thus, there is an urgent need to develop chemical sen-
sors that are capable of detecting the presence of Fe3+ and Al3+ in
environmental and biological samples. To date, some fluorescent
chemosensors have been developed for detection of Fe3+ [1–11]
and Al3+ [12–27] with moderate success. These chemosensors are
based on conventional signaling mechanisms such as photoinduced
∗ Corresponding author. Tel.: +86 20 87110245; fax: +86 20 87110245.
E-mail address: lingyun@scut.edu.cn (L. Wang).
charge transfer, twisted intramolecular charge transfer, fluo-
rescence resonance energy transfer, excimer/exciplex forma-
tion, excited-state intramolecular proton transfer and chalation
enhanced fluorescence. Among them, chalation enhanced fluo-
rescence sensor is a current thrust in the active research field
interesting. Since paramagnetic Fe(III) is described as one of the
most efficient fluorescence quenchers among the transition metal
ions, the signal transduction occurrence via chelation enhanced
fluorescence with these inherent quenching metal ions is desirable.
It is well known that C N isomerization usually results in weak
fluorescence emission of the attached chromophore. If this isomer-
ization is stopped by bonding to metal ions, high-intensity emission
can be achieved. Although many Schiff base derivatives incorpo-
rating a fluorescent moiety have been used to detect various metal
ions [28–33], Schiff base-type Fe3+ and Al3+ chemosensors are very
rare [11,15,18]. On the other hand, coumarin-based fluorescent
chemosensors have received increasing interest in recent years
by virtue of their less toxicity and easy to be modified [34–38].
To our knowledge, Schiff bases (compound L) derived from the
condensation of 4-(diethylamino)salicylaldehyde with 6-amino-
7-hydroxycoumarin have not been reported, where coumarin
fluorophore is chosen due to its characteristics of high emission
yield, excellent photostability, and significant fluorescent behav-
ior in the visible region. Herein, we describe this new compound
L as chemosensor selectively for Al3+ and Fe3+ utilizing “turn-on”
fluorescence enhancement. Moreover, the room light triggered flu-
orescence enhancement of L via structural changes (E → Z) is also
investigated, which is found for coumarin-based Schiff base for

0925-4005/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2013.01.090
750 L. Wang et al. / Sensors and Actuators B 181 (2013) 749–755

the first time. We then investigate the remarkable differences in

coordination chemistry between E and Z conformers with Al3+ and
Fe3+ .

2. Experimental

2.1. Chemicals and instruments

All reactants were commercially available and used with-

out further purification. The IR spectra were measured on a
Nicolet/Nexus-870 FT-IR spectrometer with KBr pellets in the
range 4000–400 cm−1 . Nuclear magnetic resonance spectra were
recorded on Bruker Avance III 400 MHz and chemical shifts are
expressed in ppm using TMS as an internal standard. The UV–vis
absorption spectra were recorded using a Helios Alpha UV–vis scan-
ning spectrophotometer. Fluorescence spectra were obtained with
a Hitachi F-4500 FL spectrophotometer with quartz cuvette (path
length = 1 cm).
The recognition between coumarin Schiff base compound (L or
its isomer) and different metal cations was investigated by UV–vis
and fluorescence spectroscopy in MeOH solution at room temper-
ature. The stock solution of L and metal ions was at a concentration
of 10.0 mM. After the L and metal ions with desired concentrations
were mixed in dark, they were measured by UV–vis and fluores-
cence spectroscopy as soon as possible.

2.2. Synthesis of coumarin Schiff base compound (L)

6-Amino-7-hydroxycoumarin was synthesized from 7-

hydroxycoumarin as starting material using a slightly modified
literature method [39].
A portion of 6-amino-7-hydroxycoumarin (177 mg, 1 mmol)
and 4-(diethylamino)salicylaldehyde (212 mg, 1.1 mmol) were
combined in hot absolute ethanol (20 mL). The solution was stirred
under reflux conditions for 6 h to yield a yellow precipitate. The
precipitate was filtrated, washed with hot absolute ethanol three
times, then recrystallized with ethanol to get yellow solid L
(281 mg, 0.80 mmol) in 80% yield. All synthesis and workup pro-
cedures were performed in dark. 1 H NMR (CD3 OD-d4 , 400 MHz, ı):
8.76 (s, 1H), 7.89 (t, 2H, J = 8 Hz), 7.53 (d, 1H, J = 8 Hz), 6.88 (s, 1H),
6.62 (d, 1H, J = 8 Hz), 6.27 (t, 2H, J = 8 Hz), 3.60 (q, 4H, J = 8 Hz), and
1.29 (t, 6H, J = 8 Hz).
2.3. Synthesis of photoisomer of L (L )
A solution containing L (0.281 g, 0.80 mmol) in MeOH was
explored under room light for 30 min and evaporated under vac-
uum. The brown powder was obtained to give pure L . 1 H NMR
(CD3 OD-d4 , 400 MHz, ı): 8.72 (s, 1H), 7.87 (s, 2H), 7.51 (s, 1H), 6.87
(s, 1H), 6.60 (s, 1H), 6.27 (d, 2H, J = 4 Hz), 3.58 (q, 4H, J = 8 Hz), and
1.28 (t, 6H, J = 8 Hz).
3. Results and discussion
3.1. Selective recognition of Al3+ and Fe3+ with L
Over 7-hydroxycoumarin was added concentrated nitric
acid/acetic acid yielding 6-nitro-7-hydroxycoumarin [39]. Further-
more the nitro group of 6-nitro-7-hydroxycoumarin was reduced
by the addition of hydrazine with Pd/C in absolute ethanol, yield-
ing 6-amino-7-hydroxycoumarin. L was readily synthesized by
condensation of 4-(diethylamino)salicylaldehyde and 6-amino-7-
hydroxycoumarin in absolute ethanol.
Fig. 1 shows the fluorescence emission changes of L in MeOH
upon the addition of Fe3+ and Al3+ . The fluorescence spectra were
Fig. 1. Fluorescence spectra of L (10 ␮M) with addition of various concentrations of
(0,2, 4, 6, 8 and 10 ␮M) (a) Al3+ and (b) Fe3+ in MeOH with an excitation at 448 nm.
obtained by excitation at 448 nm. When no metal ion was added to
the solution of L, weak fluorescence signal in the range from 455
to 600 nm could be observed, whereas significant enhancements
of fluorescence at 488 and 516 nm were present with addition
of Fe3+ or Al3+ . When L was titrated with Fe3+ or Al3+ , the max-
imum fluorescence intensity was obtained up to 1 equiv. of Al3+
or Fe3+ , leading to 7-fold and 4-fold fluorescence enhancement at
em,max = 488 nm respectively. The enhancement of fluorescence
was attributed to occurrence of the strong complexation of Al3+ or
Fe3+ with L, resulting in the inhibition of the C N isomerization
process and decreased non-radiative decay of the excited-state.
The binding constants (log Ka ) of L with Al3+ in MeOH solution
was calculated to be 6.4, which was within the range 2.9–8.7 of
those reported for Al3+ -binding sensors [12–15]. However, log Ka
of 2.7 were obtained for L with Fe3+ , indicating Fe3+ showed weaker
binding ability with L than that of Al3+ under the same conditions.
A linear correlation between the emission intensity of L and the
concentration of Al3+ (or Fe3+ ) was observed in the concentration
range 1–10 ␮m. The limited detection concentrations for Al3+ and
Fe3+ were 2.4 ␮m and 4.3 ␮m, respectively.
Selectivity is an important characteristic of an ion-selective
chemosensor. To examine the selectivity of L, the affinity of L
for other surveyed metal ions, such as K+ , Li+ , Na+ , Cu+ , Mg2+ ,
Ca2+ , Ba2+ , Cu2+ , Fe2+ , Hg2+ , Ni2+ , Sb3+ , Sn2+ , Zn2+ , Ce3+ , Cr3+ , Ga3+ ,
In3+ , Pr3+ , Sm3+ and Sn4+ was investigated by UV–vis and fluo-
rescence spectra. As shown in Fig. 2(a), addition 1 equiv. of these
alkali-, alkaline earth-, transition and rare earth metal ions did not
cause significant UV–vis absorption spectral changes of L. However,
 L. Wang et al. / Sensors and Actuators B 181 (2013) 749–755 751

0.4 of 1.0 equiv. of all other metal ions. The results indicated miscella-
(a) neous competitive cations did not lead to any significant spectral
change and the Al3+ ions still resulted in the similar fluorescence
0.3 changes in the presence of competitive cations, as shown in Fig. 3.
The data clearly suggest that there is no interference of other metal
ions for sensing of Al3+ . Similarly, we have studied the selectivity
Absorbance

0.2
of L toward Fe3+ in the presence of various other metal ions. L was
treated with 1.0 equiv. of Fe3+ in the presence of 1.0 equiv. of all
other metal ions (Fig. 4). L also showed selectivity for the detection
of Fe3+ in the presence of various other metal ions. The results from
0.1
Figs. 3 and 4 indicated L detected Al3+ more selectively in the pres-
ence of other metal ions, maybe the fact that Al3+ showed higher
binding ability with L than that of Fe3+ under the same conditions
0.0 due to its higher log Ka . Thus, L can serve as selective fluorescent
sensors for Fe3+ and Al3+ , which is similar to many dual selective
300 400 500 600 metal ion sensors [9,11,40–46].
Wavelength (nm) In general, transition and post-transition cations with open shell
d-orbitals often quench the fluorescence of fluorophores due to the
electron or energy transfer between the metal cations and fluo-
400 (b) rophores, providing a very fast and efficient nonradiative decay of
350
the excited states. In contrast, the transition cations with close shell
d-orbitals do not introduce low-energy metal-centered or charge
300 separated excited states so energy and electron-transfer processes
PL Intensity (a. u.)

cannot take place. In the present work, we observed an obvious

250
enhancement of fluorescence intensity in the presence of Al3+ and
200 Fe3+ , as well as slightly fluorescence enhancement in the presence
of In3+ and Ga3+ . The reason can be explained by the competition
150 between the fluorescence enhancement due to the inhibition of
100
C N isomerization and quenching of fluorescence from the metal
cation-induced electron or energy transfer processes. This result
50 indicates that the C N isomerization plays a predominant role,
although the restriction of s-cis versus s-trans conformation in the
0
fluorophore may also be a little partial cause of the observed flu-
460 480 500 520 540 560 580 600 orescence turn-on (vide infra) and gives rise to more significantly
Wavelength (nm) spectral and photophysical response to transition metal cations.
There are some reports in the recent past describing the specific
Fig. 2. (a) UV–vis and (b) fluorescence spectra of L (10 ␮M) in the absence and detection of various metal ions with Schiff base receptors, based
presence of 1 equiv. of different metal ions in MeOH.
on the C N isomerization mechanism [18,47–51].

under the same conditions, Fe3+ and Al3+ showed different UV–vis
absorption response to L. Addition of Fe3+ resulted in increased
absorbance at 343 nm with a concomitant blue shift from 443 nm to
432 nm. Moreover, the shoulder peak at 465 nm was absent. On the
other hand, upon addition of Al3+ , the absorption intensity at 443
and 465 nm significantly increased, whereas absorbance band at
343 nm showed no change. Fig. 2(b) shows fluorescence response of
different metal ions to L. As compared with fluorescence enhance-
ment induced by Fe3+ and Al3+ , however, other ions, such as K+ ,
Li+ , Na+ , Cu+ , Mg2+ , Ca2+ , Ba2+ , Cu2+ , Fe2+ , Hg2+ , Ni2+ , Sb3+ , Sn2+ ,
Zn2+ , Ce3+ , Cr3+ , Pr3+ , Sm3+ and Sn4+ gave no distinct response to
the solution of L in fluorescence spectra, whereas 1 equiv. In3+ and
Ga3+ belonging to the same group on the periodic table of Al3+
induced slightly fluorescence enhancement (about 40%). Similar
results were shown by others. Maity and his coworker reported
on naphthaldehyde–thiocarbonohydrazone Schiff base ligand for
selective Al3+ detection, whereas In3+ resulted in a little enhance-
ment of emission intensity of ligand [18]. Kim et al. also found Ga3+
generated a similar fluorescence enhancement for salicylimine-
based fluorescent chemosensor for aluminum ions [15]. However,
such a variation in fluorescence intensity by In3+ and Ga3+ is rel-
atively small compared with Al3+ and Fe3+ (7-fold and 4-fold,
respectively), indicating that L shows the stronger response in flu-
orescence spectrum to Al3+ and Fe3+ among these metal cations.
To test whether L can detect Al3+ and Fe3+ selectively even in the
presence of other metal ions, competitive metal ion titrations were
carried out. L was treated with 1.0 equiv. of Al3+ in the presence
3.2. Photoisomerized product of L
Owing to reversible photodimerization and photocleavage char-
acteristics of coumarin [51,52], photoexcitation (room light) of
L in MeOH solution was investigated. When a solution con-
taining L in MeOH was explored under room light for 30 min
and evaporated under vacuum, the brown powder (L ) was
obtained. The subtle difference in color with respect to those
obtained from the synthetic/purification route in dark (yellow
powder) might imply structural variation. Similar results have
been obtained by others. Chou et al. reported Z–E isomer-
ization of salen Schiff base ligand 2,3-bis[4-(di-p-tolylamino)-
2-hydroxybenzylideneamino]maleonitrile took place by rotation
about maleonitrile C C double bond, which took on single-bond
character due to the charge-transfer reaction [53]. In that case, Z
isomer was red–brown powder, whereas E isomer was deep green
crystals.
The light-induced structural changes can be easily evaluated if
they are directly related to a fluorescent readout [54]. The Schiff
base L emits weak fluoresces at 488 nm with a shoulder emis-
sion peak at 516 nm which was probably due to the fact that C N
isomerization was the predominant decay process of the excited
states for L with an unbridged C N structure. To examine the
photostability of L, fluorescence spectra of the same solution was
acquired repeatedly with 2 min time interval, which showed grad-
ual increase in the fluorescence intensity (Fig. 5(a)). The maxima
and shapes of the fluorescence spectra did not change and no
752 L. Wang et al. / Sensors and Actuators B 181 (2013) 749–755

4
I/I 0

0
controlFe3+ Li+ Na+ K+ Cu+ Mg2+Ca2+ Ba2+Cu2+ Fe2+ Hg2+ Zn2+ Sn2+ Ni2+ In3+ Ga3+ Cr3+Sm3+Pr3+ Ce3+ Sb3+ Sn4+

Fig. 3. Relative fluorescence of L (10 ␮M, emission intensity at 488 nm) with 1 equiv. of Al3+ and 1 equiv. of the metal ion stated.

new peaks appeared. The trend continued and attained satura-
tion after 30.0 min. There were 130-fold and 65-fold fluorescence
enhancement at em,max = 488 and 516 nm, respectively. Fluores-
cence “turn-on” without any significant change in Stokes shift
suggested the possibility of structural changes rather than photo-
cleavage.
Closer examination of the absorption spectra of L and L (Fig. 5
(b)) indicated some structural changes (i.e., orientation, geome-
try, etc.). Evidently, despite the similarity in the region of 343 nm,
salient differences are observed around 400–500 nm, in which L
exhibits stronger absorption bands at about 443 and about 465 nm.
The difference in absorption, especially band at 465 nm, becomes
much more significant. This can be proposed that L with E con-
figuration should be obtained through synthetic route, similar to
numerous reports on Schiff base compound [55–57]. In the pres-
ence of room light, it is reasonable to propose that the originally
prepared isomer E is converted to Z by photoexcitation during the
workup procedure in solution. Although photoinduced isomeriza-
tion has been reported in numerous Schiff bases [53,58,61–67], to
the best of our knowledge, no examples have been demonstrated
in coumarin Schiff base ligand. Lin and co-workers studied the pho-
toinduced isomerization pathways in a qualitative manner [53].
They found facile rotation around the maleonitrile C C bond was
expected, inducing Z → E isomerization of salen Schiff base ligand.
In addition, Pandey et al. [58] reported Schiff base prepared from
pyridine-2-carboxaldehyde and 2,4,6-trimethylbenzene showed
UV-triggered E–Z structural changes by assuming the movement
of pyridyl ring (E, Z) to form an eight membered cyclic ring (Z, Z)
involving C H· · ·N hydrogen bonding between methyl protons and
nitrogen lone pair. In addition, Hagen et al. evaluated the under-
lying mechanism responsible for the light-induced isomerization
of tetra-tert-butyl-azobenzene. In the gas and liquid phase direct
electronic excitation induces isomerization of azobenzenes and its
derivatives via a n → * (S1 ) and  → * (S2 ) electronic excitation,

4.0

3.5

3.0

2.5
I/I0

2.0

1.5

1.0

0.5

0.0
controlAl3+ Li+ Na+ K+ Cu+ Mg2+Ca2+ Ba2+Cu2+ Fe2+ Hg2+ Zn2+ Sn2+ Ni2+ In3+ Ga3+ Cr3+Sm3+Pr3+ Ce3+ Sb3+ Sn4+

Fig. 4. Relative fluorescence of L (10 ␮M, emission intensity at 488 nm) with 1 equiv. of Fe3+ and 1 equiv. of the metal ion stated.
 L. Wang et al. / Sensors and Actuators B 181 (2013) 749–755
Fig. 5. (a) Fluorescence titrations of L to L (10 ␮M) with respect to fraction of visible
light/min and (b) absorption spectra of L and L (10 ␮M).
respectively [68]. In our case, it was possible that the movement
of 4-(diethylamino)-3-hydroxy-phenyl (Z) formed a six membered
cyclic ring via intramolecular O H· · ·N CH hydrogen bonding
between hydroxy protons and nitrogen of imine (Scheme 1), which
inhibited C N isomerization in L and controlled vibrational motion
and in turn, fluorescence“turn-on”.
Interestingly, addition of base (NaOH) into the MeOH solution of
L , the fluorescence intensity of L is greatly decreased and the initial
broad shoulder band is further broadened and red-shifted (Fig. 6).
The fluorescence of L at 488 nm was quenched 89% in presence of
Scheme 1. Structures of L and L and approach of metal ions toward the coordination sites of both isomers.
753
Fig. 6. Fluorescence spectra of L (10 ␮M) in presence of NaOH aqueous solution.
3 equiv. OH− . Upon addition of 10 equiv. OH− , the fluorescence of
L is completely quenched. These observations may be rationalized
that OH− ion destroyed initial intramolecular O H· · ·N CH hydro-
gen bonding interactions of L and the OH− ion further binds with
free OH group through acid–base interaction, leading to effec-
tive deconjugation. Thus, unbridged C N structure is recovered and
the forming charge transfer compound is non emissive, resulting
in stronger quenching effect. For twisted -conjugated systems, a
rapid intersystem crossing and subsequent nonradiative relaxation
could also make the molecule nonemissive [59,60].
1 H NMR spectra in CD OD-d were used to investigate struc-
3 4
tural changes between L and L (Fig. 7). In the 1 H NMR spectrum
of L, H3/H5 and H1/H6 protons resonated as triplets at ı 7.89 and
6.27 ppm, while H2 and H7 as doublets at ı 6.62 and 7.53 ppm.
The singlets at ı 6.88 and 8.76 ppm ( CH N ) has been assigned
to H8 and H4 proton resonances. Methyl and methylene pro-
tons of ethyl group resonated at ı 1.29 (H10) and 3.60 ppm
(H9), respectively. Although the 1 H NMR signals ascribed to the
aromatic protons for L exhibited small upfield shift, they are
complicated and hence may not be convincing enough to differen-
tiate L and L . However, they are readily distinguishable for both
imine protons (L: ı = 8.76 ppm, L : ı = 8.72 ppm). Similar results
were found for E–Z or Z–E photoisomerization of different Schiff
bases, where imine proton of E isomer was present in downfield
[53,59]. The large upfield shift of the imine proton also supports
some sort of structural changes were present in L with Z con-
former.
Based on the report by Pandey et al. [58], fluorescence titrations
spectra with respect to fraction of visible light/min and OH− ion as
754 L. Wang et al. / Sensors and Actuators B 181 (2013) 749–755

Fig. 7. 1
H NMR spectra of L and L .

well as 1 H NMR spectra, we propose that light-induced structural
changes in L to give L retain the extent of conjugation and con-
trolled by intramolecular O H· · ·N CH interactions. The resulting
a six-membered ring create rigidity and inhibited C N isomeriza-
tion in the molecule which controls vibrational motion and in turn,
fluorescence enhancement [69]. Recently, similar intramolecular
C H· · ·N interaction between methyl protons and pyridyl nitrogen
in Schiff base was reported, resulting in gradual increase in the
fluorescence intensity [58].
One can speculate that L would be less reactive or inert toward
metal ions. To affirm our postulation, various metal ions (1 equiv.)
were added to a solution of L (Fig. 8). It was observed that the
fluorescence spectrum of L did not cause significant changes
indicating inertness of L toward the metal ions. The strong flu-
orescence emission of L was moderate quenched (no more than
40%) by K+ , Li+ , Na+ , Cu+ , Mg2+ , Ca2+ , Ba2+ , Cu2+ , Fe2+ , Hg2+ ,
Ni2+ , Sb3+ , Sn2+ , Zn2+ , Ce3+ , Cr3+ , Ga3+ , In3+ , Pr3+ , Sm3+ and Sn4+ .
However, the fluorescence emission of L increased 31% and 16%
at em,max = 488 nm with the addition of Al3+ and Fe3+ , respec-
tively.
Fig. 9 shows UV–vis absorbance response of different metal ions
to L . For Fe3+ and Al3+ , the absorbance peaks at 442 and 464 nm
remain unaltered. However, there was slight increase at 343 nm
upon addition of Fe3+ . In contrast, 1 equiv. of Al3+ resulted in red
shift from 343 nm to 355 nm with slight decrease of absorbance
band. Other ions, such as K+ , Li+ , Na+ , Cu+ , Mg2+ , Ca2+ , Ba2+ ,
Cu2+ , Fe2+ , Hg2+ , Ni2+ , Sb3+ , Sn2+ , Zn2+ , Ce3+ , Cr3+ , Ga3+ , In3+ , Pr3+ ,
Sm3+ and Sn4+ gave no distinct response to the solution of L
in UV–vis absorbance spectra. Interactions between L and vari-
ous metal ions led to insignificant changes from fluorescence and
UV–vis spectra suggesting L becomes inert toward the tested
metal ions. The decrease of a coordination site, together with
steric hindrance, should account for the low reactivity of L toward
metal ions complexation. Thus, L cannot be used as chemosen-
sor selectively for Fe3+ and Al3+ , further indicating L has different
structure.

1800
0.30
1600

3+
0.25
1400 Al
PL intensity (a.u.)

1200 0.20
L'
Absorbance

1000 + + + 2+ 2+
K , Li+, Na , Cu , Mg , Ca , 0.15
2+ 2+ 2+ 2+ 2+ 3+
800 Ba , Cu , Fe , Hg , Ni , Sb ,
2+ 2+ 3+ 3+ 3+ 3+
Sn , Zn , Ce , Cr , Pr , Sm 0.10
3+ 4+
600 Fe , Sn

400 0.05

200 0.00

0
-0.05
500 550 600 650 300 400 500 600
Wavelength (nm) Wavelength (nm)

Fig. 8. Fluorescence spectra of L (10 ␮M) in the absence and presence of 1 equiv. of Fig. 9. UV–vis absorbance spectra of L (10 ␮M) in the absence and presence of
different metal ions in MeOH. 1 equiv. of different metal ions in MeOH.
 L. Wang et al. / Sensors and Actuators B 181 (2013) 749–755
4. Conclusions
In conclusion, we developed a “turn-on” fluorescence method
to detect Fe3+ and Al3+ using a simple coumarin-based Schiff base
(L) chemosensor with high selectivity. L exhibited room light-
triggered fluorescence ‘turn-on’ due to E–Z structural changes
controlled by intramolecular O H· · ·N CH interaction, leading to
less reactive or inert toward metal ions. Fluorescence titrations
spectra with respect to fraction of visible light/min and OH− ion as
well as 1 H NMR spectra provide support of E–Z structural change.
Acknowledgements
The supports by National Natural Science Foundation of China
(nos. 20904010 and 21274045) and the Pearl River in Guangzhou
city of Nova of Science and Technology Special Funded Projects (no.
2012J2200009) are gratefully acknowledged.
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Biographies
Lingyun Wang received her PhD degree in chemistry from Sun Yat-Sen University
in 2006. After post-doctoral training at the South China University of Technology
(SCUT), she joined SCUT where she is currently an assistant professor in the School
of Chemistry and Chemical Engineering. Her current research focuses on the design
and synthesis of functional water-soluble conjugated polymers and exploration of
their applications in chemosensors, biosensors and optoelectronic. She has over 30
peer-reviewed publications.
Huihui Li is an undergraduate currently. In 2014, she will receive MSc in organic
chemistry from the South China University of Technology, China.
Derong Cao is a professor in the School of Chemistry and Chemical Engineering,
South China University of Technology, China. His research focus is biosensor based
on conjugated polymer mainly on the synthesis, application as well as dye-sensitized
solar cells.