Recognition of Al3+ based on a naphthalene-based "off-On" chemosensor in near 100% aqueous media

Article abstract of DOI:10.1016/j.ica.2015.03.029

An efficient fluorescent Al³⁺ sensor, 2-hydroxy-1-naphthylaldehyde nicotinoyl hydrazone (HL) has been designed and synthesized. The receptor shows "off-on" fluorescent responses toward Al³⁺ in near 100% aqueous media. Other relevant metal ions such as Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, Cu²⁺, Co²⁺, Mn²⁺, Ni²⁺, Zn²⁺, Ba²⁺, Fe²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Sc³⁺, Fe³⁺, Cr³⁺ caused almost no fluorescence increase. The reason for this phenomenon is that the addition of Al³⁺ to the solution of HL induce the formation of a 1:1 stoichiometry of the binding mode of L-Al(III) which inhibits the excited-state intramolecular proton transfer (ESIPT) and photoinduced electron transfer (PET). More importantly, the reversibility of the recognition process of HL was performed by adding a Al³⁺ bonding agent Na₂EDTA.

Full text of DOI:10.1016/j.ica.2015.03.029

Accepted Manuscript
Recognition of Al3+ based on a naphthalene-based “Off-On” chemosensor in
near 100% aqueous media
Jing-can Qin, Zheng-yin Yang, Peng Yang
PII:
S0020-1693(15)00163-2
http://dx.doi.org/10.1016/j.ica.2015.03.029
ICA 16479
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Inorganica Chimica Acta
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27 March 2015
Please cite this article as: J-c. Qin, Z-y. Yang, P. Yang, Recognition of Al3+ based on a naphthalene-based “Off-
On” chemosensor in near 100% aqueous media, Inorganica Chimica Acta (2015), doi: http://dx.doi.org/10.1016/
j.ica.2015.03.029
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Recognition of Al3+ based on a naphthalene-based “Off-On”
chemosensor in near 100% aqueous media
Jing-can Qin，Zheng-yin Yang*，Peng Yang
College of Chemistry and Chemical Engineering, State Key Laboratory of Applied
Organic Chemistry, Lanzhou University, Lanzhou 730000, P.R. China
**Corresponding author. Tel.: +86 931 8913515; Fax: +86 931 8912582; e-mail:
yangzy@lzu.edu.cn (Z.Y. Yang)
Abstract: An efficient fluorescent Al3+ sensor, 2-hydroxy-1-naphthylaldehyde
nicotinoyl hydrazone (HL) has been designed and synthesized. The receptor shows
„„off–on‟‟ fluorescent responses toward Al3+ in near 100% aqueous media. other
relevant metal ions such as Li+, Na+, K+, Ca2+, Mg2+, Cu2+, Co2+, Mn2+, Ni2+, Zn2+,
Ba2+, Fe2+, Cd2+, Hg2+, Pb2+, Sc3+, Fe3+, Cr3+ caused almost no fluorescence
increase.The reason for this phenomenon is that the addition of Al3+ to the solution of
HL induce the formation of a 1:1 stoichiometry of the binding mode of L-Al(III)
which inhibits the excited-state intramolecular proton transfer (ESIPT) and
photoinduced electron transfer (PET). More importantly, the reversibility of the
recognition process of HL was performed by adding a Al3+ bonding agent Na2EDTA.
.Keywords: naphthalene; fluorescence sensor; Al3+; aqueous media; ESIPT/ PET
1. Introduction
The development of selective and sensitive fluorescent sensor for the detection of
metal ions has received more and more attention due to fundamental roles in medicine,
1

living systems and the environment [1-5]. Among metals, aluminium, the most
abundant metal on earth, found in natural waters and most biological tissues is in its
ionic form Al3+ , nevertheless, Al3+ also be potentially toxic, high concentration of Al3+
can hamper plant growth, kill fish and other species in aquatic ecosystems.
More importantly, as a non-essential element for living systems, the superfluous
ingestion of Al3+ is responsible for a serious of diseases, such as Alzheimer's disease,
osteoporosis, etc [6-14]. In 1989, the WHO listed aluminum ion as a source of food
pollution and limited its concentration in drinking water to 200 mg L-1[15]. Therefore,
Owing to the importance of Al3+, it is necessary to develop a fluorescent probe for
detecting the excessive of aluminum ions in the environment.
In recent decades, the reported Al3+-selective fluorescent sensor is becoming
increasingly more common [16-20]. However, most of them worked well in organic
solvents or mixed solvents which are difficult for practical application. The design of
fluorescent sensor in water or in near 100% aqueous media is still a challenge.
Naphthalene with short fluorescence life-time, low fluorescence quantum yield is
extensively suitable to act as an ideal component of a fluorescent chemosensor
[21-23]. Schiff-bases are well known to be good ligands, which provide
nitrogen–oxygen-rich coordination environments as hard-base donor sites [24-25].
Therefore, it can be conceived that 2-hydroxy-1-naphthaldehyde schiff-bases would
develop
a
fluorescent probe
for
detection
of
Al3+
Additionally,
.
2-hydroxy-1-naphthaldehyde schiff-bases are characterised by the existence of the
-OH···N intramolecular hydrogen bond which is a prerequisite for ESIPT process
2

[26-27]. More specifically, the ESIPT process commonly involves the transfer of a
proton donor (–OH, –NH2) to an adjacent proton acceptor (–C=O, –N=) through a
six-membered ring of hydrogen-bonding configuration. In the presence of Al3+, the
proton of the donor will be removed, as a result, the excited-state intramolecular
proton transfer process is inhibited and a significant emission enhancement can be
observed [28-32].
With this in mind, we report a naphthalene-based “Off-On” chemosensor for
distinct detection of Al3+ which was synthesized by 2-hydroxy-1-naphthylaldehyde
and nicotinohydrazide (Scheme 1). The hydroxyl group of HL forms an intra-
molecular hydrogen bond with the adjacent imine bond (–CH=N–), which gives
ESIPT. The hydroxyl and adjacent “hydrazone” groups also provide a strong binding
site to Al3+. Upon addition of Al3+, the sensor displays a large fluorescence
enhancement at 474 nm, which is because that the Al binding turned off the ESIPT
and PET.
2. Experimental
2.1 General information
All chemicals were obtained from commercial suppliers and used without further
purification. JNM-ECS400 instruments using TMS as an internal standard, Bruker
esquire 6000 ESI-MS spectrometer, Perkin Elmer Lambda 35 UV-Vis
spectrophotometer. Hitachi RF-5301 spectrophotometer equipped with quartz cell of 1
cm path length, Beijing XT4-100x microscopic melting point apparatus were also
3

used for the characterization of novel compound.
2.1 Synthesis
2.2.1. Synthesis of 2-hydroxy-1-naphthaldehyde [33]
A mixture of 2-naphthol (10.5g, 73 mmol) and Hexamethylenetetramine (12g, 86
mmol) was dissolved in 20 ml of Acetic acid and stirred and heated for 1h at
50~60°C.Then rising the temperature to 90°C, H2SO4 (98%, 9 ml) was added
dropwise by dropping funnel within 30 min. Upon completion, the reaction mixture
was heated to 96°C and stirred for additional 6h, and then cooled to room temperature
pouring into 100 ml H2O. The crude product was filtered and washed to pH 7 with
cold water. The final product was recrystallized from ethanol to afford 2 as a yellow
solid and allowed to vacuum drying in low temperature. Yield: 55%, Mp: 79-80°C.
1HNMR (400 MHz; CDCl3) (Fig.S1) δ (ppm) = 13.1(s, 1H), 10.83(s, 1H), 8.36(d, 1H),
7.99(d, 1H), 7.81(d, 1H), 7.63(m, 1H,), 7.45(m, 1H), 7.15(d, 1H).
2.2.2. Synthesis of HL
An ethanol solution ( 20 mL) of nicotinohydrazide (0.274g, 2mmol) was added
to another ethanol (20 mL) containing 2-hydroxy-1-naphthaldehyde (0.344g，2 mmol).
Then the solution was refluxing for 10 h under stirring. After cooling to room
temperature, the mixture was filtered, washed 3 times with EtOH (3×10mL) and the
final product was filtered, dried and recrystallized from ethanol and DMF to give the
final product as yellow powder , Yield: 83%, Mp: 257-258°C. 1HNMR (400 MHz;
DMSO-d6) (Fig.S2) δ (ppm) = 12.51(s, 1H), 12.22 (s, 1H), 9.43 (s, 1H), 9.11 (s, 1H),
8.76 (d, J=3.5 Hz 1H), 8.28 (d, J=7.6 Hz 1H), 8.24 (d, J=8.6 Hz 1H), 7.85~7.91 (m,
4

2H,), 7.56~7.61 (m, 2H,), 7.38 (t, J=7.5 Hz 1H), 7.20 (d, J=8.9 Hz 1H). ESI-MS
(Fig.S3): [M+1]+: 292.10. [M+Na]+: 314.08. IR (KBr, cm-1): (Fig.S4): 3217, 1691,
1596.
3. Results and discussion
3.1. Analysis
Stock solutions of various metal ions (10 mM) were prepared using nitrate salts.
A stock solution of HL (2 mM) was prepared in DMF. Tris-HCl buffer stock solution
prepared using 10 mM, 10 mM Tris and proper amount of HCl, The solution of HL
was then diluted to 100 times in aqueous media (Tris-HCl, pH = 7.2). In experiments,
each time a 2 mL solution of HL (20 μL) was filled in the quartz optical cell of 1 cm
optical path length, and the ions stock solution were added into the quartz optical cell
gradually by using a pipette. Both the excitation and emission slit widths were 3 nm.
3.2. UV-vis titration
The chelating ability of HL with Al3+ was initially investigated by UV-Vis
analysis in aqueous media (Tris-HCl, pH = 7.2). The changes in the absorption spectra
of HL as a function of the concentration of Al3+ were shown in Fig. 1. In the absence
of Al3+, the receptor exhibited characteristic absorption bands at 317nm and 362 nm
which should be assigned to π→π* transitions of naphthalene ring [34-36]. Upon
addition of Al3+ to aqueous solution of HL, the absorption bands at 317 nm and 362
gradually decreased while two new absorption bands appeared at 340 nm and 409 nm
with increasing intensity. Moreover, two clear isosbestic points at 347 nm and 380 nm
were observed, which clearly indicated the presence of new complex in equilibrium
5

with the receptor. All of these might be attributed to the binding mode of HL with Al3+
which was further confirmed by ESI-MS, 1HNMR titration, Job‟s plot analysis.
3.3. Selectivity studies and effects of metal ions
The selectivity of HL was investigated upon addition of several metal ions such
as Li+, Na+, K+, Ca2+, Mg2+, Cu2+, Co2+, Mn2+, Ni2+, Zn2+, Ba2+, Fe2+, Cd2+, Hg2+, Pb2+,
Sc3+, Fe3+, Cr3+ and Al3+ in aqueous media (Tris-HCl, pH = 7.2). As shown in Fig.
2, the free sensor showed no fluorescence emission at 474 nm when it was excited at
409 nm. Upon the addition of Al3+, the sensor showed a large fluorescence
enhancement. This was because that the addition of Al3+ resulted in breaking
intra-molecular hydrogen bond (OH····N) with the imine-nitrogen and the
deprotonation of the naphthol hydroxyl, thus inhibiting excited state intramolecular
proton transfer [28], [31-33], [37]. In addition, part of the reason was attributed to the
chelation of the nitrogen atom of the –C=N group with Al3+, which induced the
efficient inhibition for the PET process of the –C=N group [38-39] (Scheme 2). In
contrast, addition of other relevant metal ions caused almost no fluorescence increase,
which indicated HL was a highly selective fluorescent sensor for Al3+.
3.4. The practical applicability of HL
To check the practical applicability of HL as a selective fluorescent sensor for
Al3+, it was necessary to carry out the competition experiment and the reversible
experiment in aqueous media (Tris-HCl, pH = 7.2). In competition experiment, the
systems of other metal ions and Al3+ coexisted were examined in aqueous media. As
shown in Fig. 3, the receptor HL was treated with 5.0 equiv of Al3+ in the presence of
6

other metal ions. We found that all the coexistent metal ions had no obvious
interference with the detection of Al3+ except in the case of Cu2+, which were
attributed to their inherent to the magnetic property [40-41]. Reversibility is also a
prerequisite in developing novel chemosensors for practical application, the
reversibility of recognition of Al3+ was performed by adding Na2EDTA which is a
good sequesterant in aqueous media (Tris-HCl, pH = 7.2). As shown in Fig. 4, the
sensor displayed significant fluorescence enhancement at 474 nm in the presence of
Al3+, the addition of Na2EDTA to a mixture of HL and Al3+ resulted in diminution of
the fluorescence intensity at 474 nm, which indicated the regeneration of the free
receptor HL, then keep adding HL, the fluorescence intensity recovered again.
Therefore, it means that the receptor HL can be used as a selective fluorescent sensor
for detection and recognition of Al3+ in many fields.
In addition, the detection limit was also calculated based on the fluorescence
titration (Fig. 5). As shown in Fig. S5, according to the following equation: detection
limit: 3σ/K, the detection limit reached at 4×10-6 m. Where σ was the standard
deviation of blank measurements, and K was the slope between intensity versus
sample concentration [42].
3.5. The complexation of HL with Al3+
In order to validate the conjugation of L-Al, we carried out Job‟s plot in aqueous
media (Tris-HCl, pH = 7.2). The total concentration of HL and Al3+ was 100 μM. XAl=
([Al3+]/ (Al3+] + [HL]. As shown in Fig. 6, the maximum point appeared at a mole
7

fraction of 0.5. The result has indicated that it was a 1:1 stoichiometry of the binding
mode of HL and Al3+ which is further confirmed by the appearance of a peak at m/z
334.06 assignable to [HL+H2O+Al3+-2H]+ and a peak at m/z 374.08, assignable to
[HL+ 2H2O +Al3+-3H+Na]+ in the ESI/MS (Fig. S6). Since the formation of a 1: 1
ligand-metal complex was confirmed by Job‟s plot analysis and ESI/MS, in
combination with the fluorescence titration, the binding constant of HL with Al3+ also
could be estimated using the Benesi–Hildebrand equation (A) [43],
where F0, Fx, and Fmax were the emission intensities (at 474 nm) of the organic moiety
considered in the absence of metal ion, at an intermediate metal ion concentration,
and at a concentration of complete interaction, respectively, and where Ka is the
binding constant concentration, namely: KL-Al = 4×103 (Fig.S7)
To better understand the binding behavior of receptor HL with Al3+,
1
it is necessary to HNMR titration besides the above experiments. The spectral
differences were depicted in Fig. 7. In the absence of Al3+, the spectra showed two
singlets at 12.51 ppm (Ha) and 12.22 ppm (Hd) corresponding to phenolic -OH and
-NH, respectively. The peak at 9.11 ppm (Hc) was assigned to -CH=N of HL. In the
1H NMR of the neutral HL, the normal signal was located at about 10 ppm, the signal
for –OH was obtained at a down field due to possibility of the formation of
intramolecular hydrogen bonding with azomethine nitrogen which has been reported
by related article [44-45]. In addition, the receptor did not show any peak attributed to
enolic –OH proton indicating that they exist in keto forms. Upon complexation with
8

Al3+ ions, the proton peak of the phenolic hydroxyl (Ha) at 12.51 ppm disappeared,
the proton signal of the imine (Hd) downfield shifted by 0.22 ppm. A new broad signal
appeared at 9.44 ppm, which was assigned to the imine-nitrogen of L-Al.
Compared with the signal at 7.22 ppm (Hb), a new signal which appeared in the
presence of Al3+ at 7.03 ppm upfield shifted by 0.19 ppm owing to the interaction HL
with Al3+. The results suggested that HL may chelate Al3+ through interactions with
carboxylate oxygen, imine nitrogen and oxygen of naphthol hydroxyl group. The
large differences of the IR spectra of the sensor (Fig.S8) in the absence and presence
of Al3+ indicate further proved the combination of between the sensor and Al3+ as
shown Table 1.
4. Conclusion
In summary, a highly selective and sensitive fluorescent sensor based on
naphthalene derivative for Al3+ has been has been developed. The sensor shows great
fluorescence turn-on upon binding Al3+ which inhibits ESIPT and PET. More
importantly, because of lower detection limit in aqueous solution, the chemosensor
may find potential applications to detect micromolar concentrations of Al3+ in both
biological systems and the environment.
Acknowledgments
This work is supported by the National Natural Science Foundation of China
(81171337, J1103307). Gansu NSF (1308RJZA115).
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Figure captions
Fig.1. Changes in the absorption spectra of HL (20 μM) in near 100% aqueous media
(Tris-HCl, pH = 7.2).at room temperature upon addition of different amounts of Al3+
ions (0- 5 equiv.).
Fig.2. Fluorescence spectra of HL (20 μM) upon the addition of metal salts (5 equiv.)
of Li+, Na+, K+, Ca2+, Mg2+, Cu2+, Co2+, Mn2+, Ni2+, Zn2+, Ba2+, Fe2+, Cd2+, Hg2+, Pb2+,
Sc3+, Fe3+, Cr3+ and Al3+ in near 100% aqueous media (Tris-HCl, pH = 7.2).Excitation
wavelength was 407 nm, slit = 3nm / 3nm.
Fig.3. Fluorescence intensity of HL and its complexation with Al3+ in the presence of
various metal ions in near 100% aqueous media (Tris-HCl, pH = 7.2). Red bar: HL
(20.0 μM) and HL with 5 equiv. of Li+, Na+, K+, Ca2+, Mg2+, Cu2+, Co2+, Mn2+, Ni2+,
Zn2+, Ba2+, Fe2+, Cd2+, Hg2+, Pb2+, Cr3+, and Sc3+ stated. Green bar: 20.0 μM of HL
and 5 equiv. of Al3+ with 5 equiv. of metal ions stated (λex = 407 nm, slit = 3nm /
3nm.).
Fig.4. the reversibility of recognition of Al3+ was performed by adding Na2EDTA in
near 100% aqueous media (Tris-HCl, pH = 7.2). Black: HL, Blue: HL+Al3+, Green:
HL+Al3++ Na2EDTA, Red: HL+Al3++ Na2EDTA+HL, (Ex =407nm, slit = 3nm /
3nm).
Fig.5. Fluorescence spectra of HL (20 μM) in near 100% aqueous media (Tris-HCl,
pH = 7.2), upon the addition of Al3+ (0-8equiv.) Inset: color of HL and HL+Al3+
system under UV lamp.
14

Fig.6. Job‟s plot for determining the stoichiometry of HL and Al3+ in near 100%
aqueous media (Tris-HCl, pH = 7.2) (XAl=[Al3+]/([Al3+] + [HL]), the total
concentration of HL and Al3+ was 100 μM).
1
Fig.7. HNMR spectra of HL with Al(NO3)39H2O in DMSO-d6: (I) HL; (II) HL with
1.0 eq. of Al3+ ; (III) HL with 2 eq. of Al3+ .
Table 1 Major IR data of the receptor and its complexe.
Scheme1 Synthesis of HL
Scheme 2 Proposed mechanism for detection of Al3+ by HL.
.
15

Fig.1. Changes in the absorption spectra of HL (20 μM) in near 100% aqueous media
(Tris-HCl, pH = 7.2).at room temperature upon addition of different amounts of Al3+
ions (0- 5 equiv.).
16

Fig.2. Fluorescence spectra of HL (20 μM) upon the addition of metal salts (5 equiv.)
of Li+, Na+, K+, Ca2+, Mg2+, Cu2+, Co2+, Mn2+, Ni2+, Zn2+, Ba2+, Fe2+, Cd2+, Hg2+, Pb2+,
Fe3+, Sc3+, Cr3+, and Al3+ in near 100% aqueous media (Tris-HCl, pH =
7.2).Excitation wavelength was 407 nm, slit = 3nm / 3nm.
17

Fig.3. Fluorescence intensity of HL and its complexation with Al3+ in the presence of
various metal ions in near 100% aqueous media (Tris-HCl, pH = 7.2). Red bar: HL
(20.0 μM) and HL with 5 equiv. of Li+, Na+, K+, Ca2+, Mg2+, Cu2+, Co2+, Mn2+, Ni2+,
Zn2+, Ba2+, Fe2+, Cd2+, Hg2+, Pb2+, Cr3+, and Sc3+ stated. Green bar: 20.0 μM of HL
and 5 equiv. of Al3+ with 5 equiv. of metal ions stated (λex = 407 nm, slit = 3nm /
3nm.).
18

Fig.4. the reversibility of recognition of Al3+ was performed by adding Na2EDTA in
near 100% aqueous media (Tris-HCl, pH = 7.2). Black: HL, Blue: HL+Al3+, Green:
HL+Al3++ Na2EDTA, Red: HL+Al3++ Na2EDTA+HL, (Ex =407nm, slit = 3nm /
3nm).
19

Fig.5. Fluorescence spectra of HL (20 μM) in near 100% aqueous media (Tris-HCl,
pH = 7.2), upon the addition of Al3+ (0-8equiv.) Inset: color of HL and HL+Al3+
system under UV lamp.
20

Fig.6. Job‟s plot for determining the stoichiometry of HL and Al3+ in near 100%
aqueous media (Tris-HCl, pH = 7.2) (XAl=[Al3+]/([Al3+] + [HL]), the total
concentration of HL and Al3+ was 100 μM)
21

1
Fig.7. HNMR spectra of HL with Al(NO3)39H2O in DMSO-d6: (I) HL; (II) HL with
1.0 eq. of Al3+ ; (III) HL with 2 eq. of Al3+ .
22

Table 1 Major IR data of the receptor and its complexe.
23

Scheme1 Synthesis of HL
24

Scheme 2 Proposed mechanism for detection of Al3+ by HL.
25

Compound ν(naphthalene-OH) cm-1 ν(benzoyl-C=O) cm-1
ν(-C=N) cm-1
ν (M–O) cm-1
HL
3217
weak
__
1691
1620
71
1596
1544
52
___
582
___
L-Al
∆ν(cm-1)

Highlights
1. The sensor shows ‘‘off–on’’ fluorescent responses toward Al3+ in aqueous media.
2. The detection limit reached at 10-6 m in near 100% aqueous media.
3. The sensing mechanism is attributed to ESIPT and PET.

The sensor shows ‘‘turn–on’’ fluorescent responses toward Al3+ in near 100%
aqueous media. The reason for this phenomenon is that the addition of Al3+ to the
solution of HL result in the formation of a 1:1 stoichiometry of the binding mode of
L-Al which inhibits the excited-state intramolecular proton transfer (ESIPT) and
photoinduced electron transfer (PET).