Sensors and Actuators B 257 (2018) 545–552
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Sensors and Actuators B: Chemical
jo ur nal home page: www.elsevier.com/locate/snb
Research Paper
A visible light excitable chromone appended hydrazide chemosensor
for sequential sensing of Al
+3
and F
−
in aqueous medium and in Vero
cells
Rakesh Purkait
a
, Chiranjit Patra
a
, Ananya Das Mahapatra
b
, Debprasad Chattopadhyay
b
,
Chittaranjan Sinha
a,∗
a
Department of Chemistry, Jadavpur University, Kolkata 700 032, India
b
ICMR Virus Unit, Infectious Diseases & Beliaghata General Hospital, GB-4, 57,S. C. Bannerjee Road, Beliaghata, Kolkata − 700 010, India
a r t i c l e i n f o
Article history:
Received 13 May 2017
Received in revised form 27 October 2017
Accepted 28 October 2017
Keywords:
Chromone-hydrazide
Al
+3
sensor
Quenching with F
−
Cell imaging
DFT computation
a b s t r a c t
A probe, quinoline-2-carboxylic acid (4-oxo-4H-chromen-3-ylmethylene)-hydrazide, (HL), acts as selec-
tive and specific fluorogenic sensor to Al
+3
in the visible light (435 nm) excitation in presence of
biologically available large number of cations and emission appears at (
em
) 520 nm. The limit of
detection (LOD) for Al
+3
is 7.6 nM in aqueous medium which is less than 10
−3
times of WHO recom-
mended data (7.41 mM). The Job’s plot and mass spectral data support 1:1 composition of the complex
[Al(HL)(OH)H
2
O](NO
3
)
2
. The strongly emissive complex turns off upon addition of F
−
and is detected at
the level of (LOD) 7.4 nM. Thus, F
−
, a harmful water pollutant, could be identified at much lower level
of WHO recommended toxic limit (3.68 M). The absorption and emission spectral features of HL and
its Al
+3
-complex have been explained by DFT computation of optimized geometries and calculation of
molecular functions. The devised receptor is non-toxic and has been used in detecting Al
+3
in the intra-
cellular region of African green monkey kidney cells (Vero cells) and exhibits an INHIBIT logic gate with
Al
+3
and F
−
as chemical inputs by monitoring the emission mode at 520 nm.
© 2017 Elsevier B.V. All rights reserved.
1. Introduction
Aluminium, a non-essential element and significantly avail-
able on the earth’s crust (8.3% of total mass), is useful in the
manufacturing of household utensils, water purification instru-
ments, electrical wirings, and is entering into human body through
foods and beverages [1]. It causes Al-related bone disease (ARBD),
encephalopathy, myopathy and various neurodegenerative dis-
eases such as, Alzheimer’s disease, Parkinsonism dementia etc. in
human body and can also damage plant roots [2–5]. World Health
Organization (WHO) has assigned Al
+3
as prime food pollutants
with limiting concentration 200 g/litre (7.41 mM) and has recom-
mended that tolerable weekly dietary human intake is 7.0 mg/kg
body weight [6–8]. Thus detection of Al
+3
in water is of urgent
important for monitoring human health. Exploration of selective
and sensitive chemosensor for detection of ions in solution has
been of considerable attention with biological and environmen-
∗
Corresponding author.
E-mail addresses: debprasadc@gmail.com (D. Chattopadhyay),
crsjuchem@gmail.com (C. Sinha).
tal interest [9–14]. Schiff base ligands have gained recent interest
as fluorescent sensors for metal ions including Al
+3
due to their
relatively easy one step synthesis [15–24]. However, sensing of
aluminum in aqueous medium have been rarely reported [25,26],
mainly due to sparing or insolubility of organic probe in aqueous
media. Therefore it is a challenging task today to develop new sen-
sors for selectively detecting Al
+3
in aqueous solutions.
Besides, emissive Al
+3
-complexes are serving as anion sensor,
especially to F
−
[27–30]
.
Among the entire range of biologically
useful anions, F
−
possesses significant potential in the prevention
of dental caries and treatment for osteoporosis [31,32]. Conversely
presence of excess of fluoride in the human body may be dumped
as fluorapatite in the bones and teeth leading to osteoporosis,
osteosclerosis, dental fluorosis and skeletal fluorosis [33–35]. Thus,
it is quite important to develop an efficient F
−
sensor. The design
of dual sensor which is capable to detect sequentially Al
+3
and
F
−
by fluorescence ON OFF signaling response is highly effec-
tive. Recently, coumarin based molecular switch for the sequential
detection of Al
+3
followed by its use for F
−
sensing is reported
[27,28]. Besides, rhodamine based [29] and quinaldine appended
[30] chemosensors are also available for the detection of Al
+3
and
https://doi.org/10.1016/j.snb.2017.10.168
0925-4005/© 2017 Elsevier B.V. All rights reserved.