SELECTIVE FLUOROGENIC SENSING BEHAVIOUR OF CURCUMIN

FOR SELENATE AND SELENITE IONS IN AQUEOUS SOLUTION

Rabindra Kumara, Gagandeep Kaura, Meenu Arorab, A. K. Jainb and J. N. Babua*
a

Centre for Environmental Science and Technology, Central University of Punjab, Mansa Road,
Bathinda 151 001, INDIA
d

Department of Chemistry, Multani Mal Modi College, Patiala 153 001, INDIA

Centre for Chemical Science, Central University of Punjab, Mansa Road, Bathinda 151 001,
INDIA
*Corresponding Author E-mail ID: nagendra.rd@gmail.com
Phone: +91-164-2368137

Highlights
1. Phenol based anion sensing for fluorogenic detection of selenate and selenite ion in
aqueous media.
2. Anion complexation induced selective emission enhancement of curcumin at pH 10.8.
3. Solvent mediated proton transfer essential for anion complexation by curcumin at pH
10.8.

Graphical Abstract

Abstract
Curcumin (L) is studied for its binding affinity towards different anions such as HPO 42-, H2PO4-,
OAc-, F-, Cl-, Br-, I-, NO3-, SO42-, AsO43-, AsO23-, SeO32- and SeO42- by UV-Vis and fluorescence
spectroscopy in (10% v/v) aqueous methanol maintained at pH 10.8. UV-Vis studies of curcumin
showed selective ratiometric response (A265/A440), upon complexation of selenate or selenite ions.
Fluorescence titrations of curcumin showed 4 and 3.2 fold fluorescence enhancement in emission
at 580 nm, with 1 equiv. of selenate and selenite ions, respectively. The selective fluorescence
enhancement is attributed to significant loss of excited state hydrogen/proton transfer process
and a significant proton donation by the methanol, upon complexation of selenate/selenite ion by
curcumin. The Jobs plot characterized complexation stoichiometry was found to be 1:2
(anion:curcumin). The limit of detection for selenate and selenite were determined to be 10 and
12 nM, respectively.
Keywords: Selenium, curcumin, fluorescence, absorbance, EHPT/ESPT
1. Introduction
Selenium is an essential micronutrient at low concentrations in various life forms including
humans, but show toxicity at elevated concentrations (Reilly, 2006; Fleming, 1980). It has found
application in commodities used in daily life like vulcanizing additive for rubber (Onan, 1998),
photoelectric devices (Manasevit et al., 1969), batteries, glasses colorants, insecticides/antidandruff (Monterio et al., 2009; Salvador et al. 2000F), skin disease treatment (Chan et al.,
1998), photosensitive drums and catalyst in urea/urethane synthesis (Mizuna et al., 2000). [1,2].
Selenium is widely dispersed in igneous rocks (Koljonen, 1973) and hydrothermal deposits of
Au, Sb, Hg and Ag (Tamari et al., 1990). Apart from this, it finds its way into our environment

from anthropogenic sources like sulphuric acid plants, ore processing waste, thermal plants, oil
refineries and agricultural drainage (Mason et al., 2000; Rosenfeld & Beath, 2013) [5,6].
Selenium exists in four oxidation states such as elemental (Se 0), selenide (Se2), selenite (SeO32,
Se(IV)) and selenate (SeO42, Se(VI)) [Sindeeva, 1964, 8]. However in aqueous environment,
selenite and selenate ions are the most abundant forms of selenium, whereby Se(IV) is more
toxic than Se(VI) [Graham, 1991, 9]. A high daily intake of selenium in the human diet is
directly associated with dermatitis, fatigue, chronic gastrointestinal disease, irritation of skin and
eyes and losing hair & nails [2]. Chronic exposure is also associated with liver, pancreas, heart,
kidney problems and increased risk of cancer [1]. Thus, World Health Organization (WHO) and
United State Environmental Protection Agency (USEPA) have prescribed maximum permissible
limit of 10 g/L [10] and 50 g/L [11], in potable water, respectively.
Various techniques are available for selenium analysis in water including Hydride Generator
(HG) coupled with atomic fluorescence (Ref.), Atomic absorption and Inductive Coupled Plasma
mass spectrometry (Ref.), gas chromatography (GC) (Ref.) and HPLC/ion chromatography
(Ref.), Neutron Activation analysis and cathodic stripping voltammetry (CSV) (Kot &
Namiesnik, 2000; Bednar et al., 2009; Cooke & Bruland, 1987)[4-10]. These methods are time
consuming, costly, cumbersome, require trained manpower and lack real-time monitoring for
operation (ref). Alternatively, fluorescence methods are one of the selective, sensitive, cost and
time efficient method for analysis in real-time monitoring used in environment, medicines and
in-vitro / in-vivo monitoring (Demchenko, 2008; Sahana et al., 2011). One of the methods for
selective analysis of selenium is based on the dosimetric fluorogenic sensing using 1,2diaminonapthalene (DAN) and its derivatives (Martinez, 2013). Apart from this host-guest
complexation induced fluorogenic sensing of selenium has been reported recently (Ref.).

However, this sensing behavior is attributed to the binding of selenium as either as a cation or
anion is not clearly understood.
Host-guest recognition based equilibrium approach have been recently explored to show
fluorogenic sensing of selenium with LOD upto ---- [Song, Cairui, ; Feng, Guodong]. The other
approach for selenium sensing involves the anion recognition(Evans, Nicholas H) and the basic
design of the anion receptor comprise of either a positively charged receptors carrying
ammonium[ref], imidazolium[Yoon, J.; Kim, S. K.; Singh, N. J.; Kim, K. S. Chem. Soc. Rev.
2006, 35, 355 Sensors and Acuators B (2013), 185, 188-194], pyridinium[ref] and guanidinium
[ref] functional groups and hydrogen bond donor moieties like amide[Spectrochimica Acta, Part
A: Molecular and Biomolecular Spectroscopy (2014), 121, 662-669 Chem. Soc. Rev. 42 (2013),
1652-1666 Tetrahedron Letters (2012), 53, 4819-4823, Chem. Soc. Review (2013), 240, Amide
based receptors for anions], urea/thiourea [Coordination Chemistry Reviews (2015), 295, 80124, Tetrahedron Letters (2014), 55(34), 4810-4813, ref], Benzimidazole (Singh, N., & Jang, D.
O. (2007). Benzimidazole-based tripodal receptor: highly selective fluorescent chemosensor for
iodide in aqueous solution. Organic letters, 9(10), 1991-1994. Journal of Organometallic
Chemistry (2014), 770, 85-93.); pyrrole [Sensors and Actuators, B: Chemical (2016), 225, 428435, Tetrahedron (2013), 69(6), 1725-1734.ref] and phenol [Spectrochimica Acta, Part A:
Molecular and Biomolecular Spectroscopy (2014), 121, 306-312.]. Naturally tyrosine is an
essential functional moiety for binding of anion (chloride) in the chloride channels and
halorhodopsin [[11] R. Dutzler, E.B. Campbell, R. MacKinnon, Science 300 (2003) 108112.
[12] R. Dutzler, E. Campbell, M. Cadene, B. Chait, R. MacKinnon, Nature 415 (2002) 287294.
[13] M. Kolbe, H. Besir, L.O. Essen, D. Oesterhelt, Science 288 (2000) 13901396. [14] M.T.
Facciotti, V.S. Cheung, C.S. Lunde, S. Rouhani, N.S. Baliga, R.M. Glaeser, Biochemistry 43

(2004) 49344943]. Thus, phenols play a vital role in anion recognition and various chromogenic
receptors are reported in protic as well as aprotic solvents[Spectrochimica Acta, Part A:
Molecular and Biomolecular Spectroscopy (2015), 150, 814-820 Journal of Molecular Structure
(2015), 1094, 148-160, European Journal of Organic Chemistry (2014), 2014(22), 4759-4766].
One of present authors studied the chromogenic anion sensing behavior of azophenol derivative
of thiacalix[4]arene, whereby an unusual complexation induced extended conjugation was
observed upon complexation of fluoride, hydrogenphosphate and acetate ion (Kumar, Manoj, J.
Nagendra Babu, and Vandana Bhalla. "Azophenol appended (thia) calix [4] arenes for
colorimetric sensing of anions: A complexation induced extended conjugation." Talanta 81, no. 1
(2010): 9-14.). Awual et al. 2015 studied a colorimetric phenol sensor cum adsorbent based on
N,N-di(3-carboxysalicylidene)-3,4-diamino-5-hydroxypyrazole immobilized mesoporous silica
monolith for sensing/adsorption of selenite ion with a limit of detection 1.14gL-1 (ref).

Scheme 1: Keto-enol tautomerism of curcumin

Polyphenolic natural product, Curcumin (L), was studied for selective colorimetric and
fluorogenic sensing of fluoride ion as tetrabutylammonium salt (TBA) in non-aqueous solvent
over other anions such as AcO-, H2PO4- and Cl- ion(Wu et al., 2009). Curcumin (L) consists of
two methoxyphenols attached symmetrically through , -unsaturated -diketone linker, which
leads to ketoenol tautomerism[JNP, 2007, 143-146] (Scheme 1). Due to this characteristic
phenomenon, it exhibits interesting photophysical and photochemical properties [JPPCPR, 2009,
10, 81-95] and metal complexing ability (Wanninger, S., Lorenz, V., Subhan, A., & Edelmann, F.

T. (2015). Metal complexes of curcumin - synthetic strategies, structures and medicinal

applications. Chemical Society Reviews, 44(15), 4986-5002. doi: 10.1039/C5CS00088B). The
present study investigates the use of curcumin in buffered aqueous conditions for the selective
fluorogenic sensing of selenate and selenite ions.
2. Experimental
2.1 Material
Curcumin, 2-Aminophenol, Sodium monohydrogen phosphate (Na2HPO4), sodium dihydrogen
phosphate (NaH2PO4), Sodium nitrate(NaNO3), Sodium arsenate (Na2AsO4), Sodium arsenite
(NaAsO2), Sodium selenate (Na2SeO4), Sodium selenite (Na2SeO3), Sodium acetate
(CH3COONa), Sodium fluoride (NaF), Sodium chloride (NaCl), Sodium bromide (NaBr),
Sodium iodide (NaI), Sodium sulphate (Na2SO4), Methanol (CH3OH) were of analytical or
gravimetric reagent grade. Solutions were prepared in laboratory using distilled water (<18
conductivity) RIONS INDIA RO system (Model No. Basic 360 series).
2.2 Spectroscopic measurements
Absorbance studies were done on PC based UV-1800 Shimadzu spectrophotometer using 1 ml
quartz cuvettes quartz, with the help of UV probe 2.43 software in the spectrum mode.
Florescence studies were carried out on a PC based Synergy H1 Microplate reader with the help
of Gen 5 software using biotek biocell plate and 1mL quartz cuvettes because of its high
sensitivity and narrower spectrum in the fluorescence wavelength range 300-700nm. The
samples were excited at their respective absorption maxima.
2.3 Preparation of analytical sample
10M solution of the anion receptor was prepared in 100ml methanol by dissolving 4.59mg of
the anion receptor. Similarly solutions of the anion receptor were prepared in acetonitrile,

DMSO, 10% v/v of water in methanol, 10% v/v of water in acetonitrile and 10% v/v of water in
THF.
2.4 Preparation of anion solutions
0.01M solutions of the anion solutions were prepared in distilled water using sodium salts of
mono hydrogen phosphate, dihydrogen phosphate, arsenate, arsenite, selenate, selenite, acetate,
flouride, chloride, bromide, iodide, sulphate. From the stock solutions, 1ml of the 100M
working solutions of the anions were prepared and used for fluorescence and absorbance studies.

2.5 UV-Visible Titrations

2.6 Fluorescence Titrations

3. Results and discussion

3.1 UV-Vis Studies
Curcumin (L) is a phenolic bioactive component of turmeric (Curcuma longa), a perennial plant
of the ginger family (Zingiberaceae), native to tropical South Asia. To evaluate the binding
ability of curcumin towards different anions, UVVis experiments were carried out in
H2O:CH3OH (9:1, v/v) with pH maintained at 2-12 using various buffers. The UV-Visible
absorption spectra of curcumin at different pH is shown in Fig. 1. The absorption spectrum of
curcumin is characterized by the presence of absorption maximum peak at 347 and 439 nm at pH
2, which corresponds to the electronic dipole allowed -* and intramolecular charge transfer
transition, respectively (Ref. J. Fluorescence 2010, 20, 843-850, Zsila, et al. Biochem Biphys.
Res Communication 2003, 776-782). The observed peak at 435 nm is characterized by a small

blue shift from 425 nm in water by 10 nm, accounted to the presence of methanol in polar
environment of the mixed solvent [Spectrochimica Acta A 2004, 60, 1091-97].

Figure 1: Effect of pH (2-12) on the characteristic UV-Vis absorption behavior of Curcumin in

10% (v/v) aqueous methanol.
At pH 8, a new absorption peak at 265 nm is observed characteristic of curcumin in basic media.
However, the intense absorption band observed at 435 nm showed a hyperchromic red shift to
440 nm at pH 12 with significant broadening. The decrease in absorption at 365 nm upon
increase in pH of the solution, is accounted to proton driven intramolecular charge transfer.
Whereas, the blue shift in the absorption band at 425 nm upon increase in the pH of the solution
could be accounted to the stepwise deprotonation of curcumin (Figure 2). The deprotonation of
curcumin leads to the liberation of curuminate, which is characterized by intense charge transfer
spectra at 440 nm [Zhao et al. NPC 2008, 229-232]. The new absorption band at 265 nm in basic
pH is characteristic of the phenolic moiety of curcumin [New J Chem 2014, 38, 1336-1345]. The
absorption band due to the phenolic moiety is observed to decrease further upon increasing the

pH upto 12 due to the formation phenolate ions, which supports the blue shift in curcumin charge
transfer spectra upto 440 nm.

Scheme 2: Protoptropic equilibria of Curcumin (Priyadarshini. 2009)

Curcumin solutions (1 106 M) in 10%(v/v) aqueous methanol maintained at pH 10.8, were
added 1 equiv. of representative anions like arsenate, arsenite, fluoride, chloride, bromide,
iodide, acetate, selenate, selenite, nitrate, monohydrogenphosphate, dihydrogenphosphate and
sulphate as their sodium salts. In the absence of these anions, the absorption spectrum of
curcumin was characterized by the presence of one absorption maximum peak at 440 nm (Fig.
2). The UVvis absorption band at 440 nm showed a significant decrease in the absorption
intensity upon addition of 1 equivalent of selenate/selenite ion. Curcumin showed no change in
UV-Vis

spectra

upon

addition

of

fluoride,

chloride,

bromide,

iodide,

acetate,

dihydrogenphosphate, nitrate and hydrogensulphate. However, in presence of 1 equiv. of arsenite

and arsenate there was a decrease in the UV-Vis absorption band at 4 nm. Thus, a selective
interaction between curcumin and selenite/selenite ions is evident at pH 10.8.

Figure :

Further, the binding abilities of curcumin towards Selenate and Selenite ions were investigated
by carrying out UVVis titrations. Upon addition of increasing amount of Selenate ions (01
mM) to the solution of curcumin in 10%(v/v) aqueous methanol maintained at pH 10.8, the
absorption band at 440 nm decreases in intensity, while a new peak at shorter wavelength 265
nm appeared (Fig. 2) with an isosbestic point at 303 nm. The formation of the new absorption
band at 265 nm is characteristic of phenol moiety of curcumin. This reemergence of the
absorption band due to phenol upon addition of selenate ions, is accounted to the selective
coordination driven protonation of the phenolate in basic medium upon complexation of selenate
ions. The absorbance of the characteristic bands of complexed form to uncomplexed form of
curcumin (A265/ A440) was 0.41 which increases 2.5 fold to 1.02 (Inset of Fig. 2) with addition of
1 mM (1.0 equiv) of selenate ion. Thus, UVVis behavior of curcumin showed ratiometric
behaviour upon complexation of Selenate ions by curcumin. This characteristic ratiometric
behavior was also observed upon addition of selenite ions (0-1 equiv.) to a 10% aq. Methanol
solution of curcumin maintained at pH 10.8 as given in Figure 1.

Figure 2: Absorption spectra of curcumin (1x10-6 M) in MeOH: H2O (1:9 v/v) at pH 10.8 upon
absorbance titrations with (a) selenate (b) selenite. Inset showing the ratiometric response at 265
nm and 440 nm as a function of Selenate concentration.
3.2 Fluorescence Study
Curcumin exhibited a characteristic week emission at 580 nm upon excitation at 420 nm in 10%
(v/v) aqueous methanol maintained at pH 10.8. This emission at 580 nm is attributed to locally
excited lowest (*) state in 10% (v/v) aqueous methanol solution at pH 10.8 [Patra d.,
barakat, 2011, spectrochem acta part a 79, 1034-1041]. The emission is characterized by a
large stokes shift, as reported by et al. for curcumin in protic solvents, whereby intermolecular
hydrogen bonding between the curcuminate ions, may induce change in the conformations and
thereby increasing the out of plane vibrations(Wu et al., 2009). The weak fluorescence of
curcumin in 10% (v/v) aqueous methanol maintained at pH 10.8, is attributed either to the
formation of non-fluorescent and stable charge-transfer complex of the type curcumin .- H2O+

(Bong P.H. Bull. Kor. Chem. Soc. 2000, 21, 81-86) or to the presence of Excited State proton
transfer (ESPT) mechanism existing between the curcuminate ion and the binary solvent
water/methanol (Journal of Physical Chemistry A 2012, 116, 2039-2048).

Figure 4: Emission spectra of curcumin (1M) in presence of various anions in MeOH:H 2O (9:1
v/v) under buffer conditions (g) Na2HPO4/NaOH buffer pH 10.81 (h) Na2HPO4/NaOH buffer pH
11.3.
Upon addition of 1 equivalent of Selenate/selenite ions to the aqueous methanolic solution of
curcumin maintained at pH 10.8, a significant fluorescence enhancement was observed (Fig. 2).
Under the same conditions as above no significant fluorescence changes (Fig. 2) were observed
in presence of other anions (F-, Cl-, Br-, I-, NO3-, OAc-, ----- and SO4-). However a significant
enhancement was observed in the presence of arsenate, arsenite and H 2PO4- ions. These
observations indicate that curcumin has selectivity for Selenate/selenite over other ions (Fig. 3).
The addition of various anions to curcumin (1x10-6 M) in aqueous methanol maintained at pH
from 6.6-11.3, were also carried out. It was observed that the interaction of the anions with
curcumin was not evident in the pH range 6.61-10.50, however in case of pH 11.30, a

fluorescence enhancement at emission of 580 nm was observed in presence of all the anions.
Thus, it is inferred that curcumin selectively interacts with selenate and selenite ions in 10%
aqueous methanol maintained at pH 10.8.
Fluorescence titration of curcumin with selenate/selenite were carried out in aqueous methanolic
solution maintained at pH 10.8. Upon addition of selenate ions (0-1 equiv.) to the weakly
fluorescent aqueous methanol solution of curcumin maintained at pH 10.8, a significant
enhancement in the fluorescence intensity at 580 nm was observed. Upon addition of 1 equiv. of
selenate ion, 4-fold increase in the fluorescence intensity was observed at 580 nm(Fig. ). The
limit of detection for selenate using the fluorescence titration data was found to be 10 nM.
Similarly, upon addition of 1 equiv. of selenite there is a significant increase in the emission of
curcumin upto 3.2 fold was observed.

Figure 5: Emission spectra of curcumin (1M) in MeOH:H2O (9:1 v/v) at pH 10.81 upon
fluorescence titrations with selenate and selenite

The complexation as observed from the fluorescence studies is 1:2 Se(VI/IV):Curcumin

complex, which indicates two molecules of curcumin are involved in the complexation of
selenite and selenate ions. Based on the spectroscopic evidences, the proposed complexation
mechanism of anion by curcumin is as given below in the Figure 7.

Figure 6: Complexation of curcumin with selenate and selenite by hydrogen bonding with the
phenolic OH group
The anion induced fluorescence enhancement of curcumin in aqueous methanol solution is
attributed to the disruption of the ESPT phenomenon in curcumin upon binding of anion. At pH
10.8, the anions are in completely ionized as SeO 42- or SeO32-[Atlas of Eh-pH diagrams
intercomparison of thermodynamic databases Geological Survey of Japan Open File Report
No.419

(2005)

http://www.eosremediation.com/download/Chemistry/Chemical

%20Properties/Eh_pH_Diagrams.pdf] and curcumin is completely deprotonated at pH above

10.5 [Spectrochim Acta A 60, 2004, 1091-1097]. However, it is evident that curcumin undergoes
a Excited State Intramolecular Hydrogen Transfer, ESIHT (or ESIPT) in methanolic solutions
[Adhikary et al. J. Phys. Chemistry B 2009, 113, 5255 & Adhikary et al. 2010, 114, 2997;

Journal of Physical Chemistry B 2010, 114, 12129-12143]. This ESPT induced quenching of
fluorescence is more pronounced under basic conditions due to the ground state proton transfer
in conjunction with ESPT phenomenon of curcuminate ions (Journal of Physical Chemistry A
2012, 116, 2039-2048). Thus, it is quite evident that methanol has a significant role to play in the
selenate/selenite ion binding by curcuminate ion. Thus, the proposed mechanism involves a
proton transfer in the ground state from methanol to the complex during curcuminate
complexation of Selenate/selenite ions. This binding mechanism is further supported by the UVVis absorption band due to the phenol group of curcumin being evident in presence of selenate
and selenite ion. Further, binding of selenate to curcumin was studied in aqueous acetonitrile
solution maintained at pH 10.8. No changes were observed in the fluorescence and absorbance
characteristics of the curcuminate generated in the aprotic solvent in water. This further proves
that water does not interfere with the binding of selenate and selenite ions by curcuminate ion in
aqueous acetonitrile solution maintained at pH 10.8.
Conclusion:
In this study, curcumin has been investigated for its selective fluorogenic detection of selenate
and selenite ions in aqueous solution. The proton transfer between methanol and curcuminate
during the complexation of anion, results in the pronounced radiative decay due to disruption of
the non-radiative ESPT of curcumin in presence of protic solvent. Thus, in continuation of this
phenomenon various ESPT based sensors can be deviced for real-time anion sensing in aqueous
matrix.
Acknowledgements

This work was supported in terms of funds, fellowship and Central Instrumentation Facility by
Central University of Punjab, Bathinda for M Phil-PhD work of Mr. Rabindra Kumar. J.
Nagendra Babu is thankful to DST, New Delhi for providing funds through DST Fast Track
Young Scientist as Project Ref. No. 240/2010 for research support.
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Chem. Soc. Rev., 44 (2015) 4986-5002. doi: