A highly selective dual channel hypochlorite probe based on fluorescein and 1,10-phenanthroline

Article abstract of DOI:10.1016/j.tet.2016.02.004

In this study, a highly selective dual channel (UV-vis and fluorescence) responsive hypochlorite probe based on fluorescein and 1,10-phenanthroline is described. It is found that this compound can be used as both a fluorogenic and chromogenic probe for the detection of the hypochlorite ion in aqueous solution. NMR and mass spectral analysis show that the probe reacts with the hypochlorite ion, which triggers both a remarkable enhancement of the emission intensity (turn on), and a color change from a colorless state to yellow. More importantly, the probe displays extremely high selectivity to hypochlorite among other common ROS and many ions in aqueous solution.

Full text of DOI:10.1016/j.tet.2016.02.004

Accepted Manuscript
A highly selective dual channel hypochlorite probe based on fluorescein and 1,10-
phenanthroline
Melek Pamuk Algi
PII:
S0040-4020(16)30067-9
10.1016/j.tet.2016.02.004
TET 27474
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 2 December 2015
Revised Date: 18 January 2016
Accepted Date: 1 February 2016
Please cite this article as: Algi MP, A highly selective dual channel hypochlorite probe based on
fluorescein and 1,10-phenanthroline, Tetrahedron (2016), doi: 10.1016/j.tet.2016.02.004.
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ACCEPTED MANUSCRIPT
Graphical Abstract
A highly selective dual channel hypochlorite probe based on fluorescein and 1,10-
phenanthroline
Melek Pamuk Algi*
OH
HO
N
N
-O
O
O
O
O
NaOCl
N
N
N
N
COO-
HO
OH
O
O
colourless
yellow
nonfluorescent
highly fluorescent
1

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A highly selective dual channel hypochlorite probe based on fluorescein and 1,10-
phenanthroline
Melek Pamuk Algi*
Health Services Vocational School & ASUBTAM BioNanoTech Lab., Aksaray University,
TR-68100 Aksaray, Turkey.
Abstract
In this study, a highly selective dual channel (UV-Vis and fluorescence) responsive
hypochlorite probe based on fluorescein and 1,10-phenanthroline is described. It is found that
this compound can be used as both a fluorogenic and chromogenic probe for the detection of
the hypochlorite ion in aqueous solution. NMR and mass spectral analysis show that the probe
reacts with the hypochlorite ion, which triggers both a remarkable enhancement of the
emission intensity (turn on), and a color change from a colourless state to yellow. More
importantly, the probe displays extremely high selectivity to hypochlorite among other
common ROS and many ions in aqueous solution.
Keywords: Fluorescence; Probe; Hypochlorite; 1,10-phenanthroline; Fluorescein;
Chromogenic.
*Corresponding authors. Tel.: +903822882557; Fax: +903822137850; E-mail:
melekalgi@aksaray.edu.tr (M. P. Algi)
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1. Introduction
Reactive oxygen species (ROS) are an important class of reactive intermediates, and they play
significant roles in some biological and pathological processes.1 However, ROS are mainly
produced from oxygen during the electron transport chain to stave off undesired xenobiotics.2
Also, it is now well known that over production of ROS increases oxidative stress, thus
causing many neurodegenerative and other diseases such as
Alzheimer’s, neuron
degeneration, cancer, arthritis and cardiovascular diseases. In particular, hypochlorite is one
of the most significant ROS for the immune system. The immune system can generate
hypochlorite from the reaction of chloride ions with H2O2 in the presence of the
myeloperoxidase enzyme.3,4 Furthermore, hypochlorite is indispensable for our daily life,
often used in the disinfection of drinking water, household bleach, cooling-water and cyanide
treatment in a concentration range of 10-5-10-2 M.4,5 As a consequence, the design and
synthesis of new, sensitive, selective and efficient multi-channel hypochlorite probes2-4,6-18 is
a challenging task in chemical, biological and environmental sciences.
Fluorogenic and/or chromogenic compounds which are comprised of signaling units attached
with suitable recognition motifs provide facile and prominent strategies for the selective and
sensitive detection of targeted ions. So far, a number of excellent candidates of fluorogenic
and/or chromogenic probes for many ions and/or molecules have been described.19-35 Among
these compounds, fluorescein and its derivatives represent an important class of fluorescent
compounds due to their intrinsic features and excellent photophysical properties, which
include high fluorescence quantum yields, high molar absorption coefficients, and good
chemical, thermal and photostability.36 Another advantage of this class of compounds is that
their visible excitation and emission can also be tuned by structural modification. Not
surprisingly, these features have made fluorescein and its derivatives promising candidates for
the labeling of biological materials, fluorescent sensors, probes and switches.37-39
Additionally, they are finding an increasing number of applications in both materials and
optical imaging fields.
In the present work,
a
new compound 1 (viz. 2,2'-{1,10-phenanthroline-4,7-
diylbis[(E)methylylidenenitrilo]}bis(6' hydroxyspiro[isoindole-1,9'-xanthene]-3,3'(2H,9a'H)-
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dione), based on fluorescein and 1,10-phenanthroline skeletons was designed and synthesised
for the detection of the hypochlorite ion via a chemodosimeter approach.40-46 It was found that
compound 1 reacts with hypochlorite in a highly selective manner in aqueous solution. To our
delight, hypochlorite triggers both a remarkable enhancement of the emission intensity up to
12-fold and, a color change of the solution from colourless to yellow. Notably, this shows that
1 can be used as a dual channel (fluorogenic and chromogenic) probe for the detection of
hypochlorite in aqueous solution at room temperature. More importantly, this novel probe 1
exhibits very high selectivity to hypochlorite when compared to other common ROS, anions
and metal cations (vide infra).
2. Results and Discussion
A three-step reaction sequence, outlined in Scheme 1, was used for the synthesis of compound
1. Initially, 4,7-dimethyl-1,10-phenanthroline (2) was oxidized with SeO2 in dioxane-water
mixture (4%, v/v) to afford 1,10-phenanthroline-4,7-dicarbaldehyde (3) in a moderate yield
(60%).44,47 In the second step, fluorescein (4) and hydrazine hydrate were heated under reflux
to give fluorescein hydrazide 5 (85% yield) according to a published procedure (see
Supporting Information Fig. S1-S2).49 Finally, the synthesis of compound 1 was achieved in
80% yield by treatment of 3 with 5 in refluxing ethanol. The characterization of compound 1
1
was carried out on the basis of H and 13C NMR and mass spectral data and elemental
analysis, which firmly confirmed the structure (see Supporting Information Fig. S3-S5).
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Scheme 1. Synthesis of 1. Conditions: i- SeO2, 1,4-dioxane-water (4%, v/v), 100 oC, 60%; ii-
NH2NH2, C2H5OH, 78 oC, 85%; iii- C2H5OH, 78 oC, 80%.
After characterization, the photophysical properties of compound 1 were investigated in
aqueous solution containing DMF (1.5%, v/v) at room temperature. The UV-Vis absorbtion
spectrum of 1 (1.5 x 10-5 M) displays a broad band between 250-400 nm with λmax of 280 nm
and 360 nm (Fig. 1). Initially, UV-Vis spectral changes upon addition of NaOCl were
recorded. It is noteworthy that the addition of NaOCl to a solution of 1 induced significant
changes in the absorbtion spectrum giving rise to a hypsochromic shift (λmax=292 nm) with
concomitant appearance of a new absorbtion band at 510 nm, which was ascribed to the
fluorescein unit (Fig. 1). These changes in the absorbtion spectra of 1 were also reflected in
the color of the solution, easily be detected by the naked-eye. Remarkably, the color of the
solution of 1 altered from a colourless to yellow upon addition of NaOCl (Fig. 1 inset).
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Fig. 1. UV-Vis absorbtion spectra of 1 (1.5 x 10-5 M) upon addition of NaOCl (0.0-0.9 x 10-3
M) in aqueous solution containing DMF (1.5%, v/v) at room temperature.
Next, the effect of pH on the fluorescence emission spectrum of 1 (6.0 x 10-6 M) was
examined. It was noted that the emission intensity of compound 1 was highly dependent on
the pH of the solution as expected from fluorescein derivatives21-23 (Fig. S6). After careful
examination of the effect of pH on the emission intensity of compound 1, spectrofluorometric
titrations with NaOCl were performed in aqueous solution containing DMF (0.6%, v/v) at
room temperature. Compound 1 was almost nonfluorescent under these conditions (turn-off).
Gratifyingly, the fluorescence emission of 1 was turned on upon addition of NaOCl, which
resulted in an increase of the emission intensity up to 12-fold (Fig. 2). Clearly, the emission
intensity change could also be detected by the naked-eye under UV illumination (Fig. 2 inset,
254 nm).
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Fig. 2. Emission spectra of 1 (6.0 x 10-6 M) upon addition of NaOCl (0.0-0.9 x 10-3 M) in
aqueous solution containing DMF (0.6%, v/v, λexc=470 nm) at room temperature.
In order to reveal the sensitivity and selectivity of 1 to NaOCl, other common ROS and/or
ions were also tested under identical conditions. It is important to note that compound 1 (3.0
x 10-6 M) was almost nonresponsive to the other ROS and anions such as H2O2, OH., tBuO.,
NO2 , ClO4 , Cl-, Br-, I-, F-, AcO-, PF6 , BF4 , H2PO4 , IO3 , N3 , SH-, HSO4 and SO42- albeit
KO2 induced a small increase in the emission intensity of 1 as depicted in Figures 3 and 4.
Furthermore, it was found that compound 1 was silent to the presence of metal ions such as
Hg2+, Zn2+, Cd2+, Cu2+, Fe2+, Ni2+, Fe3+, Co2+, Ag+, Mn2+, Pb2+, Mg2+, Li+, Al3+, Na+, K+,
Au3+, Pt2+ and Pd2+ which did not make any significant change in the fluorescence emission
spectrum of 1 under the given conditions (Fig. 5-6).
-
-
-
-
-
-
-
-
7

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Fig. 3. Emission spectra of 1 (3.0 x 10-6 M) in the presence of a variety of ROS and anions
-
-
-
-
-
-
-
(ClO-, H2O2, OH., tBuO., KO2, NO2 , ClO4 , Cl-, Br-, I-, F-, AcO-, PF6 , BF4 , H2PO4 , IO3 , N3 ,
SH-, HSO4 and SO4 ) (4.5 x 10-4 M) in aqueous solution containing DMF (0.3%, v/v,
-
2-
λexc=470 nm) at room temperature.
8

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Fig. 4. Relative emission intensity changes for 1 (3.0 x 10-6 M) in the presence of a variety of
-
-
-
-
ROS and anions (ClO-, H2O2, OH., tBuO., KO2, NO2 , ClO4 , Cl-, Br-, I-, F-, AcO-, PF6 , BF4 ,
H2PO4 , IO3 , N3 , SH-, HSO4 and SO4 ) (4.5 x 10-4 M) in aqueous solution containing DMF
-
-
-
-
2-
(0.3%, v/v, λexc=470 nm) at room temperature.
9

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Fig. 5. Emission spectra of 1 (3.0 x 10-6 M) in the presence of NaOCl and a variety of metal
ions (ClO-, Hg2+, Zn2+, Cd2+, Cu2+, Fe2+, Ni2+, Fe3+, Co2+, Ag+, Mn2+, Pb2+, Mg2+, Li+, Al3+,
Na+, K+, Au3+, Pt2+ and Pd2+) (4.5 x 10-4 M) in aqueous solution containing DMF (0.3%, v/v,
λexc=470 nm) at room temperature.
10

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Fig. 6. Relative emission intensity changes for 1 (3.0 x 10-6 M) (ClO-, Hg2+, Zn2+, Cd2+, Cu2+,
Fe2+, Ni2+, Fe3+, Co2+, Ag+, Mn2+, Pb2+, Mg2+, Li+, Al3+, Na+, K+, Au3+, Pt2+ and Pd2+) (4.5 x
10-4 M) in aqueous solution containing DMF (0.3%, v/v, λexc=470 nm) at room temperature.
Finally, the limit of detection (LOD) of probe 1 towards NaOCl was determined. LOD was
calculated to be 2.0 x 10-6 M under these conditions (Fig. S7). Considering the fact that the
physiological concentration2 of NaOCl is between 5.0 x 10-6 M and 200 x 10-6 M, this new
probe 1 has great potential as a highly selective fluorescent NaOCl probe in aqueous solution.
On the basis of the above results, it can be safely concluded that compound 1 displays
extremely high selectivity and sensitivity to NaOCl among other common ROS and many
ions in aqueous solution containing DMF at room temperature. Importantly, this makes
compound 1 a promising candidate as a dual-channel (chromogenic and fluorogenic)
responsive probe for the detection of NaOCl under these conditions. The highly selective
chromogenic and fluorogenic response of probe 1 to NaOCl can be rationalized on the basis
of the chemodosimeter approach.40-44 It was reasonable to assume that NaOCl would attack
11

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out the C=N bond of compound 1 before the decomposition of 1 to give fluorescein anion (6)
via hydrolysis. In order to shed light on the sensing mechanism, the reaction products, which
1
were formed after the treatment of probe 1 with NaOCl, were analyzed by H NMR
spectroscopy. 1H NMR spectrum (Fig. 7) of the mixture clearly indicated the formation of the
fluorescein anion (6) upon treatment of 1 with NaOCl. The presence of anion (6) was also
evident when the UV-Vis absorbtion spectra of probe 1, 1 + NaOCl and (6) were compared
(Fig. S8).
1
Fig. 7. Partial H NMR spectrum of the reaction mixture after treatment of 1 with NaOCl in
water-DMSO-d6 (2:1, v/v, 300 MHz) (the signals with red stars belong to fluorescein anion
(6)).
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Moreover, the reaction mixture was analyzed by mass spectrometry. LC MS (Fig. S9) of the
reaction mixture also indicated the presence of fluorescein anion (6) (m/z = 333.03) along
with the presence of some other plausible reaction intermediates such as 7-9 (Scheme 2).
O-
N
N
-O
O
O
O
N
N
N
-
NH2
CO2
-O
O
7
6
ONa
N
N
N
OHC
CHO
O
O
N
N
N
N
N
NaO
O
9
3
8
Scheme 2. Fluorescein anion (6) and plausible reaction intermadiates 7-9.
These findings strongly suggest that NaOCl triggers a distinct reaction through the C=N bond
of 1 under the given conditions, which also accounts for the observed high selectivity. The
reaction mainly affords highly emissive and colored fluorescein (6) after hydrolysis (Scheme
3). This new probe 1 has some advantages when compared with those reported in the
literature.40-44 First of all, it should be noted that previous work has been carried out with
HOCl41,42,44 rather than NaOCl40,43 as analyte. In same cases, the effect of common ROS
-.
(H2O2, OCl-, tBuO., OH. and/or O2 ) to the probes40,42,44 was not tested. Furthermore, this new
probe 1 induces very high selectivity to NaOCl over the common ROS, many anions and/or
metal cations. To our knowledge, the diversity of the ions (common ROS, many anions and
metal cations) tested to determine the selectivity of the probe 1 is unique.
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OH
N
HO
N
N
-O
O
O
NaOCl
O
O
N
N
N
COO-
HO
OH
O
O
1
6
colourless
nonfluorescent
yellow
highly fluorescent
Scheme 3. The reaction of probe 1 with NaOCl to give fluorescein anion (6).
3. Conclusions
In conclusion, a new compound 1, based on fluorescein and 1,10-phenanthroline units, has
been designed, synthesized and characterized by spectroscopic methods. This new compound
1 was devised for the detection of hypochlorite using a chemodosimeter approach. It is
noteworthy that the addition of NaOCl to a solution of 1 induced remarkable changes in both
the absorbtion spectrum and the color of the solution, which was altered from a colourless to
yellow. Furthermore, 1 was almost nonfluorescent (turn-off) and the fluorescence emission of
1 can be turned on upon addition of NaOCl, which resulted in an increase of the emission
intensity up to 12-fold. Clearly, the emission intensity change could also be detected by the
naked-eye under UV illumination (254 nm). These results suggest that 1 is a promising dual
channel (fluorogenic and chromogenic) probe for the detection of the ion in aqueous solution
at room temperature. More importantly, this novel probe 1 exhibits very high selectivity to the
hypochlorite ion when compared to some other common ROS, anions and metal cations.
Further work on the design and synthesis of new molecular probes is currently underway and
the results will be reported in due time.
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4. Experimental Section
4.1. General methods
All chemicals were purchased from Sigma Aldrich Chemicals or Merck Company and used as
received unless otherwise noted. FTIR spectra were recorded on Perkin Elmer Spectrum 100
model FTIR with an attenuated total reflectance (ATR). 1H (400 or 300 MHz) and 13C (100 or
75 MHz) NMR spectra were recorded on a Bruker DPX-400 or Ultrashield 300 NMR
Spectrometers. Combustion analyses were carried out by using a LECO CHNS-932 analyzer.
LC MS spectra were recorded on a Thermo Scientific TSQ Quantum Acces Max
spectrometer. UV-Vis and fluorescence measurements were recorded on Varian Cary 50 and
Varian Cary Eclipse spectrophotometers, respectively. Melting points were determined on a
Schorrp MPM-H2 model apparatus and are uncorrected. The synthesis of 347,48 was carried
out according to a published procedure. Compound 3 is also commercially available.
Hypochlorite solutions, which were obtained from a local supplier (Migros A.Ş.), were
prepared from commercial bleach (5% NaOCl solution). Metal solutions were freshly
prepared from the corresponding perchlorate salts.
4.1.1. Synthesis of 2-amino-3', 6'-dihydroxyspiro[isoindoline-1,9'-xanthen]-3-one (5)47
To a solution of fluorescein (4) (1.0 g, 3.0 mmol) in absolute ethanol (50 ml) was dropwise
added hydrazine hydrate (4 ml, 80%) while stirring magnetically. The mixture was heated
under reflux overnight. The resulting precipitate was filtered and washed by a small amount
of ethanol and water, dried in vacuo to give 0.88 g of fluorescein hydrazide 5, yield 85% as an
o
1
off-white powder, mp: 195-197oC (lit.47 183-185 C). H NMR (300 MHz, DMSO-d6) δ =
7.79-7.76 (m, 1H), 7.50-7.48 (m, 2H), 7.00-6.98 (m, 1H), 6.59 (bs, 2H), 6.45 (d, J = 8.7 Hz,
2H), 6.40 (d, J = 8.5 Hz, 2H), 4.40 (bs, 2H); 1C NMR (75 MHz, DMSO-d6) δ = 165.9, 158.7,
152.8, 151.9, 133.0, 129.7, 128.8, 128.3, 123.8, 122.8, 112.4, 110.34, 102.8, 65.1.
4.1.2. Synthesis of 2,2'-{1,10-phenanthroline-4,7-diylbis[(E)methylylidenenitrilo]}bis(6'
hydroxyspiro[isoindole-1,9'-xanthene]-3,3'(2H,9a'H)-dione) (1)
Dialdehyde (3) (0.075 g, 0.317 mmol) was added to a solution of 5 (0.219 g, 0.635 mmol) in
absolute ethanol (10 mL). The mixture was heated under reflux overnight. The resulting
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precipitate was filtered while the solution was hot and the brownish solid was washed with
o
1
cold ethanol: 0.226 g, yield 80%, mp.: 290-292 C. H NMR (300 MHz, DMSO-d6) δ/ppm:
9.97 (s, 4H, OH), 9.66 (s, 2H), 9.04 (d, J = 4.6 Hz, 2H), 8.12 (s, 2H), 8.04 (d, J = 6.8 Hz, 2H),
7.74-7.65 (m, 6H), 7.24 (d, J = 7.3 Hz, 2H), 6.85 (d, J = 2.2 Hz, 4H), 6.60 (d, J = 8.6 Hz, 4H),
6.51 (dd, J = 8.6-2.2 Hz, 4H; 13C NMR (75 MHz, DMSO-d6) δ/ppm: 164.6, 159.3, 152.8,
150.9, 146.8, 144.0, 137.9, 135.1, 129.9, 129.0, 128.7, 125.0, 124.5, 124.0 122.6, 120.6,
113.1, 110.2, 103.1, 66.0; FTIR-ATR (cm-1): 3194, 3087, 3065, 2930, 1734, 1686, 1655,
1609, 1590, 1504, 1465, 1387, 1305, 1264, 1236, 1210, 1186, 1104, 995, 926, 902, 874, 819,
753, 728, 716, 685, 644, 629, 612, 602. Anal Calcd for C54H32N6O8: C, 72.64; H, 3.61; N,
9.41; Found: C, 72.61; H, 3.65; N, 9.45; LCMS (m/z) Calcd. for C54H32N6O8: 892.23 [M+];
Found: 893.13 [M+H]+.
Acknowledgements M.P.A is indebted to Aksaray University for partial financial support of
this work (ASU BAP 2015-092).
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