A novel 1,10-phenanthroline based chemosensor for differential metal ion sensing and constructing molecular logic gates

Article abstract of DOI:10.1016/j.tetlet.2014.11.062

A simple tailor-made amidic functionality based on 1,10-phenanthroline unit (1) gave differential absorption changes with only metal ions viz. Cd²⁺, Zn²⁺, and Cu²⁺ ions. In CH₃CN solution of 1, addition of Cd²⁺ and Zn²⁺ ions resulted in bathochromic shift of ～65 nm, whereas Cu²⁺ ions resulted in hyperchromic effect with only ～15 nm bathochromic shift. These differential changes observed with Cd²⁺ and Cu²⁺ ions addition enabled chemosensor 1 to construct 'IMLICATION' and 'TRANSFER' logic gates. The observed binding constant values were found to be in order of Cd²⁺ > Zn²⁺ > Cu²⁺.

Full text of DOI:10.1016/j.tetlet.2014.11.062

Accepted Manuscript
A novel 1,10-phenanthroline based chemosensor for differential metal ion sens-
ing and constructing molecular logic gates
Navneet Kaur, Priya Alreja
PII:
S0040-4039(14)01955-8
DOI:
http://dx.doi.org/10.1016/j.tetlet.2014.11.062
TETL 45446
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
9 October 2014
12 November 2014
13 November 2014
Please cite this article as: Kaur, N., Alreja, P., A novel 1,10-phenanthroline based chemosensor for differential metal
ion sensing and constructing molecular logic gates, Tetrahedron Letters (2014), doi: http://dx.doi.org/10.1016/
j.tetlet.2014.11.062
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A novel 1,10-phenanthroline based
chemosensor for differential metal ion
sensing and constructing molecular logic
gates
Leave this area blank for abstract info.
Navneet Kaur and Priya Alreja
0
.3
.25
.2
.15
.1
IMP
TRANSFER
Cu2+
0
0
0
1
N
N
0
O
O
NH
HN
Cd2+
OCH3 H3CO
0
1
.05
0
2
30
280
330
380
430
480
Wavelength (nm)

1
Tetrahedron Letters
journal homepage: www.elsevier.com
A novel 1,10-phenanthroline based chemosensor for differential metal ion sensing and
constructing molecular logic gates
Navneet Kaur and Priya Alreja
Department of Chemistry, Panjab University, Chandigarh 160014, India
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A simple tailor-made amidic functionality based on 1,10-phenanthroline unit (1) gave
2
+
2+
2+
differential absorption changes with only metal ions viz. Cd , Zn and Cu ions. In CH
3
CN
2
+
2+
solution of 1, addition of Cd and Zn ions resulted in bathochromic shift of ~ 65 nm, whereas
2+
Cu ions resulted in hyperchromic effect with only ~ 15 nm bathochromic shift. These
2
+
2+
Available online
differential changes observed with Cd and Cu ions addition enabled chemosensor 1 to
construct ―IMLICATION‖ and ―TRANSFER‖ logic gates. The observed binding constant
2
+
2+
2+
Keywords:
values were found to be in order of Cd > Zn > Cu .
1
,10-phenanthroline
Amide
Molecular logic gates
UV-vis
2
014 Elsevier Ltd. All rights reserved.
Metal ion sensing
1
. Introduction
childhood cirrhosis, prion disease, Menkes disease, Parkinsons
11
disease and Wilson disease. Consequently there has been thirst
of developing molecular sensors having the potential of detecting
these important cations. 1,10-Phenanthroline is an ideal candidate
for applications in complexation studies with cations owing to its
structural features such as planarity, rigidity and the two nitrogen
atoms placed in juxtaposition create binding sites for metal
The area of molecular optical sensors has been developed to a
significant maturity where chemosensors with excellent
selectivity towards target analyte can be designed and
1
synthesized. More recently, the paradigm shift from selective to
differential receptors has provided opportunities for single
2
molecular based estimation of several analytes by single
cations, hence producing important modifications of the emission
3
detection method or alternatively by using an array of detection
8,12
properties.
Therefore, phenanthroline based chemosensors
4
methods.
bearing both strong chelating abilities and good conjugated -
systems have received great attention in recent years. These
chemosensors were all designed by expanding the conjugated -
Sensing of transition metal ions is fruitful area of exploitation
in the field of supramolecular chemistry, owing to their extreme
importance in the fields such as Biology, Chemistry, Medicine
system of phenanthroline at 5 and 6 positions as well as at 2 and
5
2+
and Environment. Amongst heavy metal ions, sensing of Cd in
particular is of considerable interest because many agricultural
activities such as the excessive use of fertilizers and pesticides,
irrigation with waste water and industrial applications such as
nickel-cadmium batteries, coating of steel etc. increase the
13
9
positions.
Recently, the developments in supramolecular chemistry
have attracted great attention in the construction of photonic
1
4
15
devices that function as molecular level logic gates based on
the optical sensing of specific analytes. In the chemosensing
field, the goal is often selectivity, that is, a particular analyte
induce specific change in color or fluorescence. In contrast,
molecular logic looks for more complex systems, which usually
contain multiple binding sites and show certain unique response
patterns, exemplifying the desired logic operation in the presence
6
percentage of cadmium in soils and water. As a result of food
chain system, cadmium exposure can cause anemia, abdominal
pain, neurological and adverse effects, kidney damage,
7
hypertension, changes in vitamin D metabolism etc. Zinc being
second most abundant metal ion in human body plays major roles
8
9
in metalloenzyme regulation, neurophysiology and metabolism
2
+
16
of cells. Cu , in addition to its third highest abundance in the
human body, plays an important role in various biological
processes. Also due to widespread use, Cu is a significant
metal pollutant and aberrant levels of Cu ions lead to oxidative
stress and has been linked with the development of Indian
of either or both inputs. The chemically encoded information
was converted into the optical changes as the output, which
results in development of molecular logic gates such as AND,
OR, NOR, INHIBIT, XOR, YES, NOT, and XNOR logic gates.
The tailor – made chemosensors can be viewed as computational
1
0
2+
2
+
—
——

Corresponding author. Tel.: +91 172 2534430; fax: +91 172 2545074;
e-mail: neet_chem@yahoo.co.in; neet_chem@pu.ac.in (N. Kaur)

2
Tetrahedron Letters
devices that use physical or chemical inputs to generate outputs
0.8
(b)
based on a set of logical operators. The integration of these
molecular logic gates at molecular level is related to the
integration and processing of binary data of conventional
0.6
1
7
microprocessor systems. The speed of the conventional
computers can be enhanced by miniaturizing electronic
components to a very small micron-size scale so that those
electrons need to travel only very short distances within a very
0
.4
1
8
short time.
0.2
In this paper, we demonstrate a new metal ions sensing
chemosensor (1) possessing an amide functionality featuring with
0
1
,10-phenanthroline unit. So far, literature reveals the
1
F
Cl
Br
I
AcO H2PO4 HSO4 SO4
applicability of 1, 10-phenanthroline-2, 9-disubstituted
-
Anions (A )
Fig. 1. UV-vis. absorption responses of 1 (10 µM) to various (a) metal ions
500 µM) and (b) anions (500 µM) in CH CN. Bars represent the intensity of
absorption at 270 nm.
1
9
carboxamides as anion chemosensors. As heteroatoms are
2
0
known to bind cations, so intorduction of number of
(
3
heteroatoms (-N) in chemosensor 1 makes it suitable for
2+
2+
2+
recognition of cations i.e. Cd , Zn and Cu ions. There are
many examples known in literature where presence of electron
density bulk near the core eases the formation of metal
2+
-
The increased absorbance due to Hg and I ions at 270 nm
was due to their own absorbance near 270 nm (Fig. S1) and for
the same reason, any actual changes observed with I and Hg
can not be identified. However, it was observed that upon
2
1
complexes.
-
2+
2
. Results and discussions
2
+
2+
2+
2
.1 Synthesis of chemosensor 1
addition of Cd , Zn and Cu ions, chemosensor 1 resulted in
dramatic absorption changes.
The chemosensor 1 was synthesized in good yield by reaction
To quantitatively study the cation-sensing ability of 1 in
of 1,10-phenanthroline 2,9-dicarboxylic acid with o-anisidine
Scheme-1). The chemical structure of the newly synthesized
chemosensor was confirmed by H NMR, C NMR and Mass
spectral data.
CH CN, UV-vis monitoring was performed by using 10 µM
(
3
2
+
1
13
solution of 1. Upon addition of Cd ions, the intensity of the
absorption peak at 270 nm was gradually decreased, while a new
peak at 335 nm evolved whose intensity gradually increased and
2
+
after the addition of 2.0 equiv. of Cd ions, reached to their
limiting value (Fig. 2a). The isosbestic point at 280 nm indicated
a clean conversion throughout the titration process. As the
absorption changes occurred below 400 nm i.e. in UV region
only, so, appearance of new red shifted band was not
accompanied with any color change. The signaling was
completed immediately after the addition. By plotting the
changes of 1 in the absorbance at 270 nm and 335 nm as a
(
i) SOCl2, DMF
N
N
(
ii) K2CO3, TBAHSO4,
O
O
CH3CN,
NH2
N
N
NH
HN
HOOC
COOH
OCH3
OCH3 H CO
3
1
(
Scheme-1)
2
.2 UV-vis spectral studies
The sensing ability of 1 was primarily investigated by adding
various cations such as Na , K , Mg , Al , Ni , Cu , Fe ,
Zn , Cd , Hg , Co and anions such as F , Cl , Br , I and AcO
tetrabutylammonium was used as a counterion) to CH CN
2
+
function of Cd ion concentration, a sigmoidal curve was
obtained and is shown in Fig. 2b. The new band located at 335
nm may be attributed to increased intramolecular charge transfer
+
+
2+
3+
2+
2+
2+
2
+
2+
2+
2+
-
-
-
-
-
2
+
(
(ICT) transition within the whole molecule arising due to Cd
ion binding (Fig. 4).
3
18
solution of 1 (10 µM). In CH CN, chemosensor 1 displayed an
3
absorption band at 270 nm which is characteristic ππ* band of
+
1
,10-phenanthroline moiety. The addition of 50 equiv. of Na ,
+
2+
3+
2+
2+
2+
2+
-
-
-
-
-
K , Mg , Al , Ni , Fe , Hg , Co , F , Cl , Br , I and AcO did
not result in any color or spectrum changes (Fig. 1).

3
0
.25
respectively and K is the association constant and [C] is the
(b)
2+
concentration of Cd ion added. Plotting of 1/(A-A ) versus
/[Cd ] showed a linear relationship (Fig. S6), which indicates
that 1 associates with Cd in a 1:1 stoichiometry. The binding
constant (K) between 1 and Cd is determined from the ratio of
intercept/slope to be 1.78 x 10 M . The binding constants of 1
with Zn and Cu ions were found to be 2.64 x 10 M and 2.11
x 10 M , respectively. Thus, chemosensor 1 showed binding
with these metal ions in order Cd > Zn > Cu , which follows
the fact that 2,9-disubstituted 1,10-phenanthroline derivatives
0
2
+
1
0
.2
2+
2
+
3
35 nm
5
-1
0.15
2
+
2+
4
-1
4
-1
2
+
2+
2+
0
.1
270 nm
forms three rigid five-membered chelate rings that favor larger
0
.05
24, 25
metal ions with an ionic radius of about 1.0 Å.
As the ionic
2
+
2+
2+
0
10
20
30
Cd conc. (mM))
Fig. 2. (a) Family of UV-vis spectra taken in the course of the titration of 1
40
50
radii of Cd is largest (0.96 Å) amongst Zn (0.74 Å) and Cu
2
+
2
+
(
0.73 Å), thus Cd binding is more stronger and large
bathochromic shift of ~ 65 nm has been observed (Fig. 4). As an
amide compound can undergo coordination, either through
oxygen or through nitrogen which may be confirmed by any
2
+
(
3
10 µM in CH CN) with Cd ions; (b) Plot of absorbances at 270 and 335 nm
2
+
vs. the concentration of Cd added.
1
chemical shift observed in case of N-H proton of amide 1. H
NMR titrations of 1 were carried out with cadmium and zinc
Similar type of absorption changes i.e. decreased absorbance
at 270 nm and emergence of new band at 335 nm, were observed
perchlorates. In general, if complexation will occur through
1
amidic nitrogen, then the H NMR spectra of diamagnetic Cd(II)
2
+
with addition of Zn ions to CH CN solution of 1 (Fig. S2a).
3
and Zn(II) complexes will show downfield shift for amidic NH
However, in this case, change in absorption intensity was much
1
proton of the complexes as compared to ligand. The H NMR
2
+
less as compared to change caused by Cd addition and thus,
spectrum of 1, in DMSO-d , showed sharp singlet at 11.156 δ
6
2
+
saturation was achieved after addition of 4.0 equiv. of Zn ions
Fig. S2b).
which has been assigned to N-H proton of amide. Upon addition
(
2+
2+
of Cd / Zn ions to solution of 1, no significant shift in position
2
+
of amidic proton has been observed. Further, participation of -
However, addition of Cu ions to solution of 1 in CH CN
3
OCH group in coordination process has also been evaluated with
perturbed the absorption band differently and resulted in
continuous bathochromic shift of the band to 286 nm (Fig. 3).
The intensity of this red-shifted band increased with increased
3
1
H NMR titrations. Only negligible change in chemical shift
value of –OCH3 at 3.33 δ also pointed towards its non-
participating nature (Fig. S7 and S8).
2
+
concentration of Cu ions and reached their limiting value after
2
+
addition of nearly 50 equiv. of Cu ions (Fig. S3). This small red
2
+
shift observed with addition of Cu ions might be attributed to
2
+
binding of Cu ions to two nitrogens of phenanthroline ring and
N
N
2
2
two amidic nitrogens only. However, increased absorbance
HN
NH
M2+
2
+
2+
below 250 nm observed with Cu addition was due to Cu ions
own absorbance in the same region (Fig. S4).
O
O
OCH3
H3CO
M = Cd, Zn, Cu
2+
2+
2+
Fig 4. Proposed binding of 1 with Cd , Zn and Cu ions
2
.4 Molecular logic gates
2
+
The differential behavior of chemosensor 1 towards Cd and
2
+
Cu ions enabled chemosensor 1 to elaborate molecular logic
gates i.e. IMPLICATION and TRANSFER at two different
wavelengths. Recent advances in molecular computing is the
subarea of unconventional computing based on chemical
reactions that has stimulated interest in the development of
molecular logic gates and devices at the molecular level.
Molecular logic gates convert input stimulations into output
signals with intrinsic protocols. It follows that the principles of
binary logic can be applied to the signal transduction operated by
molecular switches. For the analysis of their logic behaviors, first
of all, threshold values are assigned and then logic convention is
Fig. 3. Family of UV-vis spectra taken in the course of the titration of 1 (10
2+
3
µM in CH CN) with Cu ions.
+
2
+
Moreover, addition of other metal ions such as Na , Mg +, K ,
3
+
2+
2+
2+
2+
2+
2+
2+
Al , Co , Fe , Hg , Mn , Ni and Zn to solution of 1+Cu
1
/
2
+
+Cd caused only nominal changes in the absorption spectra
2
6
(
Fig. S5).
used for their inputs and outputs signals.
2
.3 Binding constants
The association constant of 1 with Cd was calculated based
The molecular switching behavior of chemosensor 1 with two
chemical inputs (5 equiv. of Cd and Cu ) can be demonstrated
with the help of binary logic. The input can take values of 0 and
2
+
2+
2
+
2
3
on the UV-vis titration through the Benesi-Hildebrand equation,
which was given as follows;
1
corresponding to the absence or the presence of input. The
output, the absorbance at a given wavelength, can be of values 0
and 1 depending on the absorbance value below or above a
certain threshold.
1
1
1
=
+
A-Ao
Amax-Ao [Amax-A ] K [C]
o
2
+
2+
Here, A , A, and A is the absorbance of free 1, measured
There are two input signals, viz. In (Cd ) and In (Cu ),
o
max
1
2
2
+
2+
with Cd and measured with excess amount of Cd at 335 nm,
whereas the output signals are, Out (A
) and out (A370 nm).
1
285 nm
2

4
Tetrahedron Letters
Fig. 5 shows different absorption spectra observed with
addition of two inputs. Monitoring the absorption changes at 285
4. Experimental
2
+
2+
Synthesis of 1,10 Phenanthroline-2,9-dicarboxylic acid bis-[(2-
methoxy-phenyl)-amide] (1)
nm and 370 nm i.e. the addition of Cd , Cu and an equimolar
2
+
2+
mixture of Cd and Cu , leads to ―IMPLICATION‖ and
TRANSFER‖ logic gates, respectively as represented in truth
table (Fig. 6).
―
The oxidation of 2, 9-dimethyl-1, 10-phenanthroline with
SeO2 in dioxane yielded 1, 10-phenanthroline-2, 9-
dicarboxaldehyde which was further oxidized to 1, 10-
―
IMPLICATION‖ logic requires that the signal is ‗0‘ only
2
9
phenanthroline-2,9-dicarboxylic acid using concentrated HNO3.
when one of the input is ‗1‘, and ‗1‘ in all other cases (i.e. when
both the inputs are ‗0‘ or ‗1‘; another input is ‗1‘). The
absorbance at 285 nm was increased with addition of Cu ions.
However, the output was read as ―0‖ only in the presence of Cd
2
7
1
,10-phenanthroline -2,9-dicarboxylic acid (0.500 g, 1.86 mmol)
2
+
was refluxed for two hours in excess SOCl (12 ml, 0.168 mol)
and a drop of DMF was added in catalytic amount. SOCl was
2
2
+
2
then removed at a reduced pressure resulting in diacyl chloride as
pale yellow residue to which was added K CO (0.567 g, 4.11
ions (Fig. 5 and 6).
2
3
mmol), 2–methoxy aniline (0.506 g, 4.11 mmol) and TBAHSO4
in catalytic amount and 25 ml of freshly dry distilled
acetonitrile. The contents were refluxed until TLC monitoring
indicated completion of the reaction .The contents were filtered
and the solvent was vacuum evaporated to yield crude yellow
solid. Recrystallization of crude product from mixture of
methanol and chloroform resulted in formation of pure amide.
-
1
Yellow solid, Yield = 60%, m.p.  245 ºC. IR (KBr, cm ): 3303
1
(
amide NH), 1683, 1650 (C=O), 1104 (C-O). H NMR (DMSO-
d , 400 MHz, ppm) δ: 3.34 (s, 6H, - OCH ), 6.97 (d, J = 8.08 Hz,
6
3
2
1
H, anilinyl-H), 7.06 (t, J = 1.04 Hz, 2H, anilinyl-H), 7.16 (t, J =
.6 Hz, 2H, anilinyl-H), 8.26 (s, 2H, phen-H), 8.49 (d, J = 7.88
A
Hz, 2H, anilinyl-H), 8.58 (d, J = 8.2 Hz, 2H, phen-H), 8.85 (d, J
1
3
=
8.2 Hz, 2H, phen-H), 11.17 (s, 1H, NH); C NMR (DMSO-d6,
7
1
5 MHz, ppm) δ: 55.21,110.26, 119.40, 120.51, 120.99, 124.56,
26.74, 128.17, 130.60, 138.93, 143.25, 148.94, 149.02, 161.46.
Fig. 5 Molecular scale implementation of different logic gates; a, blank; b, 1
+
LC-MS: m/z = 501 (M+Na) . Elemental analysis cacld for
C H N O : C, 70.28; H, 4.63; N, 11.71. Found C, 70.13; H,
2+
2+
2+ st
2+ nd
2+ nd
2+ st
+
Cd ; c, 1 + Cu ; d, 1+ Cd (1 ) + Cu (2 ); e, 1+ Cd (2 ) + Cu (1 )
2
8
22
4
4
4
.81; N, 11.58.
Moreover, by changing the observation wavelength from 285
nm to 370 nm, the spectral changes led to ―TRANSFER‖ logic
gate. The output of TRANSFER gate is high when either one of
the inputs or both of the inputs are high (Fig. 5 and 6).
Acknowledgements
2
8
The authors are greatly thankful to SAIF, Panjab University
Chandigarh for recording the NMR and Mass spectra and are
grateful to DST (Grant no. SR/FT/CS-36/2011) for the financial
assistance.
In
Cd )
1
2
In
(Cu )
2
Out
(A285
1
Out
2
(A370)
+
2+
(
)
0
1
0
(1 )
(2 )
0
0
1
1
0
1
1
1
0
1
0
1
1
Supplementry data
st
nd
1
1
1 (2 )
1 (1 )
nd
st
Supplementry data associated with this article can be found, in
the online version.
References and notes
TRANSFER
1
.
(a) de Silva, A. P.; Gunaratne, H. Q.; Gunnlaugsson, T.; Huxley,
A. J. M.; McCoy, C. P.; Rademacher, J. T.; Rice, T. E. Chem. Rev.
IMPLICATION
Fig. 6. Truth table for ―IMPLICATION‖ and ―TRANSFER‖ gates.
1
997, 97, 1515-1566; (b) Martinez-Manez, R.; Sancenon, F.
Chem. Rev. 2003, 103, 4419-4476; (c) Beer, P. D. Acc. Chem.
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. Conclusions
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Kitamura, Y.; Oka, K.; Suzuki, K. J. Am. Chem. Soc. 2005, 127,
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1
0798-10799; (b) Komatsu, H.; Citterio, D.; Fujiwara, Y.;
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2
+
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3
2
+
bathochromic shift and Cu ions resulted in hyperchromic effect.
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gates.
4
5
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.
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