A. K. Gupta, A. Dhir, C. P. Pradeep
FULL PAPER
+
m/z calcd. for C16
H
24
N
3
O
9
[M + H] 402.1512; found 402.1590 (see
materials (Eds.: P. A. Gale, J. W. Steed), John Wiley & Sons,
Ltd. 2012, p. 1225–1257; b) Y. Zhou, Z. Xu, J. Yoon, Chem.
Soc. Rev. 2011, 40, 2222–2235; c) R. Martínez-Máñez, F. San-
cenón, Chem. Rev. 2003, 103, 4419–4476; d) Z. Xu, S. K. Kim,
J. Yoon, Chem. Soc. Rev. 2010, 39, 1457–1466; e) P. A. Gale,
Chem. Soc. Rev. 2010, 39, 3746–3771; f) S. K. Kim, J. L. Sessler,
Chem. Soc. Rev. 2010, 39, 3784–3809; g) A.-F. Li, J.-H. Wang,
F. Wang, Y.-B. Jiang, Chem. Soc. Rev. 2010, 39, 3729–3745; h)
Z. Xu, X. Chen, H. N. Kim, J. Yoon, Chem. Soc. Rev. 2010,
the Supporting Information).
UV/Vis and Fluorometric Analysis: All UV/Vis and spectro-
flouoremtric titrations were performed on 5 μm solutions of the
receptors at pH 7.2 in 0.05 m TRIS buffer/water mixture. Freshly
–1
–3
prepared standard solutions (10 to 10 m) of ATP, ADP, AMP,
–
–
–
–
–
–
–
–
–
CTP, PPi, F , Cl , Br , I , CH
3
COO , CN , SCN , HSO
4 2 4
, H PO ,
–
–
ClO , and NO (as the corresponding sodium and tetrabutyl am-
4 3
ˇ
9, 127–137; i) Z. Kejík, K. Záruba, D. Michalík, J. Sebek, J.
Dain, S. Pataridis, K. Volka, V. Král, Chem. Commun. 2006,
533–1535; j) H. Wang, W. H. Chan, Org. Biomol. Chem. 2008,
3
monium salts) in pH 7.2, 0.05 m TRIS buffer/water mixture were
used to record the UV/Vis and fluorescence spectra. Solutions of
the receptors 3A–D (3 mL) were taken in a quartz cuvette (path
length 1 cm) and solutions of anions were added to these solutions
by using micropipette.
1
6, 162–168.
[
[
2] a) For enzyme-catalyzed phosphoryl transfer reactions, see:
J. R. Knowles, Annu. Rev. Biochem. 1980, 49, 877–919; b)
A. K. H. Hirsch, F. R. Fischer, F. Diederich, Angew. Chem. Int.
Ed. 2007, 46, 338–352; Angew. Chem. 2007, 119, 342; c) D. H.
Lee, J. H. Im, S. U. Son, Y. K. Chung, J.-I. Hong, J. Am. Chem.
Soc. 2003, 125, 7752–7753.
3] a) S. V. Khlyntseva, Y. R. Bazel, A. B. Vishnikina, V. Andruch,
J. Anal. Chem. 2009, 64, 657–673; b) P. Ritter, Biochemistry a
Foundation; Creation Research Society Quarterly June 1999,
Brooks/Cole, Pacific Grove, CA, 1996, 36.
Determination of Detection Limit: Fluorescence titration experi-
ments on 3A with ATP and CTP and on 3D with ATP were carried
out by adding aliquots of ATP and CTP solutions of micromolar
concentrations to receptor solutions and the curve between [(I
o
–
I)/(I – Imax)] vs. log[Anion] was plotted (I is initial intensity, Imax
o
o
is final intensity and I is change in intensity after each addition of
anions). A linear regression curve was fitted to anion concentra-
tion. The point at which this line crossed the ordinate axis was
[4] P. Mahato, A. Ghosh, S. K. Mishra, A. Shrivastav, S. Mishra,
taken as the detection limit.[
23]
A. Das, Chem. Commun. 2010, 46, 9134–9136.
[
5] J. C. M. Allen, J. R. Kalin, J. Sack, D. Verizzo, Biochemistry
978, 17, 5020–5026.
6] O. Tollbom, G. Dallner, Br. J. Exp. Path. 1986, 67, 757–764.
[7] D. Mallikarachchi, D. S. Burz, N. M. Allewell, Biochemistry
1989, 28, 5386–5391.
Determination of Quantum Yields: The fluorescence quantum yields
of receptors 3A–D were determined at room temperature in TRIS
buffer (pH 7.2) by using optically matching solutions. Quinine sulf-
1
[
r 2 4
ate (φ = 0.53 in 0.05 m H SO ) was used as the standard at an
excitation wavelength of 347 nm for these measurements. The quan-
[8] P. D. Beer, P. A. Gale, Angew. Chem. Int. Ed. 2001, 40, 486–
516; Angew. Chem. 2001, 113, 502.
tum yield was calculated by using the Equation (1):[
17]
[9] H. Ahmad, B. W. Hazel, A. J. H. M. Meijer, J. A. Thomas,
K. A. Wilkinson, Chem. Eur. J. 2013, 19, 5081–5087.
[
10] a) M. Devi, A. Dhir, Pooja, C. P. Pradeep, RSC Adv. 2014, 4,
2
7098–27105; b) M. Devi, A. Dhir, C. P. Pradeep, Dalton Trans.
2
013, 42, 7514–7518; c) A. K. Gupta, A. Dhir, C. P. Pradeep,
(
1)
Dalton Trans. 2013, 42, 12819–12823; d) S. Sharma, A. Dhir,
C. P. Pradeep, Sens. Actuators, B 2014, 191, 445–449; e) D.
Rambabu, Pooja, C. P. Pradeep, A. Dhir, J. Mater. Chem. A
where φ
radiative quantum yield of reference, A
of the sample and the reference, respectively, I
grated areas of emission for the sample and reference, respectively,
and η and η are the refractive index of the sample and the refer-
s
is the radiative quantum yield of the sample, φ
and A are the absorbances
and I are the inte-
r
is the
s
r
2
014, 2, 8628–8631; f) D. Rambabu, C. P. Pradeep, A. Dhir,
s
r
Inorg. Chem. Front. 2014, 1, 163–166.
[11] M. Mukhopadhyay, D. Banerjee, S. Mukherjee, J. Phys. Chem.
A 2006, 110, 12743–12751.
s
r
ence solutions, respectively (pure solvents were assumed).
[12] V. Chandrasekhar, S. Das, R. Yadav, S. Hossain, R. Parihar,
G. Subramaniam, P. Sen, Inorg. Chem. 2012, 51, 8664–8666.
Binding Constants: The fluorimetric titrations on 3A were per-
formed at 25 °C in TRIS buffer (pH 7.2) measuring the quenching
[
[
13] T. Yang, W. Qin, W. Liu, Talanta 2004, 62, 451–456.
14] a) S. Sen, M. Mukherjee, K. Chakrabarty, I. Hauli, S. K. Mu-
khopadhyay, P. Chattopadhyay, Org. Biomol. Chem. 2013, 11,
of the emission at 560 nm. Binding constant K
calculated from the plots of [(I – I)/I ] vs. [anion] by using nonlin-
ear curve fitting using Origin lab 8.0.
b
for the anions were
o
o
1
537–1544; b) A. Dorazco-González, M. F. Alamo, C. Godoy-
Alcántar, H. Hpfl, A. K. Yatsimirsky, RSC Adv. 2014, 4, 455–
66; c) M. Yousuf, N. Ahmed, B. Shirinfar, V. M. Miriyala, S.
[14c,21,31]
4
Supporting Information (see footnote on the first page of this arti-
cle): NMR, mass, UV/Vis, and fluorescence spectra and fluores-
cence titration data, tables Job’s plot and optimized structures.
Youn, K. S. Kim, Org. Lett. 2014, 16, 2150–2153.
[
[
15] A. Dhir, V. Bhalla, M. Kumar, Tetrahedron Lett. 2008, 49,
4227–4230.
16] a) H. Sharghi, M. N. Ali, K. Niknam, J. Org. Chem. 2001, 66,
7287–7293; b) D. K. Paul, J. P. W. Andrew, K. C. Williams, In-
Acknowledgments
org. Chem. 2008, 47, 11711–11719; c) N. K. Lifshin, L. Alber-
tazzi, M. Bendikov, P. S. Baran, D. Shabat, J. Am. Chem. Soc.
2012, 134, 20412–20420; d) A. Hryniewicka, A. Kozlowska, S.
Witkowski, J. Organomet. Chem. 2012, 701, 87–92.
C. P. P. thanks the Department of Science and Technology (DST),
New Delhi for funds under the fast track Scheme Grant SR/FT/
CS-58/2011 and IIT Mandi for infrastructural facilities as well as [17] A. M. Brouwer, Pure Appl. Chem. 2011, 83, 2213–2228.
financial support through a Seed Grant. A. K. G. thanks the Min-
istry of Human Resource Development (MHRD), Govt. of India
for a fellowship. Helpful suggestions from Mr. Ashish Bahuguna
related to some experimental procedures is acknowledged.
[18] C. B. Larsen, H. V. Salm, C. A. Clark, A. B. S. Elliott, M. G.
Fraser, R. Horvath, N. T. Lucas, X. Z. Sun, M. W. George,
K. C. Gordon, Inorg. Chem. 2014, 53, 1339–1354.
[19] a) J. R. Lakowicz, Topics in Fluorescence Spectroscopy: Probe
Design and Chemical Sensing; Plenum Press, New York, 1994,
4; b) J. P. Desvergne, A. W. Czarnik, Chemosensors of Ion and
[
1] a) E. García-España, R. Belda, J. González, J. Pitarch, A. Bian-
Molecule Recognition, NATO ASI Series, Kluwer Academic
Publishers, Dordrecht, The Netherlands, 1997.
chi, in: Supramolecular Chemistry: From Molecules to Nano-
128
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 122–129