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A. Mitra et al. / Tetrahedron Letters 51 (2010) 139–142
Figure 5. B3LYP optimized structures for the complexes of L with, (a) Trp; (b) Phe; (c) His; (d) Tyr.
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Figure 6. MM+ force field minimized structure for two complexes of Phe with L.
has been ascribed to the initial formation of 1:1 hydrogen bonded
complex between amino acid and L as demonstrated by experi-
mental (absorption and MALDI-TOF) and computational (DFT)
methods. When two such 1:1 complexes of Phe with L were min-
imized in MM+ calculations, the resultant structure indeed exhib-
ited
p–p interaction between the phenyl moieties of the glyco-
11. Glucosamine hydrochloride (0.215 g, 1 mmol) salt has been neutralized with
triethylamine in ethanol before it is used in the synthesis. To this,
salicylaldehyde (0.15 ml; 1 mmol) was added. The reaction mixture was
refluxed for 6 h at 60 °C. The solid product formed, L, (0.25 gm) was filtered and
washed with cold ethanol several times followed by diethyl ether at the end
which was dried under a vacuum. Yield: 87%. 1HNMR (DMSO-d6, ppm): 3.25–
3.80 (m, 5H, C2–H, C3–H, C4–H, C5–H), 4.54–4.95 (4d, 4H, C1–OH, C3–OH, C4–
OH & C6–OH), 5.16–5.18 (d, H, C1–H, 3JC1–H–C2–H, 5.5 Hz), 6.19–7.59 (2d, 2t, 4H,
Ar-OH), 8.6 (S, H, CH@N), 13.2 (S, H, Ar-OH). ESI-MS m/z = 284 ([M+H]+, 100%).
12. Fluorescence emission spectra were measured on Perkin–Elmer LS55
fluorescence spectrophotometer by exciting the samples at 320 nm and the
emission spectra were recorded in 330–550 nm range. The bulk solution of L
conjugate and the aromatic side chain of the amino acid, but the
H-bond(s) present in the precursor 1:1 complex were broken, as
can be seen from Figure 6. These results indeed take support of
the absorption spectral changes observed at 214 nm band. Thus L
has been shown to selectively recognize aromatic amino acids
through switch-on fluorescence and its utility in the context of bio-
molecular recognition is currently underway in our laboratory.
Acknowledgments
and amino acids were prepared in methanol in which 400 ll (4%) of water was
added for dissolving initially the amino acid. The bulk solution concentrations
C.P.R. acknowledges the financial support received from DST,
CSIR, and DAE-BRNS. A.M. and C.J.P. acknowledge CSIR for SRF.
We acknowledge Balaji Ramanujam for his help during computa-
tional calculations.
were maintained at 1 ꢄ 10ꢃ3 M. All the measurements were made in 1 cm
quartz cell and maintained the effective concentration of L as 50 lM. During
the titration different mole ratios of amino acid were added to L and the
emission of all the samples were measured after 24 h.
13. Jugun, P. C.; Acharya, A.; Kumar, A.; Rao, C. P. J. Phys. Chem. B 2009, 113, 12075.
14. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.;
Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.;
Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.;
Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,
O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken,
V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A.
J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G.
A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.;
Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.;
Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.;
Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe,
M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A.;
GAUSSIAN 03 Revision C02; Gaussian: Wallingford, CT, 2004.
Supplementary data
Supplementary data associated with this article can be found, in
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