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spectrum (ESI): m/z 659 {[Cu2(phpda)(H2O)(ClO4)]
Magnetic moment, meff (tot.): 2.26mB; meff/Cu: 1.60mB.
+
H}+.
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Catalytic hydrolysis of glycosides
In order to study the glycosidase activity of the complexes,
solutions of 1 and 2 (1.0 ꢃ 10ꢂ5 M) in water at pH ꢀ 10.5 (50
mM CAPS buffer) were treated separately with 100 equivalents
of p-nitrophenyl-a-D-glucopyranoside and p-nitrophenyl-b-D-
glucopyranoside under aerobic conditions at room tempera-
ture. Absorbance vs. wavelength plots were recorded for these
solutions at a regular time interval of 10 min in the range 365–
500 nm. The reaction was monitored over the time by formation
of p-nitrophenolate using UV-vis spectroscopy at 410 nm (3 ¼
16 190 Mꢂ1 cmꢂ1).50–52 The dependence of rate on substrate
concentration and various kinetic parameters were determined
by treating a 1.0 ꢃ 10ꢂ5 M solution of complexes 1 and 2 with
different concentrations of p-nitrophenyl-a-D-glucopyranoside
and p-nitrophenyl-b-D-glucopyranoside (2.0 ꢃ 10ꢂ4 M to 1.0 ꢃ
10ꢂ3 M).
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DFT calculations
Theoretical calculations regarding the structure optimization,
Fukui function (fk+) of the metal sites of complexes 1 and 2 were
+
performed with the Gaussian 03 soware.53 The functions (fk
)
were evaluated from single point calculations using the B3LYP54
method and 6-311G55 basis set at the optimized geometry, per-
formed for N and (N + 1) electron systems, where N is the total
number of electrons in the system. In a nite difference
approximation, fk+ of an atom k, in a molecule with N electrons,
+
is expressed by the equation fk ¼ [qk(N) ꢂ qk(N + 1)], where qk is
the charge of atom k.56 The qk values were calculated by Mul-
liken population analysis (MPA).
Acknowledgements
The authors would like to acknowledge the Council of Scientic
& Industrial Research (CSIR) (Grant no. 01(2732)/13/EMR-II),
New Delhi for funding and nancial support. The instru-
mental facilities provided by the DST-FIST and UGC-SAP
program in the Department of Chemistry are greatly acknowl-
edged. The authors acknowledge the Contingency Grant
provided by the DST-PURSE program in the Department of
Chemistry. A. P. also thanks the University of Kalyani for
providing a university research fellowship.
26 M. Gonzalez-Alvarez, G. Alzuet, J. Borras, S. Garcia-Granda
and J. M. Montejo-Bernardo, J. Inorg. Biochem., 2003, 96, 443.
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Yazigi, M. T. Garland and J. Manzur, Inorg. Chem., 2004,
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62860 | RSC Adv., 2014, 4, 62851–62861
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