electronic supplementary information for · figure s4. the cd spectra of the copper(ii)–hhgh...
TRANSCRIPT
1
Electronic supplementary information for
Attila Jancsó, Zoltán Paksi, Noémi Jakab, Béla Gyurcsik, Antal Rockenbauer and Tamás
Gajda*
Solution chemical properties and catecholase-like activity of the copper(II)-Ac-His-His-
Gly-His-OH system, a relevant functional model for copper containing oxidases
Figure S1. pH dependence of the UV-Vis spectra (A) of the copper(II)–hhgh system ([CuII] =
[hhgh] = 0.7 mM, T = 298 K, I = 0.1 M NaCl, pH = 2.6-11.0), and the individual electronic
absorption spectra of the formed species (B).
0.0
0.1
0.2
0.3
0.4
0.5
300 400 500 600 700 800
Wavelength (nm)
A
A
300 400 500 600 700 8000
100
200
300 B� � � �� � � �� � � � �� � � � �� � � � �� �(M-1 c
m-1)
Wavelength (nm)
2
Figure S2. Calculated EPR spectra of the individual species formed in the copper(II)-hhgh
system
2800 3000 3200 3400
Magnetic field (G)
Cu(II)
CuHL
CuL
CuH-1L
CuH-2L(a)
CuH-2L(b)
CuH-3L
3
Figure S3: Inhibition of the Nitroblue Tetrazolium (NBT) reduction as a function of the
copper(II) concentration in 0.05 M phosphate buffer (�: [Cu2+
] = [hhgh], pH = 6.8; �:
[Cu2+
] = [hhgh], pH = 7.5; �: [Cu2+
] = 0.1[hhgh], pH = 7.5). The inhibition caused by Cu,Zn-
SOD is shown in the insert. The following species are present in the solutions:
Cu2+
(32%), CuL (35%) and CuH–1L (28%) at pH 6.9 and [Cu2+
] = 0.95[hhgh] = 0.2 µM;
Cu2+
(10%), CuL (19%), CuH–1L (56%) and CuH–2L (13%) at pH = 7.5 and [Cu2+
] =
0.95[hhgh] = 0.2 µM;
CuL (20%), CuH–1L (63%) and CuH–2L (16%) at pH = 7.5 and [Cu2+
] = 0.1[hhgh] = 0.2 µM.
0 2x10-8
4x10-8
6x10-8
0
20
40
60
80
100
% inhibition
[Cu,Zn-SOD] (M)
0.0 2.5x10-7
5.0x10-7
7.5x10-7
1.0x10-6
0
20
40
60
80
100
% Inhibition
[Cu2+] (M)
4
Figure S4. The CD spectra of the copper(II)–hhgh system ([CuII] = [hhgh] = 0.055 mM, T =
298 K, I = 0.1 M NaCl, pH = 7.8-12.03) at different pH in 86 w% methanol-water solvent
mixture. The calculated ∆ε values are based on the total metal ion concentration.
-0.9
-0.6
-0.3
0.0
0.3
0.6
0.9
300 350 400 450 500 550 600
Wavelength (nm)
∆ε (
∆ε (
∆ε (
∆ε (M
-1cm-1)
5
Figure S5. The pH dependence of the average CD intensity between 355 and 365 nm (the
maximum detected for the spectrum of the species CuH–2L). The solid line was calculated
using pK1 = (9.6 ± 0.1) and pK2 = (11.0 ± 0.2).
0
0.2
0.4
0.6
0.8
7.5 8.5 9.5 10.5 11.5 12.5
pH
∆ε
∆ε
∆ε∆ε (M-1cm-1)