metal binding selectivity of an n-terminally free ... · 1 metal binding selectivity of an...
TRANSCRIPT
1
Metal binding selectivity of an N-terminally free multihistidine peptideNH2-HAVAHHH-NH2
Bettina Diána Balogha, Zsolt Biharia,b, Péter Buglyóa, Gizella Csirea, Zsuzsanna Kerekesa, Márton Lukácsa, Imre Sóvágóa and Katalin Várnagya *
a Department of Inorganic and Analytical Chemistry, University of Debrecen, H-4032, Debrecen, Hungary. e-mail: [email protected] Gedeon Richter Plc, PO Box 27, Budapest 10, H-1475, Hungary (current workplace)
* Corresponding author (e-mail: [email protected], tel: + 36 52 512 900, fax: + 36 52 518 660)
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018
2
Figure S1 The HPLC chromatogram (a) and MS spectrum (b) of NH2-HAVAHHH-NH2 ([C35H51N16O7]+ (Mr = 807.412)
269.
808
404.
208
807.
409
+MS, 0.3-0.4min #(19-26), Background Subtracted
0
1
2
3
4
5
6
4x10
Intens.
100 200 300 400 500 600 700 800 900m/z
[MH]+[M+2H]2+
[M+3H]3+
7m/z calculated: 807.412
a
b
3
Figure S2Metal ion speciation of the copper(II)–NH2-HAVAHHH-NH2 system (cCu(II) = 2.0 mM cL = 4.0 mM)
4
Figure S3
Metal ion speciation of the copper(II)–NH2-HAVAHHH-NH2 system (cCu(II) = 4.0 mM cL = 2.0 mM)
5
Figure S4:Metal ion speciation of the nickel(II)–NH2-HAVAHHH-NH2 system (cNi(II) = 2.0 mM cL = 1.0 mM)
6
Figure S5 Speciation of the model system containing nickel(II), histamine (A), Ac-HHGH (B) and tetraalanine (C) in equimolar concentration (2.0 mM). Data from ref. 36, 41, 42.
7
Figure S6CD spectra of the [NiH–3L] complex of tetraalanine42, the prion fragment Ac-KTNMKHMAG 44 and NH2-HAVAHHH-NH2 (pH = 10.95).
8
Figure S7Selected aliphatic region of the 1H–1H COSY spectrum of the free ligand (green) and that of the [NiH–3L]– complex (red) at pH = 11.5 (cL = cNi = 10.0 mM).
2.52.62.72.82.93.03.13.23.33.43.53.63.73.83.94.04.14.24.34.44.54.6f2 (ppm)
2.5
2.7
2.9
3.1
3.3
3.5
3.7
3.9
4.1
4.3
4.5
f1 (
ppm
)CH-CH2(His, C termini)
L, [NiH-3L]
CH-CH2(His, N termini)
L
CH-CH2(His, N termini)
[NiH-3L]
4.6 4.2 3.8 3.4 3.0 2.6 f2(ppm)
2.5
2.9
3.3
3.7
4.1
4.5
f1(p
pm)
9
Figure S8
Selected region of ESI-MS spectrum recorded in the nickel(II)–NH2-HAVAHHH-NH2 = 2:1 system at pH 11.0 (a) and the calculated spectrum for the species [Ni2H–6L]2– = [C35H44N16O7Ni2]2– (Mr = 916.230) (b)
458.109
458.611
459.108
459.609460.106
460.606461.105
NiHAVAHHH21_neg_MS-000001.d: -MS, 0.0-0.3min #2-18
458.115
458.616
459.113
459.614460.112
460.612461.111
461.612
[C H N O Ni ] , M, 458.11535 44 16 7 22-
0
500
1000
1500
2000
2500
3000Intens.
0
1000
2000
3000
4000
458.0 458.5 459.0 459.5 460.0 460.5 461.0 461.5 m/z
461.606
b
a
10
Figure S9
CD spectrum of the [CuNiH–5L]– mixed metal complex of NH2-HAVAHHH-NH2 (pH = 10.92) together with CD spectra of dinuclear copper(II) and nickel(II) complexes and the superposition of latter two spectra.
11
Figure S10
UV-Vis spectra of the major species formed in the [(η6-p-cym)Ru(H2O)3]2+–NH2-HAVAHHH-NH2 system at 1:1 (pH = 2.54) (a), 2:1 (pH = 2.70) (b) ratios and the spectra of [(η6-p-cym)Ru(H2O)3]2+ solution at pH = 2.11 (c) and pH = 3.12 (d)
0
200
400
600
800
1 000
1 200
250 300 350 400 450 500
ε[M
-1cm
-1]
λ [nm]
dc
a
b
12
Figure S11
pH-dependent 1H NMR spectra of the [(η6-p-cym)Ru(H2O)3]2+–NH2-HAVAHHH-NH2 system.
5.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.89.0f1 (ppm)
3.31
4.79
6.60
5.76
7.20
7.76
8.44
9.43
10.4811.04
δ (ppm)
Hε1complex Hε1ligand Hδ2ligand and complex p-cymolcomplex
9.0 8.6 8.2 7.8 7.4 7.0 6.6 6.2 5.8 5.4
13
Figure S12
Selected region of ESI-MS spectrum recorded in the [(η6-p-cym)Ru(H2O)3]2+–NH2-HAVAHHH-NH2 = 1:1system at pH 2.54 (b) and calculated spectrum for the species [(MH2L)Cl]3+ = [C35H52N16O7(RuC10H14)Cl]3+ (Mr = 1079.403) (b)
357.
804
358.
138
358.
470
358.
803
359.
136
359.
470 35
9.80
336
0.13
736
0.46
936
0.80
336
1.13
636
1.47
036
1.80
4
+MS, 1.3-1.9min #75-106
357.
802
358.
136
358.
468
358.
801
359.
134
359.
468 35
9.80
136
0.13
536
0.46
736
0.80
136
1.13
436
1.46
836
1.80
2
0.0
0.5
1.0
1.5
2.0
5x10
Intens.
0
500
1000
1500
2000
358 359 360 361 362 m/z
[(RuC H )C H N O ClH ] , m/z, 359.80110 14 35 50 16 7 23+
a
b