Electronic Supporting Information
Potent inhibition of protein tyrosine phosphatases by copper
complexes with multi-benzimidazole derivatives
Ying Lia, Liping Lu*a, Miaoli Zhu*ac, Qingming Wanga, Caixia Yuana, Shu Xingb, Xueqi
Fu*b and Yuhua Meic
a
Institute of Molecular Science, Key Laboratory of Chemical Biology and Molecular Engineering
of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, P. R. China
E-mail: [email protected]; [email protected]
b
Edmond H. Fischer Signal Transduction Laboratory, College of Life Sciences, Jilin University,
Changchun 130023, P. R. China
E-mail: [email protected]
c
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210093, P. R.
China
Appendix A. Supplementary data
Electrospray ionization mass spectra (ESI-MS) of the complexes 1–5, pH
titration curves of NTB and Cu(II)/NTB systems in methanol aqueous
solution, species distribution as a function of pH for NTB, fluorescence
emission spectra of the titration of PTP1B with 4.
S1 ESI-MS of the complexes 1 - 5.
Fig. S1 ESI-MS spectra of 1 in methanol solution: the positive ion mode (+p): analysi: m/z:
307.17(100%) {[(1)2-2H2O-Cl+2CH3OH+2H]3+ 307.03}, 406.25(60%)
{[1-H-H2O-2Cl+CH3OH)]+ 406.07}, 630.67(20%) {[(1)3-H-5H2O-2Cl+ CH3OH]2+ 630.02}.
Fig. S2 ESI-MS spectra of 2 in methanol solution, the positive ion mode (+p), ESI-MS:
505.83(100%), {[2-Cl]+, 506.47}; 529.00(10%), {[2-Cl-H+Na]+, 528.45}
Fig. S3 ESI-MS spectra of 3 in methanol solution, the positive ion mode (+p), m/z: 322.08(100)%
{[3-2Cl]2+ 322.12}, 642.42(14%) {[3-2Cl-H]+ 642.20}, 678.17(10%) {[3-Cl]+ 678.18}
Fig. S4 ESI-MS spectra of 4 in methanol solution, the positive ion mode (+p), m/z: 865.25(100%)
{[4-2Cl-H]+ 865.78}, 433.50(88%) {[4-2Cl]2+ 433.40}, 415.67(22%) {[4-3Cl-H]2+ 415.17},
829.33(18%) {[4-3Cl-2H]+ 829.32}.
Fig. S5 ESI-MS spectra of 5 in methanol solution, the positive ion mode (+p), m/z: 458.08(100%)
{[5-3Cl-H]2+ 457.72}, 914.33(55%) {[5-3Cl-2H]+ 914.43}, 475.53(30%) {[5-2Cl]2+ 475.95},
949.83(5%) {[5-2Cl-H]+ 950.89}, 440.25(10%) {[5-4Cl-2H]2+ 439.49}.
S2 pH-potentiometric titrations
10
9
8
pH
7
Measure
Fit
6
5
4
3
0.0
0.5
1.0
1.5
2.0
V(NaOH)/mL
Fig. S6 pH titration curves of NTB system in methanol-water solution (1:3 v/v), I = 0.2 M (NaCl), 25 ºC,
initialization: [NTB] = 0.025mM, [HCl] = 0.175mM.
Fig. S7 Species distribution as a function of pH for NTB
9
8
Measure
Fit
pH
7
6
5
4
1.0
1.5
2.0
V(NaOH)/mL
Fig. S8 pH titration curves of Cu2+/NTB system in methanol-water solution (1:3 v/v), I = 0.2 M (NaCl), 25 ºC,
initialization: [Cu2+] = [NTB] = 0.025mM, [HCl] = 0.175mM.
Fluorescence study on the interaction between PTP1B and complex 4
(a)
(b)
Figure S9 (a) Fluorescence emission spectra of the titration of PTP1B with 4 in 20 mM MOPS, 50 mM NaCl,
pH 7.2 at 310 K. [PTP1B] = 0.46 μM, [2]/[PTP1B] = 0 (a), 0.25 (b), 0.5 (c), 0.75 (d), 1.0 (e), 1.25 (f), 1.5 (g), 1.75
(f), 2.0 (g), 2.25 (h), 2.5 (i), 2.75 (j), 3.0 (k), 3.5 (l), 4.0 (m), 4.5 (n), 5.0 (o), 5.5(p), 6(q). (b). A plot of the
intensities of emission at 335 nm against the ratio [2]/ [PTP1B] at 310 K..
Figure S10 Stern–Volmer plots for the quenching of PTP1B by 4 at 310 K