On the Interaction of Copper(II) Complexes Cu(Gly)₂⁰, Cu(Bipy)Gly⁺, and Cu(Bipy)₂²⁺ with Glutathione

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The interaction of three copper(II) complexes — Cu(Gly)₂⁰, Cu(Bipy)₂²⁺, and Cu(Bipy)Gly⁺ — with glutathione in aqueous solution (pH 7.4, 0.2 M NaCl, 25°C, сCu = (1–10) × 10–4, сGSH = 1.0 × 10–3 M) was studied. These and similar complexes are often used in biological experiments to test anticancer and antimicrobial activity. It was shown that under physiological conditions copper(II) complexes are almost irreversibly converted into a more stable form of copper(I) thiolate complexes. The individuality of the initial complexes is completely lost. In all cases, the redox interaction of the copper(II) complexes with glutathione was rapid and quantitative. The main products were copper(I) bisthiolate complex and glutathione disulfide.

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作者简介

I. Mironov

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: imir@niic.nsc.ru
俄罗斯联邦, Novosibirsk

V. Kharlamova

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: imir@niic.nsc.ru
俄罗斯联邦, Novosibirsk

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2. Fig. 1. UV spectra of solutions containing Cu(I) + GSH. cCu = 1.50 × 10⁻⁴ M, cGSH (10⁻⁴ M): 1.86 (1), 2.04 (2), 2.21 (3), 2.53 (4), 2.83 (5), 4.13 (6), 5.58 (7), 7.01 (8), 8.42 (9), 9.81 (10). pH 7.4, 0.2 M NaCl, l = 1 cm.

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3. Fig. 2. UV spectra of solutions containing Cu(II) + Gly + GS*; cCu = 1.0 × 10⁻⁴ M, pH 7.4, 0.2 M NaCl, l = 1 cm, cGly = 4.21 × 10⁻⁴ M, without buffer (1); cGly = 4.0 × 10⁻⁴ M (2); cGly = 3.81 × 10⁻⁴ M, cGS* = 1.0 × 10⁻³ M (3); cGly = 4.0 × 10⁻³ M (4); cGly = 3.8 × 10⁻³ M, cGS* = 1.0 × 10⁻³ M (5); сGly = 4.0 × 10⁻² M (6); cGly = 3.9 × 10⁻² M, cGS* = 1.0 × 10⁻³ M (7); сGly = 1.0 × 10⁻³ M (without Cu2+, GS*, NaCl) (8).

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4. Scheme 1.

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5. Fig. 3. UV spectra of the forms. Initial complex Cu(Bipy)₂²⁺ (3.77 × 10⁻⁵ M) (1); solution after addition of GS* (1.0 × 10⁻³ M), time after mixing τ ≈ 6 s; symbols (∆) — calculation (2); Bipy (1.0 × 10⁻⁴ M) (3); Cu(GS)2* (4.75 × 10⁻⁵ M) (4); GS* (1.00 × 10⁻³ M) (5); GSSG* (1.0 × 10⁻⁴ M) (6). pH 7.4, 0.2 M NaCl, l = 1 cm.

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6. Fig. 4. UV spectra of solutions: Cu(Bipy)Gly+ (5.0 × 10⁻⁵ M) (1); after addition of GS* (1.0 × 10⁻³ M), τ = 6 s–5 min (2); KNO₃ (2.5 × 10⁻⁴ M) (3). pH 7.4, 0.2 M NaCl, l = 1 cm.

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7. Fig. 5. Changes in the UV spectra of Cu(Bipy)Gly⁺ solution after reduction: τ = 6 s (1); 2–6 — experimental spectra of the solution after 10, 20, 30, 50, 80 min, respectively; 2'–6' — spectrum of the new form for the same time intervals. withCu = 5.0 × 10⁻⁵ M, pH 7.4, 0.2 M NaCl, l = 1 cm.

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