On Polymer Complexes of Gold(I) with Glutathione in Aqueous Solution

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Abstract

Processes involving gold(I) glutathionate complexes in aqueous solution at t = 25°C and I = 0.2 M (NaCl) in the pH range 7.20–6.06 (CAu = (5–10 × 10–4 M)) were studied. Using mass spectrometry, it was shown that at CGS > CAu, in addition to monomeric Au(GS)2*, there can exist polymeric forms Au4(GS)4*, as well as Aun(GS)n+1*, where n ≤ 4, the symbol * means the sum of forms of different degrees of protonation. From UV spectroscopy it follows that in the entire region of 0.5 < CGS/CAu < 3, spectra of four forms, including Au(GS)2*, are sufficient to describe all spectra within experimental errors in the form of a linear combination. As pH decreases, the proportion of Au(GS)2* decreases. The equilibrium constant 0.25 Au4(GSH)44– + GSH2– = Au(GSH)23– + H+ is equal to lgK = –4.4 ± 0.1 (I = 0.2 M, NaCl).

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I. V. Mironov

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

Author for correspondence.
Email: imir@niic.nsc.ru
Russian Federation, Novosibirsk, 630090

V. Yu. Kharlamova

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

Email: imir@niic.nsc.ru
Russian Federation, Novosibirsk, 630090

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3. Scheme 1

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4. Fig. 1. a) UV spectra of solutions for pH 7.20. CAu = (7.0-5.4) × 10-4, CGS = (3.5-13.9) × 10-4 M. X = 0.5 (1), 0.75 (2), 0.84 (3), 0.93 (4), 1.19 (5), 1.36 (6), 1.53 (7), 1.84 (8), 2.13 (9), 2.56 (10). b) dependences of ε* (= A/lCAu) on X (= CGS/CAu) for pH: 7.20 (1), 6.66 (2), 6.36 (3), 6.06 (4).

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5. Fig. 2. Spectra of solutions having different pH (6.66, 6.36, 6.06) but the same A330 absorbance at λ = 330 nm. A330 = 0.800 (1), 0.600 (2), 0.400 (3), 0.200 (4). 5 - spectrum of Au(GS)2* (CAu = 5.0 × 10-4 M); l = 1 cm. At λ < 310 nm the difference increases due to different amounts of Au(GS)2*.

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6. Fig. 3. Examples of spectra decompositions, pH 7.20. Baseline spectra (CAu (10-4 M), X): 7.0, 0.50 (1); 6.7, 0.84 (2); 6.4, 1.19 (3); 4 - spectrum of Au(GS)2* (5.0 × 10-4 M). Decomposable spectra (icons are calculations): 6.75, 0.75 (5); 6.11, 1.53 (6); 5.79, 2.0 (7). X = CGS/CAu. l = 1 cm.

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