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“Dual-Probe” X-Ray Absorption Spectroscopy

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Gold(I,III) Complexes Designed for Selective Targeting and Inhibition of Zinc Finger Proteins

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Abstract

XAS represents a powerful technique for probing the oxidation state and coordination sphere of Au-containing species in solution. In addition, in the context of the interaction of metallodrugs with a metalloprotein, XAS can be used in a “dual-probe” approach, by monitoring both the absorption edge of the metal complex and also the edge of the metal present in the metalloprotein. As a proof-of-concept, we evaluated the interaction of Au(III) complexes with ZnFs by monitoring the Au L3-edge and also the Zn K-edge. Furthermore, given the unique stability and reactivity of the Au(C^N) coordination motif discussed in Part II—Chap. 5, the interaction of the compound [Au(bnpy)Cl2] with ZnFs was also studied by XAS.

Parts of this chapter has been reproduced with permission from ACS. https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b02406.

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Authors and Affiliations

  1. Institute of Chemistry, University of Campinas, Campinas, Brazil

    Raphael Enoque Ferraz de Paiva

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Appendix

Appendix

1.1 XAS of Au(III) Model Compounds and TD-DFT Calculations

The spectra in Fig. 6.1 show distinguishing features in the white line region, which originate from dipole-allowed 2p3/2 → 5d transitions, containing both metal-centered 5d3/2 and 5d5/2 final states (Fig. 6.6).

Fig. 6.6
figure 6

Gold L3 XANES spectra of the Au(III) complexes evaluated here. The spectrum obtained for a Au(0) foil is also shown and the vertical line indicates its edge position (19,919 eV)

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The Au(III) compounds ([5d86 s0] electronic configuration) have white line peaks with high intensity (Fig. 6.6) in comparison to the Au(I) model compounds discussed earlier (Part I—Chap. 3, Fig. 3.5), as consequence of empty d orbitals promoting the allowed 2p3/2 → 5d transitions in the L3-edge XAS. In principle, the intensity of the white line can be used as a fingerprint of the d-electron count in these cases; however, in some cases the standard relationships between experimental Au L3-edge white line intensities and oxidation state does not hold [36]. The XANES spectrum of compound [AuCl4]− contains a sharp peak in the white line region and presents a distinct XANES spectrum when compared to compounds II-5 and II-6, [AuCl(dien)]2+ and [Au(dien)(dmap)]3+, respectively. Compounds II-5 and II-6 have their white line maxima shifted by 0.8 and 1.0 eV respectively, in comparison to compound [AuCl4]−, indicating that the dien ligand has an oxidizing effect on the Au center (higher count of d holes on Au). That suggests a higher stability of the Au(III) species bound to chelating N- donor ligands, which directly translates into higher stability under biological reducing media. Point symmetry also contributes to the intensity of the white line in the gold L3 XAS. When coordinated, dien leads to non-centrosymmetric groups. The p-d hybridization is enhanced reducing the effective d electron count in gold, thus increasing the intensity of the white line (Fig. 6.7 and Table 6.1).

Fig. 6.7
figure 7

a Experimental Au L3-edge spectra Au(III) compounds II-5 and II-6 in comparison to [AuCl4]−. b TD-DFT-calculated Au L3-edge spectra, shifted by 465 eV to lower energies. The DFT-optimized structures of teh experimental model compounds are also shown (bottom)

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1.2 EXAFS

See Figs. 6.8, 6.9, 6.10 and 6.11.

Fig. 6.8
figure 8

Comparison of the k2-weighted EXAFS of model compound [Au(N-Ac-Cys)] (M-5), with coordination sphere S-Au-S, compound [AuCl(dien)]2+ (II-5) and the reaction product II-5+NCp7

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Fig. 6.9
figure 9

a The AuF obtained when interacting II-5+NCp7 is expected to have a similar S-Au-S coordination as observed for the compound [Au(N-Ac-Cys)] (M-5). b DFT-optimized structure of [Au(N-Ac-Cys)2], highlighting the Au-S distance of about 2.30 Å

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Fig. 6.10
figure 10

Comparison of the k2-weighted EXAFS of model compound [Au(dien)(dmap)]3+ and the reaction products II-6+NCp7 and II-6+Sp1

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Fig. 6.11
figure 11

Experimental Au L3-edge spectra of a II-5+Sp1 and II-6+Sp1 and c II-5+NCp7 and II-6+NCp7. The near-edge regions are shown in (b) and (d)

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1.3 Mass Spectrometry

See Fig. 6.12.

Fig. 6.12
figure 12

Non-covalent adduct identified between compound II-6 ([Au(dien)(dmap)]3+ and the dinuclear full-length NCp7 ZnF

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Ferraz de Paiva, R.E. (2018). “Dual-Probe” X-Ray Absorption Spectroscopy. In: Gold(I,III) Complexes Designed for Selective Targeting and Inhibition of Zinc Finger Proteins. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-00853-6_6

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