Spectrum–structure correlation for visible absorption spectra of copper(II) complexes in aqueous solution

Prenesti, Enrico; Daniele, Pier Giuseppe; Prencipe, Mauro; Ostacoli, Giorgio

doi:10.1016/s0277-5387(99)00279-x

Cited by 151 publications

(154 citation statements)

References 23 publications

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“…This shoulder is characteristic of copper in pentacoordinated environments. Moreover, the wavelength of the maximum is about 50 nm lower than expected if the complex had an octahedral arrangement with an N 3 O equatorial chromophore [32]. This red shift is characteristic of the pentacoordination on copper complexes, and the value of the shift is in agreement with the observed shift for one N axially coordinated [33].…”

Section: Characterization In Aqueous Solution: Uv-vis and Epr Spectrasupporting

confidence: 82%

Synthesis, structural characterization and cytotoxic activity of ternary copper(II)–dipeptide–phenanthroline complexes. A step towards the development of new copper compounds for the treatment of cancer

Iglesias¹,

Álvarez²,

Torre³

et al. 2014

Journal of Inorganic Biochemistry

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Section: Characterization In Aqueous Solution: Uv-vis and Epr Spectrasupporting

confidence: 82%

Synthesis, structural characterization and cytotoxic activity of ternary copper(II)–dipeptide–phenanthroline complexes. A step towards the development of new copper compounds for the treatment of cancer

Iglesias¹,

Álvarez²,

Torre³

et al. 2014

Journal of Inorganic Biochemistry

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“…The absorption maxima are consistent, for both peptides, with a Cu(II)(His) 3 site that might contain either one or two exogenous water ligands (predicted λ max of 634 ± 11 nm) (29). These observations prove the existence of the Cu(II)(His) 3 site in this pH region and eliminate a Cu(II)(His) 2 site for which a λ max ∼690 nm is expected (29).…”

Section: +supporting

confidence: 71%

Designing a functional type 2 copper center that has nitrite reductase activity within α-helical coiled coils

Tegoni

Yu²,

Bersellini

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

188

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One of the ultimate objectives of de novo protein design is to realize systems capable of catalyzing redox reactions on substrates. This goal is challenging as redox-active proteins require design considerations for both the reduced and oxidized states of the protein. In this paper, we describe the spectroscopic characterization and catalytic activity of a de novo designed metallopeptide Cu(I/II)(TRIL23H) 3 +/2+ , where Cu(I/II) is embeded in α-helical coiled coils, as a model for the Cu T2 center of copper nitrite reductase. In Cu(I/II)(TRIL23H) 3 +/2+ , Cu(I) is coordinated to three histidines, as indicated by X-ray absorption data, and Cu(II) to three histidines and one or two water molecules. Both ions are bound in the interior of the three-stranded coiled coils with affinities that range from nano- to micromolar [Cu(II)], and picomolar [Cu(I)]. The Cu(His) 3 active site is characterized in both oxidation states, revealing similarities to the Cu T2 site in the natural enzyme. The species Cu(II)(TRIL23H) 3 2+ in aqueous solution can be reduced to Cu(I)(TRIL23H) 3 + using ascorbate, and reoxidized by nitrite with production of nitric oxide. At pH 5.8, with an excess of both the reductant (ascorbate) and the substrate (nitrite), the copper peptide Cu(II)(TRIL23H) 3 2+ acts as a catalyst for the reduction of nitrite with at least five turnovers and no loss of catalytic efficiency after 3.7 h. The catalytic activity, which is first order in the concentration of the peptide, also shows a pH dependence that is described and discussed.

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“…Charges are omitted for clarity; possible structures of the Cu II complexes are shown in Scheme 4. configuration with four nitrogen donors in the equatorial positions of an elongated octahedron would absorb in the range of 540-580 nm. [32,34,35] A bis-type(ii) mode (i.e. a doubly protonated structure of M6 in Scheme 3) can thus be excluded for this particular complex.…”

Section: Resultsmentioning

confidence: 98%

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

Bartholomä¹,

Gisbrecht²,

Stucky³

et al. 2010

Chemistry A European J

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The hexadentate ligand all-cis-N(1),N(2)-bis(2,4,6-trihydroxy-3,5-diaminocyclohexyl)ethane-1,2-diamine (L(e)) was synthesized in five steps with an overall yield of 39% by using [Ni(taci)(2)]SO(4).4H(2)O as starting material (taci=1,3,5-triamino-1,3,5-trideoxy-cis-inositol). Crystal structures of [Na(0.5)(H(6)L(e))](BiCl(6))(2)Cl(0.5).4H(2)O (1), [Ni(L(e))]Cl(2).5H(2)O (2), [Cu(L(e))](ClO(4))(2).H(2)O (3), [Zn(L(e))]CO(3).7H(2)O (4), [Co(L(e))](ClO(4))(3) (5c), and [Ga(H(-2)L(e))]NO(3).2H(2)O (6) are reported. The Na complex 1 exhibited a chain structure with the Na(+) cations bonded to three hydroxy groups of one taci subunit of the fully protonated H(6)(L(e))(6+) ligand. In 2, 3, 4, and 5c, a mononuclear hexaamine coordination was found. In the Ga complex 6, a mononuclear hexadentate coordination was also observed, but the metal binding occurred through four amino groups and two alkoxo groups of the doubly deprotonated H(-2)(L(e))(2-). The steric strain within the molecular framework of various M(L(e)) isomers was analyzed by means of molecular mechanics calculations. The formation of complexes of L(e) with Mn(II), Cu(II), Zn(II), and Cd(II) was investigated in aqueous solution by using potentiometric and spectrophotometric titration experiments. Extended equilibrium systems comprising a large number of species were observed, such as [M(L(e))](2+), protonated complexes [MH(z)(L(e))](2+z) and oligonuclear aggregates. The pK(a) values of H(6)(L(e))(6+) (25 degrees C, mu=0.10 M) were found to be 2.99, 5.63, 6.72, 7.38, 8.37, and 9.07, and the determined formation constants (log beta) of [M(L(e))](2+) were 6.13(3) (Mn(II)), 20.11(2) (Cu(II)), 13.60(2) (Zn(II)), and 10.43(2) (Cd(II)). The redox potentials (vs. NHE) of the [M(L(e))](3+/2+) couples were elucidated for Co (-0.38 V) and Ni (+0.90 V) by cyclic voltammetry.

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Spectrum–structure correlation for visible absorption spectra of copper(II) complexes in aqueous solution

Cited by 151 publications

References 23 publications

Synthesis, structural characterization and cytotoxic activity of ternary copper(II)–dipeptide–phenanthroline complexes. A step towards the development of new copper compounds for the treatment of cancer

Synthesis, structural characterization and cytotoxic activity of ternary copper(II)–dipeptide–phenanthroline complexes. A step towards the development of new copper compounds for the treatment of cancer

Designing a functional type 2 copper center that has nitrite reductase activity within α-helical coiled coils

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

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Spectrum–structure correlation for visible absorption spectra of copper(II) complexes in aqueous solution

Cited by 151 publications

References 23 publications

Synthesis, structural characterization and cytotoxic activity of ternary copper(II)–dipeptide–phenanthroline complexes. A step towards the development of new copper compounds for the treatment of cancer

Synthesis, structural characterization and cytotoxic activity of ternary copper(II)–dipeptide–phenanthroline complexes. A step towards the development of new copper compounds for the treatment of cancer

Designing a functional type 2 copper center that has nitrite reductase activity within α-helical coiled coils

Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N1,N2‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine

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Chelation versus Binucleation: Metal Complex Formation with the Hexadentate all‐cis‐N¹,N²‐Bis(2,4,6‐trihydroxy‐3,5‐diaminocyclohexyl)ethane‐1,2‐diamine