Mono‐ versus Binuclear Copper(II) Complexes in Phosphodiester Hydrolysis

Abstract

(2) have been synthesized and characterized by X-ray crystallography. Complexes 1 and 2 were then tested as catalysts for the hydrolysis of bis(p-nitrophenyl)phosphate (BNPP). At pH 6, the dinuclear complex 2 was found to be 20-fold more active than complex 1 and the reaction up to 600-fold faster than the un-promoted reaction. On the basis of potentiometric studies, we were

Unique Ligand‐Based Oxidative DNA Cleavage by Zinc(II) Complexes of Hpyramol and Hpyrimol

“…The equatorial plane is defined by the pyridine nitrogen atom N11 and the bridging phenolate oxygen atom O1 of a pyramol ligand and by the two oxygen atoms O20 and O21 from an acetato ligand ( Figure 1). The inplane angles range from 58.40 (11) to 104.93(11)8, which reveals the distorted geometry. The equatorial Zn À N and Zn À O bond lengths [25,29] as well as the bond lengths observed for the bidentate acetate [30] can be considered as normal.…”

“…[31] The reaction of zinc(II) chloride with Hpyramol in acetonitrile gives rise to the formation of the crystalline complex [Zn 2 Cl 2 A C H T U N G T R E N N U N G (pyramol) 2 ]·2 CH 3 CN (3) within a day. Compound 3 (12), O21-Zn1-O20 58.40(11), O20-Zn1-O1 98.02(11), N2-Zn1-O1' 156.73 (11). Symmetry operation ': 1Àx, Ày, 1Àz.…”

“…[4,5] Among the different therapeutic strategies to eradicate cancer cells through DNA damage, the view of using small water-soluble transition-metal complexes, capable of oxidative or hydrolytic DNA cleavage as anti-cancer drugs, is a challenging topic in bioinorganic chemistry. [6,7] Many transition-metal complexes with V, [8] Fe, [9] Cu, [10,11] Co, [12] lanthanides, [13,14] and also actinides [15] have been reported as efficient DNA cleaving agents with or without sequence specificity. Of these metals, zinc is the second most abundant transition-metal ion present in the human body, [16,17] and is in the active sites of several enzymes such as superoxide dismutase, proteins containing zinc finger motifs and zinc hydrolases, in particular, owing to its Lewis acid character.…”

Supramolecular Complexes Formed by the Self-assembly of Hydrophobic Bis(Zn²⁺-cyclen) Complexes, Copper, and Di- or Triimide Units for the Hydrolysis of Phosphate Mono- and Diesters in Two-Phase Solvent Systems (Cyclen=1,4,7,10-Tetraazacyclododecane)

“…, and their activity for the hydrolysis of MNP and a phosphate diester, bis(4-nitrophenyl) phosphate (BNP) [48][49][50][51][52][53][54][55][56][57][58][59][60] in two-phase (water-organic) solvent systems. ) were synthesized as shown in Chart 3.…”

“…Although there are various artificial metal complexes that promote BNP hydrolysis, [48][49][50][51][52][53][54][55][56][57][58][59][60] complexes that function as catalysts remain limited. [49][50][51] The hydrolytic activity of 10b (20 µM) for BNP (100 µM) was examined in CHCl 3 -50 mM HEPES buffer (pH 7.4) with I=0.1 (NaNO 3 ) (2 : 8) at 37°C.…”