Biomimicking Oxidative Bromination and DNA Nuclease Activities of a New Structurally Characterised Oxido-Diperoxidomolybdenum(VI) Complex

Abstract

A new oxido‐diperoxido molybdenum complex, [MoO(O2)2(AA)]PPh4 (AA=anthranilic acid) has been designed and synthesized. The Structural characterisation suggests that the molybdenum centre is heptacoordinated with a slight distorted pentagonal bipyramidal geometry. The pentagonal plane is completed with four oxygen atoms from two peroxido moiety and one oxygen atom from the ligand carboxylate group. Among the two axial positions one is occupied by an oxygen atom of the oxido group and the other is occupied by an oxygen atom from the ligand carboxylate moiety. The biomimicking multifunctionality of this molybdenum(VI) complex has been exhibited by the application of it as a catalyst in peroxidative bromination, whereas the nuclease activity has been established by DNA cleavage. The catalytic studies suggest that the present compound is a good biological peroxidase mimic. The DNA binding of the molybdenum complex has been studied by various physicochemical tools like UV–vis, fluorescence, viscosity. The intrinsic binding constant of the complex with DNA is calculated to be (8.14 ± 0.03) x103 M−1. All the physicochemical studies and the viscosity measurements reveal that the complex is a groove binder to CT‐DNA. The extent of ability of the complex to induce DNA cleavage was studied by gel electrophoresis techniques. The complex has been found to exhibit cleavage of pUC19 plasmid DNA with good efficiency.

THE ROLE OF cis-MoO2(BHAN)2 COMPLEX IN HALOPEROXIDASE MIMICKING OXIDATIVE BROMINATION

“…One of the widely used methods to investigate catalytic ability of metal complexes as haloperoxidases is by studying the model catalytic bromination reaction of phenol red to bromophenol blue 7 . The bromoperoxidase activity of oxido-peroxidomolybdenum complexes has also been reported in other studies 2,8 .…”

“…The role of cis-MoO2(BHAN)2 complex in the Haloperoxidase mimicking oxidative bromination 8 The obtained result indicates that the order of the reaction with respect to cis-MoO2(BHAN)2 in bromination is approximately 1, which confirms first-order dependence on the molybdenum species. Overall, this approach provides a clear and quantitative means of determining rate constant and reaction orders of the bromination reaction, paving the way for further research into the mechanism and optimization of an important chemical process.…”

Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature

“…The vanadium‐based enzyme vanadium bromoperoxidase (VBPO) catalyzes the bromide oxidation to hypobromite [46–50] . Oxido‐molybdenum motifs are used as functional models of VBPO enzyme for bromination reactions [51–54] . It has been observed that KBr with H 2 O 2 facilitates oxidative bromination reactions many folds [55–59] .…”

“…[46][47][48][49][50] Oxidomolybdenum motifs are used as functional models of VBPO enzyme for bromination reactions. [51][52][53][54] It has been observed that KBr with H 2 O 2 facilitates oxidative bromination reactions many folds. [55][56][57][58][59] Reports on molybdenum corroles have shown their utility in catalysis is scarce for brominating phenols, [60] hydrogen evolution, [61,62] and epoxidation of alkenes.…”