A Chloro‐Bridged Linear Chain Imine‐Copper(II) Complex and Its Application as an Enzyme‐Free Amperometric Biosensor for Hydrogen Peroxide

Abstract

The synthesis, structural characterisation and magnetic properties of a new chloro‐bridged linear chain imine‐copper(II) compound are reported. The results indicate that uniform chains are formed by stacking of parallel pyramidal units formed from the copper centre coordinated to the imine ligands and bridged by chloride ions, with the uncoordinated perchlorate ions located between the layers to balance the charge. Magnetic measurements carried out on a powder sample at temperatures from 1.8 to 290 K and a field of 500 Oe, indicated an intramolecular magnetic coupling between the copper centres [J/k = (–12.3 ± 0.2) K]. Moreover, an antiferromagnetic interaction can also be observed between the polynuclear arrays [J′ z/k = –(10.4 ± 1.7) K]. An analysis of the sample at high temperature indicated that the overall interaction would be antiferromagnetic (ΘCW = –14 K). Furthermore, this new inorganic‐organic zigzag polymer was linked covalently to the poly(N‐vinylimidazole) polymer, PVI, on a vitreous carbon electrode surface and used as a biomimetic material for the efficient analytical determination of hydrogen peroxide. Raman spectroscopy and electrochemical techniques were used to give a complete characterisation of the hybrid film obtained. The proposed enzyme‐free biosensor for catalase‐like activity exhibited good sensitivity (268 mA mol–1 L cm–2) at –0.4 V relative to the. SCE in a phosphate buffer solution (pH 7.0) and a wide linear range from 1 to 30 mmol L–1 for hydrogen peroxide detection.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Approaches for multicopper oxidases in the design of electrochemical sensors for analytical applications

“…However, although they show outstanding activity and high specificity and selectivity, they have the drawback that they must work at near physiological conditions and are often expensive and unstable during extended usage, although their active lifetimes can be increased by immobilization on electrode surfaces via entrapment, chemical bonding, and cross-linking [15][16][17]. However, these limitations have led to extensive efforts to the synthesis of enzymeless biosensors with a center that is like the three-dimensional catalytic active site of the enzymes [18][19][20][21][22].…”

Mononuclear–Dinuclear Equilibrium of Grafted Copper Complexes Confined in the Nanochannels of MCM‐41 Silica

“…[45] In contrast, chloride ion has a strong capacity to coordinate metal cations. [70][71][72][73] We therefore concluded that a hydrogen-bonding system consisting of perchlorate anions, hydroxide ions, and the protonated amino groups is most likely present in the form of ÀOH···X À ··· + H 3 NÀ. TG analysis showed that the amount of water confined in the channels was strongly dependent on the counteranion of the copper salt and the surface hydrophobicity ( Figure 5 and Figure S5 in the Supporting Information).…”

Nanoflakes of an aminoacid-based chiral coordination polymer: Synthesis, optical and electrochemical properties, and application in electrochemical sensing of H2O2

“…Among the new type of electrochemical sensor based on CPs, which was rarely reported, [Cu 2 (tyr) 2 (bipy)] n -CPE showed performance similar to that of [Cu(tyr) 2 ] n /GCE [11] and linear detection range wider than that of GC/PVI/[Cu(2pymehist)Cl](ClO 4 ) [5]. …”

“…However, researches on the electrochemistry of CPs are rare, still less those on CPs' application in electrochemical sensing. In some of these cases, CPs just acted as supporters [3], while in others, they showed inherent electro activity [4,5]. Considering the redox activity of metal elements and/or ligands, and good electric conductivity and nanostructures that CPs may have, we think that proper designed CPs may show good electrochemical properties.…”