Dalton Transactions Blog

Christopher F. Blanford’s group from the University of Oxford have solved the x-ray structure for bilirubin oxidase from the plant pathogen Myrothecium verrucaria. This enzyme efficiently catalyses the oxidation of bilirubin to biliverdin, and can be used in O₂ reduction.

The authors look at the environment of the copper in the enzyme, to better understand and improve its stability  when is attached to the carbon surface of a pyrolytic graphite electrode. When attached to an electrode it can act as a cathode catalyst, and this enhanced electrocatalytic response of the material is an important step in developing viable low-temperature bio-fuel cells.

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Bilirubin oxidase from Myrothecium verrucaria: X-ray determination of the complete crystal structure and a rational surface modification for enhanced electrocatalytic O2 reduction
James A. Cracknell, Thomas P. McNamara, Edward D. Lowe and Christopher F. Blanford
Dalton Trans., 2011, DOI: 10.1039/C0DT01403F

This Dalton Transactions Hot article explores metalloligands inspired by the active site of enzymes.

Marcetta Y. Darensbourg and colleagues from Texas A& M University, look at NiFe-heterobimetallic complexes, and their bonding and structure, to increase their understanding of the features of natural bimetallic sites in enzymes.

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cis-Dithiolatonickel as metalloligand to dinitrosyl iron units: the di-metallic structure of Ni(μ-SR)[Fe(NO)2] and an unexpected, abbreviated metalloadamantyl cluster, Ni2(μ-SR)4[Fe(NO)2]3
Chung-Hung Hsieh, Rachel B. Chupik, Scott M. Brothers, Michael B. Hall and Marcetta Y. Darensbourg
Dalton Trans., 2011, DOI: 10.1039/C1DT10438A

In this Dalton Transactions Hot article, Yongge Wei, Yuan Wang and colleagues from Peking University and Tsinghua University make three rigid-rod conjugated organic-hexamolybdate hybrids, a type of organic-polyoxometalate or Lindqvist ion.

Polyoxometalates have potential for use in medicine for anti-tumour and anti-viral applications, and their unusual properties make them useful in catalysis and potentially in the electonics industry.

In this work the organic-polyoxometalates have different amino groups at the terminus, which allows the fabrication of more complicated polyoxometalate (POM) hybrid materials. The amino groups can have different rod lengths and substituents allowing tuning of the materials properties.

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Monosubstituted arylimido hexamolybdates containing pendant amino groups: synthesis and structural characterization
Yi Zhu, Zicheng Xiao, Longsheng Wang, Panchao Yin, Jian Hao, Yongge Wei and Yuan Wang
Dalton Trans., 2011, DOI: 10.1039/C1DT10168D

In this HOT article, a  low-dimensional compound [C₆-Apy][Ni(mnt)₂] (where mnt^2- = maleonitriledithiolate, C₆-Apy⁺ = 4-amino-1-hexylpyridinium) has been designed and synthesized, which has a layer arrangement of anions and cations and shows two steps of magnetic transitions. The low temperature magnetic transition has an uncommon hysteresis loop, while the crystal structure investigations disclosed no structural transition with the magnetic transition. The high temperature magnetic transition exhibits two remarkable features: (1) it synchronously occurs with a crystalline-to-mesophase transition in the first heating process and (2) the structural changes that accompany the solid-mesophase transition are irreversible. It is hoped that the results will shed new light on the design and preparation of a new low-dimensional molecular system combining magnetic transition and liquid crystal properties.

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A low-dimensional molecular spin system with two steps of magnetic transitions and liquid crystal property
Hai-Bao Duan, Xiao-Ming Ren, Lin-Jiang Shen, Wan-Qin Jin, Qing-Jin Meng, Zheng-Fang Tian and Shi-Ming Zhou
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C0DT01704C

This Dalton Transactions Hot article looks at the self assembly of polyhedral cages.

This builds on the authors previous work looking at coordination cages based on simple bis-bidentate bridging ligands with transition metal dications. In this paper they use new ligands with central thiophene or furan spacers, which affect the structure of the cages formed, and so the properties of these compounds.

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Molecular squares, cubes and chains from self-assembly of bis-bidentate bridging ligands with transition metal dications
Andrew Stephenson and Michael D. Ward
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10263J, Paper