Archive for the ‘Hot Articles’ Category

Hot Article: Activity-enhancing enzyme variant

In a collaboration between researchers at the University of Oxford, Nankai University and Tsinghua University, Luet-Lok Wong and colleagues determined the substrate-free crystal structure of a variant of CYP102A1 (P450BM3) with generic activity-enhancing properties (KT2).

The electronic properties and the catalytic behaviour of KT2 were investigated and the authors proposed that the rate accelerating properties arise from the substrate-free form being in a catalytically ready conformation, such that substrate-induced changes to the structure play a less significant role in promoting the first electron transfer than in the Wild Type.

This Hot Article will be included in a themed issue of the journal to celebrate 40 years of Dalton Transactions.

Read more for FREE until 22nd June 2011:

Structure, electronic properties and catalytic behaviour of an activity-enhancing CYP102A1 (P450BM3) variant
Christopher J. C. Whitehouse, Wen Yang, Jake A. Yorke, Henry G. Tufton, Lydia C. I. Ogilvie, Stephen G. Bell, Weihong Zhou, Mark Bartlam, Zihe Rao and Luet-Lok Wong
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10098J, Paper

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HOT article: Further insights into the mechanism of nitrogenases

In this HOT article, Ian Dance examines afresh the relationships between CO and H on nitrogenase cofactors following the recent finding that vanadium nitrogenase and modified molybdenum nitrogenase reduce CO to hydrocarbons. In order to assist the interpretation of kinetic infrared spectral data, vibrational frequencies and modes have been calculated for a variety of possible structures in which FeMo-co bears H atoms, or CO ligands, or both.

Fe–H stretching frequencies occur in the same spectral window as the C–O stretching frequencies, with lesser intensity, and both stretches are strongly coupled in some structures. Symmetrical bridging of CO between two Fe atoms of FeMo-co is destabilised by the presence of other ligands on Fe, and the reason for this is evident. Two results for bound formyl, HCO, are reported. These calculations of reference structures allow some interpretation of existing experimental spectra, but, perhaps more significantly, they suggest further kinetic infrared experiments to elucidate the chemical mechanism of catalysis by nitrogenase under normal turnover conditions.

Read more about nitrogenase mechanisms for FREE until 22nd June at:

Calculated vibrational frequencies for FeMo-co, the active site of nitrogenase, bearing hydrogen atoms and carbon monoxide
Ian Dance
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10505

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HOT article: Promise of vertical mesoporosity

In this HOT article, Wu and Yamauchi et al., reported the synthesis of highly ordered mesoporous alumina thin films existing both as P63/mmc and Fm-3m mesostructures by using triblock copolymer Pluronic P123 as a structure-directing agent and their framework crystallization to γ-alumina phase at 1000 °C. During the crystallization process, large uniaxial shrinkage occurred along the direction perpendicular to the substrate with the retention of horizontal mesoscale periodicity, thereby forming vertically oriented nanopillars on the film surface.

The well-ordered arrangement of the nanopillars can produce vertical mesoporosity in the films.This porosity can be regarded as “inverse mesospace” of a 2D hexagonal structure with “mesochannels” running perpendicular to the substrate.  This vertical mesoporosity in films is very exciting as it can enhance pore accessibility broadening the potential applications of these already much studied mesoporous metal oxides.

Read more about these exciting developments for FREE until 22nd June at:

Synthesis of highly ordered mesoporous alumina thin films and their framework crystallization to gamma-alumina phase
Xiangfen Jiang, Hamid Oveisi, Yoshihiro Nemoto, Norihiro Suzuki, Kevin C.-W. Wu and Yusuke Yamauchi
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10166H

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Exploring the mechanism of an unusual C-N elimination

In their Dalton Transactions Hot Article, Lauren Huffman and Shannon Stahl investigate an unusual trans C–N reductive elimination reaction from a square-planar aryl-CuIII complex. Their research provides valuable fundamental insights into the emerging area associated with the organometallic chemistry of copper(III).

Available to read for free until the 12th June – strike while the articles hot!

Mechanistic analysis of trans C–N reductive elimination from a square-planar macrocyclic aryl-copper(III) complex
Lauren M. Huffman and Shannon S. Stahl
Dalton Trans., 2011, DOI: 10.1039/C1DT10463B, Paper

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HOT Article: Bilirubin oxidase based bio-fuel cells

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.

Read the full article for FREE to find out more about bilirubin oxidase…

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

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HOT Article: Metalloligands

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.

Read the full article for FREE to find out more about these metalloligands…

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

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HOT Article: Rigid-rod Polyoxometalates

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.

Read the full article for FREE to find out more about these functionalized Lindqvist ions…

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

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HOT article: A new spin on liquid crystals

In this HOT article, a  low-dimensional compound [C6-Apy][Ni(mnt)2] (where mnt2- = 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

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HOT Article: Self assembled coordination cages

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.

Read the full article to find out more about these coordination cages…

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

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Hot Article: Picking the perfect pincer

In their recent paper Han Vinh Huynh and his team from the National University of Singapore discuss the coordination of new CSC pincer ligands with a range of transition metals and compare their catalytic activity in hydroamination reactions.

Specifically the group investigate 4,5-dichloroimidazolin-2-ylidene based ligand systems, in which pincer- versus pseudo-pincer formation is strongly influenced by the electron-donating abilities of the carbenes. Read more in their Dalton Transactions Hot Article – just published! This will be FREE to read until 24th May 2011.

CSC-pincer versus pseudo-pincer complexes of palladium(II): a comparative study on complexation and catalytic activities of NHC complexes
Dan Yuan, Haoyun Tang, Linfei Xiao and Han Vinh Huynh
Dalton Trans., 2011, DOI: 10.1039/C1DT10269A, Paper

In the mean time why not read some other recent Dalton Transactions themed issues.

The article will appear in Dalton Transactions forthcoming themed issue focussing on Pincer ligands. Look out for this issue when it is published in early autumn this year!

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