Archive for the ‘Hot Articles’ Category

Hot Article: Iron Chelators for Iron Overload

Iron is a biological necessity and the amount we take-in must be carefully controlled – normally this isn’t a problem as eating a varied, healthy diet provides us with the nutrients we need. Once we have an adequate concentration of iron our intestines then stop absorbing it, preventing a surplus building up.

Fe chelating ligand

This absorption control is usually very effective as eating and drinking is our main source of iron, however after a blood transfusion excess iron can be introduced into the body and there is no natural mechanism to remove the unwanted metal ions. Some diseases such as Diamond–Blackfan anemia or β-thalassemia can require regular treatment by blood transfusion, which can lead to acute iron overload. This can be very harmful as iron can build up in vital organs such as the heart and liver and cause irreversible organ damage.

Iron chelating agents offer a treatment for Fe overload by binding to the excess iron ions, allowing them to be safely excreted before they build up and cause damage to the body. This Hot Article by Professor Des Richardson and Professor Paul Bernhardt et al. details the synthesis and characterisation of a series of dithiocarbazate Schiff base analogues for their suitability as iron chelators. Schiff bases are previously known as chelation ligands, but the derivatives detailed here show some interesting biological activities…

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Heterocyclic dithiocarbazate iron chelators: Fe coordination chemistry and biological activity
Maram T. Basha, Jy D. Chartres, Namfon Pantarat, Mohammad Akbar Ali, Aminul Huq Mirza, Danuta S. Kalinowski, Des R. Richardson and Paul V. Bernhardt
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12387H

This article will be part of our upcoming themed issue on Metals in Medicine: Non-Cancer Therapeutics – other hot papers due to be published in this special themed issue include the HOT Article: Anti-microbials that target destabilised DNA and the Hot Perspective: Treating Wilsons Disease.

You can also keep up to date with the latest news in inorganic chemistry by following us on twitter or signing up to our e-alert service.

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Cerium cation behaviour could change water splitting studies

Scientists in Germany and Japan have shown that cerium(IV) predominantly forms a dinuclear complex in aqueous solution. Until now, scientists had thought that tetravalent cerium was a monomeric species in aqueous solution. The finding could have important implications for scientists studying water oxidation. 

Atsushi Ikeda-Ohno from the Helmholtz-Zentrum Dresden Rossendorf, Dresden, and colleagues used a combination of extended X-ray absorption fine structure and density functional theory calculations to study the cerium(IV) cation. ‘In an aqueous solution, the primary form of metal cations is generally a simple mononuclear hydrate complex or a mononuclear oxo-cation,’ says Ikeda-Ohno, ‘but cerium(IV) forms a unique oxo- or/and hydroxo-bridging dinuclear complex.’  

A combined X-ray absorption spectroscopy and density functional calculation study has revealed that a single oxo-bridging dinuclear complex is the dominant form of soluble Ce(IV) species in an aqueous perchloric acid solution.

‘We have always assumed that any reaction between a catalyst and a cerium salt is a one electron transfer reaction,’ says Curtis Berlinguette from the University of Calgary, Canada, who studies the mechanistic behaviour of homogeneous water oxidation catalysts using cerium salts as the terminal oxidant. ‘But if cerium(IV) does exist as a dimer and has an oxo bridge, then it really does question these assumptions and, more importantly, the nature of the oxygen-oxygen bond formation step.’ 

Berlinguette explains that the current assumption is that you make a catalyst with the metal oxo unit and that reacts with water. But, if the cerium salt that exists in solution contains an oxo, then you could potentially have a combination between the cerium(IV) oxo and the metal oxo, producing oxygen. Therefore, what might appear to be a water oxidation catalyst is in fact just forming dioxygen through reaction with the cerium salt. 

‘It would be really interesting if Ikeda-Ohno’s team could extend this study to the acidic conditions and concentrations that are more widely used by the homogeneous catalytic water oxidation community. Then we will have much more insight into what species we are actually studying in solution,’ says Berlinguette. 

Ikeda-Ohno says that developing time-resolved systems for X-ray techniques to probe the reactions of the cerium(IV) is the team’s next challenge. 

Written by Rachel Cooper 

Dinuclear complexes of tetravalent cerium in an aqueous perchloric acid solution
Atsushi Ikeda-Ohno, Satoru Tsushima, Christoph Hennig, Tsuyoshi Yaita and Gert Bernhard
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12406H

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A deeper understanding of Pt-guanine complexes

N7-substituted guanine intermolecular hydrogen bondingBernhard Lippert and colleagues have followed up on their previous Dalton Transactions article with further insights into the coordination of guanine to a platinum centre.

The team’s goal is to create platinated nucleobase analogues capable of recognising natural DNA. However, due to the many potential tautomeric forms of guanine, more questions on the hydrogen bonding of these Pt-guanine complexes need to be answered.

In their latest Dalton Transactions article, Lippert and co-workers discuss the solution and solid state behaviour of 7-methylguanine and determine if the Pt complex is able to recognise 1-methylcytosine through Watson–Crick base pairing.

See what they found out by downloading the HOT article now – it’s free to access until 26th March.
7-Methylguanine: protonation, formation of linkage isomers with trans-(NH3)2PtII, and base pairing properties
Ágnes Kozma, Susana Ibáñez, Radu Silaghi-Dumitrescu, Pablo J. Sanz Miguel, Deepali Gupta and Bernhard Lippert

To read their previous article…
Pt(II) complexes of unsubstituted guanine and 7-methylguanine
Deepali Gupta, Ralf Nowak and Bernhard Lippert, Dalton Trans., 2010, 39, 73–84

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Hot Paper: Schiff base-cobalt(II) coordination polymer with anti-cancer activity

The ligand, 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (isonicotinic) hydrazone, is coordinated through the ONO donor atoms to one   Co(II) metal center and bridged through the pyridine nitrogen atom to another similar Co(II) center to form a 1D polymeric unit.

The ligand, 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (isonicotinic) hydrazone, is coordinated through the ONO donor atoms to one Co(II) metal center and bridged through the pyridine nitrogen atom to another similar Co(II) center to form a 1D polymeric unit.

Karuppannan Natarajan and colleagues have synthesised and characterised the Co(II) complex, {[Co(H2L)(H2O)2](NO3)2·3H2O}n.  Human cancer cytotoxicity studies have shown the complex is very specific for cancer cells and less toxic in comparison to the well-know cancer drug, cisplatin.

To find out more you can download this article now, which is free to access for 4 weeks!

A novel water soluble ligand bridged cobalt(II) coordination polymer of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde (isonicotinic) hydrazone: evaluation of the DNA binding, protein interaction, radical scavenging and anticancer activity
Duraisamy Senthil Raja,  Nattamai S. P. Bhuvanesh and Karuppannan Natarajan
Dalton Trans., 2012
DOI: 10.1039/C2DT12274J

Take a look at some of the other papers published recently in Dalton Transactions on Schiff base complexes of transition metal ions…

Structural and luminescence studies of nickel(II) and copper(II) complexes with (1R,2R)-cyclohexanediamine derived unsymmetric Schiff base
Magdalena Barwiolek, Edward Szlyk, Tadeusz M. Muzioł and Tadeusz Lis
Dalton Trans., 2011, 40, 11012-11022
DOI: 10.1039/C1DT10882D

The unprecedented preparation of dinuclear zinc(II) complexes from 4-halido-2-[(3-cyclohexylaminopropylimino)methyl]phenol
Zhong-Lu You, Mei Zhang and Dong-Mei Xian
Dalton Trans., 2012, 41, 2515-2524
DOI: 10.1039/C1DT11566A

Heterocyclic dithiocarbazate iron chelators: Fe coordination chemistry and biological activity
Maram T. Basha, Jy D. Chartres, Namfon Pantarat, Mohammad Akbar Ali, Aminul Huq Mirza, Danuta S. Kalinowski, Des R. Richardson and Paul V. Bernhardt
Dalton Trans., 2012
DOI: 10.1039/C2DT12387H

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Organoimido derivatives of POMs

Polyoxometalates (POMs) are interesting inorganic compounds that contain transition metal ions linked together by bridging oxygen atoms to form large three dimensional frameworks. Even though POMs have been studied for a long time (the first polyoxometalate was reported nearly 200 years ago by the Swedish chemist, Jons Jacob Berzelius), there has been limited success in producing practical and functional materials.

By replacing the oxo bridging groups with organic ligands, researchers can develop new strategies for synthesising novel POM-based organic-inorganic hybrid materials through linking POMs and organic compounds together by covalent bonds. Of particular interest are the organoimido POM derivatives.

In their latest HOT Perspective article, a team of researchers from Tsinghua University, China, explore the synthetic chemistry of organoimido derivatives of POMs and the reactive chemistry for the construction of POM-based hybrid materials.  Wei et al. highlight that both the inorganic cluster skeleton and the organic ligand in organoimido-based POMs can act as reactive sites which could lead to an exciting future for the chemistry of organoimido based POMs.

To find out more, download the full article which is free to access until 26th March…
The chemistry of organoimido derivatives of polyoxometalates
Jin Zhang,  Fengping Xiao, Jian Hao and Yongge Wei

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Hot Perspective: Treating Wilsons Disease

Wilson’s disease is a rare genetic condition caused by inheriting an abnormal copy of the Wilson disease protein (ATP7B) gene. The disease affects approximately 1-4 people per 100,000 and prevents sufferers from regulating the concentration of copper within their body, inducing a copper overload.

The redox properties of copper make it a very important metal biologically and it is involved in a wide range of enzymatic processes. The anti-oxidant enzyme superoxide dismutase for example is expressed in all cells and is part of our anti-oxidant defence, while the more specialised dopamine β-hydroxylase is only expressed in the brain and is involved in dopamine conversion. Balancing the amount of copper we have in our bodies is crucial for good health, having a copper deficit would hinder vital functions, but having an excess can cause oxidative stress by promoting the formation of hydroxyl radicals.

Designing new drugs to treat Wilson’s disease which can be targeted to the liver, where excess copper is found

Treating Wilson’s disease involves life-long chelation therapy, this is the application of compounds designed to bind to the excess copper ions and allow them to be safely excreted. This Hot Perspective by Pascale Delangle and Elisabeth Mintz reviews the drugs currently in use and gives insight in to the development of more advanced treatments, highlighting the design of bio-inspired chelating agents and drug targeting.

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To find out more you can download this article now, which is free to access for 4 weeks!
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Chelation therapy in Wilson’s disease: from D-penicillamine to the design of selective bioinspired intracellular Cu(I) chelators
Pascale Delangle and Elisabeth Mintz
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12188C

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HOT Article: Anti-microbials that target destabilised DNA

Dinuclear ruthenium complex ΔΔ-Rubb7 selectively binds a destabilised segment of DNA

Richard Keene and colleagues report an inert dinuclear polypyridylruthenium(II) groove binding metal complex that exhibits slow exchange DNA binding in this HOT article.  Such compounds have potential as anti-microbial agents as they can block the interaction of important proteins with DNA.

For more details, download the article which is free to access for 4 weeks.

An approach to therapeutic agents through selective targeting of destabilised nucleic acid duplex sequences

Fangfei Li,  Daniel K. Weber,  Joy L. Morgan,  J. Grant Collins and F. Richard Keene
Dalton Trans., 2012
DOI: 10.1039/C2DT12146H

This paper is part of forthcoming themed issue on Application of Inorganic Chemistry for non-Cancer Therapeutics. Here are some other articles due to be published in this issue….

Interference of a new cyclometallated Pt compound with Cu binding to amyloid-ß peptide
Isabelle Sasaki ,  Christian Bijani ,  Sonia Ladeira ,  Valérie Bourdon ,  Peter Faller and Christelle Hureau
Dalton Trans., 2012
DOI: 10.1039/C2DT12177H

In vitro inhibitory properties of ferrocene-substituted chalcones and aurones on bacterial and human cell cultures
Keshri Nath Tiwari,  Jean-Philippe Monserrat,  Arnaud Hequet,  Carine Ganem-Elbaz,  Thierry Cresteil,  Gérard Jaouen,  Anne Vessières,  Elizabeth A. Hillard and Claude Jolivalt
Dalton Trans., 2012
DOI: 10.1039/C2DT12180H

Polyanionic N-donor ligands as chelating agents in transition metal complexes: synthesis, structural characterization and antiviral properties against HIV
Sandra García-Gallego,  Javier Sánchez Rodríguez,  José Luis Jiménez,  Michela Cangiotti,  Maria Francesca Ottaviani,  M. Ángeles Muñoz-Fernández,  Rafael Gómez and F. Javier de la Mata
Dalton Trans., 2012
DOI: 10.1039/C2DT11793B

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HOT Article: Trifluoroacetate decomposition with coinage metals

The presence of C–F bonds in organic compounds has a dramatic influence on their physical, chemical and biological properties.  Metal mediated reactions that result in C–F bond formation or C–F bond activation have attracted considerable attention as the demand for organofluorine compounds has increased. Metal-catalysed decarboxylative cross-coupling reactions using trifluoracetate as a cheap source of  introducing “CF3” represents an attractive approach.  Until now, little has been known about the fragmentation mechanisms of metal trifluoracetates.   In this Dalton Transactions HOT article,  Rijs and O’Hair use a combination of gas-phase 3D quadrupole ion trap mass spectrometry experiments and density functional theory (DFT) calculations to examine the mechanism of thermal decomposition of fluorinated coinage metal carboxylates.  Synthetic chemists should be able to use these results to design new ways of incorporating CF3 and F fragments using trifluoroacetate.

Read more for FREE until the 13th March 2012 at:

Forming trifluoromethylmetallates: competition between decarboxylation and C–F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]
Nicole J. Rijs and Richard A. J. O’Hair
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12117D

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How big is a Cp?

Ferrocene is a sandwich complex of two cyclopentadienyl (Cp) units bound to an Fe centre and is probably the most famous organometallic compound containing a Cp ligand. There are a huge variety of organometallic complexes with a range of metal centres and ligands and there is a great deal of interest in their structural, chemical and physical properties.

This Hot Article details the preparation of a series of [(η7-C7H7)Zr(η5-L)] (L = Cp and Ind) complexes and their structural characterisation. The authors use this information to develop a system to measure the steric bulk of Cp ligands………..so how big is a Cp?

To find out, you can download this article now, which is free to access for 4 weeks

How big is a Cp? Cycloheptatrienyl zirconium complexes with bulky cyclopentadienyl and indenyl ligands
Andreas Glöckner, Heiko Bauer, Miyuki Maekawa, Thomas Bannenberg, Constantin G. Daniliuc, Peter G. Jones, Yu Sun, Helmut Sitzmann, Matthias Tamm and Marc D. Walter
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12132H

You can also keep up-to-date with the latest news in Dalton Transactions by following us on twitter or signing up to our e-alert service.

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Porphyrinic MOFs

If you’re interested in finding out more about MOFs, and in particular those based on metalloporphyrins, then look no further… Chao Zou and Chuan-De Wu’s recent Perspective article provides an interesting overview of these functional materials. The researchers from Zhejiang University, China, discuss synthetic strategies and applications ranging from hydrogen storage to photocatalysis. Although the application of porphyrinic MOFs is considerably underdeveloped compared to other porphyrinic materials, say Zou and Wu, this article demonstrates that metalloporphyrins are an ideal choice for designing crystalline solid frameworks.

To read more, download the article now – it’s free to access.
Functional porphyrinic metal–organic frameworks: crystal engineering and applications

This Perspective article is part of the upcoming themed issue on Coordination Chemistry in the Solid State, guest edited by Dalton Transactions Associate Editor, Russell Morris. Keep your eyes peeled for many of our other coordination chemistry articles which have already been published, including Burnett and Choe’s Perspective article on “Sequential self-assembly in metal–organic frameworks”.

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