Archive for August, 2011

Hot Article: Opening up oxidative addition

Feliu Maseras and co-workers from ICIQ in Tarragona, Spain examine the complicated, yet ubiquitous, process that is oxidative addition (OA). The team use DFT to systematically study OA of CH3Br to palladium bis-phosphine and mono-phosphine complexes. A number of trends can be identified, resulting in a complex picture where the nature of the phosphine and the solvent can be tuned to favor one of the two possible mechanisms, with the corresponding stereochemical implications that can be extrapolated to the behaviour of more sophisticated substrates. Access for free until the 16th September…………

Phosphine and solvent effects on oxidative addition of CH3Br to Pd(PR3) and Pd(PR3)2 complexes
Maria Besora, Christophe Gourlaouen, Brian Yates and Feliu Maseras
Dalton Trans., 2011, DOI: 10.1039/C1DT10983A

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HOT Article: New heterojunction structured materials

In this HOT article, Yuliang Li and coworkers synthesized p–n axial heterojunction inorganic/organic semiconductor nanowire arrays on porous anodic aluminum oxide (AAO) templates via electrochemical deposition. This novel synthesis is based on a common concept of using an AAO template. The electrical properties of the heterojunctions of these organic–inorganic materials were investigated, indicating a diode nature and a rectifying feature. These heterojunction nanowire arrays are at the frontier of the materials field, for next-generation electrical and optoelectronic devices.

Read more for FREE until 24th September about these nanowire arrays at:
Synthesis and characterization of axial heterojunction inorganic–organic semiconductor nanowire arrays
Nan Chen, Xuemin Qian, Haowei Lin, Huibiao Liu, Yongjun Li and Yuliang Li
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10926J

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HOT Article: Role of Cu binding in neurodegenerative disorders

The formation of peptide or protein aggregates is a common feature of many different forms of neurodegenerative disorders including Alzheimer’s disease, Parkinson’s disease and prion diseases. It is also widely accepted that various metal ions can play a significant role in the conformational changes of these peptides/proteins.

In this HOT article, Kállay and co-workers report on the synthesis and study of the copper complexes of rIAPP fragments. First of all the terminally protected tridecapeptide rIAPP(17–29) was investigated in which the potentially metal binding amino acid residues are located in the N-terminus. The surprisingly high affinity of this peptide towards complexation with copper(II) promoted a systematic study on the shorter fragments including rIAPP(17–22) (Ac-VRSSNN-NH2), rIAPP(17–20) (Ac-VRSS-NH2), its mutant peptides (Ac-VASSNH2 and Ac-VRAA-NH2) and rIAPP(19–22) (Ac-SSNN-NH2). The peptides can be classified into two different categories: (i) the tetrapeptides Ac-VRSS-NH2, Ac-VASS-NH2 and Ac-VRAA-NH2 can interact with copper(II) only under strongly alkaline conditions (pH > 10.0) and the formation of only one species with four amide nitrogen coordination can be detected; (ii) the peptides Ac-VRSSNNLGPVLPP-NH2, Ac-VRSSNN-NH2 and Ac-SSNN-NH2 can form complexes above pH 6.0 with the major stoichiometries [CuH−2L], [CuH−3L] and [CuH−4L]2−. The data supports the idea that  rIAPP(17–29) can interact with copper(II) ions under physiological conditions and the SSNN tetrapeptide fragment can be considered as the shortest sequence responsible for metal binding.

Read more for FREE until 21st September at:
Copper(II) complexes of rat amylin fragments
Csilla Kállay, Ágnes Dávid, Sarolta Timári, Eszter Márta Nagy, Daniele Sanna, Eugenio Garribba, Giovanni Micera, Paolo De Bona, Giuseppe Pappalardo, Enrico Rizzarelli and Imre Sóvágó
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10835B

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HOT Article: Towards new lanthanide architectures

In this HOT article, Faulkner and co-workers describe the self-assembly between di-carboxylate ions and a binuclear europium compound and some stable adducts and heterometallic lanthanide complexes. The synthetic approach may shed light on the design and synthesis of other new lanthanide architectures by spatial matching the interactions between two kinetically stable complexes or by well designed building blocks.

This article is part of a forthcoming themed issue on self assembly in inorganic chemistry, with Guest Editors Paul Kruger (University of Canterbury) and Thorri Gunnlaugsson (Trinity College Dublin).

Read more for FREE about these developments in self assembly at:
Self-assembly between dicarboxylate ions and a binuclear europium complex: formation of stable adducts and heterometallic lanthanide complexes
James A. Tilney, Thomas Just Sørensen, Benjamin P. Burton-Pye and Stephen Faulkner
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11103E

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Hot Article: Triazamacrocycles templated on iron

Peter G. Edwards and colleagues from Cardiff University and the University of Southampton investigate P3 and As3 macrocycles on an iron template in this Dalton Transactions Hot article.

The authors look at 9-membered triphospha- and triarsamacrocycles with unsaturated benzo-backbones that they make using a [CpRFe]+ template.

The complexes from an interesting ‘cup-shaped’ cavity, which could potentially accommodate anions.

Read the full article for FREE until 21st September to find out more…

Iron(II) template synthesis of benzannulated triphospha- and triarsamacrocycles
Thomas Albers, Julia Baker (neé Johnstone), Simon J. Coles, Peter G. Edwards, Benson Kariuki and Paul D. Newman
Dalton Trans., 2011, DOI: 10.1039/C0DT01724H

Keep up to date with the latest news and research in inorganic chemistry: sign up to the Dalton Transactions e-alert, check out our blog, and get the RSS feed.

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Hot Article: Cleaning up crude oil

A new system, using a solid state catalyst, to remove impurities from petroleum has been developed by US scientists.

With current oil consumption levels high, light crude oil reserves will be exhausted, giving way to heavy and extra heavy bitumen refinery feeds. These contain a higher proportion of large polycyclic hydrocarbons, together with N- and S-heteroaromatics, which need to be removed or transformed, without catalyst poisoning. Current methods to do this require high temperatures and pressures.

The catalyst made by the researchers, composed of ruthenium nanoparticles immobilised on a polymer, hydrogenates aromatic compounds under moderate conditions with no poisoning.

Hydrogenation of arenes and N-heteroaromatic compounds over ruthenium nanoparticles on poly(4-vinylpyridine): a versatile catalyst operating by a substrate-dependent dual site mechanism
Minfeng Fang, Nataliya Machalaba and Roberto A. Sánchez-Delgado
Dalton Trans., 2011, DOI: 10.1039/C1DT10801H

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Hot Article: Understanding the intermediates in reductive coupling of carbon monoxide

Read this Dalton Transactions Hot article to find out about how uranium can reductively couple carbon monoxide, an interesting reaction in Fischer-Tropsch chemistry.

Jennifer Green and co-workers at Oxford University use density functional theory to look at the reductive di- tri- and tetramerization of CO. They look at the linear yne diolate complex which forms if there is no further CO to react with the dimeric C2O2 reaction intermediate, amongst other intermediates. With the insight provided by this computational study a better understanding can be gained of Fischer-Tropsch chemistry.

Read the full article for FREE until 15th September to find out more…

Reductive coupling of carbon monoxide by U(III) complexes—a computational study
Georgina Aitken, Nilay Hazari, Alistair S. P. Frey, F. Geoffrey N. Cloke, O. Summerscales and Jennifer C. Green
Dalton Trans., 2011, DOI: 10.1039/C1DT10692A

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DD13: Inorganic Photophysics and Photochemistry

Dalton Discussions 13 will be held at the University of Sheffield in September next year. The meeting focuses on Inorganic Photophysics and Photochemistry – Fundamentals and Applications.

The aim of the meeting is to bring together people from a wide range of disciplines – from theory and ultrafast spectroscopy to medicinal chemistry and biology – but all with a shared interest in the use of light.

Dalton Discussions are an excellent forum for scientists to present and discuss their work, allowing an invaluable exchange of views and ideas. Researchers submit their abstracts to the Scientific Committee, then selected authors are chosen to present their work at the meeting. Prior to the meeting the authors submit their work as an article, which is then peer reviewed and circulated amongst the participants. At the meeting itself the author has 5 minutes to summarise their article and then the floor is opened to questions and debate – the real focus of Dalton Discussions.

The call for papers is now open, submit your oral abstract now to be part of Dalton Discussions 13.

Key note speakers:

Professor Majed Chergui, Switzerland
Professor Luisa de Cola, Germany
Professor Richard Eisenberg, USA
Professor Peter Ford, USA

The key themes of the meeting have been identified as solar energy, energy and electron transfer, applications of strongly emissive complexes and bond breaking and isomerisation.

Deadlines:

Oral abstract deadline 9 October 2011
Poster abstract deadline 6 July 2012
Early bird registration deadline 6 July 2012
Standard registration deadline 3 August 2012

Visit the DD13 website for more information.

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Jamie Humphrey reports from ICBIC 15

This week I attended the 15th International Conference on Biological Inorganic Chemistry (ICBIC), organised under the auspices of the Society of Biological Inorganic Chemistry.

This was my fourth ICBIC, and as I have been before at previous meetings, I was very impressed with both the quality of the science presented, and the breadth of science covered. There were too many session headings to list here (the full programme can be found on the conference website), but to give an idea of the breadth of biological inorganic chemistry presented, the different sessions covered therapeutics (treatments for malaria, cancer and Alzheimer’s); enzymes (nitrogenase, oxygenase, peroxidase); trafficking (Cu, Ni, Fe); imaging; sensing; bioorganometallic chemistry; and metallomics – with all this great chemistry to cover, the conference spanned 6 days. Sadly, I was only able to attend the first half of the conference.

I knew to expect a warm welcome for delegates at this conference: the biological inorganic chemistry community is very friendly and welcoming. However, we were also blessed to be welcomed by perfect weather in the beautiful city of Vancouver. We could not have wished for a better location for the meeting –  I had heard some very good things about Vancouver, but the reality surpassed the imagination!

With about 700 delegates, ICBIC15 was busy enough to have a buzz about it, but not too busy to feel anonymous (and to ensure everyone could have one of the great cakes served during the morning coffee break – I noticed that I am not the only one with a weakness for cinnamon buns).

The organisers had made a conscious decision to open up the presentations, by having a larger number of contributed talks than there has been in recent ICBICs. This seemed to have worked very well, as it helped to encourage a good number of talks by early career members of the community. While it is always a pleasure to listen to more established chemists, there is something particularly special about hearing from those who are just starting to build their scientific presence and reputation.

The first ICBIC was held 35 years ago, and to celebrate, a number of Jade Anniversary lectures were given by Harry Gray, Ed Solomon, Ken Raymond, Jan Reedijk and David Garner, to name but a few. The Jade speakers had the significant challenge of covering 35 years of chemistry in 20-30 minutes, but they were all up to the challenge!

The organising committee, in particular Chris Orvig, are to be congratulated for selecting an exciting programme of scientific talks and social events for us all  to enjoy, and Sheri and Alison for ensuring all worked well behind the scenes for the week. Everything ran smoothly and seemingly effortlessly, a sure sign of excellent organisation.

You know when you have attended a good conference when you feel reluctant to leave and say goodbye, to the friends who you saw  again and to those you met for the first time. 2013 seems too long to wait for the next ICBIC… ICBIC16 will be held 14-19 July 2013 in Grenoble, France.

Where you also at ICBIC15? What was your favourite part of the meeting? Tell us about your own ICBIC experience by posting a comment below…..

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Hot Article: Leonard Lindoy’s latest metallosupramolecular research

Read Leonard Lindoy’s latest supramolecular host-guest formation research in this Dalton Transactions Hot article.

Lindoy’s group make helicates and tetrahedral Ni and Fe host complexes from quaterpyridine ligand derivatives, and look how they can control which products they get. They are particularly interested in the cavity volumes of the tetrahedral cages they make, and hope in the future to look at the host-guest chemistry of the cages with the largest cavities.

Read the full article for FREE to find out more…

New nickel(II) and iron(II) helicates and tetrahedra derived from expanded quaterpyridines
Christopher R. K. Glasson, George V. Meehan, Cherie A. Motti, Jack K. Clegg, Peter Turner, Paul Jensen and Leonard F. Lindoy
Dalton Trans., 2011, DOI: 10.1039/C1DT10667H

This manuscript will be part of the issue celebrating the 40th Anniversary of Dalton Transactions. Click on the 40th Anniversary link on the right hand side to find out what else we are doing.

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