Archive for June, 2012

Extracting nuclear energy from seawater

It’s estimated that there’s more than 4.5 billion tons of uranium in the ocean

It’s estimated that there’s more than 4.5 billion tons of uranium in the ocean

US scientists have used a ligand that can form a complex with a uranyl ion to enable uranium to be extracted from seawater. The concentration of uranium in seawater is low at 3.3 parts per billion, but in the vast oceans, it’s estimated that there’s more than 4.5 billion tons of uranium; considerably more than the amount of uranium in terrestrial ores, say the researchers.

Extracting uranium from the sea is a challenge because it exists as a stable carbonate complex. Linfeng Rao from the Lawrence Berkeley National Laboratory, and colleagues, say that a cyclic imide dioxime ligand – glutarimidedioxime – can compete with carbonate to bind strongly to the uranyl ion to form the complex.

Rao says that there are two unique features in the structure of the uranium–glutarimidedioxime complex. ‘The protons of both oxime groups (–CH=N–OH) are rearranged from the oxygen atom to the nitrogen atom,’ he explains. ‘The middle imide group (–CH–NH–CH–) is deprotonated, resulting in a -1 charged ligand that coordinates to the uranyl cation in a tridentate mode (via the two oxime oxygen atoms and the imide nitrogen atom).’ With such a configuration, he adds, the electron density on the ligand could be delocalised, forming a conjugated system that coordinates strongly to the uranyl cation.

‘It will be interesting to learn how the ligand performs in competition with a peroxide anion, which forms an even stronger complex than carbonate with the uranyl ion in the natural marine photic zone,’ says Mark Antonio, a separation science expert from Argonne National Laboratory, US. He adds that the results from the investigation provide insights that may lead to a viable sequestration of uranium from amongst a myriad other cations.

‘Uranium availability becomes even more important as developing countries such as China and India are ramping up their nuclear power capacities,’ says Wenbin Lin, whose group from the University of North Carolina at Chapel Hill, US, focuses on addressing  fundamental chemical problems relevant to societal issues. ‘If an economically viable technology can be developed to extract uranium from seawater, nuclear power becomes a virtually sustainable clean energy source.’

Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime
Guoxin Tian,  Simon Teat,  Zhiyong Zhang and Linfeng Rao
Dalton Trans., 2012
DOI: 10.1039/C2DT30978E

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Photochemical carbon dioxide reduction

Reducing carbon dioxide to methanePhotochemical reduction of  greenhouse gas, carbon dioxide into higher energy content fuels is attractive because it utilises a renewable energy source – the sun. Most catalysts that are already used for this process  (TiO2 and metallic clusters based on Cu, Pt and Rh) need ultraviolet light for excitation and have a low conversion efficiency, prohibiting wide scale industrial application. 

There is need for a photocatalyst that is efficient, low cost and can be excited by visible light.

Zhi-Gang Zou and his team at Nanjing University have synthesised an air stable  copper (I) bipyridine complex which binds to TiO2. The Cu(I)complex/TiO2 hybrid system when irradiated with visible light can reduce  CO2 to CH4 with high efficiency and selectivity.

This is an exciting development — no other products were formed during photoreduction of carbon dioxide and copper is an inexpensive and abundant metal. The possiblilty for using copper complexes  in carbon dioxide reduction catalysis has now been opened up for further work…

To find out more (including how Zou and team also used the complex in a dye-sensitised solar cell), read the full Dalton Transactions article:

A Copper(I) Dye-Sensitized TiO2-Based System for Efficient Light Harvesting and Photoconversion of CO2 into Hydrocarbon Fuel
Yong-Jun Yuan, Z.T. Yu, Jiyuan Zhang and Zhigang Zou

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Compound 1000 times more effective than first choice drug for parasitic disease

Scientists in Mexico have devised a new synthetic pathway to a nitrogen-containing ligand, which, when bound to divalent nickel or manganese, is a 1000 times more effective than the leading clinical drug at reducing the profileration of the parasite responsible for amoebiasis. This disease causes 70 thousand deaths a year.

Potential cytotoxic and amoebicide activity of first row transition metal compounds

The same ligand bound to other divalent metal ions also shows remarkable anti-cancer properties with activities superior to cisplatin.

Want to know more? Download the article now…
Potential cytotoxic and amoebicide activity of first row transition metal compounds with 2,9-bis-(2′,5′-diazahexanyl)-1,1-phenanthroline (L1)
Juan Carlos García-Ramos, Yanis Toledano-Magaña, Luis Gabriel Talavera-Contreras, Marcos Flores-Álamo, Vanessa Ramírez-Delgado, Emmanuel Morales-León, Luis Ortiz-Frade, Anllely Grizett Gutiérrez, Adriana Vázquez-Aguirre, Carmen Mejía, Julio César Carrero, Juan Pedro Laclette, Rafael Moreno-Esparza and Lena Ruiz-Azuara

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∏-conjugated multinuclear metalladithiolenes and metalladithiolene clusters

Gigantic multinuclear transition metal cluster complexes have unique properties and reactivities.

Gigantic multinuclear transition metal cluster complexes have unique properties and reactivities.

Metalladithiolenes, along with their cluster complexes, are excellent compounds for studying multinucleation and electronic communication in mixed-valent states.  Electronic communication in mixed-valent states is particularly important for single-molecule magnets, enzymes and for the creation of molecular devices.  Ryota Sakamoto, Satoru Tsukada and Hiroshi Nishihara detail synthetic strategies for the successful multinucleation of metalladithiolenes in this Hot Perspective. 

Download it today…
Multinuclear metalladithiolenes: focusing on electronic communication in mixed-valent states
Ryota Sakamoto, Satoru Tsukada and Hiroshi Nishihara

Here are some of the authors’ other recent Dalton Transactions publications:

Synchronized motion and electron transfer of a redox-active rotor
Shoko Kume and Hiroshi Nishihara
Dalton Trans., 2011,40, 2299-2305
DOI: 10.1039/C0DT01084G

Conjugation of Au11 cluster with Cys-rich peptides containing the α-domain of metallothionein
Shinya Ariyasu, Akira Onoda, Ryota Sakamoto and Takeshi Yamamura
Dalton Trans., 2009, 3742-3747
DOI: 10.1039/B900570F

Development of a versatile synthesis method for trinuclear Co(III), Rh(III), and Ir(III) dithiolene complexes, and their crystal structures and multi-step redox properties
Yusuke Shibata, Baohua Zhu, Shoko Kume and Hiroshi Nishihara
Dalton Trans., 2009, 1939-1943
DOI: 10.1039/B815560G

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Top ten most accessed articles in May

This month sees the following articles in Dalton Transactions that are in the top ten most accessed:-

Synthesis and characterization of a tris(2-hydroxyphenyl)methane-based cryptand and its triiron(iii) complex
Gary L. Guillet ,  Forrest T. Sloane ,  Matthieu F. Dumont ,  Khalil A. Abboud and Leslie J. Murray
Dalton Trans., 2012,41, 7866-7869    DOI: 10.1039/C2DT30312D

Recent progress in the synthesis of inorganic nanoparticles
C. N. R. Rao ,  H. S. S. Ramakrishna Matte ,  Rakesh Voggu and A. Govindaraj
Dalton Trans., 2012,41, 5089-5120    DOI: 10.1039/C2DT12266A

New catalysts with unsymmetrical N-heterocyclic carbene ligands
Johanna Tornatzky ,  Axel Kannenberg and Siegfried Blechert
Dalton Trans., 2012,41, 8215-8225    DOI: 10.1039/C2DT30256J

Application of inorganic chemistry for non-cancer therapeutics
Katherine J. Franz
Dalton Trans., 2012,41, 6333-6334    DOI: 10.1039/C2DT90061K

Applications of luminescent inorganic and organometallic transition metal complexes as biomolecular and cellular probes
Kenneth Kam-Wing Lo ,  Alex Wing-Tat Choi and Wendell Ho-Tin Law
Dalton Trans., 2012,41, 6021-6047    DOI: 10.1039/C2DT11892K

A carboxylate-based dinuclear dysprosium(iii) cluster exhibiting slow magnetic relaxation behaviour
Biplab Joarder ,  Abhijeet K. Chaudhari ,  Guillaume Rogez and Sujit K. Ghosh
Dalton Trans., 2012,41, 7695-7699    DOI: 10.1039/C2DT30643C

Selective anion sensing by a ruthenium(ii)–bipyridyl-functionalized tripodal tris(urea) receptor
Yongjing Hao ,  Peiju Yang ,  Shaoguang Li ,  Xiaojuan Huang ,  Xiao-Juan Yang and Biao Wu
Dalton Trans., 2012,41, 7689-7694    DOI: 10.1039/C2DT12488B

Magnetic and optical bistability in tetrairon(iii) single molecule magnets functionalized with azobenzene groups
Thazhe Kootteri Prasad ,  Giordano Poneti ,  Lorenzo Sorace ,  Maria Jesus Rodriguez-Douton ,  Anne-Laure Barra ,  Petr Neugebauer ,  Luca Costantino ,  Roberta Sessoli and Andrea Cornia
Dalton Trans., 2012,41, 8368-8378    DOI: 10.1039/C2DT30172E

A tris(2-quinolylmethyl)amine scaffold that promotes hydrogen bonding within the secondary coordination sphere
Cameron M. Moore and Nathaniel K. Szymczak
Dalton Trans., 2012,41, 7886-7889    DOI: 10.1039/C2DT30406F

Targeted therapy vs. DNA-adduct formation-guided design: thoughts about the future of metal-based anticancer drugs
Gianni Sava ,  Gérard Jaouen ,  Elizabeth A. Hillard and Alberta Bergamo
Dalton Trans., 2012,41, 8226-8234    DOI: 10.1039/C2DT30075C

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Dalton Transactions? Then why not submit to us today  or alternatively email us your suggestions.

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Confused porphyrins transport oxygen atoms

Unique cooperation has been observed between rhenium atoms and non-innocent N-confused porphyrin ligands in new oxorhenium(V) complexes.

The simplest porphyrin, porphine (left), and the N-confused porphyrin used to synthesize unique oxorhenium complexes.

Hiroyuki Furuta et al. have synthesised two new porphyrin oxorhenium(V) complexes which have been shown to be remarkably effective at oxygen atom transport. Through a catalytic process the oxygen atom from pyridine N-oxide can be transferred to PPh3 in a 97% yield, notably higher than that of some other rhenium(V) complexes. The authors propose that the reason for their success is the existence of a Re-C bond, believing that this bond is important for efficient oxygen transport.

Atom transport is at the heart of successful catalysis, and as usual nature has already beaten us to it. Galactose oxidase for example converts a primary alcohol into an aldehyde by transporting a hydrogen atom from one part of the enzyme to another. But if the oxygen atom transfer seen in these synthetic N-confused porphyrin oxorhenium(V) complexes can be extended to other systems, exciting advancements in the field of catalysis could be on the horizon.

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To find out more about these exciting new complexes and the atom transport they facilitate, take a look at the full Dalton Transactions communication.

Cooperation between metal and ligand in oxygen atom transport by N-confused porphyrin oxorhenium(V) complexes
Takaaki Yamamoto, Motoki Toganoh and Hiroyuki Furuta

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By Katie Renouf, Web Writer

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N-heterocyclic carbenes themed issue – submissions open

Dalton Transactions is now welcoming submissions for a themed issue in N-heterocyclic carbenes, guest edited by Dr Catherine Cazin from the University of St Andrews.

Submission deadline: 28th November 2012

N-Heterocyclic carbenes (NHCs) have become ubiquitous in coordination and organometallic chemistry and have had profound impact in homogeneous catalysis. This class of ligands has attracted significant attention during the last fifteen years, with hundreds of papers published every year, and four books dedicated to the topic. This Dalton Transactions themed issue will seek to highlight to the inorganic research community the latest and very best research in the field ranging from synthetic to applications-oriented contributions.

All article types will be considered – Communications, Full Papers, Frontiers and Perspectives. See our author guidelines for more information.

Click here to submit

Please note that inclusion in the themed issue will be subject to the guest editor’s discretion. All manuscripts will undergo peer-review in accordance with the Dalton Transactions mandate.

For enquiries, please contact the Editorial Office.

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Upcoming Conference: Eurobic 2012

The 11th European Biological Inorganic Chemistry Conference (Eurobic 11) will be in Granada, Spain, from September 12-16, 2012.

The sessions will take place in the Conference Centre of Granada, in a beautiful part of the city within a few minutes walking distance to local hotels. The event is being hosted by the Inorganic Chemistry Department at the Faculty of Pharmacy of the University of Granada, under the auspices of the University of Granada (UGR).

The conference will cover all topics of biological inorganic chemistry and includes lectures from the following plenary speakers

John H. Dawson, University of South Carolina, USA
Henryk Kozlowski, University of Wroclaw, Poland
Luis Liz Marzan, University of Vigo, Spain
Claudio Luchinat, University of Florence
Juan Manuel García Ruiz, Granada, Spain
Roland K.O. Sigel, University of Zurich, Switzerland
Montserrat Filella, University of Geneva, Switzerland
Thomas Hamelryck, University of Copenhagen, Denmark
Michael John Hannon, University of Birmingham, UK

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Registration to the conference is still open and you can find out more details by visiting the Eurobic11 website.

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Fast Synthesis of C-dots

Electrochemical synthesis of C-dotsQuantum dots are nanoparticles of semiconductor material which, because of their very small size, display different optical and electrical properties to that of the corresponding material in the bulk phase. Traditional semiconductor quantum dots are used in optical applications such as cell imaging, LEDs and photodetectors due to their high extinction coefficient.

Due to their cheaper cost and intrinsic low toxicity, carbon nanodots (C-dots) have the potential to replace traditional semiconductor quantum dots. To overcome some of the drawbacks with previous methods of fabricating C-dots, Zhenui Kang and his team at Soochow University, China have developed a facile one step electrochemical synthesis. This exciting new method produces c-dots of high purity and uses only pure water as an electrolyte, which is attractive because it is low cost and more environmentally friendly .

The team also synthesized nanohybrid TiO2/C-dots which possess good photocatalytic activity.

To find out more about the photoluminescence and photocatalytic properties of C-dots, read the full Dalton Transactions article…

Large Scale Electrochemical Synthesis of High Quality Carbon Nanodots and Their Photocatalytic Property
Zhenhui Kang,  Hai Ming,  Zheng Ma,  Yang Liu,  Keming Pan,  Hang Yu and Fang Wang

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Lewis Pair polymerization

In this HOT article, Chen et al. extend their previous work to present a combined experimental and computational investigation of Lewis Pair polymerization incorporating 11 Lewis acids and 10 achiral and chiral Lewis bases, for the polymerization of 12 different types of monomers.

Read more about the polymerization mechanism for FREE for 4 weeks at:

Lewis pair polymerization by classical and frustrated Lewis pairs: acid, base and monomer scope and polymerization mechanism
Yuetao Zhang, Garret M. Miyake, Mallory G. John, Laura Falivene, Lucia Caporaso, Luigi Cavallo and Eugene Y.-X. Chen
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30427A

This article will form part of a themed issue on Frustrated Lewis Pairs guest edited by Douglas W. Stephan.  Other papers in this issue include:

Exchange chemistry of tBu3P(CO2)B(C6F5)2Cl
Rebecca C. Neu, Gabriel Ménard and Douglas W. Stephan

Fixation of carbon dioxide and related small molecules by a bifunctional frustrated pyrazolylborane Lewis pair
Eileen Theuergarten, Janin Schlösser, Danny Schlüns, Matthias Freytag, Constantin G. Daniliuc, Peter G. Jones and Matthias Tamm

[2.2]Paracyclophane derived bisphosphines for the activation of hydrogen by FLPs: application in domino hydrosilylation/hydrogenation of enones
Lutz Greb, Pascual Oña-Burgos, Adam Kubas, Florian C. Falk, Frank Breher, Karin Fink and Jan Paradies

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