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A touch of gold for cycloisomerisation reaction

Gold-catalysed cycloisomerisation of alkynyl hydroxyallyl tosylamides has led to the concise synthesis of oxaazatricyclic compounds and revealed an interesting skeleton structure, say scientists in South Korea.

Research groups across the globe have reported cycloisomerisation reactions of alkynyl allyl alcohols (AAAs) with rhodium, iridium, palladium and nickel catalysts. Naturally, research groups have been led into investigating the use of gold catalysts, providing plausible reaction pathways for these reactions. 

Young Keun Chung and colleagues from Seoul National University and Sangmyung University, used subtly different reaction conditions than have been previously reported, resulting in an usual oxaazatricyclic skeleton compound being uncovered for the first time, as shown in the X-ray structure obtained below.

X-ray structure of cycloisomerised oxaazatricyclic compound

To find out more about this unexpected result and the reaction conditions used, why not download the communication today? The results have been published in ChemComm and will be freely available until the 13th May 2011!

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Unique sorption properties for isomeric frameworks

Two porous supramolecular isomeric frameworks have shown unique sorption properties, say a collaboration of Chinese and Japanese scientists. 

One framework shows temperature dependent and selective sorption of CO2, while the other framework shows gas uptake capacity for CO2, N2, H2 and CH4 at low temperature and selective sorption of CO2 over N2 around room temperature. Wei-Yin Sun and colleagues believe that the results provide useful guidance for improving metal organic framework (MOF) designs for gas storage and separation techniques. 

 

Two porous supramolecular isomeric frameworks show unique sorption properties

Find out more, by reading the research results published in ChemComm. This article has been made free to access until the 13th May 2011, so why not download the communication today? 

  

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All systems GO for biosensing platform

Graphene oxide (GO) plays a crucial role in a new, sensitive biosensing platform, acting as an efficient quencher for upconversion nanophosphors, say scientists in China. 

Zhengping Li, Chenghui Liu and colleagues from Hebei University, have constructed a sensitive and practical biosensing platform by combining lanthanide-doped upconversion nanoparticles (UCNPs) with single-stranded DNA (ssDNA). Upon the addition of water soluble GO the upconversion fluorescence is quenched, effectively turning ‘off’ the fluorescence signal. To test the platforms sensing ability and performance, the team introduced adenosine triphosphate (ATP) resulting in the formation of an aptamer-ATP complex, preventing the UCNPs interacting with the GO surface and thus decreasing the quenching efficiency, resulting in the fluorescence staying ‘on’. Other phosphates were tested, like guanosine triphosphate (GTP), cytidine triphosphate (CTP) and uridine triphosphate (UTP) but no dramatic fluorescence enhancement was observed, so this indicates that the aptamer system is specific to ATP alone.

Upconversion FRET between ssDNA-UCNPs and GO for ATP sensing

Interestingly, the team also tested the biosensing platform with mercury ions, which caused the ssDNA to form double-stranded DNA (dsDNA), preventing the UCNPs interacting with the GO surface and again resulted in enhanced fluorescence emission. Other similar cations were tested in comparison, but the biosensor only shows selectivity for mercury ions, providing a good indication into the high specificity that this biosensing platform has, in addition to its future potential for uses in clinical diagnostic and biosensing applications.

Fancy finding out more? Then why not download the communication today – published in ChemComm, the article has been made free to access until the 13th May 2011.

Please also let us know what you think to this research by blogging some comments below.

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A new and simple polymer synthesis for polymer solar cells

A team of Swedish chemists have presented a novel and straightforward method for synthesising polymers for use in polymer solar cells (PSC) with a wide absorption spectrum.

The researchers, led by Mats R. Andersson from the Chalmers University of Technology in Sweden, synthesised the polymer from a widely available stannyl thiophene and an easily synthesised bromoisoindigo monomer. These were then coupled together using a Stille coupling reaction. Overall this represents just 3 steps and was achieved with a high overall yield of 68%.

 

The polymer itself is a low band-gap polymer with a donor–acceptor structure, which is important for harvesting photons from sunlight. The team found that the polymer exhibited promising performance when used in a PSC device and expect to be able to further improve this by varying the indigo groups.

If you would like to read more about this topic then download the ChemComm article for free today. Also, why not check out these other great ChemComm articles on PCSs?

Synthesis of annulated thiophene perylene bisimide analogues: their applications to bulk heterojunction organic solar cells
Hyunbong Choi, Sanghyun Paek, Juman Song, Chulwoo Kim, Nara Cho and Jaejung Ko
Chem. Commun., 2011, DOI: 10.1039/C0CC05448H

Crystalline conjugated polymer containing fused 2,5-di(thiophen-2-yl)thieno[2,3-b]thiophene and thieno[3,4-c]pyrrole-4,6-dione units for bulk heterojunction solar cells
Guan-Yu Chen, Yu-Hsin Cheng, Yi-Jen Chou, Ming-Shin Su, Chia-Min Chen and Kung-Hwa Wei
Chem. Commun., 2011, DOI: 10.1039/C1CC10585J

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Reusable template for pattern transfer

Contact area lithography has been used for directly patterning and transferring self-assembled monolayers (SAMs) onto silicon-based substrates.

 

One-step patterning & transfer of SAMs on SiO2/Si substrates

Hyunjung Shin and colleagues from Kookmin University, in South Korea used a patterned (hard) silicon oxide template and placed it on substrates of interest, introducing a small amount of water in the process.
After drying off the water, the non-contacted areas served directly as growth sites of OTS-SAMs by simple solution deposition. The hard template was then detached from the substrate and the patterns of SAMs were obtained.

In principal, the hard template is cleansable by simple chemical etching without causing any damage. It is also 100% recyclable and can be reused up to ~50 times.

Fancy finding out more about this technique? Then why not download the communication today, which has been published in ChemComm and will be free to access until the 13th May 2011.

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Beads clicking into place

Scientists in Belgium have designed a microfluidic setup that manufactures thiol and yne beads, which can then undergo several click-type reactions.

Filip Du Prez and his team at Ghent University demonstrated the yne beads reacting with an azide or two thiols, whereas the thiol beads were tested using nine different reaction conditions. The thiol–isocyanate reaction was seen to be the fastest, being closely followed by the thiol–norbornene reaction.

 

Light Microscopy image of monodisperse thiol beads (left image). Fluorescent yne beads after clicking with coumarin-derivative (right image).

Du Prez believes that this discovery may help to guide researchers, especially in the field of solid phase synthesis, to choose the most suitable ligation reaction according to their needs since many of the conjugations studied are part of the click family. 

Published in ChemComm this communication will be freely available until the 13th May 2011. Why not download the communication today and find out more about the beads and their clicking abilities?

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A rare example of synthon polymorphism

Scientists in India have reported a rare example of synthon polymorphism in co-crystals of 4,4′-bipyridine and 4-hydroxybenzoic acid.

Graphical abstract: Synthon polymorphism and pseudopolymorphism in co-crystals. The 4,4′-bipyridine–4-hydroxybenzoic acid structural landscape

Polymorphism is defined as the ability of a material to exist in more than one form or crystal structure. It has important implications for the properties of such materials; for example in pharmaceuticals, the dissolution rate of a drug can be dependent on the polymorphic form. While this is a common phenomenon in single crystals it is much less common in co-crystals, systems where the structure has at least two distinct components.

Gautam Desiraju from the Indian Institute of Science, found that when 4,4′-bipyridine and 4-hydroxybenzoic acid were dissolved together in a solvent such as methanol they would co-crystallise to form two different polymorphs. They noticed that a third form, a pseudopolymorph, was also present.

If you would like to read more about Desiraju’s discovery then why not download his ChemComm article for free today? This article is also part the ChemComm web themed issue on Supramolecular Chemistry to mark the International Year of Chemistry 2011.

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A supramolecular approach to zwitterionic metal silanides

Zwitterionic metal silanides represent a structurally novel class of tri-coordinated silyl anions in which the cationic metal centre is separated from the silicon anion by internal donor bridges.

Clemens Krempner and co-workers have now reported that key to the synthesis of stable, isolable species is the use of pendant polydonor groups that exclusively bind to the metal cation and serve to prevent self-aggregation. 

Due to the shape of these unusual compounds, the electron pair located at the central silicon anion is available for additional metal binding. This has allowed for the synthesis of hitherto unknown zwitterionic heterobimetallic silanides, by reaction of the zwitterionic metal silanides with boron, aluminium or tungsten-containing species.

To read about these intriguing compounds in more detail, download the ChemComm communication, which is available for free until April 28th.

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Catalytic reaction cascade forms substituted pyrroles

Catalytic reaction cascades present a neat, efficient way to synthesise valuable organic molecules. However, their success relies upon the compatibilty of the reactants and catalysts involved, and identifying this requires ingenuity and experimentation.

Now Darren Dixon and co-workers at the University of  Oxford have reported a one-pot nitro-Mannich/hydroamination cascade for direct synthesis of 2,5-disubstituted pyrroles from imines and nitro alkynes. The reaction is catalysed by base and a gold(I) catalyst, and has been optimised to achieve yields up to 86%.  

To find out more download the ChemComm communication, which is free to access until April 28th

Start a discussion by leaving your comments below

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Novel methodologies for synthesising pyroglutamates

Several pyroglutamate-based natural products have been found to exhibit potent anti-cancer and anti-microbial properties. Although their syntheses have been a focus of research for many groups, their is still room for improvement in the development of highly tunable methodologies for the diverse functionalisation of the pyroglutamate ring.

Venkatram R. Mereddy and co-workers have  developed a novel and exceptionally short methodology for the synthesis of such functionalised pyroglutamates via alkylation of amino acid-derived iminoesters with allyl bromides or allyl acetates, easily obtained by Bayliss-Hilman reaction.

To learn more download the ChemComm communication, available for free until March 28th

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