Archive for the ‘Hot Articles’ Category

Tetrafluorocyclohexane: a novel polar motif

The cyclohexane motif is among the most common in organic chemistry but selectively fluorinated versions are rare. The high polarity of C–F bonds can influence the conformation and reactivity of molecules, making fluorinated molecules high on the target list of many chemists, including David O’Hagan at the University of St Andrews, UK.

His team have managed to make 1,2,3,4-tetrafluorocyclohexane, the first example of a cyclohexane with more than two vicinal fluorine atoms. The all syn stereochemistry forces two of the C–F bonds into 1,3-diaxial orientations. This diaxial interaction makes the molecule polar, which O’Hagan suggests could make it a novel polar structural motif for organic materials.

Graphical abstract: Synthesis and structure of all-syn-1,2,3,4-tetrafluorocyclohexane

Find out more: download O’Hagan’s ChemComm communication for free until 28th July.

Also of interest: Fluorine chemistry web theme

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Magnetic nanoparticles detect low levels of cyanide

Chinese scientists have reported dumbbell-shaped nanoparticles capable of detecting cyanide concentrations as low as 4 x 10-7 M in drinking water. This low detection limit, which is below the acceptable limit advised by the World Health Organization, is attributed to a combination of fluorescence detection with a filtering process called ‘magnetic concentration-washing’.

The toxicity of cyanide and its potential prevalence in drinking water has made easy detection of cyanide an active area of research. Gold nanoparticles have attracted attention as cyanide sensors due to their selectivity for cyanide over other anions. Now, Shaojun Dong and colleagues at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, have adapted a bifunctional nanoparticle made up of Au and magnetic Fe3O4 nanoparticles for sensitive detection of cyanide, even in the presence of interfering species. 

Schematic depiction of the turn-on fluorescent detection of cyanide based on the dual-functional Au–Fe3O4 dumbbell nanoparticles.

The group detected cyanide by relying on what is known as the ‘inner filter effect’, observed when two molecules present in a solution have overlapping absorption and emission wavelengths. The fluorescence emission from a fluorophore is blocked, or reabsorbed, by the second molecule, reducing or even quenching the overall fluorescence of the solution. In the present system, the excitation and emission energy for the fluorophore Rhodamine B is quenched by the Au-Fe3O4 nanoparticles. However, addition of cyanide to the sample reduces the gold component of the nanoparticles by forming an Au(CN)2 complex. This change in the structure alters the nanoparticles’ absorbance spectra and the Rhodamine B emissions are no longer fully absorbed. The team calculated the amount of cyanide present in a sample by monitoring the change in fluorescence.

To extend this detection method for use with environmental samples, which may contain dyes or other contaminants that absorb or emit at a similar wavelength to Rhodamine B, Dong and colleagues implemented a ‘magnetic concentration-washing process’. In it, the Au-Fe3O4 nanoparticles are magnetically separated from the sample solution after they have reacted with any cyanide present in the sample. This magnetic separation retains the bifunctional nanoparticles and leaves any interfering species behind. Pure buffered water containing additional Rhodamine B is added and the fluorescence is monitored. The authors showed that two cycles of this process were enough to remove any interfering species and accurately detect cyanide levels. 

To find out more, read the full article:

Dual-Functonal Au-Fe3O4 Dumbbell Nanoparticles for Sensitive and Selective Turn-on Fluorescent Detection of Cyanide Based on the Inner Filter Effect
Yueming Zhai, Lihua Jin, Ping Wang and Shaojun Dong, Chem. Commun., 2011, DOI: 10.1039/C1CC13149D 

Posted on behalf of Patricia Pantoș, web writer for ChemComm.

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Lysozymes on silica – seeing is believing

Human lysozyme on mesoporous silica (SBA-15) has been visualised in 3D, say scientists in Italy.

Ultrathin section of embedded mesoporous materials

Maura Monduzzi and her co-workers at Università di Cagliari, used an immunochemical method to investigate the location of human lysozyme molecules loaded onto SBA-15. Using post-embedding immunogold staining and transmission electron microscopy results in a 3D reconstruction and shows that the protein molecules were located on the external and internal surfaces of the mesoporous silica. This result may have important consequences in biocatalysis and applications requiring sustained drug release.

Want to know more? Then download the ChemComm communication, which will be free to access until the 15th July 2011.

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Improving bulk-heterojunction solar cells

Making new n-type materials for bulk-heterojunction solar cells (BHJ) can be achieved by simply modifying the fullerene framework, say scientists in Japan.

Looking at LUMO and charge-density of modified fullerene

The BHJ solar cells may be an alternative to conventional silicon-based solar cells, if the low power conversion efficiency can be overcome. Yasujiro Murata and colleagues from Kyoto University have shown that structurally manipulating the C60 skeleton is a promising approach for creating better acceptor materials for BHJ solar cells. This new approach means that the team can effectively control the lowest unoccupied molecular orbital (LUMO) level of the  C60 pi-system, resulting in a clear improvement in open-circuit voltage – a promising development.

Fancy finding out more? Then download the ChemComm communication, which will be free to access until the 15th July 2011.

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New template has potential for bone tissue engineering

British scientists at working at Imperial College, London have synthesised a macroporous hydroxyapatite bioceramic with potential uses in bone regeneration.

Porous hydroxyapatite (HA) bioceramics are widely studied for their potential use in bone regeneration. These materials are biocompatible and have a structure that contains many connected pores. This allows fluid to flow through the material and provides nucleation points for bone growth. The best results are obtained when the the pores are smaller than 1 μm and therefore synthetic methods that give good control over the pore size and material structure are highly desirable.

Prof. Molly Stevens and her team have now demonstrated a way of making an HA bioceramic with a 3D ordered (DOM) macroporous structure. They used an ordered macroporous carbon template (OMC)  in combination with a sol-gel method to form the desired bioceramic. They found that the DOM HA, when compared with HA material made without the OMC template, allowed the nucleation of calcium phosphate on the surface of the pores, thus demonstrating that the template method used affects the crystallisation of material.

hydroxyapatite bioceramics

The team hopes that these materials will find applications not only in the generation of bone but also in the generation of other materials. Want to find out more? Then download the ChemComm article for free today and leave a comment below to let us know what you think.

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Lanthanide discs learn to chillax

A team of UK scientists have made gadolinium and dysprosium discs that can ‘chill well and relax slowly’ with interesting magnetic properties.

Structure of the gadolinium heptametallic complex

David Collison and his colleagues from the University of Manchester have designed heptametallic discs (i.e. with 7 metal centers) and have studied their structures and magnetic properties. The dysprosium disc shows single molecule magnetism behaviour and the gadolinum analogue shows a large magnetocaloric effect.

 Fancy finding out more? Then download the ChemComm communication, which will be free to access until the 15th July 2011.

Also, are you interested in molecule-based magnetism research? Then take a look at Chem Soc Rev‘s recently published themed issue on Molecule-based Magnets, (Issue 6, 2011) guest edited by Joel Miller and Dante Gatteschi.
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New acetylene polymerisation catalyst is best yet

A team of chemists working in the UK and Australia have developed a new, highly active catalyst for acetylene polymerisation.

Polyacetylene is an important material as it has a degree of conjugation that leads to good conductive properties. It has found uses in areas such as synthetic metals and plastic electronics. New routes to make this polymer are constantly sought and, to date, the majority of catalysts for this task have low activities.

This problem has now been solved by two teams at the University of Tasmania and Imperial College London led by David McGuinness and George Britovsek, respectively. They took a bis(imino)pyridine iron catalyst, normally used for ethylene polymerisation, along with methylaluminoxane and successfully produced polyacetylene.

Graphical abstract: High activity acetylene polymerisation with a bis(imino)pyridine iron(ii) catalyst

An activity of 62 500 h-1 (turn over frequency; TOF) was obtained, which compares excellently with the 100  h-1 TOF obtained when using a standard existing acetylene polymerisation catalyst under the same conditions. This represents the most active acetylene polymerisation reported to date. Curently, the team are studying the effects of ligand modification and chain transfer reagents on the reaction.

Want to find out more? Then download  the full ChemComm article for free today.

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The importance of chemistry in sequencing nucleic acids

 

Solid phase DNA sequencing

Chemistry has played a vital role towards making routine, affordable sequencing of human genomes a reality. Leading UK scientist, Shankar Balasubramanian, provides a compelling review of the last 60 years, from the Sanger sequencing method through to the human genome project. In particular, Balasubramanian focuses on the achievements of Solexa (latterly, Illumina) on the modern developments of high throughput nucleic acid sequencing that originated in Cambridge, in the UK.
   

In association with the International Year of Chemistry (IYC), this Highlight in Chemistry emphasises the importance of chemistry and how it continues to contribute towards many other fields, most notably the biological and biomedical sciences. This sequencing approach is helping to transform science and offers intriguing prospects for the future of medicine.

Fancy reading more? Download the ChemComm Highlight, which will be free to access until the 1st July 2011.

 For your info, ChemComm is publishing Highlights in Chemistry articles throughout 2011, which has been recognised as an official activity for celebrating the IYC. Take a look at the IYC website to keep up-to-date on what else is happening throughout 2011 to celebrate the achievements of chemistry and its contributions to the well-being of humankind.

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Totally synthetic over bryostatin

Bryostatins are macrocyclic natural products with various biological activities, including potent anti-cancer activity due to protein kinase C inhibition. Eric Thomas and his team from the University of Manchester have shown that it is possible to prepare 20-deoxybryostatin, using a modified Julia olefination to form the tricky 16,17-double-bond, followed by macrolactonisation, selective deprotection and oxidation.Fancy finding out more about the reaction conditions?

Download the ChemComm communication, which will be free to access until the 1st July 2011. 

20-deoxybryostatin

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Inducing protein heterodimerisation

Scientists in The Netherlands and Germany have shown that cucurbit[8]uril (CB[8]) induces selective heterodimerisation between two different proteins.
 

Supramolecular induced protein dimerisation

Luc Brunsveld and his team functionalised the two proteins with methylviologen (electron deficient) and napthalene (electron rich) guest molecules, which formed a charge transfer complex inside the CB[8] cavity.  Interestingly, the resulting dimerisation can be visually observed and has established that there is distinct interplay between the supramolecular components within the proteins.

Fancy reading more? Then download the ChemComm communication,which will be free to access until the 24th June 2011.

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