Archive for October, 2010

Engineered enzyme makes important building block

By replacing a single active-site amino acid residue in an aminomutase enzyme, scientists in the Netherlands have engineered a variant that can catalyse the formation of β-tyrosine, an important building block in bioactive compounds.

Phenylalanine aminomutase (PAM) is an enzyme that catalyses a chemically challenging α,β-amine shift, forming β-phenylalanine from β-phenylalanine. It can tolerate a wide variety of substituents on the aromatic ring of the substrate but not a para hydroxyl group and so it cannot be used to synthesis β-tyrosine. Although tyrosine aminomutase (TAM) catalyses the amine shift in α-tyrosine to generate β-tyrosine, it has a more limited substrate scope than PAM and has low enantioselectivity towards β-tyrosine.

So Dick Janssen and colleagues replaced a cysteine residue with serine in phenylalanine aminomutase to make an enzyme with both TAM and PAM activity and high enantioselectivity. This engineering enzyme can catalyse the formation of β-tyrosine from p-coumaric acid and may prove useful for synthesising enantiopure β-tyrosine and its derivatives, Janssen says.

For more details, read Janssen’s ChemComm communication, free to access until 12th November. This communication is part of the Enzymes and Proteins web theme issue.

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Carbon NMR reveals absolute configuration

13C NMR shifts can be used, alone or in combination with 1H NMR, to assign the absolute configuration of organic compounds, claim Spanish scientists.

Ricardo Riguera and colleagues at the University of Santiago de Compostela examined the 13C NMR data for a collection of chiral samples, including carboxylic acids and cyanohydrins, derivatised with common auxiliaries. In all cases they found a perfect correlation between the sign of ΔδRS (the difference in chemical shift for the protons around the asymmetric carbon in the R and S substrates) and the absolute configuration of the substrate.

Graphical abstract:          13C NMR as a general tool for the assignment of absolute configuration

The foundations of the method reside in the aromatic shielding effect produced by the auxiliary on the protons and carbons of the substrate, Riguera explains.

Read the full report in Riguera’s ChemComm communication, free to access until 12th November 2010. And if you enjoy the communication, you might also enjoy NMR methods for unravelling the spectra of complex mixtures, a review in Natural Product Reports by Riguera et al.

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Carbon dioxide used in copolymerisation

A bimetallic iron(III) catalyst can couple together an epoxide (cyclohexene oxide) and carbon dioxide (CO2) to yield poly-(cyclohexene carbonate), under mild conditions.

Charlotte K. Williams and co-workers at the Imperial College London, in the UK, believe that this method provides a sustainable alternative for the synthesis of carbonates, as metal catalysed coupling of CO2 and epoxides is one of the few processes that actually consumes (rather than releases!) this harmful greenhouse gas.

Fancy reading more? Why not download the article today and blog some comments below? Published in ChemComm, this article is free to access until the 12th November.

This article is also part of the ‘Emerging Investigators’ issue, due to be published later on this year. This issue will highlight the very best work from scientists in the early stages of their independent career from across the chemical sciences.

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High purity for block copolymer

Highly pure poly(3-hexylthiophene)-containing block copolymers have been made, which is a great result for future optoelectronic applications, say US scientists.

Christopher Bielawski and colleagues as the University of Texas at Austin used click chemistry and a clever purification procedure to produce the block copolymers without the typical homopolymer impurity.

To find out more, why not download the article today? Published in ChemComm, this article is free to access until the 12th November. If you enjoyed reading this article, why not let us know your thoughts by blogging some comments below.

This article is also part of the ‘Emerging Investigators’ issue, due to be published later on this year. This issue will highlight the very best work from scientists in the early stages of their independent career from across the chemical sciences.

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Recognition for Heck, Negishi and Suzuki

Having watched, read and listened to many news stories since they announced this year’s Nobel Laureate winners for chemistry, the same resounding opinion across the chemistry community seems to be that Heck, Negishi and Suzuki are well deserved winners of this prize.

Looking back over the years, it is clear to see that this award-winning chemistry has inspired many articles and reviews published in ChemComm, Chem Soc Rev and it has already featured in the newest flagship journal, Chemical Science. 

 

Plenio’s trialkylphosphines for Pd-catalysed cross coupling reactions

 

Recent critical and tutorial reviews in Chem Soc Rev highlight the diversity of palladium (Pd)-catalysed cross coupling reactions and their applications in modern day chemistry. Whether it is developing trialkylphosphines for Pd-catalysed cross coupling reactions as alternatives to Platinum systems or using oxime-derived palladacycles as a source of palladium nanoparticles for catalysed Heck reactions, it has certainly made an impact. A recent Chemical Science perspective discusses the catalytic power of Pd in asymmetric allylic alkylation reactions to form C-X bonds. Then, from lab bench to desktop computer, the theoretical aspects of Pd-catalysed carbon-carbon cross coupling reactions have long been studied by scientists, to gain a better understanding of the cross coupling reactions.

The Nobel Prize was awarded to Richard Heck, Ei-ichi Negishi and Akiro Suzuki for their contributions to Pd-catalysed cross coupling reactions in organic synthesis, but the story doesn’t end here. Now thousands of research groups worldwide are applying and adapting this chemistry on a day-to-day basis, discovering exciting results of their own and showing that other transition metals (not just Pd!) can catalyse important reactions and form different carbon bond variations.

 
 
 

Ei-ichi Negishi's recent ChemComm article showing the total synthesis of (+)-scyphostatin

 

 

As shown in a recent communication (see scheme on the left) published in ChemComm from Ei-ichi Negishi’s research group, we are continually reminded of the importance of Heck, Negishi and Suzuki’s research contributions and it has definitely, without a doubt, shaped, moulded and advanced the chemical sciences.

 

 

 

 

Fancy reading Ei-ichi Negishi’s latest ChemComm article? Why not download the communication, which is free to access to all, until the end of November.

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Muscling in on toxic seafood

A fluorescent probe could provide a tool for real-time toxin screening in shellfish and help put an end to seafood related food-poisoning, claim US scientists. Dinoflagellates are organisms commonly found in sea water. Some can be toxic and are associated with harmful algae and bacteria accumulation, which can lead to toxins transferring into shellfish tissue, posing a major threat to food safety.

It is often thought that symbiotic bacteria – bacteria that live or interact with other organisms for a long time – play a key role in the biosynthesis of toxins from dinoflagellates. But this toxin-bacteria interaction has not been confirmed, until now. Michael Burkart and colleagues at the University of California at San Diego have used their findings to develop a fluorescence microscopy tool to screen shellfish for toxin producing dinoflagellates.

Burkart’s team fluorescently-labelled a protein that is taken up by the marine cells responsible for biosynthesising the toxin, okadaic acid. In vivo studies clearly show that the samples producing the toxin glow fluorescent blue under the microscope. The samples that provide a positive response to the probe also show signs of symbiotic bacteria in the cell walls, confirming the toxin-bacteria association.

Bacteria in mussels show a blue response under fluorescence

Using this information, Burkhart’s assay is able to select mussels that contain live toxin producing dinoflagellates at different stages of infection by counting the number of cells that fluoresce. Imaging shellfish during dinoflagelate infection detects okadaic acid much quicker than present techniques which can only detect the dinoflagellates once they have been fully absorbed into the shellfish tissue.

Jon Clardy, a pharmacology researcher at the Harvard Medical School in Cambridge, US, says that this work has ‘the beginnings of a potentially useful surveillance tool for public health.’ The main surprise for him was to find out that the bacteria are somehow involved in the biosynthesis of okadaic acid and possibly related to dinoflagellate toxins. This is all the more impressive as Clardy explains, ‘the biosynthesis of these compounds has been untouchable because of the enormous size of dinoflagellate genomes, which are much larger than human genomes, and the lack of genetic systems, which has frustrated commonly used approaches.’

Burkhart says that if this method can be applied to an automated system then it could prove to be a useful screening tool for the aquafarming industry. And looking further to the future he adds, ‘one could imagine a mobile phone application that would let you see if your crop or plate of oysters is safe for consumption. There is a tremendous potential in visual methods for food quality screening and its merge with the modern digital devices and networks.’

Emma Shiells

Fancy reading more? Then why not download the article today and blog your feedback below.

Link to Article

Metabolic probes for imaging endosymbiotic bacteria within toxic dinoflagellates
Carolina P. Reyes, James J. La Clair and Michael D. Burkart, Chem. Commun., 2010
DOI: 10.1039/c0cc02876b

 
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ChemComm symposia

We left the rain of Osaka and just one hour later arrived bathed in Korean sunshine at the impressive Incheon Airport. We followed a relaxed dinner in the hotel with a walk around Seoul’s lively streets. It seems the city does not sleep – it was Wednesday evening but it seemed like a Friday or Saturday. Apparently it’s the same every night! The day finished with discussions over red wine about who would win the 2010 Nobel prize in chemistry, but not before some confusion over price and the corking of a bottle…..

Professor Nam opened day one of the ChemComm symposium at Ewha Womans University and I was invited to say a few words. Short and sweet with many thanks!

After finishing proceedings in Japan, Professor Harry Gray opened the show in Korea. He spoke about his very early work in the 1960’s on the metal-oxo wall, before moving on to his current focus: building an artificial leaf without wires aided by a solar army of high school kids (see the interesting critical review by Woodhouse and Parkinson from the Chem Soc Rev Renewable Energy themed issue and the EES Opinion article by Parkinson). Professor Fukuzumi followed but he didn’t need a microphone – his voice boomed!  

At lunch I took a stroll around campus. The building where the symposium was being held was truly spectacular but I passed very few men on campus. Now I understand: Ehwa Womans University.

The night ended with a dinner reception for all speakers and a mixture of drinks, including a local favourite, the atomic bomb (soju and beer).

The second day continued in equally impressive style. High quality talks on water oxidation from Brudvig and Llobet were followed by the ChemComm speakers, Jonathan Sessler, Adrian Mulholland and Luet Wong. To finish the day, Jonathan Sessler became the ruthless session chair under strict instructions to finish by 6pm. Five presentations were given by young researchers and assistant professors. It was nice to see Youngmin You give an excellent talk on the sensing of biological zinc. The results had been published in ChemComm and highlighted in Nature Chemical Biology.

In closing the symposium, Professors Nam and Fukuzumi thanked the speakers but also the tremendous efforts of the local organisers, and in particular, girl power! A fabulous Korean banquet and performance showcasing Korean music and drums was the perfect way to finish the symposium…well almost. That honour was given to Adrian Mulholland, who in true British style could not resist the opportunity to join the performers on stage and bang the drum…

This was a tremendous serious of events, intense, with around 50 lectures in four days. The hospitality from both organisers was incredible and the selection and quality of the science was first rate. A big thank you also to Luet, Jonathan and Adrian for doing such a great job as the ChemComm speakers.

Next stop is Japan and China in May 2011 for the 5th ChemComm Symposia on organic chemistry and catalysis. Sign up for the ChemComm Chronicle and e-alert to receive more information as soon as it is available.

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Greener oxidations with iodine organocatalyst

A new type hypervalent iodine reagent could enable more efficient and green catalytic oxidations, report Japanese chemists.

Hypervalent iodine reagents have emerged as promising organo-oxidants, replacing classical heavy metal oxidants such as lead and mercury. m-Chloroperbenzoic acid is commonly used as a stoichiometric reoxidant to regenerate the reactive iodine species, but scientists would like to use other, more environmentally friendly oxidants, such as peracetic acid, instead. Until now, however, no efficient iodine catalyst that works well with peracetic acid has been found.

Yasuyuki Kita, at Ritsumeikan University, Kusatsu, and colleagues discovered that their µ-oxo-bridged hypervalent iodine(III) compounds, in the presence of peracetic acid, could catalyse spirolactam formation. They also believe the compounds can catalyse other types of oxidation, such as phenolic oxidation, and, because they have a chiral structure, could have potential in asymmetric oxidative transformations.

Graphical abstract: Designer μ-oxo-bridged hypervalent iodine(iii) organocatalysts for greener oxidations

Download the communication for free until 5th November 2011. And if you have some exciting research of your own to report, submit your manuscript to ChemComm today.

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The power of depletion attraction

Depletion attraction forces can be used to assemble nanorod superlattices and branched nanocrystal networks, say Italian chemists. The nanostructures could be used in a variety of applications, including photovoltaics, they claim.

Liberato Manna and colleagues at the Italian Institute of Technology, Genova, discovered that in the presence of molecules such as oleic acid, nanorods assemble into superlattices. They also found that tetrapod-shaped nanocrystals form networks under similar conditions.

Graphical abstract: Assembly of shape-controlled nanocrystals by depletion attraction

Want to find out how this works? Read the ChemComm article, which is free to access until 5th November, and add your comments on the work below.

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Is titanium the new platinum?

A new titanium dioxide-supported polyaniline iron catalyst exhibits improved catalytic activity for oxygen reduction when compared to traditional carbon-supported materials. With prohibitive costs of current platinum-based catalysts used in polymer electrolyte fuel cells this new catalyst material might be the cheaper alternative.

 

Piotr Zelenay, Gang Wu and co-workers at Los Alamos National Laboratory and a collaborator from the University of South Carolina, published their findings in ChemComm.

Interested to read more, then why not download the article today, which is free to access until the 5th of November and leave some blog comments below.

 

 Having trouble accessing the free content in ChemComm? Register for an RSC Publishing personal account today.

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