Metal-organic frameworks as nanostructure templates

Nanoporous metal-organic frameworks (MOFs) loaded with silver can serve as templates for ordered nanostructures, say US scientists.

Mark Allendorf, at Sandia National Laboratories, Livermore, and colleagues impregnated a MOF with silver then exposed the MOF to an electron beam. The beam broke down the template, leading to silver coalescence and the formation of ordered silver nanostructures.

The method forms either silver nanoparticles or nanowires depending on the MOF’s structure and the extent of silver loading, explains Allendorf.

Graphical abstract: Ordered metal nanostructure self-assembly using metal–organic frameworks as templates

Although the synthesis of silver nanowires and nanoparticles have been previously reported, this new route can generate structures with diameters less than 10 nanometres, which has previously been very challenging.

Allendorf’s Chemical Science Edge article is available to download for free.

Be seen with the best and submit to Chemical Science today.

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Stereoselective additions with a twist

A helical framework around an electrophilic centre is an effective control element for the stereoselective addition of nucleophiles, according to European scientists.

Stereoselective additions of nucleophiles to trivant carbon atoms are common organic reactions. Chemists often rely on stereogenic elements close to the reactive centres to influence the stereochemical outcome. For example, nucleophiles can preferentially add to one of the two diastereotopic faces of a carbenium ion when there is an α-stereocentre.

Now Jérome Lacour, at the University of Geneva, Switzerland, and colleagues have shown that nucleophiles can also distinguish between the diastereotopic faces of chiral cationic helicenes. Using hydride and organolithium reagents, the group achieved diastereomeric ratios higher than 49:1.

Graphical abstract: Highly selective additions of hydride and organolithium nucleophiles to helical carbenium ions

More information can be found in Professor Lacour’s Edge article.

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Metal free catalysts for aliphatic C-H bond oxidation

Metal-free polymers have the potential to replace toxic metal catalysts in hydrocarbon oxidation reactions, according to an international team of chemists.

Yong Wang, at the Max-Planck Institute of Colloids and Interfaces, Potsdam, Germany, and colleagues replaced some of the carbon atoms in graphitic carbon nitride with boron. The resulting polymeric material was better than previous biomimetic homogeneous oxidation catalysts at oxidising substituted aromatics.

Graphical abstract: Synthesis of boron doped polymeric carbon nitride solids and their use as metal-free catalysts for aliphatic C–H bond oxidation

Oxidations of sp3 hybridised C-H bonds are challenging because the oxidised products are more reactive than the starting materials and so they tend to over-oxidise. This was not a problem for Wang’s catalyst, which was highly selective at forming ketones or aldehydes.

For more information, download Wang’s Edge article for free.

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Industrial method for improving China’s environment

Sulfonated graphene solid acid catalysts could be cheap, environmentally friendly alternatives to concentrated sulfuric acid for use in industry because they can be recycled, say scientists from China.

Xiaobin Fan, at Tianjin University, and colleagues made the catalyst by adding 4-benzenediazoniumsulfonate to a graphene suspension. When they tested its activity against other catalysts in ethyl acetate hydrolysis, they found that it had comparable activity to concentrated sulfuric acid catalysts and had higher activity than Nafion NR50, a commercial solid acid known for its excellent activity.

Acid sites in most solid catalysts can be degraded by water in reactions, but Fan’s catalyst is stable in water and can be reused without decrease in activity.

To find out more, download the Chemical Science Edge article for free.

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Top ten most accessed articles in October

This month sees the following articles in Chemical Science that are in the top ten most accessed:-

Amine directed Pd(ii)-catalyzed C-H bond functionalization under ambient conditions 
Benjamin Haffemayer, Moises Gulias and Matthew J. Gaunt 
Chem. Sci., 2011, Advance Article, DOI: 10.1039/C0SC00367K, Edge Article  

Site-specific photocatalytic splitting of methanol on TiO2(110) 
Chuanyao Zhou, Zefeng Ren, Shijing Tan, Zhibo Ma, Xinchun Mao, Dongxu Dai, Hongjun Fan, Xueming Yang, Jerry LaRue, Russell Cooper, Alec M. Wodtke, Zhuo Wang, Zhenyu Li, Bing Wang, Jinlong Yang and Jianguo Hou 
Chem. Sci., 2010, 575-580, DOI: 10.1039/C0SC00316F, Edge Article  

Dialkylbiaryl phosphines in Pd-catalyzed amination: a user’s guide 
David S. Surry and Stephen L. Buchwald 
Chem. Sci., 2011, Advance Article, DOI: 10.1039/C0SC00331J, Perspective  

Total synthesis of all (-)-agelastatin alkaloids 
Mohammad Movassaghi, Dustin S. Siegel and Sunkyu Han 
Chem. Sci., 2010, 561-566, DOI: 10.1039/C0SC00351D, Edge Article  

Cyclopropenium-activated Beckmann rearrangement. Catalysis versus self-propagation in reported organocatalytic Beckmann rearrangements 
Christine M. Vanos and Tristan H. Lambert 
Chem. Sci., 2010, 705-708, DOI: 10.1039/C0SC00421A, Edge Article  

N-heterocyclic carbenes which readily add ammonia, carbon monoxide and other small molecules
Ulrich Siemeling, Christian Färber, Clemens Bruhn, Michael Leibold, Detlef Selent, Wolfgang Baumann, Moritz von Hopffgarten, Catharina Goedecke and Gernot Frenking 
Chem. Sci., 2010, 697-704, DOI: 10.1039/C0SC00451K, Edge Article  

Diamine ligands in copper-catalyzed reactions 
David S. Surry and Stephen L. Buchwald 
Chem. Sci., 2010, 13-31, DOI: 10.1039/C0SC00107D, Perspective  

Palladium-catalyzed coupling of functionalized primary and secondary amines with aryl and heteroaryl halides: two ligands suffice in most cases 
Debabrata Maiti, Brett P. Fors, Jaclyn L. Henderson, Yoshinori Nakamura and Stephen L. Buchwald 
Chem. Sci., 2011, Advance Article, DOI: 10.1039/C0SC00330A, Edge Article  

Continuous flow multi-step organic synthesis 
Damien Webb and Timothy F. Jamison 
Chem. Sci., 2010, 675-680, DOI: 10.1039/C0SC00381F, Minireview  

The organocatalytic three-step total synthesis of (+)-frondosin B 
Maud Reiter, Staffan Torssell, Sandra Lee and David W. C. MacMillan 
Chem. Sci., 2010, 37-42, DOI: 10.1039/C0SC00204F, Edge Article  

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

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

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Fingerprinting red wine

A sensor that can discriminate between different tannins and be used to fingerprint a wide variety of red wines to confirm their authenticity has been developed by US scientists. 

Eric Anslyn and colleagues at the University of Texas at Austin and University of California Davis have developed a sensor made with colour-changing indicators. They used the sensor to test wine samples from different vintners and managed to distinguish between specific flavonoids – chemicals found in fruit and vegetables, tea and red wine – in particular looking at tannins, which are responsible for colour, aging ability and texture. 

When wine is added to the sensor, the indicators are displaced, which results in a colour change that can be monitored and recorded. The team found that patterns emerged for different wine varietals. They tested Pinot Noir, Zinfandel, Beaujolais, Cabernet Sauvignon, Shiraz and Merlot and assigned signatures to each wine type. The team could also classify wines from the same varietal. They tested different brands of Shiraz (and Zinfandel in a separate study) and they were able to link the tannins to the genome of the specific grape. 

The sensor can assign signatures to different wine types and to wines within types

 

‘The ability to fingerprint mixtures of metabolic origin, without knowing their exact compositions, has huge potential for applications in medical diagnostics, environmental science and the food industry,’ says Anslyn. 

Kim Janda, a detection expert at the Scripps Research Institute in the US, has visions of the sensor being used for ‘biodefense purposes where rapid and accurate identification is at a premium.’ Janda adds: ‘if Anslyn improved the method further he could put sommeliers out of business!’ 

‘Product authenticity is an important issue with food and beverages, particularly with high value products such as wine,’ says Bob Dambergs, a senior research scientist at the Australian Wine Research Institute, Glen Osmond. ‘Flavonoid compounds define red wines and this study makes clever use of specific interactions of flavonoids with peptides to produce a sensor array with high discriminatory power. Most wine producing countries have strict label-integrity regulations to protect consumers – the availability of rapid analysis methods utilising chemical sensors will facilitate compliance monitoring.’

Fancy reading more? Then why not download and read the Chemical Science Edge Article for yourself, details can be found below:-

Discrimination of flavonoids and red wine varietals by arrays of differential peptidic sensors
Alona P. Umali, Sarah E. LeBoeuf, Robert W. Newberry, Siwon Kim, Lee Tran, Whitney A. Rome, Tian Tian, David Taing, Jane Hong, Melissa Kwan, Hildegarde Heymann and Eric V. Anslyn, Chem. Sci., 2011
DOI: 10.1039/c0sc00487a

  

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Bismuth medicines: insight into mechanism of action

Scientists have converted a protein from a pathogenic bacterium into a FRET-based fluorescent probe to help find out why bismuth therapeutics can treat gastric illnesses.

Helicobacter pylori is a bacterium that colonises the digestive track and causes chronic gastritis, ulcers and even some gastric cancers. Bismuth-containing medicines are known treatments for H. pylori. It is thought that bismuth ions bind to metal binding sites in H. pylori’s metalloproteins but their exact mechanism of action is unknown.

Chuan He and colleagues at the University of Chicago investigated the metal binding properties of their FRET probe, made from the Hpn protein found in H. pylori, with different biometals in vitro. They showed that the sensor has a high affinity for Ni2+ and Zn2+ and moderate affinity for Bi3+. They then used the sensor in E. coli cells, which act as a model system for H. pylori, to measure uptake of these three ions. To their surprise, E. coli concentrated significant amounts of Bi3+, but not Ni2+ or Zn2+.

Graphical abstract: Metal-binding properties of Hpn from Helicobacter pylori and implications for the therapeutic activity of bismuth

If Bi3+ accumulates to similarly high levels in H. pylori, says He, it may target Hpn, eventually killing the bacteria.

Read the Edge article online today and let us know what you think of this work by leaving your comments below.

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Meet the General Chemistry team

Find out where Editor Robert Eagling and Deputy Editor Joanne Thomson will be in 2011

The General Chemistry (ChemCommChem Soc Rev and Chemical Science) team will be attending a number of conferences in 2011. Here’s where you can meet up with us next year:
Robert Eagling (Editor) and Joanne Thomson (Deputy Editor)

Please do let us know if you will be attending any of these meetings – we’d love to meet you!

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Freezing the action in living things

A fast, high-resolution infrared imaging technique that can ‘freeze’ living specimens has been designed by UK scientists and tested on human ovarian cancer cells. The technique could lead to a better understanding of how cancer drugs work.

Infrared spectroscopy of cell images can be used in a number of fields including forensic science and cancer research. However, taking pictures of samples can take up to 12 hours. Chris Phillips and his team at Imperial College London have developed a technique to produce 2D images that takes a fraction of a second. By combining a purpose-built pulsed IR laser source with a charge-coupled device camera, rather like a digital camera, they were able to generate pictures 1011 times faster than current IR spectroscopic imaging methods. The IR source generates very short pulses (~100 psec) that keep the illumination levels below cell phototoxicity limits and allow moving specimens to be frozen in a way that mimics conventional flash photography.

Previous attempts to image cells in this way have required long illumination times, which causes the cells to move away from the light source or can kill them. ‘Because you can do it so quickly, you can freeze the action in living things, and because you have so much more light signal, you can get right inside the cells to take chemical maps,’ says Phillips.

The sharpest focus cell images are visually selected for the cell-level spectroscopy analysis

Link to journal article
Ultrafast infrared chemical imaging of live cells
Hemmel Amrania, Andrew P. McCrow, Mary R. Matthews, Sergei G. Kazarian, Marina K. Kuimova and Chris C. Phillips
Chem. Sci., 2011, DOI: 10.1039/c0sc00409j

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Editor’s diary

A round up of the latest activities in the RSC General Chemistry Editorial Office

Over the past week or two we’ve been writing the editorials for Chemical Science, ChemComm and Chem Soc Rev issue 1s, 2011. It seems strange to be wishing people a Happy New Year in October but the issues will be sent to the printers next month so we need to plan in advance. It has been great to reflect on all the success of 2010 – we’ve launched a new journal, published more articles than ever before…but I’ll stop there before I give too much away. All will be revealed in issue 1.

We’ve also been planning our conference attendance for next year. There are so many great events to choose from so it has been really difficult to narrow them down to a manageable and affordable number. We’ll of course be at the ISACS meetings in July and September but if you have any suggestions of where else we should be, please do let us know.

Particularly exciting during the past month has been a short Chemical Science information film we’ve been working on with Anne from the RSC communications team. Thankfully I was behind the scenes only but Robert (the Editor) gave a stellar performance on camera – Anne described him as “a natural”. The film will be screened at the RSC general assembly in November.

Please keep sending us your feedback and suggestions for Chemical Science, ChemComm and Chem Soc Rev. You can leave comments below or email me.

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