Archive for the ‘Hot Articles’ Category

Proof-of-principle concept for label-free detection of glucose and alpha-glucosidase activity

Glycogen storage disease type II (GSD II), also known as Pompe disease, is a genetic disorder that results in muscle and nerve cell damage caused by deficiency of the lysosomal acid a-glucosidase enzyme. In an effort to achieve a better technique for screening enzyme activity in patients suffering from Pompe disease, Prof. Vivian Yam and colleagues at the Institute of Molecular Functional Materials, University of Hong Kong, have synthesised a two-component platinum (II) complex-polymer ensemble for glucose sensing and a-glucosidase assay.

The system works by strongly binding glucose, resulting in a 46-fold increase in the low energy emission band (800 nm) of the electronic emission spectrum. Additionally, in the presence of a-glucosidase and maltose (which is broken down to glucose by a-glucosidase), the intensity of the 800 nm emission band was found to increase with time. These results provide a “proof-of-principle” concept for label-free detection of glucose and open the way for rapid and sensitive detection of a-glucosidase.

To find out more download the ChemComm communication for free until 25th February 2011.

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Novel concept for switchable olefin metathesis catalysts

Chemists have discovered a novel triggering mechanism for olefin metathesis catalysts while unravelling the mechanism of a crucial ligand rearrangement step.

Olefin metathesis is a widely used reaction in organic and polymer synthesis. cis Dichloro ruthenium benzylidene complexes bearing an N-heterocyclic carbene ligand have recently gained considerable attention as stable metathesis catalysts. They are known as latent catalysts as they initiate slowly, which is thought to be because the cis dichloro precursors have to rearrange to their trans dichloro counterparts to become active.

While studying the reaction mechanism, Christian Slugovc and colleagues at Graz University of Technology, Austria, discovered that a cationic complex is an intermediate in the rearrangement step. They also observed that pyridine, which is a donor ligand, facilitates the displacement of one of the chloride ligands, the first step in the rearrangement.

Graphical abstract: Pyridine as trigger for chloride isomerisation in chelated ruthenium benzylidene complexes: implications for olefin metathesis

But most striking, says Slugovc, is that the chloride counterion (or, more generally, a counterion that can coordinate to ruthenium) is indispensible for the catalytic activity. Changing the counterion for the non-coordinating hexafluorophosphate ion produced an almost inactive catalyst, but the activity was triggered again by adding chloride. Slugovc says this constitutes a novel concept for switchable olefin metathesis catalysts.

Download Slugovc’s ChemComm communication to find out more.

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New polymer hydrogels offer step forward in desalination

Chemists working in Australia have used polymer hydrogels as a ‘draw’ agent in a desalination process.

Forward osmosis (FO) desalination is an emerging area of interest for chemists as it provides a low energy method of obtaining salt free water from the sea. Typically in FO, saline water is separated by a membrane from a ‘draw’ solute. Water passes through the membrane from the saline side to the ‘draw’ solute via osmosis. The water is then recovered from the ‘draw’ agent using distillation.

Now Huanting Wang and colleagues at Monash University have investigated the use of polymer hydrogels as the draw agent for FO desalination. Polymer hydrogels can reversibly change their volume when exposed to certain stimuli such as temperature and pressure. This gives them an advantage over traditional draw agents as they can potentially be recycled and release the water at lower energy and therefore cost.

Graphical abstract: Stimuli-responsive polymer hydrogels as a new class of draw agent for forward osmosis desalination

The team found that it is indeed possible to release significant amounts of water from the polymer hydrogels tested and are investigating other stimuli, such as light, to further increase the efficiency of this process.

Read more about this exciting advance by downloading  the full ChemComm communication today and let us know what you think below.

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Lack of luminescence quenching does not prove DNA intercalation by Ru(II) complexes

The binding of luminescent complexes to DNA is a popular area of research, with applications ranging from molecular switches to photodynamic therapy. It has commonly been reported in the literature that a lack of luminescence quenching by ferrocyanide, [Fe(CN)6]4−, can be used as evidence of the intercalation of a complex with DNA. 

Claudia Turro and colleagues at Ohio State University have now shown that a Ru(II) complex that binds strongly to DNA electrostatically rather than by intercalation is equally resistant to 3MLCT (metal-to-ligand charge transfer) emission quenching as one known to be a DNA intercalator.

These findings indicate that the absence of emission quenching by [Fe(CN)6]4− cannot be used alone as proof of DNA intercalation by a complex. Hence, researchers using this method will need to take extra care when interpreting their results.

To find out more and start a discussion download the communication (for free until 18th Feb 2011) and leave your comments below.

 

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Hot article round up for December

So, it’s a new calendar year, new resolutions have been made (and broken!) but before we leave 2010 behind us for good, let’s take a look at some of the hot articles that caught our eye back in December.

 

 

Real-time nucleic acid analysis
The quantification of genes in human cDNA and malaria in blood samples using a real-time PCR technique has been developed by scientists in South Korea. To find out more, download the communication, published by Dae-Ro Ahn and colleagues.

Rauhut–Currier reaction strikes again
Phosphinothioureas can be used as organocatalysts for asymmetric Rauhut-Currier reactions of bis(enones). Xin-Yan Wu and co-workers achieved good yields (up to 99%) with excellent enantioselectivities (up to 99.4% ee). If you’re interested to know more about the reaction conditions used then why not download their communication today?

Observing atomic hydrogen
A nitrogen-induced ionic hydrate system can produce a hydrogen radical from water without direct energy sources, like hydrogen and methane. Read more about this impressive chemistry in the authors’ communication published in ChemComm.

The power of light
A photo-controlled anticancer drug release system has been designed by scientists in China. Based on photo-induced electron transfer between semiconductor quantum dots and an ester derivative, the anticancer drug can be released upon shining visible light onto the sample. Read more about their discovery in their communication article.

Hard graft for better fuel
Grafting highly dispersed Cu(I) onto beta-cyclodextrin shows better adsorptive desulfurisation capacity than other more conventional methods, an important development for the petroleum refining industry, say scientists in China. Xiao-Qin Liu and colleagues from Nanjing University of Technology, have published their communication in ChemComm, read all about it here first!

Imitating micelles
A metal complex has been disguised as a
 micelle using amphiphilic phosphine ligands. The system cleverly switches between a coordination polymer and a discrete cage in response to solvent polarity or pH, acting just like a micelle. Want to know more? Then read Stuart James’ exciting communication published in ChemComm.

Let us know what you think to these hot articles by blogging some comments below. If you have some of your own hot research to publish, then why not submit to ChemComm today!

 

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High performance “ionic liquid” chromatography

Japanese scientists have demonstrated the first use of ionic liquids (ILs) as eluents for high performance liquid chromatography (HPLC).

Hiroyuki Ohno at the Tokyo University of Agriculture and Technology heated the ILs to reduce their natural viscosity and allow them to pass through the column. They showed that it was possible to separate a variety of biopolymers including cellulose which is notoriously difficult to dissolve.

This new technique will offer advantages in the separation of a wide variety of both synthetic and naturally occuring polymers, especially those that are not easily dissolved. Ohno also believes that High Performance Ionic Liquid Chromatography (HPILC) could be a powerful tool in not only characterising polymers but also studying dynamic processes such as polymerisation.

Download the full ChemComm communication today to discover more.

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The hydrogen evolution

An inexpensive, easy to assemble light-activated water-splitting system for generating hydrogen has been devised by UK scientists.

Erwin Reisner at the University of Manchester* attached an inexpensive metal, cobalt, to ruthenium dye-sensitised titania nanoparticles. They placed the nanoparticles in water, added triethanolamine (which donates an electron), stirred the mixture at room temperature and found that hydrogen was generated.

Nanoparticles show excellent dispersibility in water and the high surface area allows for easy variation of the catalyst loading and ratio for the optimisation of light absorption and catalysis, says Reisner.

Download Reisner’s ChemComm communication to find out more. This article is part of the ChemComm Hydrogen web theme.

*now at the University of Cambridge

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Toxin sensor for drinking water

A green and simple method to make a sensor to detect one of the most toxic cyanotoxins, microcystin-LR, has been devised by scientists from China. Cyanotoxins are produced by blue-green algae and can contaminate drinking water.

In 1998 the World Health Organisation (WHO) set up a provisional guideline limit of 1 mg L-1 for  microcystin-LR in drinking water so detecting it in the environment is important.

Huangxian Ju and colleagues from Nanjing University made their sensor to detect  microcystin-LR by  assembling gold nanoparticles on nitrogen-doped carbon nanotubes. Nitrogen-doped carbon nanotubes are less toxic to cells and have better biocompatibility than un-doped carbon nanotubes, making them more suitable for use in biosensors. The nitrogen incorporated in the nanotubes also provides an active site to anchor gold nanoparticles onto. 

 

 The team immobilised an antibody for microcystin-LR on their nanosensor and used it to detect the cyanotoxin in water samples. They found that microcystin-LR could be detected at levels much lower than the limit set out in the WHO guidelines. 

Ju explains that although several methods can detect the presence of microcystin-LR, they are time-consuming, need expensive equipment and advanced technical expertise. Ju’s nanocomposite is cheap to make and shows a wide concentration range, low detection limit, good reproducibility and could successfully detect microcystin-LR in polluted water samples, said the researchers.

‘This system is more biocompatible than existing systems, so leads to enhanced sensitivity for microcystin-LR immunosensing,’ says Dianping Tang, an expert in electrochemical immunoassay technologies from Fuzhou University in China.

Ju hopes to immobilise different metal nanoparticles onto the nitrogen-doped carbon nanotubes to make metal nanoparticle/nanotube composites as biocompatible platforms for biosensing and biocatalysis.

Rachel Cooper

 

Link to the ChemComm article:-

 In situ assembly of gold nanoparticles on nitrogen-doped carbon nanotubes for sensitive immunosensing of microcystin-LR
Jing Zhang, Jianping Lei, Rong Pan, Chuan Leng, Zheng Hu and Huangxian Ju, Chem. Commun., 2011, 47, 668
DOI: 10.1039/c0cc04198j

 

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Bacteria-based AND gate: a decision-making and self-powered biosensor

Scientists have made the first Boolean logic gate that is purely bacteria-based. It uses the biochemical networks of whole and living bacteria to perform its biocomputing function.

Various logic gates (i.e. AND, OR, XOR) have been made using enzymatic bioelectrochemical systems (BESs), where enzymatic reactions form the core parts of the gates. But until now, microbial BESs, which have electrochemically active bacteria at the electrodes to catalyse oxidation and reduction reactions, have never been used as logic systems.

Largus Angenent, at Cornell University, Ithaca, US, and colleagues used Pseudomonas aeruginosa mutant bacteria in their AND logic gate. P. aeruginosa is an opportunistic pathogen that infects humans (and other organisms), causing a range of problems including inflammation and sepsis. Angenent claims his bacteria-based AND gate could be used in a self-powered, decision-making biosensor to detect or monitor pathogens such as P. aeruginosa.

Graphical abstract: Bacteria-based AND logic gate: a decision-making and self-powered biosensor

To find out more, download Angenent’s ChemComm communication.

If you have some hot research to report, make the right decision and submit to ChemComm.

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Doubt cast on X-ray structure of trapped reactive species

Immobilisation inside a cavity can be a very effective strategy for stabilising reactive species. In fact, earlier this year, a team of French scientists claimed in Science1 to have used this technique to elucidate the solid state crystal structure of 1,3-dimethylcyclobutadiene trapped along with carbon dioxide inside an optimised host.

But, says Henry Rzepa from Imperial College London, UK, this claim should be treated with caution as his calculations suggest that the Science report is incorrect.

Based on his quantum chemical modelling studies, Rzepa proposes that reported crystal structure in fact is not that of 1,3-dimethylcyclobutadiene and carbon dioxide, but more probably that of the precursor used to attempt to generate the pair.

Graphical abstract: Can 1,3-dimethylcyclobutadiene and carbon dioxide co-exist inside a supramolecular cavity?

Find out more about this controversial issue in Rzepa’s ChemComm communication (free to access until 25th January 2011) and let us know what you think by leaving your comments below.

For further discussion, see Crystallographic Confusion in Chemistry Views magazine and Henry Rzepa’s blog.

1. Y.-M. Legrand, A. van der Lee, M. Barboiu, Science 2010, 329, 299-302

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