Archive for the ‘Hot articles’ Category

Graphene and platinum are brought together for fuel cells

Graphene is certainly a hot topic in research right now. A quick look down this very blog shows that it featured in no fewer than seven of the top ten accessed articles in RSC Advances during 2012 (including all of the top three)!

This versatile material appears as oxides, composites, quantum dots, nanomaterials and foams and it has been investigated for uses in photocatalysis, energy, environmental applications and more.

Now researchers in India and China have been investigating graphene supported platinum catalysts for fuel cells.Platinum nanostructures on graphene catalysing oxygen reduction

Sreekuttan M. Unni and colleagues report the first synthesis of a 3D self-assembled single crystalline platinum nanostructure directly on a graphene surface without structural directing agents, by using a slow reduction method. In their paper, they show superior electrocatalytic activity towards the oxygen reduction reaction, a crucial reaction for hydrogen-fuelled polymer electrolyte fuel cells. They show that their material also has less vulnerability to strong hydroxyl adsorption and a higher limiting current density than other graphene supported platinum or commercial platinum-on-carbon catalysts.

Meanwhile Jian Zhao and colleagues have published about their supercritical fluid route for preparing graphene-supported platinum-ruthenium nanoparticles in an effective, simple, low temperature and environmentally benign way. They used supercritical CO2 to uniformly distribute ultrafine PtRu nanoparticles with an average size of 2.87 nm on the surfaces of functionalized graphene sheets. They found considerably improved catalytic activity and stability for methanol oxidation from their supported nanoparticles because of the uniform distribution. Their supercritical approach may have promise for development of direct methanol fuel cells.

Find out more about this research in RSC Advances:

3-Dimensionally self-assembled single crystalline platinum nanostructures on few-layer graphene as an efficient oxygen reduction electrocatalyst, Sreekuttan M. Unni, Vijayamohanan K. Pillai and Sreekumar Kurungot, RSC Adv., 2013, 3, 6913-6921

Methanol electrocatalytic oxidation on highly dispersed platinum–ruthenium/graphene catalysts prepared in supercritical carbon dioxide–methanol solution, Jian Zhao, Lin Zhang, Hao Xue, Zhaobo Wang and Haiqing Hu, RSC Adv., 2012, 2, 9651–9659

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Creative assemblies for targeted drug delivery

Stimuli-responsive assemblies have generated a lot of interest in recent years especially in view of their biological applications.  Enzyme-responsive assemblies for controlled drug release have gained particular interest as this offers potentially selective and targeted delivery of therapeutics.Graphical Abstract for C3RA40453F

A team of scientists from Nankai University (China) led by Yu Liu have fabricated a supramolecular assembly based on the host-guest complexation of amphiphillic calixarene with adenosine triphosphate (ATP).  Complextion of the calixarene with ATP markedly lowers it’s critical aggregation concentration, forming hollow spherical nanoparticles.  The nanospheres were shown to be responsive to phosphatase – an enzyme over-expressed in many tumor cells - and thus may have applications in drug delivery and cancer therapy.

Read the full article for free until the 24th May 2013:

Phosphatase-responsive amphiphilic calixarene assembly, Yi-Xuan Wang, Dong-Sheng Guo, Yu Caoa and Yu Liu, RSC Adv., 2013, DOI: 10.1039/C3RA40453F

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Energy storage of the future?

Supercapacitors, also known as electrochemical capacitors, are used as highly reliable energy storage devices with the advantage of rapid charge and discharge compared to batteries. However to further expand their use it is necessary to improve their performance in other areas including energy density.

Ruthenium oxide is the material widely used for supercapacitor electrodes. Its use is reviewed by Wentao Deng and colleagues in China and the UK, in a comprehensive overview of the state-of-the-art in this area.Ruthenium oxide decorated carbon nanotubes for supercapacitors

Work has not stopped on improving the performance of these highly promising devices – far from it. Just to take a couple of examples, Sho Makino and colleagues from Japan have used nanostructured ruthenium oxide in an aqueous hybrid supercapacitor with a specific energy comparable to modern rechargeable batteries, opening the possibility of using these materials in a post-lithium ion battery technology. Meanwhile Beena Balan and colleagues from India have looked at decorating carbon nanotubes with ruthenium oxide to produce a ternary electrode material to increase the specific capacitance by 103%, with enhanced rate and excellent electrochemical stability.

Read more about this valuable research in RSC Advances – free to access for 4 weeks:

Electrochemical capacitors utilising transition metal oxides: an update of recent developments, Wentao Deng, Xiaobo Ji, Qiyuan Chen and Craig E. Banks, RSC Adv., 2011, 1, 1171

4 V class aqueous hybrid electrochemical capacitor with battery-like capacity,Sho Makino, Yuto Shinohara, Takayuki Ban, Wataru Shimizu, Keita Takahashi, Nobuyuki Imanishib and Wataru Sugimoto, RSC Adv., 2012, 2, 12144

Carbon nanofiber–RuO2–poly(benzimidazole) ternary hybrids for improved supercapacitor performance, Beena K Balan, Harshal D Chaudhari, Ulhas K Kharul and Sreekumar Kurungot, RSC Adv., 2013, 3, 2428

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Electron-conjugation facilitates electron transfer of hemoglobin by Ce(OH)3 nanorods

Scientists from the University of Chinese Academy of Sciences (Beijing, China) led by Kebin Zhou investigated the interaction between nanorods of Ce(OH)3 and CeO2 and the redox protein hemoglobin.

Graphical abstract for C3RA40336JThe nano-bio interfaces, such as those between inorganic nanomaterials and biological systems, are gaining a significant amount of interest due to their importance in biomedical applications, but also out of concerns over the bio-safety of nano-engineered particles.  In the case of ceria-based nanomaterials, some studies have found they were able to prevent the increase of reactive oxygen species (ROS) in vitro and in vivo due to the existence of Ce3+.  However, others have found that some of these materials could actually generate ROS and cause toxicity to cells as Ce4+ is reduced to Ce3+.

In this work, Zhou and co-workers hydrothermally prepared Ce(OH)3 and CeO2 nanorods and studied their interaction with a typical redox protein hemoglobin through an electrochemical method combined with Electron Paramagnetic Resonance spectroscopy.  Ce(OH)3 was found to be more efficient in enhancing the direct electron-transfer of hemoglobin which may be due to the strong electron-conjugation interaction.

Read the full article for free until the 7th May 2013.

Strong electron-conjugation interaction facilitates electron transfer of hemoglobin by Ce(OH)3nanorods, Lei Wang, Qingfen Luan, Dan Yang, Xin Yao and Kebin Zhou, RSC Adv., 2013, DOI: 10.1039/C3RA40336J

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Flexible ligand secret to solvent-free success

Steven P. Nolan’s group at the University of St Andrews in Scotland, UK, have reported a new solvent-free protocol for carrying out Buchwald-Hartwig aminations, an important class of reactions, for unactivated aryl chlorides using a palladium pre-catalyst. The reaction proceeds to complete conversion in around five minutes when initiated at room temperature, compared to zero conversion when using a solvent (DME). The secret to their success appears to be the use of a bulky yet flexible ligand, IPr*, in the pre-catalyst.

A highly effective solvent-free protocol for the Buchwald–Hartwig amination of unactivated aryl chlorides by palladium pre catalyst

The reaction requires 1 mol% of the [Pd(NHC)] pre-catalyst – halving the amount of catalyst halved the conversion rate. An exotherm was observed in many cases: the reaction self-heated to 80ºC for a few seconds, therefore the group concludes that the protocol could be dangerous if carried out at a large scale. Interestingly the coupling could also be carried out with a solid substrate, leading to conversion of 73% after 24h, with no observed exotherm but a longer reaction time.

To learn more about this intriguing class of reactions, read the original article in RSC Advances:

Solvent-free aryl amination catalysed by [Pd(NHC)] Complexes, Anthony Chartoire, Arnaud Boreux, Anthony R. Martin and Steven P. Nolan, RSC Adv., 2013, 3, 3840–3843

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Bone-repairing nanoparticles laced with DNA

A bone-repairing nanoparticle paste has been developed that promises faster repair of fractures and breakages. DNA containing two growth-factor genes is encapsulated inside synthetic calcium-phosphate nanoparticles. These genes can enter cells and induce the synthesis of proteins that are able to accelerate bone growth.

The treatment of bone loss or fracture – after trauma, surgery or tumour extractions, for instance – represents a major challenge in clinical medicine. Matthias Epple at the University of Duisburg-Essen, Germany, who leads the team that developed the new bone paste, explains that ‘alternatives, such as bone from donors and synthetic calcium phosphate, suffer from infection problems, poor mechanical stability or inadequate resorption to form new bone.’ The team’s approach combines the bone-forming action of calcium phosphate – the principal component of bone – at the site of injection with further stimulation of bone growth in the surrounding tissue.

Injecting the paste into the boneGenes for two growth factors are encapsulated within the nanoparticles: bone morphogenetic protein 7 (BMP-7), which stimulates bone-forming cells, and vascular endothelial growth factor (VEGF), which induces the growth of blood vessels for bone-cell nutrition. Following injection, the nanoparticles are taken up by the surrounding cells, where the acidic conditions of the lysosomes dissolves the calcium phosphate and releases the DNA. These transfected cells then produce the growth factors that accelerate bone growth and reduce the amount of time a patient is immobile. Epple expects a long-lasting stimulatory effect that will aid growth over the months and years required for bones to heal fully, preventing the need for multiple injections.

Michael Hofmann, who works on bone cements and drug delivery at the University of Birmingham, UK, remarks: ‘The bioresorbable paste would be replaced quickly by newly formed bone, so effectively you would have a vanishing implant. In a population where an increasing number of people have impaired bone-growth abilities – for instance, the elderly – the findings have tremendous potential for accelerating the regrowth of any bone loss or fracture in orthopaedic and dental applications.’

Epple’s team plan to extend their work on calcium-phosphate nanoparticles to target specific cell types by attaching antibodies to the nanoparticle surface.

by Michael Parkin

The above story was published in Chemistry World on the 13th February 2013: Bone-repairing nanoparticles laced with DNA

Read the full article for free until the 29th March 2013! 

A genetically active nano-calcium phosphate paste for bone substitution, encoding the formation of BMP-7 and VEGF-A, Svetlana Chernousova, Jan Klesing, Nadia Soklakova and Matthias Epple, RSC Adv., 2013, DOI: 10.1039/C3RA23450A

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Synthesis, mesomorphism and dielectric behaviour of basket shaped scaffolds

Polarized optical textures of the new scaffoldsShobhana Menon and colleagues from Gujarat University, India, have designed a new series of lower rim azocalix[4]arene basket-type mesogens.  Along with their rigid core, calix[4]arenes are easy to functionalize with various linkages and flexible aliphatic chains at the hydrophilic hydroxyl groups.  They are therefore promising candidates for liquid crystal applications.

The new basket-shaped scaffolds were fully characterised, and the proposed supramolecular organisation displays needle shaped, focal conic, rod like and schlieren textures (see image). 

Read the full article for free until the 25th March 2013!

Synthesis, mesomorphism and dielectric behaviour of novel basket shaped scaffolds constructed on lower rim azocalix[4]arenes, Pinkesh G. Sutariya, Nishith R. Modi, Alok Pandya, V. A. Rana and Shobhana K. Menon, RSC Adv., 2013, DOI: 10.1039/C3RA22422H

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Elements for efficient energy

If asked to name a promising element to contribute to highly efficient, clean energy, few chemists would immediately think of lead.

Graphical Abstract of C2RA22536KNevertheless Xiao Zhao and colleagues at the Chinese Academy of Sciences, in Changchun, Jilin, China, have used an alloy of this metal with platinum, which is much better known  for its catalytic properties, to create a more efficient catalyst for the direct electrooxidaton of formic acid, useful for direct formic acid fuel cells (DFAFC). These have the potential to provide clean, efficient energy conversion devices. The group used a self-sacrifice templating method to tune the structure and composition of Pt-Pb catalysts, which show enhanced kinetics due to reduced poisoning by carbon monoxide.

Meanwhile Yuan-Yuan Feng and colleagues, at Tsinghua University in Beijing, China, have worked with a more conventional catalyst combination in the form of palladium and gold for the same reaction. They found that controlled deposition of Pd on Au nanoparticles could tune the Pd dispersion and produce higher catalytic activity for the electrooxidation of formic acid. They have also characterised in detail the interaction of Pd with the reactive species.

To find out more, read about the work in RSC Advances for free until the 14th March 2013:

Pt–Pb hollow sphere networks: self-sacrifice-templating method and enhanced activity for formic acid electrooxidation, Xiao Zhao, Jianbing Zhu, Weiwei Cai, Meiling Xiao, Liang Liang, Changpeng Liu and Wei Xing, RSC Adv., 2013, 3, 1763–1767

Catalytic Pd-on-Au nanostructures with improved Pd activity for formic acid electro-oxidation, Yuan-Yuan Feng, Gui-Rong Zhang and Bo-Qing Xu, RSC Adv., 2013, 3, 1748–1752

By Sara Coles

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Importance of hydrophobic groups in ice recrystallization inhibitors

Ice recrystallization inhibitors (IRIs) are very important when it comes to preventing cell damage which can occur during cryopreservation.  This is particularly crucial for the cryopreservation of progenitor cells (such as certain types of stem cells) where the clinical outcome in regenerative therapies to treat acute injuries, is directly linked to an increased supply and quality of cells.  Therefore there has been considerable interest in designing effective IRIs.

Graphical abstract for C3RA23220D In this work, Robert Ben and colleagues from the University of Ottawa, Canada, investigated whether lysine-based surfactants/gelators and anti-ice nucleating agents could also possess IRI activity.  The authors found that long alkyl chains were very important for potent IRI activity and that the position of these chains is critical.  Although the exact mechanisms which would explain the role of these long alkyl chains in this process are still unclear, the results from this study will facilitate the design of IRIs for medical, commercial and industrial uses.

Read the full article for free until the 7th March 2013!

The importance of hydrophobic moieties in ice recrystallization inhibitors, Anna K. Balcerzak, Michela Febbraro and Robert N. Ben, RSC Adv., 2013, DOI: 10.1039/C3RA23220D

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Natural products meet nanotechnology

One goal of nanoparticle synthesis is to produce the lowest possible polydispersity – in other words, the best possible average size distribution. ‘Greener’ routes to achieve this without harmful solvents and capping agents often come from the natural world. In this case Graham Hutchings at Cardiff University, UK, plus collaborators in Bristol, UK, and Niigata, Japan, have used chitosan, a derivative of natural chitin found in crab and shrimp shells, to template the formation of supported gold-palladium nanoparticles.Graphical abstract of C2RA01336C

These precious alloys are used as catalysts in the solventless aerobic oxidation of benzyl alcohol to benzaldehyde, an important class of reactions in the fine chemicals industry.

Hutchings and co-workers have previously found supported gold-palladium catalysts to be most active and stable for a range of other reactions including direct synthesis of hydrogen peroxide from H2 and O2, and for the oxidation of polyols such as glycerol. It is to be hoped that the new chitosan-templated synthesis will pave the way for new, greener routes to commercial scale production of fine chemical intermediates, for example allowing the replacement of traditional oxygen donors like chromate or permanganate.

To find out more, read about the work in RSC Advances for free:

Biotemplated synthesis of catalytic Au–Pd nanoparticles, Simon R. Hall, Andrew M. Collins, Natalie J. Wood, Wataru Ogasawara, Moataz Morad, Peter J. Miedziak, Meenakshisundaram Sankar, David W. Knight and Graham J. Hutchings, RSC Adv., 2012, 2, 2217–2220

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By Sara Coles

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