Lowering a barrier for heterogeneous catalysis

Heterogeneous catalysis is widely used industrially to assist in the production of many man made materials.  The world economy is reliant upon production of these materials, therefore catalysts which are reliable and cheap are hugely important.  Heterogeneous catalysts generally fulfill these criteria, hence their wide application, but the understanding of how they function is often poorly defined.

Academic investigations of single site homogeneous catalysts are generally simpler to study, which makes defining what reactions occurs at each stage and the factors which influence them clearer to interpret.  Heterogeneous catalysts are more complex to study.  The interaction between the different phases must be considered along with the nature of the catalyst itself.  The catalysts are generally solid materials whose bulk composition may not provide an accurate picture of the surface where the reactions will ultimately be occurring and the activity may be quite different.  Analysis of the subtleties of what is happening at the surface is incredibly difficult with many of the commonly used techniques not capable of providing the detail required.  But in order to fully understand a heterogeneous catalyst it is essential to have an understanding of the how the separate phases interact.

Tristan Youngs of the ISIS Facility, Christopher Hardacre of Queen’s University Belfast, and their co-workers have reported a new method to study a heterogenous process in real time.  Neutron scattering experiments (which were only made possible by the state of the art facilities at ISIS) provide the ability to simultaneously examine the rate at which reactions occur and also the speed with which the different phases in a heterogeneous system can interact.  A commonly held principle of heterogeneous catalysis is that by constructing pores and channels in the catalyst we can increase the effective surface area of the catalyst, increasing the number of sites where reactions can occur, thereby increasing the effectiveness of the catalysts.

This study, for the first time, highlights that the speed of the process is critically dependent on how easily the molecules can pass in and out of these pores.  While this may not be the case for every process, challenging some of these commonly held beliefs will surely lead to a rethink of how catalysts are designed in the future.

Interested in more?  Read this HOT, Open Access Chem Sci Edge article now!

Probing chemistry and kinetics of reactions in heterogeneous catalysts
Tristan G. A. Youngs, Haresh Manyar,  Daniel T. Bowron,  Lynn F. Gladden and Christopher Hardacre
Chem. Sci., 2013, Advance Article
DOI: 10.1039/C3SC51477C

Ruaraidh McIntosh is a guest web-writer for Chemical Science.  His research interests include supramolecular chemistry and catalysis.  When not working as a Research Fellow at Heriot-Watt University, Ruaraidh can usually be found in the kitchen where he has found a secondary application for his redoubtable skills in burning and profanity.

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Chem Sci articles in 2013 Cancer Nanotechnology collection– free till 28 July

We are pleased to present a web collection of articles from publications across the RSC journal portfolio demonstrating the use of (nano)technology in the diagnosis, imaging and treatment of cancer.

This web collection will be free to access until the 28th July, so register for an RSC Publishing personal account and read this cutting edge research for free this week!

Read these Chemical Science Edge Articles as part of this special cancer nanotechnology collection:

A platinum anticancer theranostic agent with magnetic targeting potential derived from maghemite nanoparticles
Jinzhuan Wang, Xiaoyong Wang, Yajie Song, Jing Wang, Changli Zhang, Cunjie Chang, Jun Yan, Lin Qiu, Mingmin Wu and Zijian Guo
Chem. Sci., 2013,4, 2605-2612
DOI: 10.1039/C3SC50554E

Graphical abstract: A platinum anticancer theranostic agent with magnetic targeting potential derived from maghemite nanoparticles

Poly(ethylene oxide)-block-polyphosphester-based paclitaxel conjugates as a platform for ultra-high paclitaxel-loaded multifunctional nanoparticles
Shiyi Zhang, Jiong Zou, Mahmoud Elsabahy, Amolkumar Karwa, Ang Li, Dennis A. Moore, Richard B. Dorshow and Karen L. Wooley
Chem. Sci., 2013,4, 2122-2126
DOI: 10.1039/C3SC50252J

Graphical abstract: Poly(ethylene oxide)-block-polyphosphester-based paclitaxel conjugates as a platform for ultra-high paclitaxel-loaded multifunctional nanoparticles

Lipid-coated nanoscale coordination polymers for targeted delivery of antifolates to cancer cells
Rachel C. Huxford, Kathryn E. deKrafft, William S. Boyle, Demin Liu and Wenbin Lin
Chem. Sci., 2012,3, 198-204
DOI: 10.1039/C1SC00499A

Graphical abstract: Lipid-coated nanoscale coordination polymers for targeted delivery of antifolates to cancer cells

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Turning carbon dioxide into something useful

Andria Nicodemou writes on a HOT Chemical Science article in Chemistry World

New research shows that a water-soluble catalyst developed by scientists in the US can electrocatalytically transform carbon dioxide into a useful chemical feedstock.

The global demand for fuel is rising, as are carbon dioxide levels in the atmosphere. Recent studies have attempted to address the global carbon imbalance by exploring ways to recycle carbon dioxide into liquid fuels. Formate, the anion of formic acid, is an intermediate of carbon dioxide reduction and can be used as a fuel in formic acid fuel cells. However, the selective production of formate, without using organic solvents, is challenging. Water, being inexpensive and environmentally-friendly, is obviously preferred over organic solvents as a reaction medium. On the other hand, the reduction of carbon dioxide in water is complicated by the reduction of water to hydrogen being a more kinetically favourable process.

Thomas Meyer, Maurice Brookhart and Peng Kang at the University of North Carolina, have designed an iridium pincer catalyst that can selectively reduce carbon dioxide into formate in almost pure water…

Read the full article in Chemistry World

Read the original journal article in Chemical Science:
Selective electrocatalytic reduction of carbon dioxide to formate by a water-soluble iridium pincer catalyst
Peng Kang, Thomas J. Meyer and Maurice Brookhart  
Chem. Sci., 2013, Advance Article
DOI: 10.1039/C3SC51339D

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ISACS12 Challenges in Chemical Renewable Energy: Early bird deadline 12 July 2013

UPDATE – Challenges in Chemical Renewable Energy (ISACS12)

Early Bird Deadline – 12 July 2013

Don’t forget that early bird registration for Challenges in Chemical Renewable Energy (ISACS12) closes this Friday. Make sure you register for this significant conference before 12 July 2013 to guarantee your place at the reduced fee.

For full details including themes and speaker details, please visit the dedicated website.

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Mapping receptors in the brain

Jeanne Therese Andres writes on a HOT Chemical Science article in Chemistry World

Scientists from the UK and Germany have developed new compounds that target and bind to brain proteins linked to serious neurological disorders. By acting as markers, these compounds enhance the contrast of magnetic resonance imaging (MRI) scans to show the location of receptors.
 
Receptor proteins on the surface of brain cells interact with specific chemicals to induce a neural response. The glutamate receptor N-methyl-D-aspartate (NMDA) plays a key role in memory, learning and neurotransmission. Misregulation and overstimulation of NMDA receptors has been associated with Parkinson’s and Alzheimer’s diseases. Neuroscientists and psychologists have been trying to find evidence of this link at a molecular level, but current diagnostic and imaging tools are still relatively crude.

David Parker and Anurag Mishra at Durham University, and colleagues, have synthesised a series of novel MRI contrast agents that can pinpoint NMDA receptors in vitro, effectively mapping the location…

Read the full article in Chemistry World»

Read the original journal article in Chemical Science:
Responsive MR-imaging probes for N-methyl-D-aspartate receptors and direct visualisation of the cell-surface receptors by optical microscopy
Neil Sim, Sven Gottschalk, Robert Pal, Jörn Engelmann, David Parker and Anurag Mishra  
Chem. Sci., 2013, 4, 3148-3153
DOI: 10.1039/C3SC50903F

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Double Chem Sci covers for Southampton University

HOT Edge Articles on supramolecular chemistry and chemical biology grace the covers of Issue 8

We are delighted to announce that Issue 8 of Chemical Science is now online, with both cover articles by researchers from the University of Southampton.

The Front cover features a HOT Edge Article by the group of Chem Soc Rev Chair Philip Gale, while Ali Tavassoli‘s team’s HOT chemical biology work is highlighted on the Inside front cover.

C3SC90023ATowards predictable transmembrane transport: QSAR analysis of anion binding and transport
Nathalie Busschaert, Samuel J. Bradberry, Marco Wenzel, Cally J. E. Haynes, Jennifer R. Hiscock, Isabelle L. Kirby, Louise E. Karagiannidis, Stephen J. Moore, Neil J. Wells, Julie Herniman, G. John Langley, Peter N. Horton, Mark E. Light, Igor Marques, Paulo J. Costa, Vítor Félix, Jeremy G. Frey and Philip A. Gale
Chem. Sci., 2013, 4, 3036-3045
DOI: 10.1039/C3SC51023A

C3SC90024J
A cyclic peptide inhibitor of C-terminal binding protein dimerization links metabolism with mitotic fidelity in breast cancer cells
Charles N. Birts, Sharandip K. Nijjar, Charlotte A. Mardle, Franciane Hoakwie, Patrick J. Duriez, Jeremy P. Blaydes and Ali Tavassoli
Chem. Sci., 2013, 4, 3046-3057
DOI: 10.1039/C3SC50481F

Both are Open Access, so read and download these excellent articles now for free.

The issue includes many exciting and referee-recommended Edge Articles, plus Perspectives and Minireviews from leading researchers– read the whole issue here!

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Self-contained chemical synthesis

Rachel Cooper writes on a HOT Chemical Science article in Chemistry World

Scientists in the UK have used reactors made on a 3D printer to complete a three stage organic synthesis. The reagents, catalyst and purification step for the synthesis are completely integrated into the chambers of the sealed reactor. When the reactor is rotated, gravity pulls reactants through the different chambers to complete the synthesis.

3D-printing

Initially, Leroy Cronin, who lead the work at the University of Glasgow, had envisaged a ‘Rubik’s cube for synthesis’, where different manipulations of the reactor would produce different products. ‘The code, like opening a safe, would be in the rotation,’ he explains. ‘I thought it was genius. My group told me I was stupid.’ The team convinced Cronin to start with an easier L-shaped three step reactor, but he still plans to create the Rubik’s cube in the future.

A three-step organic reaction sequence was performed in the L-shaped reactor. The sequence began with…

Read the full article in Chemistry World»

Read the original journal article in Chemical Science:
Combining 3D printing and liquid handling to produce user-friendly reactionware for chemical synthesis and purification
Philip J. Kitson, Mark D. Symes, Vincenza Dragone and Leroy Cronin  
Chem. Sci., 2013, Advance Article
DOI: 10.1039/C3SC51253C

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HOT Chem Sci articles for June

Here are this month’s referee-recommended HOT Chem Sci articles– download them for FREE for a limited time!

Optimising in situ click chemistry: the screening and identification of biotin protein ligase inhibitors
Andrew D Abell, William Tieu, Tatina Soares da Costa, Min Yap, Kelly Keeling, Matthew C. J. Wilce, John Wallace, Grant Booker and Steven William Polyak
Chem. Sci., 2013, Accepted Manuscript
DOI: 10.1039/C3SC51127H, Edge Article

Free to access until 28th July 2013


One-shot indole-to-carbazole p-extension by Pd-Cu-Ag trimetallic system
Kyohei Ozaki, Hua Zhang, Hideto Ito, Aiwen Lei and Kenichiro Itami
Chem. Sci., 2013, Advance Article
DOI: 10.1039/C3SC51447A, Edge Article

Free to access until 28th July 2013


Oxygen activation by homoprotocatechuate 2,3-dioxygenase: a QM/MM study reveals the key intermediates in the activation cycle
Wenzhen Lai, Geng Dong and Sason Shaik
Chem. Sci., 2013, Accepted Manuscript
DOI: 10.1039/C3SC51147B, Edge Article

Free to access until 28th July 2013

Click here for more free HOT Chemical Science articles for June!

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Two labels, two locations, one protein

Research reported in Chemical Science describes a new method for labelling proteins with two different chemical components at two separate, selected locations on the protein structure.

Scientists in the UK used the local protein microenvironment to control the outcome of reactions between cysteine residues on the surface of a double cysteine mutant of green fluorescent protein (GFP).

They formed sulfonium salts of the two cysteine residues and found that, dependent on the different environments of their α-protons, one underwent an elimination reaction to form a dehydroalanine while the other residue was protected from elimination by another part of the protein. They were able to convert this second sulfonium salt to an azide, presenting two different functional groups on the protein that could react in different ways to label the protein surface.

The team demonstrated that they could successfully label the protein with both an alkyne dye via the azide and a simple thiol via the dehydroalanine, presenting a simple method for site-selective dual labelling of proteins.

Read this ‘HOT’ Chemical Science article today for free:

A novel approach to the site-selective dual labelling of a protein via chemoselective cysteine modification
Ramiz I. Nathani, Paul Moody, Vijay Chudasama, Mark E. B. Smith, Richard J. Fitzmaurice and Stephen Caddick*
Chem. Sci., 2013, Advance Article
DOI: 10.1039/C3SC51333E

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Top 10 most-accessed articles in Chemical Science (January–March 2013)

The 10 most accessed Chemical Science articles between January and March were as follows:

Carbofluorination via a palladium-catalyzed cascade reaction
Marie-Gabrielle Braun, Matthew H. Katcher and Abigail G. Doyle  
Chem. Sci., 2013, 4, 1216-1220
DOI: 10.1039/C2SC22198E, Edge Article

Chelation-assisted Rh(III)-catalyzed C2-selective oxidative C–H/C–H cross-coupling of indoles/pyrroles with heteroarenes
Xurong Qin, Hu Liu, Dekun Qin, Qian Wu, Jingsong You, Dongbing Zhao, Qiang Guo, Xiaolei Huang and Jingbo Lan  
Chem. Sci., 2013, 4, 1964-1969
DOI: 10.1039/C3SC22241A, Edge Article

Pd-catalyzed oxidative C–H/C–H cross-coupling of pyridines with heteroarenes
Bo Liu, Yumin Huang, Jingbo Lan, Feijie Song and Jingsong You  
Chem. Sci., 2013, 4, 2163-2167
DOI: 10.1039/C3SC50348H, Edge Article

A visible-light-promoted aerobic C–H/C–N cleavage cascade to isoxazolidine skeletons
Jin Xie, Qicai Xue, Hongming Jin, Huamin Li, Yixiang Cheng and Chengjian Zhu  
Chem. Sci., 2013, 4, 1281-1286
DOI: 10.1039/C2SC22131D, Edge Article

Oxidative cycloaddition and cross-coupling processes on unactivated benzene derivatives
Guillaume Jacquemot, Marc-André Ménard, Chloé L’Homme and Sylvain Canesi  
Chem. Sci., 2013, 4, 1287-1292
DOI: 10.1039/C2SC22318J, Edge Article

The role of organometallic copper(III) complexes in homogeneous catalysis
Alicia Casitas and Xavi Ribas  
Chem. Sci., 2013, 4, 2301-2318
DOI: 10.1039/C3SC21818J, Perspective

Cross coupling of thioethers with aryl boroxines to construct biaryls via Rh catalyzed C–S activation
Fei Pan, Hui Wang, Peng-Xiang Shen, Jing Zhao and Zhang-Jie Shi  
Chem. Sci., 2013, 4, 1573-1577
DOI: 10.1039/C3SC22242J, Edge Article

Design and preparation of new palladium precatalysts for C–C and C–N cross-coupling reactions
Nicholas C. Bruno, Matthew T. Tudge and Stephen L. Buchwald  
Chem. Sci., 2013, 4, 916-920
DOI: 10.1039/C2SC20903A, Edge Article

Highly stereoselective Michael addition of azlactones to electron-deficient triple bonds under P-spiro chiral iminophosphorane catalysis: importance of protonation pathway
Daisuke Uraguchi, Yusuke Ueki, Atsushi Sugiyama and Takashi Ooi  
Chem. Sci., 2013, 4, 1308-1311
DOI: 10.1039/C2SC22027J, Edge Article

Dialkylbiaryl phosphines in Pd-catalyzed amination: a user’s guide
David S. Surry and Stephen L. Buchwald  
Chem. Sci., 2011, 2, 27-50
DOI: 10.1039/C0SC00331J, Perspective

Take a look at the articles, and then let us know your thoughts and comments below.

Fancy submitting your own work to Chemical Science? You can submit online today, or email us with your ideas and suggestions.

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