Archive for the ‘Inorganic’ Category

ChemComm Emerging Investigator Lectureship: Louise Berben

Professor Louise A. Berben (University of California Davis, USA) was one of the recipients of the 2013 ChemComm Emerging Investigator Lectureships.

ChemComm Lectureship

ChemComm Lectureship recipient Louise Berben with Deputy Editor Jane Hordern

Louise has just completed her lectureship tour which took her to Imperial College London and the University of Bristol in the UK; she concluded her tour by giving a plenary lecture at Challenges in Inorganic and Materials Chemistry (ISACS13), in Dublin, Ireland. Congratulations Louise!

Our annual lectureship recognises an emerging scientist in the early stages of their independent academic career.

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Metal-organic frameworks (MOFs): ChemComm web-themed issue

We would like to celebrate with our authors and the community our web themed collection entitled “Metal-organic frameworks” recently published in ChemComm.

The issue was Guest Edited by Neil Champness (University of Nottingham, UK), Christian Serre (University of Versailles, France) and Seth Cohen (University of California, San Diego, USA), and contains an impressive collection of articles, including:

Feature Articles:

MOFs for CO2 capture and separation from flue gas mixtures: the effect of multifunctional sites on their adsorption capacity and selectivity
Zhijuan Zhang, Yonggang Zhao, Qihan Gong, Zhong Li and Jing Li
Chem. Commun., 2013, 49, 653-661, DOI: 10.1039/C2CC35561B

Commercial metal–organic frameworks as heterogeneous catalysts
Amarajothi Dhakshinamoorthy, Mercedes Alvaro and Hermenegildo Garcia
Chem. Commun., 2012, 48, 11275-11288, DOI: 10.1039/C2CC34329K

Communications:

Understanding excess uptake maxima for hydrogen adsorption isotherms in frameworks with rht topology
David Fairen-Jimenez, Yamil J. Colón, Omar K. Farha, Youn-Sang Bae, Joseph T. Hupp and Randall Q. Snurr
Chem. Commun., 2012, 48, 10496-10498, DOI: 10.1039/C2CC35711A

Targeted functionalisation of a hierarchically-structured porous coordination polymer crystal enhances its entire function
Kenji Hirai, Shuhei Furukawa, Mio Kondo, Mikhail Meilikhov, Yoko Sakata, Osami Sakata and Susumu Kitagawa
Chem. Commun., 2012, 48, 6472-6474, DOI: 10.1039/C2CC31421E

Take a look at the excellent work published in this themed collection: http://rsc.li/cc-mofs

We encourage you to share the link to this collection with your colleagues.

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The chemists’ enzyme

The title of this post was taken from the website of Barry Trost, one of the world’s leading scientists and author of an astonishing 924 papers. Describing his work, he states:

One major activity in designing new reactions and reagents involves the development of “chemists’ enzymes” – non-peptidic transition metal based catalysts that can perform chemo-, regio-, diastereo-, and especially enantioselective reactions.

Chemists have, for a long time, sought to reproduce the incredible feats of nature. Natural biology has evolved over many years to achieve the efficiency and reactivity that most lab-based chemists could only dream of. Nature achieves this by employing incredibly sophisticated enzymes which are, sadly, almost impossible to replicate by a synthetic chemist due to their complexity. An alternative idea is to use these enzymes as inspiration for new catalysts and try to focus on the general reasons why they work rather than trying to create direct copies.

Supramolecular catalysts for decarboxylative hydroformylation and aldehyde reduction.

Dr Bernhard Breit, Lisa Diab and Urs Gellrich at Albert-Ludwigs-Univertat in Germany have shown in a HOT ChemComm article that a highly selective catalyst can be created when combining a metal catalyst with a directing ligand to control the reaction. In this Communication, they report excellent results using  rhodium, the classic metal of choice for hydroformylation, and a functional group for recognition of the substrate. The net effect of these features combined is that the substrate is held in a specific way at the catalytic site. As a result, the reaction which follows can only occur in a specific way. This is similar to how enzymes control the chirality.

The concept behind this catalyst is one which could be applied to a great number of different reactions – no doubt we can look forward to reading about these in the near future.

Read this HOT ChemComm article today!

Tandem decarboxylative hydroformylation–hydrogenation reaction of α,β-unsaturated carboxylic acids toward aliphatic alcohols under mild conditions employing a supramolecular catalyst system
Lisa Diab, Urs Gellrich and Bernhard Breit
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC45547E, Communication

Ruaraidh McIntosh is a guest web-writer for ChemComm.  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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Mind the gap – Enhancing intercalation of luminescent aggregates

Particular molecules, which are not luminescent in solution, can luminesce intensely upon molecular aggregation; this is known as aggregation-induced emission (AIE). AIE luminogens are used widely as efficient electroluminescent materials, sensitive chemosensors, and as bioprobes. The main cause of the AIE effect is the restriction of intramolecular rotation. Therefore it can be promoted by introducing the molecules into inorganic materials with a rigid skeleton such as α-zirconium phosphate layers.

Jihong Yu and colleagues from Jilin University in China have published a method describing the intercalation of a quaternary tetraphenylethene (TPEN) cation, an AIE chromophore, into α-zirconium phosphate. At first glance, this does not seem to be too difficult a task– after all, the TPEN has two permanent positive charges on either end suitable to interact with the negatively charged phosphate layers. But, in this case, size does matter. The chromophore is almost three times larger than the distance between phosphate layers, more than a tight fit!

Stretching the layers of α-zirconium phosphate by preintercalation of butylamine before introduction of the chromophore

To overcome this problem, Yu and colleagues carried out a preintercalation step with butylamine before performing a cation exchange step to place the TPEN chromophore within the phosphate layers. Ultimately, they stretched the layer before putting the final molecule inside, just like you would stretch a pair of shoes in an effort to make them fit before placing your sensitive feet inside.

The intercalated product was found to be highly emissive in the blue region of the electromagnetic spectrum and was readily internalized by cells. The system also showed good biocompatibility, suggesting that it would make an excellent base for fluorescent labels in future biomedical imaging applications.

To read the details, check out the HOT Chem Comm article in full:

AIE cation functionalized layered zirconium phosphate nanoplatelets: ion-exchange intercalation and cell imaging

Dongdong Li, Chuanlong Miao, Xiaodan Wang, Xianghui Yu, Jihong Yu and Ruren Xu
Chem. Commun., 2013, 49, Accepted Manuscript
DOI: 10.1039/C3CC45041D

Iain Larmour is a guest web writer for ChemComm.  He has researched a wide variety of topics during his years in the lab including nanostructured surfaces for water repellency and developing nanoparticle systems for bioanalysis by surface enhanced optical spectroscopies.  He currently works in science management with a focus on responses to climate change.  In his spare time he enjoys reading, photography and art.

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A cloak of many carbons

Catalysts can be exceedingly useful in the real world, from treating our car’s exhaust fumes to creating fertilisers.  There are many ways to make catalysts and even multiple ways to make the same catalyst.  The path that you choose to a catalyst can have a significant impact on the quality of the end product.

Eloy del Rio and team from the Structure and Chemistry of Nanomaterials group at the University of Cadiz in Spain have investigated ceria-based oxide-supported gold catalysts for carbon monoxide oxidation.  The routine for depositing the metal phase onto the oxide support and the subsequent catalyst activation step can ultimately affect the activity of the catalyst.  Catalysts prepared by deposition-precipitation with urea followed by activation under oxidising conditions result in significantly more activity than those prepared under reducing conditions.

Variation in catalyst activity under oxidising and reducing activation protocols.

This had previously been observed by others, but the reason for the difference was never discussed.  The authors set out to find out why the activity differed.  They used a suite of nano-analytical and nano-structural techniques to probe the catalysts, finding that the catalyst prepared under reducing conditions had a coat of amorphous carbon which severely hampered the catalyst activity.  This could be removed by a re-oxidation treatment that burnt away the carbon layer and produced an active catalyst similar to the one produced under oxidising conditions.

The precipitating agent used in the synthesis can also influence the resulting activities of catalysts prepared via the deposition-precipitation method.  No difference between oxidising and reducing activations is observed when sodium carbonate is used in place of urea.

To read the details, check out the ChemComm article in full:

Dramatic effect of redox pre-treatments on the CO oxidation activity of Au/Ce0.50Tb0.12Zr0.38O2-x catalysts prepared by deposition-precipitation with urea: a nano-analytical and nano-structural study
E. del Rio, M. López-Haro, J.M. Cies, J.J. Delgado, J.J. Calvino, S. Trasobares, G. Blanco, M.A. Cauqui and S. Bernal
Chem. Commun., 2013, 49, Accepted Manuscript
DOI: 10.1039/C3CC42051e

Iain Larmour is a guest web writer for ChemComm.  He has researched a wide variety of topics during his years in the lab including nanostructured surfaces for water repellency and developing nanoparticle systems for bioanalysis by surface enhanced optical spectroscopies.  He currently works in science management with a focus on responses to climate change.  In his spare time he enjoys reading, photography and art.

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ChemComm-RSC Prizes and Awards Symposium: Supramolecular Chemistry

Last month we were delighted to hold a ChemComm-RSC Prizes and Awards Symposium on supramolecular chemistry at Trinity College Dublin, Ireland. The free one-day event was a great success, with over 160 delegates and a fantastic programme featuring RSC Award winners and leaders in the field.

CC supramolecular symposium

Speakers from the ChemComm-RSC Prizes and Awards Symposium on Supramolecular Chemistry, 24 May 2013, Dublin, Ireland

Speakers included:

  • Jerry Atwood, University of Missouri-Columbia – Winner of the 2012 RSC Supramolecular Award
  • John Callan, University of Ulster
  • Chris Chang, University of California, Berkeley – Winner of the 2012 RSC Chemistry of Transition Metals Award
  • Sylvia Draper, Trinity College Dublin
  • Phil Gale, University of Southampton – ChemComm sponsored lecture
  • David Leigh, University of Manchester – ChemComm sponsored lecture
  • Donal O’Shea, University College Dublin
  • Susan Quinn, University College Dublin
  • Eoin Scanlon, Trinity College Dublin
  • Jonathan Steed, Durham University – ChemComm sponsored lecture

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It’s getting hot in here…

Stimuli-responsive nanoparticles are the focus of much current research, and what could be better than a nanoparticle that responds to one stimulus?  A nanoparticle which responds to two or three.

Xianmao Lu and his team have coupled plasmonic silver nanoparticles to magnetic iron oxide nanoparticles and wrapped both in a thermoresponsive polymer – poly(n-isopropylacrylamide).

When illuminated by sunlight the silver nanoparticles absorb the light and convert it to heat.  The increase in temperature causes the polymer wrapping to collapse and reduces steric repulsion between the nanoparticle dimers leading to clustering.

Sunlight induced clustering of Magnetic-Plasmonic Heterodimers.

This clustering enhances the magnetic separation of the very small dimers from the solution (the nanoparticles are less than 9 nm each).  When you’ve caught the nanoparticles and are done with them, you can turn the lights off and they will re-disperse.

Don’t worry if you live in a cloudy part of the world, you can use a solar simulator to induce the clustering.  It would probably be easier to turn off than the sun, too.

To read the details, check out this HOT Chem Comm article in full:
Thermoresponsive Nanoparticles + Plasmonic Nanoparticles = Photoresponsive Heterodimers: Facile Synthesis and Sunlight-Induced Reversible Clustering
Hui Han, Jim Yang Lee and Xianmao Lu
Chem. Commun., 2013, 49, Accepted Manuscript
DOI: 10.1039/C3CC42273A

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Photocatalysis in a nanocup

Written by Geoff Nelson, web writer.

Nanocups of anatase TiO2 coated with Au nanoparticles are efficient photocatalysts, as reported in a recent ChemComm article by Chemical Science and Chem Soc Rev Advisory Board member Jinlong Gong and  his group at Tianjin University, China.

This new shape promises to increase reactive surface area by exposing the normally inaccessible surface of hollow spheres.  Compared to TiO2 hollow spheres, TiO2 nanocup particles increase the rate of the photocatalytic degradation of methylene blue in the visible light region by 46%.

This performance and the ease of nanocup synthesis are reasons to promote further research.  Thus, we may expect nanocups made from other metal oxides and inorganic materials to be incorporated into solar, photochemical, and catalytic applications in the future.

In addition, the ability of nanocups to confine small amounts of reactants may find utility in nanofluidic devices.

Gong et al.‘s work has recently been highlighted as part of a C&EN article on novel nanostructures.

Read this ChemComm article in full:

Mesoporous anatase TiO2 nanocups with plasmonic metal decoration for highly active visible-light photocatalysis

Jianwei Lu, Peng Zhang, Ang Li, Fengli Su, Tuo Wang, Yuan Liu and Jinlong Gong
Chem. Commun., 2013, Advance Article
DOI: 10.1039/C3CC42029A

Geoff Nelson is a guest web-writer for ChemComm.  He currently works as a post-doctoral research associate in Dr David Payne’s research group in the Department of Materials at Imperial College, London.  Geoff’s current research concerns the synthesis and characterization of post-transition metal oxides for use in the energy sector.  His other research interests include carbon-based materials, biophysical chemistry, and surface science.

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ChemComm Emerging Investigator Lectureship 2013: Winners Announced

louise

Louise Berben

On behalf of the ChemComm Editorial Board we are delighted to announce the winners of the ChemComm Emerging Investigator Lectureship 2013.

Marina Kuimova

Marina Kuimova

This year we received a high number of excellent nominations and therefore the Editorial Board have decided to award two Emerging Investigator Lectureships in 2013. The winners are Professor Louise A. Berben (University of California Davis, USA) and Dr Marina Kuimova (Imperial College London).

This annual lectureship recognises an emerging scientist in the early stages of their independent academic career.

The Editorial Board commended Louise’s contributions to the field of synthetic and physical inorganic chemistry, and Marina was awarded the lectureship for her excellent work within biophysical chemistry. Further details of the two Lectureships, including lecture locations, will be announced soon.

To find out more about the winners’ research, read some of their latest articles in ChemComm:

Redox active aluminium(III) complexes convert CO2 into MgCO3 or CaCO3 in a synthetic cycle using Mg or Ca metal
Thomas W. Myers and Louise A. Berben
Chem. Commun., 2013, DOI: 10.1039/C2CC37208H

Simple routes to bulky silyl-substituted acetylide ligands and examples of V(III), Fe(II), and Mn(II) complexes
Gereon M. Yee, Kristin Kowolik, Shuhei Manabe, James C. Fettinger and Louise A. Berben
Chem. Commun., 2011,47, 11680-11682, DOI: 10.1039/C1CC14758G

Reactive oxygen species in photochemistry of the red fluorescent protein “Killer Red”
Russell B. Vegh, Kyril M. Solntsev, Marina K. Kuimova, Soohee Cho, Yue Liang, Bernard L. W. Loo, Laren M. Tolbert and Andreas S. Bommarius
Chem. Commun., 2011,47, 4887-4889, DOI: 10.1039/C0CC05713D

Also of interest: You can now browse the 2013 Emerging Investigators Issue – which features research from outstanding up-and-coming scientists

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ChemComm-RSC Prizes and Awards Symposium: Supramolecular Chemistry

We invite you to join us for the ChemComm-RSC Prizes and Awards Symposium which will be taking place on 24 May 2013 in Dublin, Ireland.

This free one-day event will comprise of stimulating lectures reflecting the academic and industrial breadth of supramolecular chemistry, delivered by RSC Prize and Award winners and leaders in the field.

Confirmed Speakers:

  • Jerry Atwood, University of Missouri-Columbia – Winner of the 2012 RSC Supramolecular Award
  • John Callan, University of Ulster
  • Chris Chang, University of California, Berkeley – Winner of the 2012 RSC Chemistry of Transition Metals Award
  • Sylvia Draper, Trinity College Dublin
  • Phil Gale, University of Southampton – ChemComm sponsored lecture
  • David Leigh, University of Manchester – ChemComm sponsored lecture
  • Donal O’Shea, University College Dublin
  • Susan Quinn, University College Dublin
  • Eoin Scanlon, Trinity College Dublin
  • Jonathan Steed, Durham University – ChemComm sponsored lecture

We hope you and your colleagues will be able to attend the ChemComm-RSC Prizes and Awards Symposium. For further information about this event and to register, please visit the dedicated webpage.

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