Exotic interactions uncovered in actinide systems

Jennifer Newton writes about a HOT Chemical Science article for Chemistry World

The six orbital phase changes around the internuclear axis are unique to phi interactions

Theory had predicted the presence of Φ interactions in actinide systems but it had never been observed experimentally, until now. Scientists in the US using high-energy x-ray spectroscopy to study the involvement of the f-orbitals in actinide sandwich complexes have experimental evidence for this unusual interaction in thorocene.

At its most basic level, bonding in actinide molecules is typically comprised of a small amount of covalent orbital mixing in the presence of overwhelming ionic attractions. However, in many cases it is proposed that these small changes in f-element covalency are responsible for profound changes in chemical reactivity and actinide properties.

Covalency is a fundamental concept used to describe how elements share electrons in chemical bonds. For the d-block transition metal series, 3d, 4d, and 5d orbitals extend well into the periphery of the atom and can interact with valence orbitals of ligand atoms to form covalent chemical bonds. In contrast, the 4f orbitals of lanthanides are very core-like and their interactions with ligands are – in general – assumed to be of comparatively little chemical consequence. The actinide elements lie between these two extremes, and the extent to which valence f and d orbitals participate in chemical bonding is a subject of debate in the community.


You can also read this article in Chemistry World

Read the original journal article in Chemical Science:

New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory
Stefan G. Minasian, Jason M. Keith, Enrique R. Batista, Kevin S. Boland, David L. Clark, Stosh A. Kozimor, Richard L. Martin, David K. Shuh and Tolek Tyliszczak
Chem. Sci., 2014, Advance Article
DOI: 10.1039/C3SC52030G, Edge Article

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Hole hopping in solar cells

Jason Woolford writes about a HOT Chemical Science article for Chemistry World

The technique estimates the energetic cost of a dye molecule changing conformation

Researchers in the UK, Spain and Switzerland say a method they have developed for probing electron transfer reactions could help them design more efficient solar cells.

Monitoring the behaviour of charges in photovoltaic devices is important for improving charge collection, especially in dye sensitised solar cells (DSSCs) that convert sunlight to electricity. Creating efficient solar cells is pivotal for meeting increasing energy demands especially as the world looks to move away from fossil fuels. DSSCs have many attractive features being simple to make, flexible and transparent, but they still have a way to go in terms of efficiency.

A research team led by Piers Barnes of Imperial College London has pioneered a technique that measures the diffusion coefficient of a less well reported phenomenon known as hole hopping, which occurs between sensitised dye molecules anchored to surfaces (in this case TiO2).


You can also read this article in Chemistry World

Read the original journal article in Chemical Science:

The reorganization energy of intermolecular hole hopping between dyes anchored to surfaces
Davide Moia, Valérie Vaissier, Ismael López-Duarte, Tomás Torres, Mohammad K. Nazeeruddin, Brian C. O’Regan, Jenny Nelson and Piers R. F. Barnes
Chem. Sci., 2014, Advance Article
DOI: 10.1039/C3SC52359D

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Chemical Science chemical biology symposium – the highlights

Matthew Gibson, University of Warwick, gives us the highlights from the recent Chemical Science–RSC Prizes and Awards Symposium

On 6th November 2013, the Department of Chemistry at the University of Warwick hosted a Chemical-Science sponsored symposium on Chemical Biology. The symposium was convened to celebrate several prizes and awards from the RSC Chemistry Biology Interface Division. There were over 130 attendees from industry and many different UK Universities, including a healthy number of local attendees from Warwick.

The first talk of the day was from Prof. Richard Silverman, winner of the RSC Centenary Prize medal, who got things off to a great start and some excellent discussion/questions from the audience. Prof Thomas Carell (Chemical Science invited speaker) and Prof Gregory Challis (from the home team) completed an excellent first session. After a quick break, we had talks from Prof Benjamin Davis (President of RSC Chemistry Biology Interface Division and Chemical Science Associate Editor) and last but not least, Prof Rein Ulijn gave his Norman Heatley Award lecture.

It is also important to thank the Warwick Centre for Analytical Science for sponsoring lunch and the student helpers who helped make this a great event. It goes without saying that the speakers enjoyed a well-earned dinner in the evening to celebrate the awards!

Dr. Matthew I. Gibson
University of Warwick and Conference Chair
@LabGibson on Twitter

Warwick speakers

Speakers at the Chemical Science-RSC Awards Symposium

Click here for more photos!

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Moving the goalposts for MRI

Jennifer Newton writes about a HOT Chemical Science article for Chemistry World

A new class of MRI (magnetic resonance imaging) contrast agents developed by scientists in the UK is promising to deliver clearer images in less time. ‘In any NMR experiment you are chasing sensitivity. We have enhanced the intrinsic ability to observe an MRI probe signal by a factor of 20,’ explains David Parker of Durham University who led the study. 

MRI is used in clinical settings to image the inside of the body. It uses strong magnetic fields and radio waves to probe the behaviour of nuclei that possess nuclear spin. Chemical shifts from proton NMR normally fall between 0–12ppm but water and fat resonate at 4.7 and 1.3ppm, respectively, and can overlap with MRI probe signals. Parker’s new probes shunt the spectral window of MRI scans well away from these interfering signals, a concept he describes as ‘moving the goalposts’. The probes consist of lanthanide complexes with a t-butyl group and the distance between the lanthanide and t-butyl group was fixed to optimise the rate of decay of the t-butyl signal as well as move its chemical shift. Data acquisition was possible just a few minutes after administering the probe and the signal from the lanthanide induced relaxation of the nine protons in the t-butyl groups has been shifted by up to 80ppm. 

Proton NMR spectra showing the shifted t-butyl resonances in some of the new dysprosium and thulium complexes

 


 

  Read the full article in Chemistry World»

Read the original journal article in Chemical Science:
Moving the goal posts: enhancing the sensitivity of PARASHIFT proton magnetic resonance imaging and spectroscopy
Peter Harvey, Andrew M. Blamire, J. Ian Wilson, Katie-Louise N. A. Finney, Alexander M. Funk, P. Kanthi Senanayake and David Parker  
Chem. Sci., 2013,4, 4251-4258, DOI: 10.1039/C3SC51526E

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Light harvesting with many man-made leaves

Jeanne Andres writes about a HOT Chemical Science article for Chemistry World

Scientists from Japan have harvested light energy using an exceptionally large number of light absorbers to relay photons via antennas into one final energy acceptor. This two-step sequence closely mimics natural photosynthesis, resulting in greater and more efficient energy transfer.

Previously, researchers had only used one-step light harvesting systems, greatly limiting the number of absorbers able to feed light into a single reaction centre. Now, by imitating photosynthetic systems, Osamu Ishitani at the Tokyo Institute of Technology, Shinji Inagaki at the Toyota Central R&D labs and their co-workers have efficiently harvested light using the highest number of artificial leaves to date.


Read the full article in Chemistry World»

Read the original journal article in Chemical Science:
Efficient Light Harvesting via Sequential Two-Step Energy Accumulation Using a Ru–Re5 Multinuclear Complex Incorporated into Periodic Mesoporous Organosilica
Yohei Yamamoto, Hiroyuki Takeda, Tatsuto Yui, Kotaro Ueda, Kazuhide Koike, Shinji Inagaki and Osamu Ishitani 
Chem. Sci., 2013, Accepted Manuscript, DOI: 10.1039/C3SC51959G

 

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HOT Chemical Science articles for October

Here are our referee-recommended HOT Chem Sci articles – download them for FREE for a limited time!

Ligation of anti-cancer drugs to self-assembling ultrashort peptides by click chemistry for localized therapy
Michael R Reithofer, Kiat-Hwa Chan, Anupama Lakshmanan, Dang Hoang Lam, Archana Mishra, Began Gopalan, Mangesh Joshi, Shu Wang and Charlotte A. E. Hauser
Chem. Sci., 2013, Accepted Manuscript
DOI: 10.1039/C3SC51930A, Edge Article

Free to access until 1st December 2013


Inaccessibility of the μ-hydride species in [FeFe] hydrogenases
Arndt R. Finkelmann, Martin T. Stiebritz and Markus Reiher
Chem. Sci., 2014, Advance Article
DOI: 10.1039/C3SC51700D, Edge Article

Free to access until 1st December 2013


Development of cell-impermeable coelenterazine derivatives
Eric Lindberg, Shin Mizukami, Keiji Ibata, Takashi Fukano, Atsushi Miyawaki and Kazuya Kikuchi
Chem. Sci., 2013,4, 4395-4400
DOI: 10.1039/C3SC51985F, Edge Article

Free to access until 1st December 2013


Mechanism of electrophilic fluorination with Pd(IV): fluoride capture and subsequent oxidative fluoride transfer
Jochen R. Brandt, Eunsung Lee, Gregory B. Boursalian and Tobias Ritter
Chem. Sci., 2014, Advance Article
DOI: 10.1039/C3SC52367E, Edge Article

Free to access until 1st December 2013

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

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Top ten most accessed articles July-September 2013

The 10 most accessed Chemical Science articles between July and September 2013 were as follows:

Intramolecular C(sp3)–H amination
Jenna L. Jeffrey and Richmond Sarpong
Chem. Sci., 2013,4, 4092-4106
DOI: 10.1039/c3sc51420j

Pd(ii)-catalyzed alkoxylation of unactivated C(sp3)–H and C(sp2)–H bonds using a removable directing group: efficient synthesis of alkyl ethers
Fa-Jie Chen, Sheng Zhao, Fang Hu, Kai Chen, Qi Zhang, Shuo-Qing Zhang and Bing-Feng Shi  
Chem. Sci., 2013,4, 4187-4192
DOI: 10.1039/c3sc51993g

1,2,3-Triazoles as versatile directing group for selective sp2 and sp3 C–H activation: cyclization vs substitution
Xiaohan Ye, Zhengrong He, Tonia Ahmed, Keith Weise, Novruz G. Akhmedov, Jeffrey L. Petersen and Xiaodong Shi  
Chem. Sci., 2013,4, 3712-3716
DOI: 10.1039/c3sc51211h

Benzofuran synthesis via copper-mediated oxidative annulation of phenols and unactivated internal alkynes
Ruyi Zhu, Jiangbo Wei and Zhangjie Shi  
Chem. Sci., 2013,4, 3706-3711
DOI: 10.1039/c3sc51489g

Pd(ii)-catalyzed alkylation of unactivated C(sp3)–H bonds: efficient synthesis of optically active unnatural a-amino acids
Kai Chen, Fang Hu, Shuo-Qing Zhang and Bing-Feng Shi  
Chem. Sci., 2013,4, 3906-3911
DOI: 10.1039/c3sc51747k

Palladium-catalyzed heteroallylation of unactivated alkenes – synthesis of citalopram
Joanne F. M. Hewitt, Lewis Williams, Pooja Aggarwal, Craig D. Smith and David J. France  
Chem. Sci., 2013,4, 3538-3543
DOI: 10.1039/c3sc51222c

Gold(i)-catalyzed enantioselective bromocyclization reactions of allenes
Dillon H. Miles, Marcos Veguillas and F. Dean Toste  
Chem. Sci., 2013,4, 3427-3431
DOI: 10.1039/c3sc50811k

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

“Phosphite–urea” cooperative high-turnover catalysts for the highly selective bromocyclization of homogeranylarenes
Yasuhiro Sawamura, Hidefumi Nakatsuji, Akira Sakakura and Kazuaki Ishihara  
Chem. Sci., 2013,4, 4181-4186
DOI: 10.1039/c3sc51432c

Prediction of suitable catalyst by 1H NMR: asymmetric synthesis of multisubstituted biaryls by chiral phosphoric acid catalyzed asymmetric bromination
Keiji Mori, Yuki Ichikawa, Manato Kobayashi, Yukihiro Shibata, Masahiro Yamanaka and Takahiko Akiyama  
Chem. Sci., 2013,4, 4235-4239
DOI: 10.1039/c3sc52142g

If you have any thoughts or comments on any of these articles, why not leave these in the comment box below?

Fancy submitting your own work to to Chemical Science? You can submit online today or alternatively you can email us your suggestions.

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5 minutes with Tom Muir, Chemical Science Associate Editor

Get to know our Editor-in-Chief and all of our Associate Editors on this blog over the coming months!
Read on to get acquainted with Chem Sci Associate Editor Tom Muir.

050112-muir-tom-200x300.jpgTom Muir is the Van Zandt Williams Jr. Class of ’65 Professor of Chemistry at Princeton University, USA.  His laboratory investigates the physiochemical basis of protein function in complex systems of biomedical interest. By combining tools of organic chemistry, biochemistry and cell biology, Tom and his group have developed a suite of new technologies that provide fundamental insight into how proteins work.

Tom serves as one of Chemical Science’s Associate Editors, handling submissions in chemical biology.

What made you keen to specialise in chemical biology? When did you know this was THE research area for you?

I was indoctrinated into the wonderful world of proteins at a young and admittedly impressionable age. Once you have your eyes opened to the power of using synthetic chemistry to manipulate protein structure and function, well, there is really no going back. Like many, I was re-branded a chemical biologist in the late 1990s. I have come to terms with this now and even think I know what chemical biology is.

Name one useful tip you wish someone had told you when you were an undergraduate?

Buy stock in Apple computer!

If you could go back in time and be whoever you wanted, which scientific discovery would you want to have been part of?

Not sure whether this qualifies as a scientific discovery, but I think it would have been pretty wild to have been present when early humans first harnessed fire. Surely, that was the signal moment in our cultural evolution.

"Pirates are fun and fearless, which, funny enough, are qualities that I see in the scientists I admire most" – Tom Muir (Image © Shutterstock)

Morning person or night owl?

Depends on the week and the flavour of jetlag I am dealing with.

Your favourite thing to do on a Sunday afternoon?

I like to enter the deranged world of my young kids – this invariably leads to me being a pirate for a few hours. I have learned that pirates are fun and fearless, which, funny enough, are qualities that I see in the scientists I admire most.

Describe Chemical Science in three words.

Quality over hype

Your personal message to Chem Sci authors and readers?

The key thing I look for is rigour, whether in the chemical aspects of the work or the biology. I hate loose ends. Like all fields, chemical biology has a lot of noise associated with it, I am looking for papers that add to the “signal.” I am much less interested in whether a paper is in a “hot” area as opposed to whether it makes a solid contribution to the field generally and is reported in a manner that others can try to replicate if they choose to.

Tom Muir and our dynamic international team of Associate Editors make direct decisions on the content of Chemical Science and actively drive its scientific development – submit your best and most innovative work to any of their Editorial Offices.

Associate Editors Tom Muir and Ben Davis have highlighted their recommended chemical biology papers on Chemical Science – Read their Editor’s Choice selection for FREE today!

Find many more excellent articles on chemical biology here: Online collection: Chemical biology

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Editors’ Choice: Chemical Biology

Meet our Editors

Ben DavisProfessor Ben Davis (University of Oxford) handles submissions to Chemical Science in the areas of bioorganic chemistry and chemical biology and Professor Tom Muir (Princeton) welcomes papers in chemical biology.

Tom MuirRead their interviews on our blog to find out more about them. We invite you to submit your next high-quality research paper to their editorial offices.

Looking for the best articles at the chemistry-biology interface?

Ben and Tom have picked some of their favourite articles recently published in Chemical Science. You can read these articles for free for a limited period by clicking on the links below.

Chemical Science citationsChemical Science is the Royal Society of Chemistry’s flagship journal; publishing articles of exceptional significance and high-impact reviews from across the chemical sciences. The journal’s latest (2012) Impact Factor is 8.3. Research in Chemical Science is not only of the highest quality but also has excellent visibility; this is reflected in our latest citation profile.

Read our chemical biology Editor’s Choice selection for FREE today:

Chemical fidelity of an RNA polymerase ribozyme
James Attwater,   Shunsuke Tagami,   Michiko Kimoto,   Kyle Butler,  Eric T. Kool,   Jesper Wengel,   Piet Herdewijn,   Ichiro Hirao and   Philipp Holliger*
Chem. Sci., 2013,4, 2804-2814

Remodeling a β-peptide bundle
Matthew A. Molski, Jessica L. Goodman, Fang-Chieh Chou, David Baker, Rhiju Das and Alanna Schepartz  
Chem. Sci., 2013,4, 319-324

Clickable, photoreactive inhibitors to probe the active site microenvironment of fatty acid amide hydrolase
Susanna M. Saario, Michele K. McKinney, Anna E. Speers, Chu Wang and Benjamin F. Cravatt    
Chem. Sci., 2012,3, 77-83

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

Chemical biology toolkit for exploring protein kinase catalyzed phosphorylation reactions
Sanela Martić and Heinz-Bernhard Kraatz  
Chem. Sci., 2013,4, 42-59

Metallohelices with activity against cisplatin-resistant cancer cells; does the mechanism involve DNA binding?
Viktor Brabec, Suzanne E. Howson, Rebecca A. Kaner, Rianne M. Lord, Jaroslav Malina, Roger M. Phillips, Qasem M. A. Abdallah, Patrick C. McGowan, Alison Rodger and Peter Scott
Chem. Sci., 2013, DOI: 10.1039/C3SC51731D

You can find many more excellent articles on chemical biology on our dedicated webpage:

Online collection: Chemical biology

Stay up to date with Chemical Science
Be among the first to hear about the newest articles being published – Sign-up to our journal news alert to receive information about most read articles, themed issues, journal news, as well as calls for papers and invitations.

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Chemical Science–RSC Prizes and Awards Symposium: Chemical Biology

 
  
Dear Colleague   Join Now

Join us for the Chemical Science–RSC Prizes and Awards Symposium, which will be taking place on 6 November 2013, Warwick.We invite you to connect with distinguished professionals and RSC Prize and Award winners at this engaging event, which will reflect on issues of chemical biology. Strong networking opportunities will be provided through a diverse range of presentations, and a wine reception will complete the evening activities.  

Confirmed Speakers Include:  

Prof. Thomas Carrel, Zurich
 
Prof. Greg Challis, Warwick
 
Prof. Ben Davis, University of Oxford
 
Prof. R Silverman, Northwestern
Winner of the Centenary prize 2013
 
Prof. R. Ulijn, Strathclyde
Winner of the Norman Heatley award 2013 
  

We hope that you and your colleagues will take advantage of this opportunity to attend the Chemical Science–RSC Prizes and Awards Symposium.  

For further information about this free event, and to register, please visit the dedicated webpage.  

Kind Regards

Dr Robert D. Eagling
Editor, Chemical Science  
  Dr James Hutchinson
Senior Programme Manager – Life Sciences  

Supported by the Chemistry Biology Interface Division  

 
 
  

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