Chemical Science Blog

We’ve picked out a few more referee-recommended articles in Chemical Science for you to enjoy – all are open access:

Making the longest sugars: A chemical synthesis of heparin-related [4]n oligosaccharides from 16-mer to 40-mer
Steen Uldall Hansen, Gavin John Miller, Matthew John Cliff, Gordon C Jayson and John M Gardiner 
Chem. Sci., 2015, Accepted Manuscript, DOI: 10.1039/C5SC02091C, Edge Article

Cell paintballing using optically targeted coacervate microdroplets
James P.K. Armstrong, Sam Olof, Monika Jakimowicz, Anthony Hollander, Stephen Mann, Sean A Davis, Mervyn Miles, Avinash Patil and Adam Periman 
Chem. Sci., 2015, Accepted Manuscript, DOI: 10.1039/C5SC02266E, Edge Article

Well-defined silica supported aluminum hydride: another step towards the utopian single site dream?
Baraa Werghi, Anissa Bendjeriou-Sedjerari, Julien Sofack-Kreutzer, Abdesslem Jedidi, Edy Abou-Hamad, Luigi Cavallo and Jean-Marie Basset 
Chem. Sci., 2015, Advance Article, DOI: 10.1039/C5SC02276B, Edge Article

Interaction of silver metal clusters with living organisms: bactericidal effect of Ag3 clusters mediated by disruption of topoisomerase-DNA complexes
José Neissa, Cristina Pérez-Arnaiz, Vanessa Porto, Natalia Busto, Erea Borrajo, José Maria Leal, M. Arturo Lopez-Quintela, Begona Garcia and Fernando Domínguez 
Chem. Sci., 2015, Accepted Manuscript, DOI: 10.1039/C5SC02022K, Edge Article

Scientists from Germany have reported a breakthrough in borole stability, using bulky fluoromesityl groups, which could help these anti-aromatic molecules realise their potential in optoelectronic devices.

Boroles are heterocycles with a 4π-electron BC4 ring and subsequent electron-accepting abilities. This makes them great candidates for electron-transporting and accepting materials in organic light-emitting diodes and photovoltaics. Read the full article in Chemistry World»

Read the original journal article in Chemical Science – it’s open access:
Taming the beast: fluoromesityl groups induce a dramatic stability enhancement in boroles
Zuolun Zhang, Robert M. Edkins, Martin Haehnel, Marius Wehner, Antonius Eichhorn, Lisa Mailänder, Michael Meier, Johannes Brand, Franziska Brede, Klaus Müller-Buschbaum, Holger Braunschweig and Todd B. Marder 
Chem. Sci., 2015, Advance Article, DOI: 10.1039/C5SC02205C, Edge Article

A debate over whether photoredox-catalysed reactions proceed via chain processes may now be settled, thanks to new mechanistic insight brought to light by scientists in the US. The research, led by Tehshik Yoon at the University of Wisconsin–Madison, shows that commonly used light/dark experiments can result in mechanistic misdiagnosis.

Whilst interest in photoredox catalysis has recently burgeoned – the reactions are used in natural product and pharmaceutical synthesis – our understanding of their mechanisms hasn’t kept pace. In particular, the extent to which the reactions involve chain processes is not fully understood, leading to conflicting explanations. Several groups have reported that the final product-generating step proceeds only by reduction of the radical cation product by the reduced photocatalyst in a closed catalytic cycle, whilst others have reported that the product is formed by an additional chain propagation step involving another equivalent of substrate. Read the full article in Chemistry World»

Read the original journal article in Chemical Science – it’s open access:
Characterizing chain processes in visible light photoredox catalysis
Megan A. Cismesia and Tehshik P. Yoon 
Chem. Sci., 2015, Advance Article, DOI: 10.1039/C5SC02185E, Edge Article

Here are some recent referee-recommended Chemical Science articles for you to enjoy – all are open access and free to download:

Theoretical studies on a carbonaceous molecular bearing: association thermodynamics and dual-mode rolling dynamics
Hiroyuki Isobe, Kosuke Nakamura, Shunpei Hitosugi, Sota Sato, Hiroaki Tokoyama, Hideo Yamakado, Koichi Ohno and Hirohiko Kono 
DOI: 10.1039/C5SC00335K, Edge Article

Molecular understandings on the activation of light hydrocarbons over heterogeneous catalysts
Zhi-Jian Zhao, Cheng-chau Chiu and Jinlong Gong 
DOI: 10.1039/C5SC01227A, Perspective

Selective glycoprotein detection through covalent templating and allosteric click-imprinting
Alexander Stephenson-Brown, Aaron L. Acton, Jon A. Preece, John S. Fossey and Paula M. Mendes 
DOI: 10.1039/C5SC02031J, Edge Article

Biomimetic versus enzymatic high-potential electrocatalytic reduction of hydrogen peroxide on a functionalized carbon nanotube electrode
Bertrand Reuillard, Solène Gentil, Marie Carrière, Alan Le Goff and Serge Cosnier 
DOI: 10.1039/C5SC01473E, Edge Article

Small molecular logic systems can draw the outlines of objects via edge visualization
Jue Ling, Gaowa Naren, Jessica Kelly, David B. Fox and A. Prasanna de Silva 
DOI: 10.1039/C5SC01537E, Edge Article

Imaging metals in biology: balancing sensitivity, selectivity and spatial resolution
Dominic J. Hare, Elizabeth J. New, Martin D. de Jonge and Gawain McColl
DOI: 10.1039/C5CS00055F, Tutorial Review

The exploitation of porous frameworks, both metal-organic and wholly organic in nature, for their ability to take up and store gases and small molecules, has been well reported over the past few decades. The modularity of these frameworks with respect to their size, flexibility and chemical functionality gives rise to their propensity to adsorb a myriad of chemicals; however, this process is not always selective and the chemical instability of these frameworks can cause difficulties in their extension towards real-life applications. A framework that a) is able to favourably and preferentially adsorb chemicals with high sensitivity, and b) exhibits chemical stability under a wide range of conditions, remains somewhat elusive and is thus a hot topic of investigation in many research groups.

Whilst the uptake and sensing properties of two-dimensional porous polymers have been well studied, the bulk nature of these materials often results in the decrease of their properties on account of the extensive aggregation of the polymer layers and resulting reduction of electrons available to interact with guest molecules. Rahul Banerjee and researchers from the Council of Scientific and Industrial Research – National Chemical Laboratory set out to address this limitation in the field of porous polymers through the Liquid Phase Exfoliation of an imide-based covalent organic framework to its covalent organic nanosheet (CON) analogue. Such a CON, which contains between five and fifteen layers of the material, has chemical and thermal stability equal to that of its bulk counterpart; however, its sensing ability down to 10^–5 M towards 2,4,6-trinitrophenol (TNP) and other nitroaromatic explosive chemicals is far superior. Furthermore, this reversible detection upon uptake can be seen both spectroscopically in solution and visually in the solid state via the turning off and on of the CON luminescence respectively.

Metal-organic frameworks (MOFs) have received over a decade’s worth of attention from scientists worldwide. These porous materials can be constructed from almost an infinite combination of organic ligands and metal ions, which has spurred scientists to become creative in their designs, delivering materials with a wide range of useful applications.

In this recently published Chemical Science Perspective, Christopher Hendon and Aron Walsh (recently announced as the winner of the 2015 Chemical Society Reviews Emerging Investigator Lectureship) provide unique insight on the importance of the electronic, magnetic and physical properties of MOFs, focusing their attention on the body of evidence available on HKUST-1.

Many of the most successful MOFs contain arrays of copper paddle wheel motifs, and HKUST-1 is no exception. First reported by Williams in 1999¹, HKUST-1 remains one of the most high-performing materials of its kind and, thanks to it being high in demand, is one of few commercially available MOFs on the market.

With fresh analysis in hand, this report provides researchers with key design principles for the construction of MOFs with tailored chemical and electronic properties, potentially furthering the high-performance applications of these materials.

Read Walsh and Hendon’s Perspective in Chemical Science – it’s open access, and free to download:
Chemical principles underpinning the performance of the metal–organic framework HKUST-1
Christopher H. Hendon and Aron Walsh  
Chem. Sci., 2015, Advance Article
DOI: 10.1039/C5SC01489A, Perspective

¹S. S. Chui, S. M. Lo, J. P. H. Charmant, A. G. Orpen and I. D. Williams, Science, 1999, 283, 1148