Archive for the ‘Hot Articles’ Category

Probing for a better way to detect important antioxidants in cells

Glutathione is an antioxidant enzyme and the most abundant biothiol in human cells. It plays a crucial role in protecting cells against oxidative damage from various toxins that the body produces. However, abnormal levels of glutathione can lead to oxidative stress, which in turn can lead to premature aging and conditions such as Alzheimer’s or Parkinson’s disease. 

There is, therefore, a need for the selective detection of glutathione, so that its role in biological systems can be better understood. However, it is challenging to design a selective fluorescent probe for a specific biothiol due to the structural and reactivity similarities with other biothiols. This is the challenge that David Churchill and team from the Department of Chemistry at the Korea Advanced Institute of Science and Technology set out to meet.

Fluorescence response seen in Hep3B cells treated with the probe molecule

The team has previously explored the use of fluorescent probes containing selenium as the reactive centre and they have taken a similar approach with this challenge, using a phenylselenide group. The images below show the phenylselenide probe reacting with cellular glutathione, which fluoresces green in the images. The intensity of the fluorescence was around a hundred times greater than for cysteine or homocysteine, which are closely related to glutathione.

Until now, there has been no probe that can selectively detect glutathione in real time, so it will be interesting to see what future results come from this advance.

To read the details, download the Chemical Science article and read it in full – it’s open access:
Exceptional time response, stability and selectivity in doubly-activated phenyl selenium-based glutathione-selective platform
Youngsam Kim, Sandip V. Mulay, Minsuk Choi, Seungyoon B Yu, Sangyong Jon and David G Churchill
Chem. Sci., 2015, 6, Advance Article
DOI: 10.1039/C5SC02090E 

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Antioxidant assumptions flipped for garlic thiosulfinates

Garlic bulbs

Garlic is often called the world's oldest know medicine © Shutterstock

New mechanistic investigations at the interface of chemistry and biology reveal thiosulfinates of garlic and petiveria are not the superstars of the antioxidant world they were once thought to be.

Allicin, a thiosulfinate from garlic, well-known for its potent antimicrobial activity, is a popular molecule under investigation for its medicinal potential to treat diseases such as cardiovascular and neurodegenerative diseases. It has long been hoped that its biocidal properties would translate into therapeutic effects in human cells. Previous studies carried out in organic solution indicated that allicin and petivericin, an analogous thiosulfinate derived from the South American plant Petiveria alliacea, were potent radical-trapping antioxidants because they decompose to give sulfenic acids that reduced free radicals and inhibited the undesirable oxidation of important biomolecules. Read the full article in Chemistry World»


Read the original journal article in Chemical Science:
The medicinal thiosulfinates from garlic and Petiveria are not radical-trapping antioxidants in liposomes and cells, but lipophilic analogs are
Bo Li, Feng Zheng, Jean-Philippe R. Chauvin and Derek A. Pratt 
Chem. Sci., 2015, Advance Article
DOI: 10.1039/C5SC02270C, Edge Article

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Streamlined synthesis yields longer sugar chains

By using bigger building blocks, scientists in the UK have shown they can make much longer oligosaccharide sequences than previously possible.

The traditional synthetic route to long chain oligosaccharides is drawn out and complicated; they require numerous steps to produce the precursor tetrasaccharides, then further steps to connect these precursors into long chains. Normally they’re made by an iterative two block process, generating chains up to 12 units long. Now, a four block approach, developed by John Gardiner and colleagues at the University of Manchester, significantly reduces the number of steps enabling longer sugar lengths from 16 up to 40 units. Read the full article in Chemistry World»


Read the original journal article in Chemical Science – it’s open access:
Making the longest sugars: a chemical synthesis of heparin-related [4]n oligosaccharides from 16-mer to 40-mer
Steen U. Hansen, Gavin J. Miller, Matthew J. Cliff, Gordon C. Jayson and John M. Gardiner 
Chem. Sci., 2015, Advance Article
DOI: 10.1039/C5SC02091C, Edge Article

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More hot Chemical Science articles for July

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

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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

 

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Boroles get a stability boost

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

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Photoredox catalysis mechanisms seen in new light

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

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Hot Chemical Science articles for July

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

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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

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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

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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

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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

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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

C5CS00055F GA

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Smaller, better chemosensing porous polymers

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.

The ability to quickly and selectively detect chemicals is of paramount interest to researchers worldwide, particularly those chemicals that pose a threat to societal health and safety. The methodology involving covalent organic nanosheets developed in this research offers a new approach to and a first step towards increasing the selectivity and sensitivity of detection by porous frameworks for chemicals, in this case nitroaromatics like TNT.

Read this HOT ChemSci article in full – it’s open access and free to download:

Chemical sensing in two dimensional porous covalent organic nanosheets
Gobinda Das, Bishnu P. Biswal, Sharath Kandambeth, V. Venkatesh, Gagandeep Kaur, Matthew Addicoat, Thomas Heine, Sandeep Verma and Rahul Banerjee
Chem. Sci., 2015, 6, 3931–3939.
DOI: 10.1039/C5SC00512D, Edge Article

About the Writer

Anthea Blackburn is a guest web writer for Chemical Science. Anthea is a recent graduate student hailing from New Zealand, who studied at Northwestern University in the US under the tutelage of Prof. Fraser Stoddart (a Scot), where she exploited supramolecular chemistry to develop multidimensional systems and study the emergent properties that arise in these superstructures. When time and money allow, she is ambitiously attempting to visit all 50 US states.

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Insights on a high performing MOF

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

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DNA inspires smart phospholipids

Researchers in China and Ireland have developed a simple way of building new stimuli-responsive phospholipids that can self-assemble into hollow spheres and trigger the release of anticancer drugs only when inside the cell lysosome.

Liposomes made from synthetic nucleoside phospholipids could benefit drug delivery

Liposomes are nanoscale three-dimensional hollow vesicles with a phospholipid-based outer shell. They are widely used as drug and gene delivery agents and have been approved for various clinical trials. Liposomes are easily internalised by cells and are sealed off from the rest of the cell by the endosome and later in the internalisation process by the lysosome. These compartments specifically isolate foreign objects from the cell and remove them. Controlled release from them can significantly enhance delivery of a therapeutic drug directly within the targeted cell. Since the internal lysosome environment is acidic, pH sensitive liposomes capable of braking up and releasing their cargo have been widely studied. Due to the covalent nature of most of the phospholipids used to prepare liposomes, the latter do not respond promptly to the acidic environment, limiting the fast release of their cargos, and require tedious covalent synthesis procedures. Read the full article in Chemistry World»


You can read the original journal article in Chemical Science – it’s open access and free to download:
Supramolecularly engineered phospholipids constructed by nucleobase molecular recognition: upgraded generation of phospholipids for drug delivery
Dali Wang, Chunlai Tu, Yue Su, Chuan Zhang, Udo Greiser, Xinyuan Zhu, Deyue Yan and Wenxin Wang 
Chem. Sci., 2015,6, 3775-3787
DOI: 10.1039/C5SC01188D, Edge Article

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