Archive for the ‘Hot Articles’ Category

Accessing Chiral Space with Visible Light

Researchers have made tremendous efforts to unlock stereoselective, catalytic organic transformations. In this recent ChemComm Feature Article, Professor Eric Meggers, one of the pioneers in the field of photoredox catalysis, provides a comprehensive review of the recent advances in asymmetric catalysis driven by visible light.

Asymmetric catalysis has been one of the most attractive yet challenging areas of organic chemistry for the synthesis of unique, biologically active natural products such as Taxol, Rapamycin, or Vinblastine that possess numerous stereocenters.

C4CC09268F gaRecently, visible light, a sustainable and affordable energy resource, gained substantial interest with its capability to selectively access chiral molecules from prochiral substrates without undesirable by-products. Transformations including aldehyde α-functionalization and [2+2] cycloadditions demonstrate the potential of visible light in the presence of a photosensitizer.

These photosensitizers are typically ruthenium or iridium complexes that can facilitate electron/energy transfer upon photoinduction. In most cases, a photoredox catalyst has to be coupled with a chiral co-catalyst to introduce stereocenters in the products.

Notable advances in the Meggers, Melchiorre, and MacMillan research groups have recently demonstrated that photoactivation can be achieved with a single chiral photosensitizer to provide products of high enantiomeric excess and good yield.

This inspirational review was just published in Chemical Communications as a Feature Article. I recommend reading “Asymmetric catalysis activated by visible light” (DOI: 10.1039/c4cc09268f) by Professor Eric Meggers to learn more about the recent advances with mechanistic details and his forecast for one of the rapidly-growing research topics in organic chemistry.

This article is free to access until 17th March.* Download it here:
Asymmetric catalysis activated by visible light
Eric Meggers �
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC09268F, Feature Article


Dr. Tezcan Guney is a guest web writer for Chemical Communications. Dr. Guney received his Ph.D. from the Department of Chemistry at Iowa State University with Prof. George Kraus, where he focused on the synthesis of biologically active polycyclic natural products and multifunctional imaging probes. Currently, he is a postdoctoral research scholar at the Memorial Sloan-Kettering Cancer Center in New York with Prof. Derek Tan, contributing to the efforts to access biologically active small molecules using the diversity-oriented synthetic approach.

*Access is free through a registered RSC account

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Hot ChemComm articles for January

Here are some of the latest referee-recommended articles in ChemComm – all free to access for a  limited time:   

Multiplex plasmonic anti-counterfeiting security labels based on surface-enhanced Raman scattering
Yan Cui, In Yee Phang, Yih Hong Lee, Mian Rong Lee, Qi Zhang and Xing Yi Ling  
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC08596E, Communication
From themed collection 2015 Emerging Investigators   

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A tale of two forces: simultaneous chemical and acoustic propulsion of bimetallic micromotors
Wei Wang, Wentao Duan, Zexin Zhang, Mei Sun, Ayusman Sen and Thomas E. Mallouk  
Chem. Commun., 2015,51, 1020-1023
DOI: 10.1039/C4CC09149C, Communication   

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Nanoparticle–blood interactions: the implications on solid tumour targeting
James Lazarovits, Yih Yang Chen, Edward A. Sykes and Warren C. W. Chan  
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC07644C, Feature Article   

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Bulk graphdiyne powder applied for highly efficient lithium storage
Shengliang Zhang, Huibiao Liu, Changshui Huang, Guanglei Cui and Yuliang Li  
Chem. Commun., 2015,51, 1834-1837
DOI: 10.1039/C4CC08706B, Communication   

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Cascade catalysis – strategies and challenges en route to preparative synthetic biology
Jan Muschiol, Christin Peters, Nikolin Oberleitner, Marko Mihovilovic, Uwe Bornscheuer and Florian Rudroff  
Chem. Commun., 2014, Accepted Manuscript
DOI: 10.1039/C4CC08752F, Feature Article
From themed collection Directed Evolution   

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Virus-like particles as virus substitutes to design artificial virus-recognition nanomaterials
Sabine Sykora, Alessandro Cumbo, Gaël Belliot, Pierre Pothier, Charlotte Arnal, Yves Dudal, Philippe F.-X. Corvini and Patrick Shahgaldian  
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC08843C, Communication   

C4CC08843C ga   

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Super-dipoles linked to chloroform’s outstanding solvent properties

Super-dipoles uncovered in chloroform by chemists in the UK could explain the solvent’s powerful ability to dissolve a large range of substances at high concentrations.

Chloroform is one chemistry’s most extensively used forms of liquid reaction media. However, as a suspected carcinogen, chloroform’s role in the extraction of natural products from plant materials, in NMR spectroscopy and as a reagent for chemical reactions underscores scientists’ aspirations to understand the science behind its remarkable properties.


Read the fulll article in Chemistry World»

Read the original journal article in ChemComm – it’s free to access until 25th February:
Polar stacking of molecules in liquid chloroform

J. J. Shephard, A. K. Soper, S. K. Callear, S. Imberti, J. S. O. Evans and C. G. Salzmann  
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC09235J, Communication

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Organic synthons yield hyperbranched crop

Resembling a bundle of cereal stalks, this atomic force microscopy (AFM) image depicts the first ionic organic nanocrystals to have a sheaf-like structure. Ursula Mazur, of Washington State University, US, and colleagues grew the π-conjugated molecules from two electroactive porphyrin synthons: tetra(4-aminophenyl)porphyrin and tetra(4-sulfonatophenyl)porphyrin. These building blocks assembled themselves into branched structures – the higher the reaction temperature the longer and more numerous their branches.


Read the full article in Chemistry World»

Read the original journal article in ChemComm:
Hyperbranched Crystalline Nanostructure Produced from Ionic π-Conjugated Molecules
Ursula Mazur , K W Hipps, Jeremy R. Eskelsen and Kara J Phillips Chem. Commun., 2014, Accepted Manuscript
DOI: 10.1039/C4CC09288K, Communication

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σ meets π for a hole lot of bonding

Researchers in India have provided experimental verification that a co-operative σ-hole and π-hole are responsible for holding the molecules of an isothiocyanate based peptide together in its crystal lattice, showcasing the importance of weak, but highly directional interactions in structure–activity relationships.

Understanding weak intermolecular interactions, like hydrogen bonding, π-stacking and ion– π -interactions, is vital to probing the relationship between structure and properties for pharmaceutically important molecules such as highly reactive organic isothiocyanates, which display anti-carcinogenic activity.


Read the full article in Chemistry World»

Read the original journal article in ChemComm – it’s free to download until 21st January 2015:

Observation of a reversible isomorphous phase transition and an interplay of “σ-holes” and “π-holes” in Fmoc-Leu-ψ[CH2-NCS]
Rumpa Pal, Govindappa Nagendra, M. Samarasimhareddy, Vommina V. Sureshbabu and Tayur N. Guru Row
Chem. Commun., 2015,51, 933-936
DOI: 10.1039/C4CC08751H, Communication

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Novel optical trapping of aerosolised inhaler particles

The inhaler, or pressurised metered-dose inhaler (pMDI), is a well-known medical device commonly used to help people all over the world with conditions such as asthma. However little is known about the form and phase of particles ejected from the inhaler on their route from the inhaler to the lung. It is important to understand the way that the solid particles behave once they are discharged from an inhaler as the size of a particle affects where it is delivered in the respiratory tract, ultimately determining the efficacy of the treatment.

Experimental setup used to trap and study particles discharged from a Salamon® inhaler.

In a collaboration between the University of Cambridge, Imperial College London, the University of Birmingham and the Central Laser Facility in Oxford, Tong et al. have used an optical trap to stably suspend individual particles discharged from a Salamon® inhaler for the first time. After stably trapping the particles the authors were able to determine the phase of the particles by comparing them to both a solid crystalline sample and nebulised aqueous droplets of the drug used in the Salamon® inhaler (salbutamol sulphate). Particles were also trapped and studied after being passed through a humidity chamber designed to mimic the lungs.

When first dispensed from the inhaler the particles had analogous properties to the solid crystalline sample of the drug. As the particles were exposed to a higher humidity they became more spherical as they absorbed water from the environment around them. Particles trapped at a relative humidity >92% had properties very similar to that of nebulised aqueous droplets of the drug. This change in morphology of the particles was confirmed by a combination of Raman spectroscopy and brightfield images.

Tong et al. have been able to show that once released into the body the crystalline particles take up    water, causing the particles to increase in size and sphericity. This information will be of great aid in understanding and improving the efficiency of aerosol-based inhalation products.

To download the full article for free for a limited time* click the link below:

Rapid interrogation of the physical and chemical characteristics of salbutamol sulphate aerosol from a pressurised metered-dose inhaler (pMDI)
H.-J. Tong, C. Fitzgerald, P. J. Gallimore, M. Kalberer, M. K. Kuimova, P. C. Seville, A. D. Ward and F. D. Pope
DOI: 10.1039/c4cc05803h

*Access is through a registered RSC account – click here to register

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Boron and beryllium finally shake hands

The first non-cluster bond between boron and beryllium has been reported by scientists in Germany.

10 years ago, few reactions existed where boron behaved as an nucleophile. That all changed with the advent of lithium diazaborolide in 2006, and boron has been partnering up with myriad main-group, transition metal and lanthanide elements ever since. However, despite beryllium sitting right next to boron in the periodic table, a classical two-centre/two-electron bond had never been reported between the two neighbours, until now.


Read the full article in Chemistry World»

Read the original journal article in ChemComm – it’s free to access until 6th January 2015:
Beryllium bis(diazaborolyl): old neighbors finally shake hands
T. Arnold, H. Braunschweig, W. C. Ewing, T. Kramer, J. Mies and J. K. Schuster  
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC08519A, Communication

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Hot ChemComm articles for November

Here is a selection of the latest referee-recommended articles in ChemComm:

Diffusion of vaporous guests into a seemingly non-porous organic crystal
Simon A. Herbert, Agnieszka Janiak, Praveen K. Thallapally, Jerry L. Atwood and Leonard J. Barbour  
Chem. Commun., 2014,50, 15509-15512
DOI: 10.1039/C4CC07366E, Communication


Azobenzene-based chloride transporters with light-controllable activities
Ye Rin Choi, Gyu Chan Kim, Hae-Geun Jeon, Jinhong Park, Wan Namkung and Kyu-Sung Jeong  
Chem. Commun., 2014,50, 15305-15308
DOI: 10.1039/C4CC07560A, Communication


Fluorescent polymers from non-fluorescent photoreactive monomers
Jan O. Mueller, Dominik Voll, Friedrich G. Schmidt, Guillaume Delaittre and Christopher Barner-Kowollik  
Chem. Commun., 2014,50, 15681-15684
DOI: 10.1039/C4CC07792J, Communication


Is it possible to achieve a complete desaturation of cycloalkanes promoted by o-benzyne?
Francisco Cervantes-Navarro, Abel de Cózar, Fernando P. Cossío, María A. Fernández-Herrera, Gabriel Merino and Israel Fernández  
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC07311H, Communication


Thiol-modified gold nanoparticles for the inhibition of Mycobacterium smegmatis
Jennifer C. Gifford, Jamee Bresee, Carly Jo Carter, Guankui Wang, Roberta J. Melander, Christian Melander and Daniel L. Feldheim  
Chem. Commun., 2014,50, 15860-15863
DOI: 10.1039/C4CC06236A, Communication


Redox-responsive organometallic hydrogels for in situ metal nanoparticle synthesis
B. Zoetebier, M. A. Hempenius and G. J. Vancso  
Chem. Commun., 2015, Advance Article
DOI: 10.1039/C4CC06988A, Communication

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Aptamers and gold nanoparticles whisked up to spot influenza

Researchers in the UK have developed a new visual bioassay that can detect flu viruses by making them heavier.

Early diagnosis is fundamental to slowing viral outbreaks. The latest (since 2003) outbreak of avian flu from Asia resulted in millions of chickens being culled and, according to the World Health Organization, the death of 393 people. Many laboratory-based tests, such as viral culture assays and the polymer chain reaction (PCR), are incredibly sensitive and accurate. However, they are costly, time consuming and require specialist training, so are unsuitable for transition to the field. It is therefore vital to introduce simple, quick and cheap field tests to control the spread of diseases and guide preventative measures, especially in countries like Vietnam where livestock is still a backyard affair.

Gold nanoparticles are conjugated with aptamers. Binding to the virus forms a gold nanoshell on the viral envelope

 Read the full article in Chemistry World»

Read the original journal article in ChemComm:
Aptamer-based biosensors for the rapid visual detection of flu viruses
T. T. Le, B. Adamiak, D. J. Benton, C. J. Johnson, S. Sharma, R. Fenton, J. W. McCauley, M. Iqbal and A. E. G. Cass  
Chem. Commun., 2014,50, 15533-15536
DOI: 10.1039/C4CC07888H, Communication

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Capturing C60 in a Crystalline Copolymer Chain

Since its structural realisation in 1985, C60 has garnered much attention in the chemical world for not only its spherical shape, but also its stability, electronic properties and the ability to do chemistry on its surface.

One such avenue that has proven popular in recent times is the incorporation of C60 into one-, two- and three-dimensional arrays, either covalently or non-covalently, in attempts to control the distribution of the molecules in the solid- or solution-phase.  One problem that arises in the synthesis of these extended frameworks, however, is that there often a large amount of disorder and void space in the structure, so it can be difficult to ascertain with much degree of certainty how these C60 molecules are oriented. This uncertainty can consequentially result in the properties and behaviours of the new materials remaining unidentified.

Now, researchers from the University of California, DavisMarilyn Olmstead and Alan Balch – have shown that coordination chemistry can be used to not only generate polymers that covalently link molecules of functionalised C60 in such a manner that can they can be studied crystallographically, but also that these polymers can be used to capture free C60 and C70.

Initially, polymers of C60 were synthesised through the mono-functionalisation of C60 with a piperazyl group, which, on account of its two tertiary amines, can coordinate in a linear fashion with transition metal ions, in this case rhodium(II) acetate. Upon the combination of these two components, a linear one-dimensional polymer was formed, in which it could be seen crystallographically that the C60 moieties were positioned on alternating sides of the polymer chain. These polymer chains were further found to extend into two dimensions through the interdigitation of neighbouring chains in a zipper-like fashion. C60-Rh(II) polymers can capture free C60

Perhaps more interestingly is that when these polymer chains were synthesised in the presence of either C60 or C70, free molecules of C60 or C70 were seen to occupy the void spaces between the C60 molecules of the polymer. Additionally, if a mixture of C60 and C70 was present in the polymer synthesis, it was observed that only C60 was captured by the polymer, most likely as a result of a better geometric match between the polymer and the spherical C60 in preference to the more elongated shape of C70.

This work elegantly demonstrates the generation of not only a self-assembling C60-containing polymer that can be characterised structurally in the solid state, but of one  that can entrap free molecules of C60 selectively over molecules of C70. Based on the properties of free C60 and transition metal complexes, the electronic and chromophoric properties of such a crystalline system could also be expected to offer some noteworthy results.

Read this HOT ChemComm article in full!

Zipping up fullerenes into polymers using rhodium(II) acetate dimer and N(CH2CH2)2NC60 as building blocks
Amineh Aghabali, Marilyn M. Olmstead and Alan L. Balch
Chem. Commun., 2014, Advance Article.
DOI: 10.1039/C4CC06995A

Biography

Anthea Blackburn is a guest web writer for Chemical Communications. Anthea is a graduate student hailing from New Zealand, studying at Northwestern University in the US under the tutelage of Prof. Fraser Stoddart (a Scot), where she is exploiting 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 before graduation.

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