Tuesday, May 24, 2016

Nature Chemistry Contents June 2016 Volume 8 Number 6 pp 517 - 634

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TABLE OF CONTENTS

June 2016 Volume 8, Issue 6

Editorial
Commentary
Interview
News and Views
Review
Articles
In Your Element
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Editorial

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Coordinating chemists for global development   p517
doi:10.1038/nchem.2541
Chemistry research and education face challenges anywhere in the world, but more so in less developed — or less stable — economies. These countries and their more economically fortunate neighbours can all contribute to the development of chemistry and its ability to tackle local and global issues.

Commentary

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Challenges and opportunities for chemistry in Africa   pp518 - 522
Berhanu Abegaz
doi:10.1038/nchem.2533
Chemistry education and research in Africa is challenging — a fact that is clearly reflected by publication metrics. Yet this is far from the full story on a continent that has youth on its side, a cultural link to chemistry through its strong interest in plants and indigenous medicine, and an increasing number of ways forward.

Interview

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A lab in Argentina   pp523 - 524
Interview with Mauricio Erben
doi:10.1038/nchem.2532
Mauricio Erben, a researcher at the National University of La Plata and the National Scientific and Technical Research Council, talks to Nature Chemistry about his experience of research in Argentina, and how it is inherently linked to the country's political climate.

News and Views

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Two-dimensional materials: Polyphony in B flat   pp525 - 527
Zhuhua Zhang, Evgeni S. Penev and Boris I. Yakobson
doi:10.1038/nchem.2521
Early theories suggested the possibility of atomically thin boron layers, but electron-deficient boron favours multicentre bonds and assembles into various polymorphs, making the synthesis of such layers challenging. Now, in two independent experiments, the deposition of atomic boron has offered this long-sought material on a silver platter.

See also: Article by Feng et al.

Surface spectroscopy: Between a rock and a soft place   pp527 - 528
Heather Vanselous and Poul B. Petersen
doi:10.1038/nchem.2531
The critical step in water splitting is the formation of a peroxo bond; the mechanism, thought to involve oxyl radical formation, remains elusive. Now, experiments reveal a distinct bond vibration directly connected to an oxyl radical that is simultaneously coupled to both the semiconductor electronic states and the motion of the surrounding water.

See also: Article by Herlihy et al.

Membraneless organelles: Phasing in and out   pp528 - 530
James Shorter
doi:10.1038/nchem.2534
The low-complexity-protein, liquid phases of membraneless organelles have now been established to selectively partition biomolecules. The specialized microenvironment that they provide differs chemically from the surrounding medium and enables specific nucleic-acid remodelling reactions.

See also: Article by Nott et al.

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Review

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Counting on natural products for drug design   pp531 - 541
Tiago Rodrigues, Daniel Reker, Petra Schneider and Gisbert Schneider
doi:10.1038/nchem.2479



Natural products are a prime source of innovative molecular fragments and privileged scaffolds for drug discovery and chemical biology. Advanced machine-learning approaches can help analyse and design synthetically accessible, natural-product-derived, compound libraries and provide insight into the high selectivity of such compounds.

Articles

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An autonomous molecular assembler for programmable chemical synthesis   pp542 - 548
Wenjing Meng, Richard A. Muscat, Mireya L. McKee, Phillip J. Milnes, Afaf H. El-Sagheer et al.
doi:10.1038/nchem.2495



Molecular machines that assemble polymers in a programmed sequence are fundamental to life. Now, synthetic machinery built from DNA has been used to execute a molecular program that produces peptides, or olefin oligomers, with a defined sequence. The oligomeric product is linked to a double-stranded DNA product that records the sequence of reactions that were executed.

Detecting the oxyl radical of photocatalytic water oxidation at an n-SrTiO3/aqueous interface through its subsurface vibration   pp549 - 555
David M. Herlihy, Matthias M. Waegele, Xihan Chen, C. D. Pemmaraju, David Prendergast et al.
doi:10.1038/nchem.2497



Water oxidation on titanate surfaces is thought to occur via an oxyl-radical intermediate (Ti­–O), which precedes O–O bond formation, and for which there is indirect evidence. Using ultrafast infrared spectroscopy and theoretical calculations of photocatalytic water oxidation at the n-SrTiO3/aqueous interface, the oxyl radical has now been detected through its subsurface vibration.

See also: News and Views by Vanselous & Petersen

Evolution of thermophilic DNA polymerases for the recognition and amplification of C2'-modified DNA   pp556 - 562
Tingjian Chen, Narupat Hongdilokkul, Zhixia Liu, Ramkrishna Adhikary, Shujian S. Tsuen et al.
doi:10.1038/nchem.2493



Naturally occurring DNA polymerases can amplify DNA efficiently via PCR, but they cannot utilize C2′-modified substrates to make non-natural nucleic acids. Such C2′-modified nucleic acids are of interest as they are resistant to nucleases. Now, a Stoffel fragment DNA polymerase has been evolved to transcribe C2′-modified DNA from a DNA template, reverse transcribe C2′-modified DNA back into DNA, and PCR-amplify C2′-modified DNA.

Experimental realization of two-dimensional boron sheets   pp563 - 568
Baojie Feng, Jin Zhang, Qing Zhong, Wenbin Li, Shuai Li et al.
doi:10.1038/nchem.2491



A variety of two-dimensional materials have been reported in the past few years, yet single-element systems—such as graphene and black phosphorus—have remained rare. 2D allotropes of boron have long been predicted and recently investigated. Two boron sheets have now been grown on a Ag(111) surface by molecule beam epitaxy that exhibit significant chemical stability against oxidation.

See also: News and Views by Zhang et al.

Membraneless organelles can melt nucleic acid duplexes and act as biomolecular filters   pp569 - 575
Timothy J. Nott, Timothy D. Craggs and Andrew J. Baldwin
doi:10.1038/nchem.2519



Membraneless organelles form as liquid droplets inside cells. These bodies are effectively a separate organic phase, with unique biochemical properties. Now, the solvent interior of membraneless organelles has been shown to have a significant effect on the properties and structure of biomolecules. In addition to selectively partitioning and trafficking proteins, they can melt DNA without using ATP.

See also: News and Views by Shorter

A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II   pp576 - 583
Marcus Schulze, Valentin Kunz, Peter D. Frischmann and Frank Würthner
doi:10.1038/nchem.2503



Designing improved catalysts is predicated on understanding how they work. Now, by positioning three ruthenium centres in a macrocyclic framework, a remarkable acceleration of catalytic water oxidation has been achieved. Detailed mechanistic studies revealed that the catalyst operates through the ‘water nucleophilic attack’ pathway—similar to the natural oxygen-evolving cluster of photosystem II.

Controlling activity and selectivity using water in the Au-catalysed preferential oxidation of CO in H2   pp584 - 589
Johnny Saavedra, Todd Whittaker, Zhifeng Chen, Christopher J. Pursell, Robert M. Rioux et al.
doi:10.1038/nchem.2494



The preferential oxidation of CO is a potentially efficient means of purifying industrial hydrogen, however, no catalytic systems are known with sufficiently high activity and selectivity. Now Au/Al2O3 catalysts are shown to have outstanding activity and selectivity when both the feed flow-rate and the amount of surface water are carefully controlled.

Sequence-defined bioactive macrocycles via an acid-catalysed cascade reaction   pp590 - 596
Mintu Porel, Dana N. Thornlow, Ngoc N. Phan and Christopher A. Alabi
doi:10.1038/nchem.2508



Macrocyclic oligomers are a unique structural class of compounds in which the ring size and structure can be tuned through the precise control of the primary sequence. Now, it has been shown that oligothioetheramide (oligoTEA) macrocycles can be synthesized using a one-pot acid-catalysed cascade reaction. Preliminary results indicate that cationic oligoTEAs are promising bactericidal agents.
Chemical compounds

Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry   pp597 - 602
Christopher R. Ryder, Joshua D. Wood, Spencer A. Wells, Yang Yang, Deep Jariwala et al.
doi:10.1038/nchem.2505



Few-layer black phosphorus (BP) is a promising semiconductor, but it is highly reactive and susceptible to ambient degradation. Covalent functionalization with aryl radicals has now been shown to significantly improve the stability of exfoliated BP, as well as the performance of BP-based electronic devices through a controllable p-type doping effect.

Tuning the driving force for exciton dissociation in single-walled carbon nanotube heterojunctions   pp603 - 609
Rachelle Ihly, Kevin S. Mistry, Andrew J. Ferguson, Tyler T. Clikeman, Bryon W. Larson et al.
doi:10.1038/nchem.2496



The influence of the thermodynamic driving force for photoinduced electron-transfer between single-walled carbon nanotubes and fullerene derivatives has been investigated. The Marcus inverted region and small reorganization energies were observed for this model organic heterojunction. Small reorganization energies aid in minimizing energy losses for solar conversion to electricity or fuels.

Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes   pp610 - 617
Zachary L. Niemeyer, Anat Milo, David P. Hickey and Matthew S. Sigman
doi:10.1038/nchem.2501



The choice of ligand used in a reaction can drastically influence the overall outcome. Using a combination of classic physical organic chemistry and modern mathematical modelling, phosphine ligand effects are probed. The methods described provide the groundwork for future mechanistic studies of this ubiquitous ligand class.

A highly stretchable autonomous self-healing elastomer   pp618 - 624
Cheng-Hui Li, Chao Wang, Christoph Keplinger, Jing-Lin Zuo, Lihua Jin et al.
doi:10.1038/nchem.2492



Polymers that are both elastic and self-healing are desirable for a variety of applications, but often rely on hydrogen bonding which makes them moisture-sensitive. Now, by incorporating metal–ligand interactions with different bond strengths into flexible polymer backbones, an elastomer has been devised that combines high stretchability and high dielectric strength with autonomous self-healing and mechanical actuation capabilities.

Fast response dry-type artificial molecular muscles with [c2]daisy chains   pp625 - 632
Kazuhisa Iwaso, Yoshinori Takashima and Akira Harada
doi:10.1038/nchem.2513



Photoresponsive wet- and dry-type actuators can be built up from rotaxane-like structures through the polycondensation of four-armed polyethylene glycols with [c2]daisy chains comprised of cyclodextrin rings and azobenzene side chains. The response of the dry-type (xerogel) actuator to UV light was found to be more than 10,000 times faster than the wet-type (hydrogel) actuator.

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In Your Element

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Probing bohrium   p634
Philip Wilk
doi:10.1038/nchem.2530
Bohrium behaves just as a group 7 element should — but this is in fact surprising, Philip Wilk explains.

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