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June 2018 Volume 10, Issue 6

News & Views
In Your Element
High Voltage Power Supplies for Mission-Critical Applications

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News & Views


Vibrations that live long and prosper    pp577 - 578
Arthur L. Utz

Hitting the sweet spot    pp578 - 580
Lara R. Malins

Communicating catalysts    pp580 - 582
Bert M. Weckhuysen



Manganese-catalysed benzylic C(sp3)–H amination for late-stage functionalization    pp583 - 591
Joseph R. Clark, Kaibo Feng, Anasheh Sookezian & M. Christina White

A manganese phthalocyanine has been shown to catalyse intermolecular C–H amination reactions—proceeding through an electrophilic metallonitrene intermediate—with high levels of reactivity and site selectivity. Demonstrating good tolerance for tertiary amine, pyridine and benzimidazole moieties, nitrogen functionality can be selectively installed at electron-rich, sterically exposed benzylic sites in bioactive molecules.


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Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface    pp592 - 598
Pranav R. Shirhatti, Igor Rahinov, Kai Golibrzuch, Jörn Werdecker, Jan Geweke et al.

The vibrational relaxation of molecules adsorbed at metal surfaces is considered to be relatively fast and thus examples of vibrationally induced chemistry at surfaces are rare. The adsorption and subsequent desorption of long-lived vibrationally excited CO molecules from a gold surface have now been observed, suggesting that vibrational promotion of surface chemistry might be more prevalent than currently thought.


Fragment-derived inhibitors of human N-myristoyltransferase block capsid assembly and replication of the common cold virus    pp599 - 606
Aurélie Mousnier, Andrew S. Bell, Dawid P. Swieboda, Julia Morales-Sanfrutos, Inmaculada Pérez-Dorado et al.

An effective antiviral against the common cold could prevent exacerbations in asthma and chronic obstructive pulmonary disease, but the diversity and adaptability of the virus makes it a highly challenging target. Now, picomolar inhibitors of a human lipid transferase have been developed. Targeting this human lipid transferase could provide an effective and broad-spectrum approach to block viral replication in the host.


Cooperative communication within and between single nanocatalysts    pp607 - 614
Ningmu Zou, Xiaochun Zhou, Guanqun Chen, Nesha May Andoy, Won Jung et al.

Nanocatalysts can undergo various dynamic phenomena that affect their activity, such as restructuring and spillover. Now, using spatially and temporally resolved imaging of individual catalytic reactions, cooperative communication between different sites within single palladium- and gold-based nanocatalysts, and between different nanocatalysts, has been observed during three distinct catalytic reactions.


A new fundamental type of conformational isomerism    pp615 - 624
Peter J. Canfield, Iain M. Blake, Zheng-Li Cai, Ian J. Luck, Elmars Krausz et al.

Isolable compounds displaying new fundamental forms of conformational isomerism were last discovered in 1914 (atropisomerism) and 1961 (hindered pyramidal inversion). Now, a new form—referred to as akamptisomerism—has been described through four resolved stereoisomers of a transoid (BF)O(BF)-quinoxalinoporphyrin compound. The stereodescriptors parvo and amplo, necessary for their classification, have also been introduced.


Ring-through-ring molecular shuttling in a saturated [3]rotaxane    pp625 - 630
Kelong Zhu, Giorgio Baggi & Stephen J. Loeb

Controlled motion in mechanically interlocked molecules, such as a macrocycle moving back and forth along the axle of a rotaxane, forms the basis of complex functions in molecular machinery. Now, ring-through-ring shuttling has been achieved using two macrocycles that switch position between two anchoring sites, which involves the smaller ring passing through the larger one.


I-motif DNA structures are formed in the nuclei of human cells    pp631 - 637
Mahdi Zeraati, David B. Langley, Peter Schofield, Aaron L. Moye, Romain Rouet et al.

I-motif DNA structures are thought to form in cytosine-rich regions of the genome and to have regulatory functions; however, in vivo evidence for the existence of such structures has so far remained elusive. Now an engineered antibody that is selective for i-motif structures has been developed and used to detect i-motifs in the nuclei of human cells.


High phase-purity 1T′-MoS2- and 1T′-MoSe2-layered crystals    pp638 - 643
Yifu Yu, Gwang-Hyeon Nam, Qiyuan He, Xue-Jun Wu, Kang Zhang et al.

The phase in which a crystal exists can have a direct influence over its properties; however, it is usually difficult to control during synthesis. Now it has been shown that micrometre-sized metallic 1T′-MoS2- and 1T′-MoSe2-layered crystals can be prepared in high phase purity on a large scale, and that they display promising electrocatalytic activity towards the hydrogen evolution reaction.


Rapid phenolic O-glycosylation of small molecules and complex unprotected peptides in aqueous solvent    pp644 - 652
Tyler J. Wadzinski, Angela Steinauer, Liana Hie, Guillaume Pelletier, Alanna Schepartz et al.

Glycosylation is an attractive strategy to functionalize natural products and peptides for biomedical use, but non-enzymatic approaches usually require organic solvent and protecting groups. Now, an aqueous phenolic O-glycosylation reaction that uses glycosyl fluoride donors and a calcium salt has been developed for a wide range of substrates, including complex unprotected peptides.


Direct observation of forward-scattering oscillations in the H+HD→H2+D reaction    pp653 - 658
Daofu Yuan, Shengrui Yu, Wentao Chen, Jiwei Sang, Chang Luo et al.

Our understanding of reaction dynamics has developed as more accurate measurements of product state-resolved angular distributions have become available. Now, fast forward-scattering oscillations in the product angular distribution of the benchmark chemical reaction H + HD → H2 + D have been observed and are in excellent agreement with quantum-mechanical dynamics calculations.


Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface    pp659 - 666
Mijanur Rahaman Molla, Poornima Rangadurai, Lucas Antony, Subramani Swaminathan, Juan J. de Pablo et al.

Biological systems are made up of complex networks that can respond to stimuli and function across relatively long distances in molecular terms. Now, it has been shown that a local disruption (the isomerization of just a single azobenzene unit) at the interface of supramolecular glassy polymersomes can immediately spread through over 500 bonds, significantly changing membrane permeability and enabling controllable release of guest molecules.


Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage    pp667 - 672
Meng Wang, Chunlei Jiang, Songquan Zhang, Xiaohe Song, Yongbing Tang et al.

Calcium-ion batteries are potentially attractive alternatives to lithium-ion batteries, but remain largely unexplored because of low performance. A reversible calcium alloying/de-alloying reaction with the tin anode has now been coupled with the intercalation/de-intercalation of hexafluorophosphate in the graphite cathode to enable a calcium-ion battery that operates stably at room temperature.


Cholesterol catalyses Aβ42 aggregation through a heterogeneous nucleation pathway in the presence of lipid membranes    pp673 - 683
Johnny Habchi, Sean Chia, Céline Galvagnion, Thomas C. T. Michaels, Mathias M. J. Bellaiche et al.

Cholesterol embedded in lipid membranes strongly promotes the aggregation of Aβ42 that is associated with Alzheimer's disease. Now, a kinetic analysis has shown that the mechanism of action responsible for this effect involves the introduction of a heterogeneous nucleation pathway that enhances the primary nucleation rate of Aβ42 aggregation by up to 20-fold.


In Your Element


Tritium trinkets    p686
Brett F. Thornton & Shawn C. Burdette

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