Friday, April 22, 2016

Nature Chemistry Contents April 2016 Volume 8 Number 4 pp 283 - 392

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Nature Chemistry

TABLE OF CONTENTS

May 2016 Volume 8, Issue 5

Commentary
Thesis
News and Views
Review
Articles
In Your Element


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Commentary

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One-world chemistry and systems thinking   pp393 - 398
Stephen A. Matlin, Goverdhan Mehta, Henning Hopf and Alain Krief
doi:10.1038/nchem.2498
The practice and overarching mission of chemistry need a major overhaul in order to be fit for purpose in the twenty-first century and beyond. The concept of 'one-world' chemistry takes a systems approach that brings together many factors, including ethics and sustainability, that are critical to the future role of chemistry.

Thesis

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Physics 3 - 0 Chemistry   pp399 - 400
Bruce C. Gibb
doi:10.1038/nchem.2504
A trio of recent discoveries in physics should be celebrated by everyone, even chemists, argues Bruce Gibb.

News and Views

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Molecular transport: Catch the carbon dioxide   pp401 - 402
Barbara Kirchner and Barbara Intemann
doi:10.1038/nchem.2499
Understanding the minute details of CO2 transport is key to finding new technologies that reduce the hazardous levels of CO2 in our atmosphere. Now, the observation that the transport of CO2 in molten calcium carbonate occurs faster than standard molecular diffusion brings us one step closer.

See also: Article by Corradini et al.

Systems chemistry: All in a spin   pp402 - 404
Lucy Clark and Philip Lightfoot
doi:10.1038/nchem.2510
A fundamental challenge in systems chemistry is to engineer the emergence of complex behaviour. The collective structures of metal cyanide chains have now been interpreted in the same manner as the myriad of magnetic phases displayed by frustrated spin systems, highlighting a symbiotic approach between systems chemistry and magnetism.

See also: Article by Cairns et al.

Mechanical chirality: A chiral catalyst with a ring to it   pp404 - 406
Stephen M. Goldup
doi:10.1038/nchem.2509
A chiral [2]rotaxane in which the asymmetry is derived from the way in which the two components are mechanically interlocked — rather than being encoded in the covalent connectivity of the components themselves — has been shown to act as an enantioselective organocatalyst.

Molecular materials: Captivating COFs   p406
Lorna G. Christie
doi:10.1038/nchem.2500

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Review

Top

Expanding the chemical toolbox for the synthesis of large and uniquely modified proteins   pp407 - 418
Somasekhar Bondalapati, Muhammad Jbara and Ashraf Brik
doi:10.1038/nchem.2476



Chemical protein synthesis can enable the preparation of proteins containing post-translational modifications or unnatural variations such as D-amino acids. Such modified proteins are not easily fabricated by other methods. This Review provides an overview of the current approaches for the chemical synthesis of proteins.

Articles

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Discovery of a regioselectivity switch in nitrating P450s guided by molecular dynamics simulations and Markov models   pp419 - 425
Sheel C. Dodani, Gert Kiss, Jackson K. B. Cahn, Ye Su, Vijay S. Pande et al.
doi:10.1038/nchem.2474



A collaborative approach between experiment and simulation has revealed a single mutation in the F/G loop of the newly described nitrating cytochrome P450 TxtE that controls loop dynamics and, more surprisingly, the regioselectivity of the reaction. This mutation is present in a subset of homologous nitrating P450s that produce a previously unidentified biosynthetic intermediate, 5-nitro-L-tryptophan.

Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts   pp426 - 434
Martin R. Busche, Thomas Drossel, Thomas Leichtweiss, Dominik A. Weber, Mareike Falk et al.
doi:10.1038/nchem.2470



Li+-selective solid electrolytes may enable next-generation battery systems, such as Li–S and Li–O2. Now, in an exemplar system, it is shown that a resistive interphase forms at the interface between solid and liquid electrolytes, termed the solid-liquid electrolyte interphase (SLEI). An in situ study of this undesirable effect is supported by state-of-the-art surface analysis.

Synthesis of a distinct water dimer inside fullerene C70   pp435 - 441
Rui Zhang, Michihisa Murata, Tomoko Aharen, Atsushi Wakamiya, Takafumi Shimoaka et al.
doi:10.1038/nchem.2464



Endohedral C70 fullerenes containing either one or two water molecules have now been prepared using a molecular-surgery approach. The structure of H2O@C70 was determined by single-crystal X-ray analysis, revealing the encapsulated water molecule to be in an off-centre position. In (H2O)2@C70, the two water molecules form a discrete dimer held together with a single hydrogen bond.
Chemical compounds

Encoding complexity within supramolecular analogues of frustrated magnets   pp442 - 447
Andrew B. Cairns, Matthew J. Cliffe, Joseph A. M. Paddison, Dominik Daisenberger, Matthew G. Tucker et al.
doi:10.1038/nchem.2462



Competing metallophilic and electrostatic interactions between gold and/or silver cyanide chains govern their assembly into different structures. An analogy has now been drawn between these systems and two-dimensional magnets. Supramolecular interactions between the chains have been tuned to mimic different magnetic interactions, leading to the realization of complex states predicted for magnets.

See also: News and Views by Clark & Lightfoot

A simple physical mechanism enables homeostasis in primitive cells   pp448 - 453
Aaron E. Engelhart, Katarzyna P. Adamala and Jack W. Szostak
doi:10.1038/nchem.2475



The development of cells requires a mechanism to support homeostasis—the maintenance of constant internal conditions—as cellular growth results in internal dilution. Now, a simple physical process is described in which short oligonucleotide inhibitors enable dilution-driven activation of encapsulated ribozymes via membrane growth, suggesting homeostatic mechanisms could have existed in the earliest cells.

Carbon dioxide transport in molten calcium carbonate occurs through an oxo-Grotthuss mechanism via a pyrocarbonate anion   pp454 - 460
Dario Corradini, François-Xavier Coudert and Rodolphe Vuilleumier
doi:10.1038/nchem.2450



The solvation behaviour of CO2 in carbonate melts is important from both a geochemical point of view and with respect to its electroreduction. Now, simulations have shown that solvation of CO2 in molten CaCO3 leads to the formation of the pyrocarbonate anion, C2O52–, which significantly enhances the transport of CO2 via a Grotthuss-like mechanism.

See also: News and Views by Kirchner & Intemann

Chemical polyglycosylation and nanolitre detection enables single-molecule recapitulation of bacterial sugar export   pp461 - 469
Lingbing Kong, Andrew Almond, Hagan Bayley and Benjamin G. Davis
doi:10.1038/nchem.2487



Capsular polysaccharides are a protective layer enveloping pathogenic bacteria. Understanding their export could guide the design of therapeutics that render bacteria vulnerable to attack by the immune system or other therapeutic agents. Now, a synthetic strategy of polyglycosylation has been developed to obtain defined capsular polysaccharide fragments. Subsequent nanolitre detection enables their export to be studied at the single-molecule level.

Controlled growth of high-density CdS and CdSe nanorod arrays on selective facets of two-dimensional semiconductor nanoplates   pp470 - 475
Xue-Jun Wu, Junze Chen, Chaoliang Tan, Yihan Zhu, Yu Han et al.
doi:10.1038/nchem.2473



Controlling the morphology and composition of hybrid nanostructures is desirable for applications, but it has proven challenging to precisely combine different nucleation sites and growth modes. Now, three types of hierarchical 1D/2D nanostructures have been prepared by selectively growing semiconductor nanorod arrays (CdS or CdSe) on the different facets of hexagonal nanoplates.

Self-assembly of size-controlled liposomes on DNA nanotemplates   pp476 - 483
Yang Yang, Jing Wang, Hideki Shigematsu, Weiming Xu, William M. Shih et al.
doi:10.1038/nchem.2472



Precise control of vesicle size is highly desirable both for basic biochemical research and biomedical applications. Now, monodispersed sub-100-nm vesicles with predefined sizes have been produced using a method based on membrane self-assembly within a DNA-nanostructure guide.

Molecular rectifier composed of DNA with high rectification ratio enabled by intercalation   pp484 - 490
Cunlan Guo, Kun Wang, Elinor Zerah-Harush, Joseph Hamill, Bin Wang et al.
doi:10.1038/nchem.2480



Understanding the correlation between structure and charge transport properties of a DNA-based single molecule device is crucial to the creation of nanoscale functional devices. Now, a DNA-based molecular rectifier with a high rectification ratio has been constructed by site-specific intercalation of small molecules (coralyne) into native double-stranded DNA.

Carbon–sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE   pp491 - 500
Roman Rohac, Patricia Amara, Alhosna Benjdia, Lydie Martin, Pauline Ruffié et al.
doi:10.1038/nchem.2490



L-Cysteine-derived thiazolidines have now been shown to be artificial substrates of the radical SAM enzyme HydE, which converts them into S-adenosyl-L-cysteine. Carbon–sulfur bonds are formed in a concerted mechanism that involves the formation of a C-centred radical that concomitantly attacks the S atom of a thioether. This is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting an H-atom.

Charge-ordering transition in iron oxide Fe4O5 involving competing dimer and trimer formation   pp501 - 508
Sergey V. Ovsyannikov, Maxim Bykov, Elena Bykova, Denis P. Kozlenko, Alexander A. Tsirlin et al.
doi:10.1038/nchem.2478



Phase transitions in materials are intriguing, and can also be of practical importance. Below ∼150 K, mixed-valent iron oxide Fe4O5 has now been shown to undergo an unusual charge-ordering phase transition that involves the competing formation of iron dimers and trimers, and leads to a significant increase in electrical resistivity.

Unimolecular dissociation dynamics of vibrationally activated CH3CHOO Criegee intermediates to OH radical products   pp509 - 514
Nathanael M. Kidwell, Hongwei Li, Xiaohong Wang, Joel M. Bowman and Marsha I. Lester
doi:10.1038/nchem.2488



An important source of atmospheric hydroxyl radicals is from the dissociation of Criegee intermediates produced in alkene ozonolysis reactions. The dissociation dynamics of the prototypical CH3CHOO Criegee intermediate have now been determined. Complementary experimental and theoretical studies were carried out and the translational and internal energy distributions of the OH radical products were characterized.

In Your Element

Top

Curious curium   p516
Rebecca J. Abergel and Eric Ansoborlo
doi:10.1038/nchem.2512
From secretive beginnings to serving in missions on Mars, Rebecca J. Abergel and Eric Ansoborlo take a look at the glowing mark curium has left on contemporary science and technology.

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