Thursday, September 22, 2016

Nature Chemistry Contents October 2016 Volume 8 Number 10 pp 897 - 986

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TABLE OF CONTENTS

October 2016 Volume 8, Issue 10

Thesis
News and Views
Articles
Corrigendum
In Your Element
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Thesis

Top

A brief history of water   pp897 - 898
Michelle Francl
doi:10.1038/nchem.2620
Michelle Francl wonders just how old the water in her tea is.

News and Views

Top

Synthesis: Click chemistry gets reversible   pp899 - 900
David A. Fulton
doi:10.1038/nchem.2626
'Click' chemistry allows for the linking together of chemical modules, however, there are currently no methods that also allow for facile 'declicking' to unlink them. Now, a method has been developed to click together amines and thiols, and then allow a chemically triggered declick reaction to release the original molecular components.

See also: Article by Diehl et al.

Organic chemistry: A light touch breaks a strong ring   pp900 - 901
Martin G. Banwell
doi:10.1038/nchem.2623
The high stability of aromatic compounds often limits the types of reaction that can be conducted on them. Now, a series of photochemically promoted addition reactions has been used to effect the oxidative dearomatization of benzene derivatives. These reactions provide a suite of versatile new building blocks for chemical synthesis.

See also: Article by Southgate et al.

Heterogeneous catalysis: More than skimming the surface   pp902 - 903
Franklin (Feng) Tao and Yu Tang
doi:10.1038/nchem.2630
The high temperatures and pressures used in heterogeneous catalysis make it difficult to observe catalysts using conventional techniques. Now, adsorbed product molecules on the surface of a single-crystal model catalyst have been observed during catalysis using a custom-built scanning tunnelling microscope that can work in situ.

See also: Article by Navarro et al.

Organometallic chemistry: Taking ferrocenium up a notch   p903
Marshall Brennan
doi:10.1038/nchem.2627

Homogeneous catalysis: Eight irons hit the right spin   pp904 - 905
Robin B. Bedford
doi:10.1038/nchem.2621
After remaining elusive for 40 years, 'Kochi's complex', a key intermediate in iron-catalysed cross-coupling, has finally been pinned down, and its structure comes as something of a surprise.

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Articles

Top

Creating complex molecular topologies by configuring DNA four-way junctions   pp907 - 914
Di Liu, Gang Chen, Usman Akhter, Timothy M. Cronin and Yossi Weizmann
doi:10.1038/nchem.2564



The synthesis of topologically non-trivial compounds requires the manipulation of molecular recognition with an extraordinarily high level of control. Now, DNA four-way junctions have been configured to construct synthetic DNA knots and links, which can then be used to investigate important DNA-processing enzymes.

Oligoarginine peptides slow strand annealing and assist non-enzymatic RNA replication   pp915 - 921
Tony Z. Jia, Albert C. Fahrenbach, Neha P. Kamat, Katarzyna P. Adamala and Jack W. Szostak
doi:10.1038/nchem.2551



Identifying a non-enzymatic method of replicating RNA for multiple cycles has been problematic because rapid strand reannealing outcompetes slow non-enzymatic template copying. Now, oligoarginine peptides have been shown to inhibit reannealing while still allowing short primers and activated monomers to bind to the template strand, facilitating the next round of template copying.

Dearomative dihydroxylation with arenophiles   pp922 - 928
Emma H. Southgate, Jola Pospech, Junkai Fu, Daniel R. Holycross and David Sarlah
doi:10.1038/nchem.2594



Dearomatization reactions that can simultaneously introduce functionality are valuable transformations that are largely underdeveloped. Now, a synthetic strategy based on the combination of arenophiles with catalytic dihydroxylation reactions enables rapid and controlled access to synthetically useful cyclohexene and cyclohexadiene derivatives from readily available arene starting materials.
Chemical compounds
See also: News and Views by Banwell

In situ observation of self-assembled hydrocarbon Fischer–Tropsch products on a cobalt catalyst   pp929 - 934
Violeta Navarro, Matthijs A. van Spronsen and Joost W. M. Frenken
doi:10.1038/nchem.2613



During the Fischer-Tropsch catalytic reaction, alkanes are synthesized from carbon monoxide and hydrogen at high pressure and temperature. Now it is shown using scanning tunnelling imaging of a cobalt surface during reaction that linear alkane product molecules of a specific length self-assemble on terraces, facilitating the desorption of new product molecules created at step sites.

See also: News and Views by (Feng) Tao & Tang

Force-induced tautomerization in a single molecule   pp935 - 940
Janina N. Ladenthin, Thomas Frederiksen, Mats Persson, John C. Sharp, Sylwester Gawinkowski et al.
doi:10.1038/nchem.2552



Force-induced tautomerization in a single porphycene molecule is investigated on a Cu(110) surface at 5 K by using non-contact atomic force microscopy. The force needed to trigger the tautomerization process is quantified by force spectroscopy and theoretical calculations reveal the atomistic mechanism behind the reaction.

Engineering nanometre-scale coherence in soft matter   pp941 - 945
Chaoren Liu, Limin Xiang, Yuqi Zhang, Peng Zhang, David N. Beratan et al.
doi:10.1038/nchem.2545



The existence (or not) of electronic coherence in homopolymers is dependent on a balance between monomer–monomer interactions and environmental heterogeneity. Now, by understanding how even–odd orbital symmetry influences coherence and produces resistance oscillations as a function of distance—it is shown that DNA sequences can be designed to support coherent charge transport.

Directionally tunable and mechanically deformable ferroelectric crystals from rotating polar globular ionic molecules   pp946 - 952
Jun Harada, Takafumi Shimojo, Hideaki Oyamaguchi, Hiroyuki Hasegawa, Yukihiro Takahashi et al.
doi:10.1038/nchem.2567



A major drawback of molecular ferroelectric crystals, low dimensionality, has now been overcome by ionic plastic crystals. Molecular rotation and phase transitions intrinsic to the crystals make the materials unique molecular ferroelectrics, where the polarization axis direction in a grown crystal can be flexibly altered by applying an electric field.

The dipolar endofullerene HF@C60   pp953 - 957
Andrea Krachmalnicoff, Richard Bounds, Salvatore Mamone, Shamim Alom, Maria Concistrè et al.
doi:10.1038/nchem.2563



Hydrogen fluoride has been encapsulated in C60-fullerene using molecular surgery. The quantum rotor system has been studied by NMR and infrared spectroscopy as well as neutron scattering. The fullerene cage causes a small red-shift in the HF rotational and vibrational constants, and shields around 75% of its dipole.
Chemical compounds

Allosteric activation of membrane-bound glutamate receptors using coordination chemistry within living cells   pp958 - 967
Shigeki Kiyonaka, Ryou Kubota, Yukiko Michibata, Masayoshi Sakakura, Hideo Takahashi et al.
doi:10.1038/nchem.2554



The controlled activation of proteins inside living cells is an important goal in protein design research. Now, a strategy for allosteric activation using coordination chemistry has been demonstrated for two different kinds of neurotransmitter receptors, an ion-channel and a G-protein coupled glutamate receptor.

Click and chemically triggered declick reactions through reversible amine and thiol coupling via a conjugate acceptor   pp968 - 973
Katharine L. Diehl, Igor V. Kolesnichenko, Scott A. Robotham, J. Logan Bachman, Ye Zhong et al.
doi:10.1038/nchem.2601



It has now been shown that amines and thiols can be tethered together through a Meldrum's acid-derived conjugate acceptor for applications ranging from dynamic combinatorial chemistry to biochemistry to polymer chemistry. Furthering the utility of this chemistry, the ability to then chemically ‘declick' back to the unaltered amine and thiol components is also demonstrated.
Chemical compounds
See also: News and Views by Fulton

Switchable photooxygenation catalysts that sense higher-order amyloid structures   pp974 - 982
Atsuhiko Taniguchi, Yusuke Shimizu, Kounosuke Oisaki, Youhei Sohma and Motomu Kanai
doi:10.1038/nchem.2550



Selectively degrading the pathogenic, aggregated amyloid state of proteins, without affecting the functional state, is a potential therapeutic strategy for treating amyloid diseases. Now, photooxygenation catalysts that are active only when bound to the cross-β-sheet structure of the amyloid form have been developed.
Chemical compounds

In Your Element

Top

Brief encounters with dubnium   p986
Lars Ohrstrom
doi:10.1038/nchem.2610
Lars Ohrstrom tells of the fleeting, but still tangible, chemistry of dubnium, the heaviest of the group 5 elements.

Corrigendum

Top

Corrigendum: Self-assembled molecular p/n junctions for applications in dye-sensitized solar energy conversion   p983
Byron H. Farnum, Kyung-Ryang Wee and Thomas J. Meyer
doi:10.1038/nchem.2611

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