Friday, November 20, 2015

Nature Chemistry Contents December 2015 Volume 7 Number 12 pp 941 - 1034

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Nature Chemistry

TABLE OF CONTENTS

December 2015 Volume 7, Issue 12

Commentary
News and Views
Perspective
Articles
Erratum
Corrigendum
In Your Element
Correction
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Commentary

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The role of chemistry in inventing a sustainable future   pp941 - 943
Stephen A. Matlin, Goverdhan Mehta, Henning Hopf and Alain Krief
doi:10.1038/nchem.2389
The Sustainable Development Goals adopted at a UN summit in September 2015 address many of the great challenges that our planet faces this century. Chemistry can make pivotal contributions to help realize these ambitious goals, but first it must undergo major changes in its priorities, approaches and practices.

News and Views

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Interlocked molecules: Aqueous assembly   pp944 - 945
Linyi Bai and Yanli Zhao
doi:10.1038/nchem.2409
The quantitative self-assembly of mechanically interlocked molecules in water, instead of organic solvents, opens up the possibility of such systems being used in a biological context where their functions can be interfaced with biomolecular systems.

See also: Article by Li et al.

Photochemistry: A coherent picture of vision   pp945 - 947
Richard A. Mathies
doi:10.1038/nchem.2406
Vision is initiated by photoisomerization of 11-cis retinal in the visual pigment rhodopsin — a fast and efficient process. Spectroscopic studies now demonstrate that the transition from the reactant photoexcited-state to the ground-state photoproduct, which mediates this important reaction, occurs on a sub-50-fs timescale and is vibrationally coherent.

See also: Article by Johnson et al.

2015 Nobel Prize in Chemistry: Requiring repair   p947
Russell Johnson
doi:10.1038/nchem.2412

Biocatalysis: Chiral cascades   pp948 - 949
Jian-bo Wang and Manfred T. Reetz
doi:10.1038/nchem.2408
Racemic or enantiomerically pure alcohols can be converted with high yield into enantiopure chiral amines in a one-pot redox-neutral cascade process by the clever combination of an alcohol dehydrogenase and an appropriate amine dehydrogenase.

2015 Nobel Prize in Physiology or Medicine: Punishing parasites   p949
Stephen Davey
doi:10.1038/nchem.2411

Domino reactions: More than just a game   pp950 - 951
Thomas Broja, Patrick J. W. Fuchs and Kirsten Zeitler
doi:10.1038/nchem.2402
Catalytic methods are among the most valuable tools for sustainable synthesis. Domino catalysis enables multiple reactions to be combined so that synthetic efficiency may begin to approach that of nature, but significant challenges remain before this promising approach can fulfil the needs of pharmaceutical and materials chemistry.

Chemistry
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Perspective

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Recent advances in the molecular design of synthetic vaccines   pp952 - 960
Lyn H. Jones
doi:10.1038/nchem.2396



Synthetic vaccines offer one method to avoid the drawbacks associated with vaccines derived from whole organisms. This Perspective highlights the improvements and significant recent progress that has been achieved in developing well-defined synthetic vaccines using a variety of molecular antigens.

Articles

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Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy   pp961 - 967
James P. Hall, Fergus E. Poynton, Páraic M. Keane, Sarah P. Gurung, John A. Brazier et al.
doi:10.1038/nchem.2369



Uncertainty associated with solution-based electron-transfer studies of DNA–metal-complex systems has now been overcome by combining X-ray and time-resolved infrared data obtained for ruthenium polypyridyl–DNA crystals. Using these methods both the geometry of the reaction site and the kinetics of the reversible photo-induced one-electron oxidation of guanine have been determined.

Inhibition of human copper trafficking by a small molecule significantly attenuates cancer cell proliferation   pp968 - 979
Jing Wang, Cheng Luo, Changliang Shan, Qiancheng You, Junyan Lu et al.
doi:10.1038/nchem.2381



Copper is a transition metal ion essential for the regulation of cellular oxidative stress and ATP production. Now, the inhibition of copper-trafficking proteins by a small molecule has been shown to significantly reduce proliferation of cancer cells. The results indicate that copper-trafficking proteins could represent new anti-tumour therapeutic targets.
Chemical compounds

Local vibrational coherences drive the primary photochemistry of vision   pp980 - 986
Philip J. M. Johnson, Alexei Halpin, Takefumi Morizumi, Valentyn I. Prokhorenko, Oliver P. Ernst et al.
doi:10.1038/nchem.2398



The isomerization of the retinal chromophore of rhodopsin is the photochemical process that initiates the sense of vision. Now, heterodyne-detected transient grating spectroscopy has been used to resolve coherent vibrational dynamics during this process, helping to identify strictly local vibrational motions as the origin of the coherent surface crossing, which occurs on a sub-50-fs timescale.

See also: News and Views by Mathies

A manganese catalyst for highly reactive yet chemoselective intramolecular C(sp3)–H amination   pp987 - 994
Shauna M. Paradine, Jennifer R. Griffin, Jinpeng Zhao, Aaron L. Petronico, Shannon M. Miller et al.
doi:10.1038/nchem.2366



A manganese catalyst is reported that aminates C–H bonds via a mechanism that lies between that of reactive noble metals (concerted) and chemoselective base metals (stepwise). Rather than exhibiting intermediate reactivity and selectivity, [Mn(tBuPc)] is an outlier, and aminates all C(sp3)–H bonds, including 1°, while remaining tolerant of oxidizable p-functionality.
Chemical compounds

Reconstitution of [Fe]-hydrogenase using model complexes   pp995 - 1002
Seigo Shima, Dafa Chen, Tao Xu, Matthew D. Wodrich, Takashi Fujishiro et al.
doi:10.1038/nchem.2382



[Fe]-hydrogenase has an iron-guanylylpyridinol cofactor and catalyses the reversible hydrogenation of a methenyl-tetrahydromethanopterin. Now, [Fe]-hydrogenase has been reconstituted using synthetic cofactor mimics. The enzyme containing a mimic with a 2-hydroxy-pyridine group was active, whereas one containing a 2-methoxy-pyridine group was inactive. This result, together with DFT computations, supports a catalytic mechanism involving the deprotonated pyridinol hydroxy group as a proton acceptor.

Quantitative self-assembly of a purely organic three-dimensional catenane in water   pp1003 - 1008
Hao Li, Huacheng Zhang, Aaron D. Lammer, Ming Wang, Xiaopeng Li et al.
doi:10.1038/nchem.2392



Purely organic molecules with complex interlocked architectures have proved difficult to prepare in water. Now, a three-dimensional organic [2]catenane has been obtained in a weakly acidic aqueous solution, through an almost quantitative self-assembly process relying on dynamic hydrazone linkages. The catenane is kinetically stable in neutral and weakly basic environments.
Chemical compounds
See also: News and Views by Bai & Zhao

A steric tethering approach enables palladium-catalysed C–H activation of primary amino alcohols   pp1009 - 1016
Jonas Calleja, Daniel Pla, Timothy W. Gorman, Victoriano Domingo, Benjamin Haffemayer et al.
doi:10.1038/nchem.2367



The functionalization of primary amines by C–H activation is often hindered by their strong metal-coordinating properties. Now, a steric tethering approach — which temporarily converts amino alcohols into hindered secondary amines — has been developed. The approach allows these amino alcohols to be transformed into structurally complex and diverse products using palladium-catalysed aliphatic C–H activation.
Chemical compounds

A labile hydride strategy for the synthesis of heavily nitridized BaTiO3   pp1017 - 1023
Takeshi Yajima, Fumitaka Takeiri, Kohei Aidzu, Hirofumi Akamatsu, Koji Fujita et al.
doi:10.1038/nchem.2370



Oxynitrides are garnering interest because of their variety of novel properties, but their synthesis has typically involved highly reducing conditions that put significant constraints on their composition, structure and properties. Now, the lability of H in perovskite oxyhydride BaTiO3−xHx has enabled H–/N3– exchange at a lower temperature, yielding a ferroelectric oxynitride BaTiO3−xN2x/3.

Diastereoselective addition of Grignard reagents to α-epoxy N-sulfonyl hydrazones   pp1024 - 1027
Maulen M. Uteuliyev, Thien T. Nguyen and Don M. Coltart
doi:10.1038/nchem.2364



α-Substituted-β-hydroxy ketones are valuable intermediates, but their preparation by alkylation of enolates is difficult with hindered electrophiles. Now, a direct method for preparing α-substituted-β-hydroxy ketones — including those having α-quaternary centres — by addition of Grignard reagents to epoxyhydrazones has been developed, enabling the stereocontrolled incorporation of a wide range of carbon based substituents.
Chemical compounds

Efficient green methanol synthesis from glycerol   pp1028 - 1032
Muhammad H. Haider, Nicholas F. Dummer, David W. Knight, Robert L. Jenkins, Mark Howard et al.
doi:10.1038/nchem.2345



Impure glycerol is obtained as a significant by-product of biodiesel production. Now it is shown that this crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low pressure process.

Erratum

Top

Erratum: The essential role of charge-shift bonding in hypervalent prototype XeF2   p1033
Benoit Braida and Philippe C. Hiberty
doi:10.1038/nchem.2394

Corrigendum

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Corrigendum: Organocatalytic removal of formaldehyde adducts from RNA and DNA bases   p1033
Saswata Karmakar, Emily M. Harcourt, David S. Hewings, Florian Scherer, Alexander F. Lovejoy et al.
doi:10.1038/nchem.2401

In Your Element

Top

Rubidium round-the-clock   p1034
Iulia Georgescu
doi:10.1038/nchem.2407
Iulia Georgescu explains why rubidium is atomic physicists' favourite chemical element.

Correction

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Correction   p1034
doi:10.1038/nchem.2404

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