Thursday, October 22, 2015

Nature Chemistry Contents November 2015 Volume 7 Number 11 pp 855 - 940

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Nature Chemistry

TABLE OF CONTENTS

November 2015 Volume 7, Issue 11

Thesis
News and Views
Perspective
Articles
In Your Element


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Thesis

Top

Hard-luck Scheele   pp855 - 856
Bruce C. Gibb
doi:10.1038/nchem.2379
Carl Wilhelm Scheele had a hand in the discovery of at least six elements and contributed to the early development of chemistry in numerous other ways. Bruce Gibb looks into Scheele's story and considers why he doesn't get the credit that he deserves.

News and Views

Top

Fullerene stability: One rule for the electron-rich...   pp857 - 858
Patrick Fowler
doi:10.1038/nchem.2380
A vast number of possible isomers exist for each fullerene, yet few are observed experimentally. Neutral fullerenes typically minimize adjacent pentagons, but charged ones often tolerate them. Now, a simple model taking into account structural strain and π electronic aspects predicts the asymmetric relative stabilities of charged isomers.

See also: Article by Wang et al.

Foldamers: Biomimetic and built to order   pp858 - 859
W. Seth Horne
doi:10.1038/nchem.2385
Synthetic oligomers could potentially expand beyond the functions offered by proteins and nucleic acids. However, this requires precise methods for controlling their folding and self-assembly. Now, it is shown that two drastically different supramolecular architectures can be fabricated from closely related sequences using a single biomimetic scaffold.

See also: Article by Collie et al.

Natural products: Emulation illuminates biosynthesis   pp860 - 861
Jaron A. M. Mercer and Noah Z. Burns
doi:10.1038/nchem.2377
A concise synthesis of the fungal natural product epicolactone suggests that this highly stereochemically complex yet racemic natural product may come from a cascade reaction between two polyhydroxylated arenes.

See also: Article by Ellerbrock et al.

Light harvesting: Strike while the iron is cold   pp861 - 862
Elena Galoppini
doi:10.1038/nchem.2373
For many years, chemists have tried and failed to find efficient light-harvesting molecules based on Earth-abundant, environmentally friendly iron. Now, an iron complex has been developed with photoluminescent properties that are tuned to efficiently convert light to electrons.

See also: Article by Harlang et al.

Chemistry
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Perspective

Top

Palladium-catalysed norbornene-mediated C-H functionalization of arenes   pp863 - 870
Juntao Ye and Mark Lautens
doi:10.1038/nchem.2372



C-H functionalization of organic compounds is an ideal yet challenging approach to organic synthesis. This Perspective covers the most recent developments concerning the palladium-catalysed norbornene-mediated C-H functionalization of arenes, including applications of these methodologies in natural products synthesis. Challenges as well as opportunities for future studies are also presented.

Articles

Top

Shaping quaternary assemblies of water-soluble non-peptide helical foldamers by sequence manipulation   pp871 - 878
Gavin W. Collie, Karolina Pulka-Ziach, Caterina M. Lombardo, Juliette Fremaux, Frédéric Rosu et al.
doi:10.1038/nchem.2353



The self-assembly of short amphiphilic a-helicomimetic foldamers bearing proteinaceous side-chains can be controlled by manipulating the side-chain sequence. This enables the foldamers to be programmed to form either discrete helical bundles containing isolated cavities, or pH-responsive water-filled channels with controllable pore diameters.

See also: News and Views by Horne

An eight-step synthesis of epicolactone reveals its biosynthetic origin   pp879 - 882
Pascal Ellerbrock, Nicolas Armanino, Marina K. Ilg, Robert Webster and Dirk Trauner
doi:10.1038/nchem.2336



Analysis of the structure of the highly complex yet racemic secondary metabolite epicolactone suggests that it may arise biosynthetically from a cascade similar to that which produces purpurogallin. This led to a synthesis of epicolactone in only eight steps using an intricate reaction cascade.
Chemical compounds
See also: News and Views by Mercer & Burns

Iron sensitizer converts light to electrons with 92% yield   pp883 - 889
Tobias C. B. Harlang, Yizhu Liu, Olga Gordivska, Lisa A. Fredin, Carlito S. Ponseca, Jr et al.
doi:10.1038/nchem.2365



Using iron instead of the scarce ruthenium in light-harvesting complexes is challenging because iron complexes generally have short-lived excited states. Now an iron complex has been developed that has a long-lived excited state, which can lead to photo-induced electron injection into nanoporous TiO2 with a yield of 92%.
Chemical compounds
See also: News and Views by Galoppini

Unidirectional rotary motion in achiral molecular motors   pp890 - 896
Jos C. M. Kistemaker, Peter Štacko, Johan Visser and Ben L. Feringa
doi:10.1038/nchem.2362



Avoiding equal probability for clockwise and anticlockwise rotation is essential for the function of molecular motors, and both biological and synthetic systems take advantage of chirality to control the rotary direction. Now it has been shown, by integrating two rotor moieties in a symmetric meso motor design, that light-driven unidirectional rotary motion can be achieved in an achiral system.
Chemical compounds

Co-assembly, spatiotemporal control and morphogenesis of a hybrid protein–peptide system   pp897 - 904
Karla E. Inostroza-Brito, Estelle Collin, Orit Siton-Mendelson, Katherine H. Smith, Amàlia Monge-Marcet et al.
doi:10.1038/nchem.2349



Amphiphilic-peptide-driven opening of elastin-like protein molecules triggers the self-assembly of a multilayered membrane. This dynamic system can undergo morphogenesis into hierarchically ordered tubular structures that can be used to create complex scaffolds for tissue engineering.

Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts   pp905 - 912
Hong Xu, Jia Gao and Donglin Jiang
doi:10.1038/nchem.2352



Covalent organic frameworks (COFs) feature periodic layers and ordered pores that make them promising for applications in catalysis, but they typically suffer from poor stability. Now, adding methoxy groups to its pore walls has been shown to strengthen a COF's interlayer interactions, resulting in a stable, crystalline, porous material that can be further converted into chiral organocatalysts.

O-GlcNAc modification blocks the aggregation and toxicity of the protein α-synuclein associated with Parkinson's disease   pp913 - 920
Nicholas P. Marotta, Yu Hsuan Lin, Yuka E. Lewis, Mark R. Ambroso, Balyn W. Zaro et al.
doi:10.1038/nchem.2361



O-linked N-acetyl-glucosamine (O-GlcNAc) has been identified as an endogenous modification of α-synuclein; however, its effect on the properties of the protein is unclear. Now, recombinant protein and synthetic peptides have been combined to produce both unmodified and site-specifically O-GlcNAc-modified a-synuclein. The O-GlcNAc modification at threonine 72 was shown to inhibit the aggregation and associated toxicity of α-synuclein.

Molecular hydrogen interacts more strongly when rotationally excited at low temperatures leading to faster reactions   pp921 - 926
Yuval Shagam, Ayelet Klein, Wojciech Skomorowski, Renjie Yun, Vitali Averbukh et al.
doi:10.1038/nchem.2359



The rotational state of a molecule is not generally considered to play a role in how fast it reacts; however, when the temperature is low quantum effects become more important. Now, it is shown that at low temperatures rotationally excited H2 molecules react with He faster than non-rotating ground-state molecules — a process mediated by stronger long-range attraction.

Cage connectivity and frontier π orbitals govern the relative stability of charged fullerene isomers   pp927 - 934
Yang Wang, Sergio Díaz-Tendero, Manuel Alcamí and Fernando Martín
doi:10.1038/nchem.2363



The stability of charged fullerenes is not as well understood as that of their neutral counterparts, with, for example, more frequent violations of the isolated-pentagon and pentagon-adjacency penalty rules. Now, a simple model based on the concepts of cage connectivity and frontier π orbitals predicts the relative stability of cationic and anionic fullerene isomers.

See also: News and Views by Fowler

Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids   pp935 - 939
Mireia Sidera and Stephen P. Fletcher
doi:10.1038/nchem.2360



Cross-couplings between boronic acids and halides are a mainstay of synthetic organic chemistry but enantioselective Csp2–Csp3 couplings are rare, and simply retaining the stereochemistry of the starting material is problematic. Now, it is shown that racemic allylic halides can converted to single enantiomer products by a rhodium(I)-catalysed asymmetric allylic arylation using arylboronic acids
Chemical compounds

In Your Element

Top

Strontium's scarlet sparkles   p940
Francois-Xavier Coudert
doi:10.1038/nchem.2376
From sugar beets to TV screens, François-Xavier Coudert explores the history, applications and perils of the Scottish element, strontium

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