Thursday, July 23, 2015

Nature Chemistry Contents July 2015 Volume 8 Number 7 pp 611 - 680

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Nature Chemistry

TABLE OF CONTENTS

August 2015 Volume 7, Issue 8

Thesis
Research Highlights
Blogroll
News and Views
Articles
In Your Element


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Thesis

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Stretching the comfort zone   pp611 - 612
Bruce C. Gibb
doi:10.1038/nchem.2312
Bruce C. Gibb is organizing a workshop for two groups of scientists that study a similar topic, but rarely get together. The different perspectives they bring and the unusual set up of the meeting will hopefully lead to new ideas, but, as he suggests, they will also lead to the attendees leaving their comfort zones.

Research Highlights

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Polymer chemistry: Put a ring on it | Metal-metal bonding: Zinc on the line | Energy storage: Better together | Tetrahydrofuran synthesis: Carbene reaction re-routed

Blogroll

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Blogroll: Chemistry education   p615
Michael Seery
doi:10.1038/nchem.2309

News and Views

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Perovskite solar cells: Brighter pieces of the puzzle   pp616 - 617
Udo Bach
doi:10.1038/nchem.2310
Hybrid organic-inorganic lead halide perovskites have recently emerged as ground-breaking photovoltaic materials. A recent confocal fluorescence microscopy study now raises hopes that perovskite solar cells can reach efficiencies beyond the recent record of 20%.

Synthetic biology: Six pack and stack   pp617 - 619
Cheulhee Jung and Andrew D. Ellington
doi:10.1038/nchem.2313
A pair of artificial DNA bases have now been shown to adopt an edge-to-edge geometry in DNA which is similar that found in Watson-Crick base pairing. Aptamers containing these bases have also been shown to bind more strongly to a target than those developed using only the four naturally occurring bases.

Cheminformatics: Computing target complexity   pp619 - 620
Johann Gasteiger
doi:10.1038/nchem.2311
How complex is it to synthesize a given molecular target? Can this be answered by a computer? Now, a model of synthetic complexity that factors in methodology developments has resulted in a complexity index that evolves alongside them.

Charge transfer: Interfering with interference   pp621 - 622
Gemma C. Solomon
doi:10.1038/nchem.2314
Molecules can transfer charge between electron donors and acceptors, and can also transport charge when connected between metallic electrodes. These processes are assumed to show generally similar trends, however, a significant departure from this has now been observed in a series of biphenyl bridges.

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Articles

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On-surface generation and imaging of arynes by atomic force microscopy   pp623 - 628
Niko Pavliček, Bruno Schuler, Sara Collazos, Nikolaj Moll, Dolores Pérez et al.
doi:10.1038/nchem.2300



Based initially on the outcome of certain reactions but later backed up by spectroscopic evidence, chemists have proposed — for more than a century — the existence of arynes as extremely reactive intermediates in chemical transformations. Now, with the help of atomic force microscopy, it is finally possible to generate and directly visualize this elusive intermediate.
Chemical compounds

Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]2+   pp629 - 633
Gerald Auböck and Majed Chergui
doi:10.1038/nchem.2305



Fe(II) complexes display transitions between spin states that can be triggered externally. Now the light-induced ΔS = 2 transition upon excitation of the metal-to-ligand charge-transfer states of Fe(II)-polypyridine complexes has been investigated at high time-resolution in the visible and the ultraviolet range. It has been shown to occur in less than 50 fs — that is, on a sub-vibrational timescale.

Photoinduced reversible switching of porosity in molecular crystals based on star-shaped azobenzene tetramers   pp634 - 640
Massimo Baroncini, Simone d'Agostino, Giacomo Bergamini, Paola Ceroni, Angiolina Comotti et al.
doi:10.1038/nchem.2304



Rigid star-shaped azobenzene tetramers form a porous molecular crystal when the azobenzene moieties are in the trans configuration, and a non-porous amorphous material on their isomerization to the cis configuration. These two forms are reversibly interconverted in the solid state by light irradiation, thus enabling the photoswitching of optical and gas-capture properties.
Chemical compounds

Diels–Alderase-free, bis-pericyclic, [4+2] dimerization in the biosynthesis of (±)-paracaseolide A   pp641 - 645
Tao Wang and Thomas R. Hoye
doi:10.1038/nchem.2281



The facile, spontaneous dimerization of a simple alkenylbutenolide monomer is relevant to the biosynthesis of racemic paracaseolide A. As supported by computation, a fully (C2-)symmetric, bis-pericyclic Diels–Alder cycloaddition transition state structure is invoked to account for the atypical exo-selectivity and room-temperature reactivity.
Chemical compounds

Light-controlled self-assembly of non-photoresponsive nanoparticles   pp646 - 652
Pintu K. Kundu, Dipak Samanta, Ron Leizrowice, Baruch Margulis, Hui Zhao et al.
doi:10.1038/nchem.2303



Controlling the self-assembly of nanoparticles using light has been demonstrated in many systems where the particle surfaces are functionalized with photoswitchable ligands. Now, it has been shown that the light-controlled self-assembly of non-photoresponsive nanoparticles can be achieved in a quantitative and reversible fashion by placing them in a photoresponsive medium.

Enzymatic hydroxylation of an unactivated methylene C–H bond guided by molecular dynamics simulations   pp653 - 660
Alison R. H. Narayan, Gonzalo Jiménez-Osés, Peng Liu, Solymar Negretti, Wanxiang Zhao et al.
doi:10.1038/nchem.2285



The reactivity of a monooxygenase (P450 PikC) has been modified through protein and substrate engineering, and applied to the oxidation of unactivated methylene C–H bonds. The protein engineering was guided by using molecular dynamics and quantum mechanical calculations to develop a predictive model for substrate scope, site selectivity and stereoselectivity of the C–H hydroxylation.

Quantum interference between H + D2 quasiclassical reaction mechanisms   pp661 - 667
Pablo G. Jambrina, Diego Herráez-Aguilar, F. Javier Aoiz, Mahima Sneha, Justinas Jankunas et al.
doi:10.1038/nchem.2295



Often reactions can be described by classical mechanics; however, this is prohibited in cases in which quantum phenomena emerge. Now angular distributions measured for the H + D2 reaction have been seen to display characteristic oscillation patterns in backward scattering — theory shows that they are caused by quantum interferences between classical mechanisms similar to those found in the double-slit experiment.

An oxazetidine amino acid for chemical protein synthesis by rapid, serine-forming ligations   pp668 - 672
Ivano Pusterla and Jeffrey W. Bode
doi:10.1038/nchem.2282



The total chemical synthesis of large proteins requires the development of methodology that rapidly couples unprotected peptide fragments. Here a highly strained four-membered-ring amino acid is described that enables such couplings by the formation of serine residues.
Chemical compounds

Optimization of a whole-cell biocatalyst by employing genetically encoded product sensors inside nanolitre reactors   pp673 - 678
Andreas Meyer, René Pellaux, Sébastien Potot, Katja Becker, Hans-Peter Hohmann et al.
doi:10.1038/nchem.2301



A method for high-throughput analysis of whole-cell biocatalysts for industrial biotechnology has been developed. The process relies on a combination of specifically tailored bacterial sensor cells that are incubated with biocatalyst variants within nanolitre-sized compartments. The product is secreted by the whole-cell biocatalysts and taken up by the sensor cells, which initiates a sequence of reactions that finish with the synthesis of green fluorescent protein.

In Your Element

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Magically magnetic gadolinium   p680
Pekka Pyykkö
doi:10.1038/nchem.2287
Pekka Pyykkö discusses the history and characteristics of gadolinium.

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