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Editorial

A chemical century p603

doi:10.1038/nchem.2815

The launch of Nature Chemistry in 2009 prompted some criticism of journal proliferation, but 100 issues later this young offender has matured into an accepted part of the publishing landscape.


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Thesis

Pasteur and the art of chirality pp604 - 605

Joseph Gal

doi:10.1038/nchem.2790

Louis Pasteur was a scientific giant of the nineteenth century, but, as Joseph Gal asks, was his most famous contribution to the understanding of chemistry — chirality — influenced more by his artistic talents?


Identity crisis pp606 - 607

Michelle Francl

doi:10.1038/nchem.2807

Michelle Francl reminds us that you don't need to look like Einstein to be a scientist.


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News and Views

Polycyclic aromatic hydrocarbons: Synthesis successes pp608 - 609

Roser Valentí & Stephen M. Winter

doi:10.1038/nchem.2799

Disentangling the chemistry and physics behind reported unconventional superconductivity and exotic magnetism in alkali-intercalated PAHs has remained problematic due to the lack of phase-pure samples. Two synthetic pathways have now remedied this issue, facilitating studies of cooperative electronic properties based on carbon π-electrons.

See also: Article by Takabayashi et al. | Article by Romero et al.


Enzymatic catalysis: New functional twists for P450s pp609 - 611

Rudi Fasan

doi:10.1038/nchem.2810

Two papers provide insight into the reactivity of cytochrome P450s. A direct link between electron donation and reactivity has been shown with a selenocysteine-ligated P450 compound I, whereas a serine-ligated P450 (P411) has been engineered to catalyse an intermolecular C–H amination via nitrene transfer.

See also: Article by Onderko et al. | Article by Prier et al.


DNA nanotechnology: Bringing lipid bilayers into shape pp611 - 613

Stefan Howorka

doi:10.1038/nchem.2809

Lipid bilayers form the thin and floppy membranes that define the boundary of compartments such as cells. Now, a method to control the shape and size of bilayers using DNA nanoscaffolds has been developed. Such designer materials advance synthetic biology and could find use in membrane research.

See also: Article by Zhang et al.


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Articles

Cooperative polymerization of α-helices induced by macromolecular architecture pp614 - 622

Ryan Baumgartner, Hailin Fu, Ziyuan Song, Yao Lin & Jianjun Cheng

doi:10.1038/nchem.2712

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The secondary and tertiary structure of a protein has profound implications on function and catalysis. Now, both the secondary and tertiary structures of a synthetic polymer have been utilized to catalyse the polymerization of N-carboxyanhydrides. Both the folding of the resulting polypeptides into α-helices and their macromolecular organization dramatically enhance the polymerization rate.


Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity pp623 - 628

Elizabeth L. Onderko, Alexey Silakov, Timothy H. Yosca & Michael T. Green

doi:10.1038/nchem.2781

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The oxidative prowess of cytochrome P450s has been suggested to stem from the electron-donating axial ligand. Now, a selenocysteine-ligated P450 compound I has been trapped and characterized providing an avenue to examine this hypothesis. Measurements reveal that the selenolate-ligated compound I cleaves C–H bonds more rapidly than the wild-type equivalent.

See also: News and Views by Fasan


Enantioselective, intermolecular benzylic C–H amination catalysed by an engineered iron-haem enzyme pp629 - 634

Christopher K. Prier, Ruijie K. Zhang, Andrew R. Buller, Sabine Brinkmann-Chen & Frances H. Arnold

doi:10.1038/nchem.2783

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The intermolecular amination of C–H bonds is an enabling transformation for the synthesis of nitrogen-containing molecules; however, developing catalysts for this class of reactions is very challenging. Now, an iron-based enzyme for this reaction has been engineered, demonstrating that a protein can confer a difficult new function upon an otherwise unreactive base metal.

See also: News and Views by Fasan


π-electron S=½ quantum spin-liquid state in an ionic polyaromatic hydrocarbon pp635 - 643

Yasuhiro Takabayashi, Melita Menelaou, Hiroyuki Tamura, Nayuta Takemori, Takashi Koretsune, Aleš Štefančič, Gyöngyi Klupp, A. Johan C. Buurma, Yusuke Nomura, Ryotaro Arita, Denis Arčon, Matthew J. Rosseinsky & Kosmas Prassides

doi:10.1038/nchem.2764

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Cooperative electronic properties that arise purely from carbon π-electrons can lead to unconventional superconductivity and quantum magnetism. New packing architectures have now been established in two caesium-intercalated polyaromatic hydrocarbons, CsPhenanthrene and Cs2Phenanthrene, both strongly correlated multi-orbital Mott insulators. The frustrated magnetic topology in CsPhenanthrene also renders it a spin-½ quantum spin liquid candidate.

See also: Article by Romero et al. | News and Views by Valentí & Winter


Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids pp644 - 652

F. Denis Romero, M. J. Pitcher, C. I. Hiley, G. F. S. Whitehead, S. Kar, A. Y. Ganin, D. Antypov, C. Collins, M. S. Dyer, G. Klupp, R. H. Colman, K. Prassides & M. J. Rosseinsky

doi:10.1038/nchem.2765

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Reports of superconductivity in KxPicene spurred interest in alkali-intercalated polyaromatic hydrocarbon (PAH) compounds, but their compositions and structures have remained unclear. Now crystalline K2Pentacene and K2Picene — neither of which are superconducting — have been prepared by mild synthesis. Structural analysis shows that the cation sites arise within the molecular layers from reorientation of the PAHs within a herringbone packing.

See also: Article by Takabayashi et al. | News and Views by Valentí & Winter


Placing and shaping liposomes with reconfigurable DNA nanocages pp653 - 659

Zhao Zhang, Yang Yang, Frederic Pincet, Marc C. Llaguno & Chenxiang Lin

doi:10.1038/nchem.2802

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Controlling liposome shape, arrangement and dynamics is important for biophysical studies and synthetic biology applications. Now, using a family of reconfigurable DNA nanocages as templates, spherical, tubular, toroidal and helical liposomes with predefined geometry have been produced. DNA-guided membrane fusion and bending is also demonstrated.

See also: News and Views by Howorka


Probing the early stages of photoreception in photoactive yellow protein with ultrafast time-domain Raman spectroscopy pp660 - 666

Hikaru Kuramochi, Satoshi Takeuchi, Kento Yonezawa, Hironari Kamikubo, Mikio Kataoka & Tahei Tahara

doi:10.1038/nchem.2717

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Photoreceptors play an essential role in determining the fate of subsequent biological reactions, however, tracking their structural evolution on ultrafast timescales has been challenging. Now, photoactive yellow protein has been studied using time-domain Raman spectroscopy with sub-7-femtosecond pulses, revealing the ultrafast rearrangement of its hydrogen-bonding structure and also the structure of the first photocycle intermediate.


A synthetic ion transporter that disrupts autophagy and induces apoptosis by perturbing cellular chloride concentrations pp667 - 675

Nathalie Busschaert, Seong-Hyun Park, Kyung-Hwa Baek, Yoon Pyo Choi, Jinhong Park, Ethan N. W. Howe, Jennifer R. Hiscock, Louise E. Karagiannidis, Igor Marques, Vítor Félix, Wan Namkung, Jonathan L. Sessler, Philip A. Gale & Injae Shin

doi:10.1038/nchem.2706

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A squaramide-based anion transporter has now been shown to cause changes in the lysosomal pH leading to impairment of lysosomal enzyme activity and disruption of autophagic processes. The study provides the first experimental evidence that synthetic ion transporters can both disrupt autophagy and induce apoptosis.


One-thousand-fold enhancement of high field liquid nuclear magnetic resonance signals at room temperature pp676 - 680

Guoquan Liu, Marcel Levien, Niels Karschin, Giacomo Parigi, Claudio Luchinat & Marina Bennati

doi:10.1038/nchem.2723

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The analysis of complex (bio)molecules by NMR spectroscopy is often complicated by limitations in sensitivity. Now, it has been shown that 13C NMR signals are strongly enhanced in solution by resonant microwave irradiation of a nitroxide polarizer. This method exhibits up to one-thousand-fold improvements in sensitivity, which stands to greatly improve the detail with which small molecules and metabolites can be studied.


Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds pp681 - 688

Hongyin Gao, Zhe Zhou, Doo-Hyun Kwon, James Coombs, Steven Jones, Nicole Erin Behnke, Daniel H. Ess & László Kürti

doi:10.1038/nchem.2672

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The direct transfer of primary amino and hydroxyl groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge. Here, it is demonstrated that bench-stable N–H and N–alkyl oxaziridines can be used as efficient multifunctional reagents, without deprotonation, for the direct primary amination and hydroxylation of (hetero)arylmetals.


Hypersensitive dual-function luminescence switching of a silver-chalcogenolate cluster-based metal–organic framework pp689 - 697

Ren-Wu Huang, Yong-Sheng Wei, Xi-Yan Dong, Xiao-Hui Wu, Chen-Xia Du, Shuang-Quan Zang & Thomas C. W. Mak

doi:10.1038/nchem.2718

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The properties of discrete species can sometimes be improved by fixing them into extended materials. This strategy has now been applied to silver(I) chalcogenide/chalcogenolate clusters, resulting in a metal–organic framework with enhanced stability and fluorescent sensing capabilities. Crystallographic analysis allows precise structural determination of guest binding, which is responsible for both emission turn-off and multicoloured turn-on.


Post-translational modification of ribosomally synthesized peptides by a radical SAM epimerase in Bacillus subtilis pp698 - 707

Alhosna Benjdia, Alain Guillot, Pauline Ruffié, Jérôme Leprince & Olivier Berteau

doi:10.1038/nchem.2714

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Radical SAM enzymes are versatile enzymes catalysing chemically challenging reactions. Now, a radical SAM enzyme that post-translationally modifies ribosomally synthesized peptides to contain D-amino acids has been discovered in Bacillus subtilis, and its mechanism has been deciphered. These peptides, called epipeptides, efficiently inhibit bacterial growth.


Observation of electron-transfer-mediated decay in aqueous solution pp708 - 714

Isaak Unger, Robert Seidel, Stephan Thürmer, Marvin N. Pohl, Emad F. Aziz, Lorenz S. Cederbaum, Eva Muchová, Petr Slavíček, Bernd Winter & Nikolai V. Kryzhevoi

doi:10.1038/nchem.2727

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Electron-transfer-mediated decay (ETMD) is a recently discovered type of electronic relaxation that involves the refilling of a core hole by an electron from a neighbouring species. It has now been observed in LiCl solution, when previously it had only been seen in rare-gas clusters. Spectra generated during ETMD are observed to be sensitive to the immediate environment of the initially ionized ion.


A polymer nanoparticle with engineered affinity for a vascular endothelial growth factor (VEGF165) pp715 - 722

Hiroyuki Koide, Keiichi Yoshimatsu, Yu Hoshino, Shih-Hui Lee, Ai Okajima, Saki Ariizumi, Yudai Narita, Yusuke Yonamine, Adam C. Weisman, Yuri Nishimura, Naoto Oku, Yoshiko Miura & Kenneth J. Shea

doi:10.1038/nchem.2749

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Abiotic hydrogel polymer nanoparticles with affinity for a key vascular endothelial growth factor (VEGF165) have now been developed. This high-protein affinity was engineered by carefully controlling the amount and the substitution pattern of sulfated N-acetylglucosamines and the inclusion of a hydrophobic group in the monomer.


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Erratum

Erratum: Tuning underwater adhesion with cation–π interactions p723

Matthew A. Gebbie, Wei Wei, Alex M. Schrader, Thomas R. Cristiani, Howard A. Dobbs, Matthew Idso, Bradley F. Chmelka, J. Herbert Waite & Jacob N. Israelachvili

doi:10.1038/nchem.2813


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Addendum

Addendum: Aldehydes as alkyl carbanion equivalents for additions to carbonyl compounds p723

Haining Wang, Xi-Jie Dai & Chao-Jun Li

doi:10.1038/nchem.2805


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In Your Element

Frantically forging fermium p724

Brett F. Thornton & Shawn C. Burdette

doi:10.1038/nchem.2806

Brett F. Thornton and Shawn C. Burdette relate how element 100 was first identified in a nuclear weapons test, but that was classified information, so researchers had to 'discover' it again using other methods.


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