Table of contents



Chemical abstractions pp427 - 428

Michelle Francl


Michelle Francl wonders what abstract objects might be lurking in our beakers.

Subject term: General chemistry



Blogroll: Space dinosaurs! p431




Force microscopy takes charge p431



News and Views

Proton conduction: Hopping along hydrogen bonds pp432 - 433

Rodolphe Vuilleumier & Daniel Borgis


Proton conduction in both water and other hydrogen-bonded liquids occurs through successive proton transfers along the hydrogen-bond network. But first-principles simulations have revealed that the mechanism by which this occurs in orthophosphoric acid has some unusual features.

Subject terms: Physical chemistry | Theoretical chemistry

See also: Article by Vilčiauskas et al.

Flow chemistry: A light touch to a deadly problem pp433 - 435

Kevin Booker-Milburn


Flow chemistry has grown in stature as a technique with the potential to deliver synthetic complexity with assembly-line-like efficiency. Application of flow technology to the front-line antimalarial drug artemisinin promises to revolutionalize treatment.

Subject terms: Organic chemistry | Synthesis

Self-repairing polymers: Materials that heal themselves pp435 - 436

Howard M. Colquhoun


Previous approaches to the development of self-repairing polymeric materials have required either the input of external energy or the use of a healing agent. Now, a new type of elastomer, in which hard/soft phase-separation occurs at the nanoscale, displays efficient and entirely autonomic self-repair through reversible hydrogen bonding.

Subject terms: Materials chemistry | Polymer chemistry

See also: Article by Chen et al.

Enzyme mimics: Halogen and chalcogen team up pp437 - 438

Pierangelo Metrangolo & Giuseppe Resnati


The behaviour of di-selenol enzyme mimics indicates that a halogen bond between selenium and iodine, and a chalcogen interaction between the two selenium atoms, play an important role in the activation of thyroid hormones.

Subject terms: Chemical biology | Supramolecular chemistry

Asymmetric catalysis: The power of pairing pp438 - 439

Hajime Ito


Supramolecular catalysts that combine an anionic chiral scaffold, a cationic coordinating structure and a metal centre have been shown to be highly effective for asymmetric synthesis. The success opens a new avenue for the design of new catalysts with a wide variety of chiral environments.

Subject terms: Catalysis | Synthesis

See also: Article by Ohmatsu et al.

Fluorescent sensors: Bright ideas pp440 - 441

A. Prasanna de Silva


Sensing neuronal activity using fluorescence has many potential advantages over current methods. Now, by taking advantage of photoinduced electron transfer, fluorescent sensors have been developed that allow high-fidelity recording of neural signals in real time.

Subject terms: Photochemistry | Chemical biology

Alkaloid synthesis: Indolizidines with ease pp441 - 442

Peter Shapland


A dihydroboration–amination sequence provides a step-economical route to indolizidine alkaloids — a common structure in bioactive natural products.

Subject terms: Organic chemistry | Synthesis



The gold–sulfur interface at the nanoscale pp443 - 455

Hannu Häkkinen


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Thiolate-protected gold surfaces and interfaces are archetypal systems in various fields of current research in nanoscience, materials science, inorganic chemistry and surface science. Examples include self-assembled monolayers of organic molecules on gold, passivated gold nanoclusters and molecule–gold junctions. This Review discusses recent experimental and theoretical breakthroughs that highlight common features of gold-sulfur bonding in these systems.

Subject terms: Nanotechnology | Surface chemistry



Metal–organic frameworks with dynamic interlocked components pp456 - 460

V. Nicholas Vukotic, Kristopher J. Harris, Kelong Zhu, Robert W. Schurko & Stephen J. Loeb


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The dynamics of mechanically interlocked molecules such as catenanes and rotaxanes have been studied in solution as examples of rudimentary molecular switches and machines. A metal–organic framework with a [2]rotaxane as a building block demonstrates that such dynamic processes can also operate inside a solid-state material.

Subject terms: Materials chemistry | Supramolecular chemistry

The mechanism of proton conduction in phosphoric acid pp461 - 466

Linas Vilčiauskas, Mark E. Tuckerman, Gabriel Bester, Stephen J. Paddison & Klaus-Dieter Kreuer


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Proton transport in phosphate-based systems is important in biology and clean energy technologies, and phosphoric acid, being the best known intrinsic proton conductor, represents an important model. Ab initio molecular dynamics simulations now reveal that the interplay between extended, polarized, hydrogen-bonded chains and a frustrated hydrogen-bond network gives rise to the high conductivity in liquid phosphoric acid.

Subject terms: Physical chemistry | Theoretical chemistry

See also: News and Views by Vuilleumier & Borgis

Multiphase design of autonomic self-healing thermoplastic elastomers pp467 - 472

Yulin Chen, Aaron M. Kushner, Gregory A. Williams & Zhibin Guan


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Polymer materials that could spontaneously heal like tissues in living systems would significantly improve the safety, lifetime, energy efficiency and environmental impact of man-made materials. Now, a general multiphase design of autonomous self-healing elastomeric materials that do not require the input of external energy or healing agents is reported.

Subject terms: Materials chemistry | Polymer chemistry

See also: News and Views by Colquhoun

Ion-paired chiral ligands for asymmetric palladium catalysis pp473 - 477

Kohsuke Ohmatsu, Mitsunori Ito, Tomoatsu Kunieda & Takashi Ooi


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Rather than create a chiral catalyst by combining a chiral ligand with a metal, here an achiral phosphine ligand endowed with a cationic ammonium group is ion-paired with a chiral binaphtholate. A palladium catalyst based on this strategy is shown to be effective for highly enantioselective allylic alkylation of α-nitrocarboxylates.

Subject terms: Catalysis | Synthesis

See also: News and Views by Ito

Engineering methylaspartate ammonia lyase for the asymmetric synthesis of unnatural amino acids pp478 - 484

Hans Raj, Wiktor Szymański, Jandré de Villiers, Henriëtte J. Rozeboom, Vinod Puthan Veetil, Carlos R. Reis, Marianne de Villiers, Frank J. Dekker, Stefaan de Wildeman, Wim J. Quax, Andy-Mark W. H. Thunnissen, Ben L. Feringa, Dick B. Janssen & Gerrit J. Poelarends


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Substituted aspartic acids are highly valuable as tools for biological research and as chiral building blocks for pharmaceuticals. Here, engineering of the enzyme methylaspartate ammonia lyase to accept a large variety of substituted amines and fumarates and catalyse the asymmetric synthesis of aspartic acid derivatives is described.

Subject terms: Catalysis | Chemical biology | Synthesis

Light-triggered self-construction of supramolecular organic nanowires as metallic interconnects pp485 - 490

Vina Faramarzi, Frédéric Niess, Emilie Moulin, Mounir Maaloum, Jean-François Dayen, Jean-Baptiste Beaufrand, Silvia Zanettini, Bernard Doudin & Nicolas Giuseppone


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Triarylamine derivatives in solution have been self-assembled into organic nanowires between two electrodes, under white-light irradiation and in the presence of a voltage. The resulting fibres possess a very high electric conductivity as well as a metallic behaviour when cooled down to a temperature of 1.5 K.

Subject terms: Materials chemistry | Supramolecular chemistry

Biomimetic radical polymerization via cooperative assembly of segregating templates pp491 - 497

Ronan McHale, Joseph P. Patterson, Per B. Zetterlund & Rachel K. O'Reilly


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Nature synthesizes proteins and nucleic acids by polymerization methods that use well-regulated and segregated templates. Now, synthetic block-copolymer templates have been designed to assemble in a biomimetic fashion to segregate, and thus control, the synthetic radical polymerization of complementary nucleobase-containing vinyl monomers, to yield high-molecular-weight, low-polydispersity polymer chains.

Subject terms: Materials chemistry | Polymer chemistry

A soluble copper–bipyridine water-oxidation electrocatalyst pp498 - 502

Shoshanna M. Barnett, Karen I. Goldberg & James M. Mayer


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Copper and bipyridine (bpy) self-assemble in aqueous solutions at high pH into an active electrocatalyst for the oxidation of water to O2, one of the great challenges in energy catalysis. These solutions contain primarily (bpy)Cu(OH)2, and are robust and active catalysts, albeit at high overpotentials.

Subject terms: Catalysis | Inorganic chemistry | Electrochemistry

Acyclic cucurbit[n]uril molecular containers enhance the solubility and bioactivity of poorly soluble pharmaceuticals pp503 - 510

Da Ma, Gaya Hettiarachchi, Duc Nguyen, Ben Zhang, James B. Wittenberg, Peter Y. Zavalij, Volker Briken & Lyle Isaacs


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Acyclic cucurbituril-type molecular containers have been found to increase the solubility of insoluble pharmaceutical agents in water by up to 2,750-fold. In vitro and in vivo toxicology studies suggest that the containers are well tolerated, and paclitaxel solubilized in this manner efficiently kills HeLa and SK-OV-3 cancer cells.

Subject terms: Medicinal chemistry | Supramolecular chemistry



Exchange-enhanced reactivity in bond activation by metal–oxo enzymes and synthetic reagents p511

Sason Shaik, Hui Chen & Deepa Janardanan



In Your Element

Ambiguous bromine p512

Matt Rattley


Many chemical elements behave quite differently depending on the compound they are found in, but Matt Rattley argues that bromine does so in a particularly striking manner.