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Thesis

Neolexia pp417 - 418

Michelle Francl

doi:10.1038/nchem.1056

Michelle Francl thinks that new science words should have a touch of swagger and a whiff of mystery.


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Books and Arts

The element in the room p419

Andrea Sella reviews Periodic Tales: The Curious Lives of the Elements by Hugh Aldersey-Williams

doi:10.1038/nchem.1061


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Research Highlights

Our choice from the recent literature pp420 - 421

doi:10.1038/nchem.1064


Blogroll: Dear chemists... p421

doi:10.1038/nchem.1065


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News and Views

Natural product synthesis: Making nematodes nervous pp422 - 423

Scott A Snyder

doi:10.1038/nchem.1059

A highly inventive route for the synthesis of a key substance that stimulates potato cyst nematodes to hatch has been developed. This discovery has potential to impact food supplies, as treatment of crops with this compound could alleviate the devastating effect of these parasites.

Subject terms: Organic chemistry | Synthesis

See also: Article by Tanino et al.


Photochemistry: Scrambled by the Sun? pp423 - 424

Michael N R Ashfold & David R Glowacki

doi:10.1038/nchem.1058

Isotopic labelling is widely used to unravel reaction mechanisms, but are conclusions from such studies always robust? Now, studies on the photolysis of CD3CHO reveal extensive isotopic scrambling before dissociation, which could have implications for our mechanistic understanding of some key aspects of atmospheric photochemistry.

Subject terms: Physical chemistry | Photochemistry

See also: Article by Heazlewood et al.


Conjugated polymers: Watching polymers dance pp425 - 426

Lewis Rothberg

doi:10.1038/nchem.1055

Single-molecule spectroscopy allows fluctuations of conjugated polymer conformation to be monitored during solvent vapour annealing. Dramatic changes in fluorescence behaviour are observed and interpreted in terms of transformations between extended and collapsed polymer geometries.

Subject terms: Polymer chemistry | Physical chemistry


Molecular magnetism: Uranium memory pp426 - 427

Marinella Mazzanti

doi:10.1038/nchem.1057

A diuranium compound featuring an arene bridge shows single-molecule-magnet behaviour, which could arise from a mechanism different from the traditional 'super-exchange' spin coupling.

Subject terms: Inorganic chemistry | Organometallic chemistry

See also: Article by Mills et al.


Microfluidics: Pensioning off pipettes pp428 - 429

Glenn M Walker

doi:10.1038/nchem.1060

A microfluidic device design that allows a nanolitre droplet to be trapped and sequentially diluted without the need for any moving parts opens up new possibilities in high-throughput screening.

Subject terms: Analytical chemistry | General chemistry

See also: Article by Niu et al.


Metal-organic frameworks: A porous maze pp429 - 430

David S Sholl

doi:10.1038/nchem.1054

Observing the diffusion of guest molecules in large single crystals of a metal-organic framework reveals surprising insights into the blockage of the channels at the material's surface and the role of defects within its bulk.

Subject term: Materials chemistry


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Perspective

Blueprinting macromolecular electronics pp431 - 436

Carlos-Andres Palma & Paolo Samorì

doi:10.1038/nchem.1043

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The efficient engineering of nanostructures with semiconducting properties is vital to the development of organic electronics. This Perspective discusses a variety of techniques for fabricating such macromolecules, including graphene carving, the stimulus-induced synthesis of conjugated polymers and surface-assisted synthesis, and considers their potential for reproducing chemically and spatially precise molecular arrangements, that is 'molecular blueprints'.

Subject terms: Surface chemistry | Nanotechnology | Physical chemistry


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Articles

A microdroplet dilutor for high-throughput screening pp437 - 442

Xize Niu, Fabrice Gielen, Joshua B. Edel & Andrew J. deMello

doi:10.1038/nchem.1046

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Droplet microfluidics offer a convenient platform for high-throughput experimentation. It has been difficult, however, to rapidly and controllably vary concentration — a key process used in macro-scale experiments. Here, a droplet dilution module is described that traps a mother droplet and then repeatedly dilutes it releasing a series of droplets that define a digital concentration gradient.

Subject terms: Analytical chemistry | General chemistry

See also: News and Views by Walker


Near-threshold H/D exchange in CD3CHO photodissociation pp443 - 448

Brianna R. Heazlewood, Alan T. Maccarone, Duncan U. Andrews, David L. Osborn, Lawrence B. Harding, Stephen J. Klippenstein, Meredith J. T. Jordan & Scott H. Kable

doi:10.1038/nchem.1052

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Unexpected and significant isotope exchange is observed in the near-threshold photodissociation of isopically labelled acetaldehyde. Theoretical modelling indicates that, at the lowest energies considered, an average of 20 H- or D-shifts occur before dissociation — evidence for extensive isomerization.

Subject terms: Physical chemistry | Photochemistry

See also: News and Views by Ashfold & Glowacki


Synthesis of conolidine, a potent non-opioid analgesic for tonic and persistent pain pp449 - 453

Michael A. Tarselli, Kirsten M. Raehal, Alex K. Brasher, John M. Streicher, Chad E. Groer, Michael D. Cameron, Laura M. Bohn & Glenn C. Micalizio

doi:10.1038/nchem.1050

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The first total synthesis of conolidine — representing the first asymmetric synthesis of a C5-nor-stemmadenine — is described. The chemical synthesis proceeds in just nine steps and gives an 18% overall yield from a commercially available pyridine — an achievement that led to the discovery that (+)-, (–)- and (±)-conolidine are potent non-opioid analgesics.

Subject terms: Medicinal chemistry | Organic chemistry | Synthesis


A delocalized arene-bridged diuranium single-molecule magnet pp454 - 460

David P. Mills, Fabrizio Moro, Jonathan McMaster, Joris van Slageren, William Lewis, Alexander J. Blake & Stephen T. Liddle

doi:10.1038/nchem.1028

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Single-molecule magnets (SMMs) are multinuclear clusters whose behaviour typically relies on intramolecular spin-coupling interactions between neighbouring metal ions. A diuranium–arene complex has now been prepared that shows behaviour characteristic of an SMM without relying on this type of superexchange mechanism. This may enable the construction of SMMs that maintain their magnetism at higher temperatures.

Subject terms: Inorganic chemistry | Organometallic chemistry

See also: News and Views by Mazzanti


Water-oxidation catalysis by manganese in a geochemical-like cycle pp461 - 466

Rosalie K. Hocking, Robin Brimblecombe, Lan-Yun Chang, Archana Singh, Mun Hon Cheah, Chris Glover, William H. Casey & Leone Spiccia

doi:10.1038/nchem.1049

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The development of an effective, cheap and robust water oxidation catalyst is crucial to the development of solar water-splitting technology. A manganese catalyst inspired by the water oxidizing centre of photosystem II is now shown to dissociate and reform into nanoparticles resembling the known natural oxidant mineral birnessite.

Subject terms: Catalysis | Inorganic chemistry


Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures pp467 - 472

Phillip Christopher, Hongliang Xin & Suljo Linic

doi:10.1038/nchem.1032

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High operating temperatures in heterogeneous catalytic processes compromise energy efficiency, catalyst lifetime and product selectivity. Plasmonic silver nanoparticles are shown to couple thermal energy and a low-intensity photon flux to drive commercially important oxidation reactions at lower temperatures than conventional thermal processes.

Subject terms: Photochemistry | Surface chemistry | Nanotechnology


Construction of bispirooxindoles containing three quaternary stereocentres in a cascade using a single multifunctional organocatalyst pp473 - 477

Bin Tan, Nuno R. Candeias & Carlos F. Barbas, III

doi:10.1038/nchem.1039

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Spirooxindoles are important structural motifs found in an array of bioactive compounds. Here a Michael–aldol domino reaction for the construction of bispirooxindoles is presented, creating four stereocentres, including three quaternary carbon centres. Novel multifunctional organocatalysts have been developed for this transformation.

Subject terms: Catalysis | Organic chemistry | Synthesis


Core@shell bimetallic nanoparticle synthesis via anion coordination pp478 - 483

Christopher J. Serpell, James Cookson, Dogan Ozkaya & Paul D. Beer

doi:10.1038/nchem.1030

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Bimetallic core@shell nanoparticles often have properties that are different from those of single-metal or alloy nanoparticles. Here, a route to such nanoparticles that binds the second metal to the core surface prior to reduction is described. The unique catalytic properties of the nanoparticles are demonstrated in the selective production of chloroaniline.

Subject terms: Catalysis | Nanotechnology | Synthesis


Total synthesis of solanoeclepin A pp484 - 488

Keiji Tanino, Motomasa Takahashi, Yoshihide Tomata, Hiroshi Tokura, Taketo Uehara, Takashi Narabu & Masaaki Miyashita

doi:10.1038/nchem.1044

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The first chemical synthesis of solanoeclepin A is described. The novel 5-4-6-7-5-5 polycyclic architecture was constructed in a stereoselective manner via a cyclopentene annulation strategy, the intramolecular cyclization of an epoxy nitrile intermediate, and an intramolecular Diels–Alder reaction of a furan derivative.

Subject terms: Organic chemistry | Synthesis

See also: News and Views by Snyder


The effect of gold loading and particle size on photocatalytic hydrogen production from ethanol over Au/TiO2 nanoparticles pp489 - 492

M. Murdoch, G. I. N. Waterhouse, M. A. Nadeem, J. B. Metson, M. A. Keane, R. F. Howe, J. Llorca & H. Idriss

doi:10.1038/nchem.1048

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The photocatalytic production of hydrogen from renewables such as ethanol and water could be a key means of future fuel production. There are few, if any, catalysts available for such a reaction, and our understanding of photocatalytic reactions generally remains poor. It is now demonstrated that gold–titania nanoparticles are effective catalysts for producing hydrogen from ethanol, and the rate is independent of gold particle size.

Subject terms: Catalysis | Nanotechnology


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Erratum

Recent advances in submolecular resolution with scanning probe microscopy p493

Leo Gross

doi:10.1038/nchem.1047


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In Your Element

Cobalt close-up p494

David Lindsay & William Kerr

doi:10.1038/nchem.1053

David Lindsay and William Kerr remind us that where cobalt is concerned, good has triumphed over evil.


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