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Thesis

The two-week sabbatical pp495 - 496

Bruce C. Gibb

doi:10.1038/nchem.1080

Could short, non-traditional sabbaticals help scientists better organize their research groups and make improvements to their laboratory's IT infrastructure? Bruce Gibb ponders this question.

Subject term: General chemistry


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Books and Arts

Big screen, big influence p497

Mark Griep reviews Lab Coats in Hollywood: Science, Scientists, and Cinema by David A. Kirby

doi:10.1038/nchem.1082


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Research Highlights

Our choice from the recent literature pp498 - 499

doi:10.1038/nchem.1084


Blogroll: MicKIE mouse p499

doi:10.1038/nchem.1085


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News and Views

Oxygen-reduction catalysts: Picking perovskites pp501 - 502

Robert F. Savinell

doi:10.1038/nchem.1083

The search for efficient oxygen reduction catalysts made from perovskite oxides rather than expensive precious metals is hindered by the sheer range of these oxides — where should the search begin? Developing design rules that can identify the best candidates is the first step towards a more targeted strategy.

Subject terms: Catalysis | Electrochemistry | Materials chemistry

See also: Article by Suntivich et al.


Nitrogen fixation: Nitrido complexes step up pp502 - 504

Yoshiaki Nishibayashi

doi:10.1038/nchem.1077

The discoveries of ruthenium– and iron–nitrido complexes that can be transformed to release ammonia could be important steps towards realizing the catalytic reduction of nitrogen under mild reaction conditions.

Subject terms: Inorganic chemistry | Organometallic chemistry | Catalysis

See also: Article by Askevold et al.


Atmospheric photochemistry: Roaming in the dark pp504 - 505

Simon W. North

doi:10.1038/nchem.1079

The mechanism of NO and O2 production through the photolysis of the nitrate radical has long proved elusive. Now, theoretical studies help to explain previous experiments, suggesting that two distinct pathways are responsible that both involve 'roaming dynamics' on the 'dark' excited electronic state.

Subject terms: Physical chemistry | Theoretical chemistry


Polymer synthesis: Making the gradient pp505 - 507

Bun Yeoul Lee & Anish Cyriac

doi:10.1038/nchem.1081

A catalyst has been developed that enables poly(propylene carbonate) chains to be made in which the configuration of the repeat units changes gradually from exclusively S at one end of the chain to exclusively R at the other. The improved physical properties of this 'stereogradient' polymer may help its adoption as an environmentally friendly material.

Subject terms: Polymer chemistry | Synthesis


Coordination chemistry: All square for high-spin iron(II) pp507 - 508

Patrick L. Holland

doi:10.1038/nchem.1078

Do unusual geometries always come from the force exerted by a protein, a solid-state lattice or bulky ligands? In a new iron(II) complex, simple ligands stabilize a square-planar high-spin complex through finesse rather than force.

Subject term: Inorganic chemistry


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Review

Contemporary strategies for peptide macrocyclization pp509 - 524

Christopher J. White & Andrei K. Yudin

doi:10.1038/nchem.1062

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Peptide macrocycles have a number of important applications. Among other things, the reduced conformational freedom of the cyclic structure enables strong binding to the extended contact regions of protein–protein complexes. Here, emerging methods directed towards the synthesis of these valuable molecules are reviewed.

Subject terms: Organic chemistry | Synthesis


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Articles

Nitrenium ions as ligands for transition metals pp525 - 531

Yuri Tulchinsky, Mark A. Iron, Mark Botoshansky & Mark Gandelman

doi:10.1038/nchem.1068

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Nitrenium salts have been known for more than 100 years. Despite being isoelectronic and isostructural to the ubiquitous N-heterocyclic carbene ligands and other main-group analogues, their coordination to metals has remained elusive. Here, the first examples of nitrenium ions as ligands for transition metals are described, along with investigations of their electronic properties.

Subject terms: Inorganic chemistry | Organometallic chemistry


Ammonia formation by metal–ligand cooperative hydrogenolysis of a nitrido ligand pp532 - 537

Bjorn Askevold, Jorge Torres Nieto, Samat Tussupbayev, Martin Diefenbach, Eberhardt Herdtweck, Max C. Holthausen & Sven Schneider

doi:10.1038/nchem.1051

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One of the hurdles facing the development of effective catalysts to produce ammonia from nitrogen is the stability of the metal nitrides that form during the reaction. Now, the hydrogenolysis of nitride ligands with hydrogen is reported and attributed to PNP pincer ligand cooperativity.

Subject terms: Inorganic chemistry | Organometallic chemistry | Catalysis

See also: News and Views by Nishibayashi


Strong exchange and magnetic blocking in N23−-radical-bridged lanthanide complexes pp538 - 542

Jeffrey D. Rinehart, Ming Fang, William J. Evans & Jeffrey R. Long

doi:10.1038/nchem.1063

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Single-molecule magnets hold great promise for device miniaturization but the blocking temperatures at which they perform must first reach practical values. Now, the electronically diffuse N23− radical bridge has been shown to endow two di-lanthanide complexes with good magnetic properties — a di-gadolinium complex displays a strong magnetic coupling and its di-dysprosium analogue a high blocking temperature.

Subject terms: Inorganic chemistry | Materials chemistry


An efficient synthesis of loline alkaloids pp543 - 545

Mesut Cakmak, Peter Mayer & Dirk Trauner

doi:10.1038/nchem.1072

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Loline is a small alkaloid with a deceptively simple-looking structure. Here, a remarkably short synthesis is reported, the key step of which is a transannular aminobromination. The synthesis provides access to loline and to several other members of the loline family in sufficient yield to support a programme investigating the complex biological interactions of these compounds.

Subject terms: Organic chemistry | Synthesis


Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries pp546 - 550

Jin Suntivich, Hubert A. Gasteiger, Naoaki Yabuuchi, Haruyuki Nakanishi, John B. Goodenough & Yang Shao-Horn

doi:10.1038/nchem.1069

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With the cost of noble metal oxygen-reduction catalysts rendering some fuel cells and batteries prohibitively expensive, the search for effective and cheaper catalysts is underway and would be speeded up by ‘design principles’. Now, the catalytic activity of oxide materials has been correlated to σ*-orbital occupation and the extent of metal–oxygen covalency.

Subject terms: Catalysis | Electrochemistry | Materials chemistry

See also: News and Views by Savinell


Facile removal of stabilizer-ligands from supported gold nanoparticles pp551 - 556

Jose A. Lopez-Sanchez, Nikolaos Dimitratos, Ceri Hammond, Gemma L. Brett, Lokesh Kesavan, Saul White, Peter Miedziak, Ramchandra Tiruvalam, Robert L. Jenkins, Albert F. Carley, David Knight, Christopher J. Kiely & Graham J. Hutchings

doi:10.1038/nchem.1066

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Small nanoparticles with controlled morphologies can be prepared for catalysis applications by colloidal methods using stabilizing ligands. A solvent-extraction method has now been described that removes the ligands without affecting the morphology of the nanoparticles, or their catalytic activity over a range of reactions.

Subject terms: Catalysis | Green chemistry


Synthesis of 3-O-sulfonated heparan sulfate octasaccharides that inhibit the herpes simplex virus type 1 host–cell interaction pp557 - 563

Yu-Peng Hu, Shu-Yi Lin, Cheng-Yen Huang, Medel Manuel L. Zulueta, Jing-Yuan Liu, Wen Chang & Shang-Cheng Hung

doi:10.1038/nchem.1073

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Oligosaccharides displayed at cell surfaces have important biological functions — such as controlling the entry of viruses — but a full understanding of this behaviour requires the synthesis of such compounds, which remains challenging. Here, two synthetic octasaccharides were shown to have remarkably similar inhibition of herpes simplex virus type 1 infection of cell cultures to the natural oligosaccharide identified in enzymatic studies.

Subject terms: Chemical biology | Synthesis


Light-induced spin-crossover magnet pp564 - 569

Shin-ichi Ohkoshi, Kenta Imoto, Yoshihide Tsunobuchi, Shinjiro Takano & Hiroko Tokoro

doi:10.1038/nchem.1067

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In extended networks, light-induced magnetic ordering through spin change typically involves a charge-transfer mechanism, and thus a valence change of the magnetic metal centres. Now, such long-range ordering has been achieved in a three-dimensional metal–organic framework through the low-spin to high-spin transition of iron(II) centres, leading to a pronounced spontaneous magnetization.

Subject terms: Materials chemistry | Photochemistry


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In Your Element

Selenium stories p570

Russell Boyd

doi:10.1038/nchem.1076

Russell Boyd ponders on how selenium — despite close similarities with its neighbours of the chalcogen family, sulfur and tellurium — continues to reveal chemical and biological activities of its own.


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