Table of contents



Information-containing macromolecules pp455 - 456

Howard Colquhoun & Jean-François Lutz


Howard Colquhoun and Jean-François Lutz consider the potential of synthetic polymers for storing information at the molecular level.


Books and Arts

Merck work p457

Michael A. Tarselli reviews Hallelujah Moments: Tales of Drug Discovery By Eugene H. Cordes




Blogroll: Real chemistry p459

Tom Branson



News and Views

Synthetic strategy: Natural products on demand pp460 - 461

Lawrence G. Hamann


Nature assembles complex natural products using bifunctional building blocks and a mere handful of reaction types. Mimicry of this method seeks to revolutionize natural product and small-molecule synthesis.

See also: Article by Woerly et al.

Atmospheric chemistry: Intermediates just want to react pp461 - 462

Craig A. Taatjes, Dudley E. Shallcross & Carl J. Percival


Many of the rate parameters used in models of tropospheric chemistry are obtained through laboratory ozonolysis experiments. Now, results on the self-reaction of an important, but long-elusive, intermediate could alter many of those inferences.

See also: Article by Su et al.

Carbon nanomaterials: From rods to sheets in a flash pp463 - 464

Jean-François Morin


The controlled synthesis of two-dimensional carbon nanomaterials enables their properties to be tailored for potential device applications. Functionalized graphene-like nanosheets with controlled thickness have now been obtained by irradiating monolayers of carbon-rich molecular precursors at room temperature.

See also: Article by Schrettl et al.

Natural products: DNA double whammy pp464 - 465

Kent S. Gates


The lomaiviticins are exceedingly potent antibiotic agents, but the mechanism responsible for this activity has so far been unclear. Now, efficient generation of double-strand breaks in DNA by lomaiviticin A has been linked to the remarkable cytotoxicity of these diazobenzofluorene-containg natural products.

See also: Article by Colis et al.

Main-group chemistry: Boron served straight up pp466 - 467

Christian Reus & Matthias Wagner


Borinium ions are difficult to isolate due to the extreme electron deficiency of the boron atom. Now, a unique two-coordinate linear dimesitylborinium cation has been synthesized that impresses with extraordinary Lewis acidity and oxophilicity.

See also: Article by Shoji et al.



Functional carbon nanosheets prepared from hexayne amphiphile monolayers at room temperature pp468 - 476

Stephen Schrettl, Cristina Stefaniu, Christian Schwieger, Guillaume Pasche, Emad Oveisi, Yannik Fontana, Anna Fontcuberta i Morral, Javier Reguera, Riccardo Petraglia, Clémence Corminboeuf, Gerald Brezesinski & Holger Frauenrath


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Carbonization of a self-assembled monolayer of a hexayne amphiphile at the air/water interface at room temperature results in the formation of functional carbon nanosheets. The nanosheets exhibit a molecularly defined thickness, are mechanically self-supporting over several micrometres, and have macroscopic lateral dimensions on the order of centimetres.

See also: News and Views by Morin

Extremely rapid self-reaction of the simplest Criegee intermediate CH2OO and its implications in atmospheric chemistry pp477 - 483

Yu-Te Su, Hui-Yu Lin, Raghunath Putikam, Hiroyuki Matsui, M. C. Lin & Yuan-Pern Lee


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Criegee intermediates play an important role in atmospheric chemistry but their direct study has proved difficult. Transient infrared absorption spectroscopy has now been used to probe the decay kinetics of the Criegee intermediate CH2OO directly, revealing that its self-reaction is extremely rapid. This may have important consequences for the interpretation of previous laboratory experiments.

See also: News and Views by Taatjes et al.

Synthesis of most polyene natural product motifs using just 12 building blocks and one coupling reaction pp484 - 491

Eric M. Woerly, Jahnabi Roy & Martin D. Burke


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Polyene motifs are found in a large number of natural products. Now, by applying a general retrosynthetic algorithm, it has been shown that the polyene motifs found in >75% of these compounds can be synthesized using just 12 bifunctional haloalkenyl MIDA boronate building blocks and one coupling reaction.

See also: News and Views by Hamann

A transferable model for singlet-fission kinetics pp492 - 497

Shane R. Yost, Jiye Lee, Mark W. B. Wilson, Tony Wu, David P. McMahon, Rebecca R. Parkhurst, Nicholas J. Thompson, Daniel N. Congreve, Akshay Rao, Kerr Johnson, Matthew Y. Sfeir, Moungi G. Bawendi, Timothy M. Swager, Richard H. Friend, Marc A. Baldo & Troy Van Voorhis


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Understanding the process of exciton fission, which occurs in certain organic materials, could lead to the development of more efficient photovoltaic devices. Here, an expression derived from first principles is used to accurately characterize the singlet fission rate of a wide array of materials, reproducing a transition from weak to strong coupling as a function of molecular separation.

A two-coordinate boron cation featuring C–B+–C bonding pp498 - 503

Yoshiaki Shoji, Naoki Tanaka, Koichiro Mikami, Masanobu Uchiyama & Takanori Fukushima


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Borinium ions are two-coordinate boron cations that contain only four valence electrons on boron, and are difficult to isolate without electron donation from adjacent heteroatoms. Now, diarylborinium salts with no lone-pair donation from heteroatoms have been isolated, characterized and found to participate in an unusual reaction with CO2.

See also: News and Views by Reus & Wagner

The cytotoxicity of (−)-lomaiviticin A arises from induction of double-strand breaks in DNA pp504 - 510

Laureen C. Colis, Christina M. Woo, Denise C. Hegan, Zhenwu Li, Peter M. Glazer & Seth B. Herzon


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(−)-Lomaiviticin A inhibits the growth of cancer cells at nanomolar to picomolar concentrations; however, the basis for this potent cytotoxicity is not known. This natural product has now been shown to induce production of DNA double-strand breaks at nanomolar concentrations. Evidence demonstrates that strand cleavage proceeds via reactive carbon-centred free radical intermediates.

See also: News and Views by Gates

Installing logic-gate responses to a variety of biological substances in supramolecular hydrogel–enzyme hybrids pp511 - 518

Masato Ikeda, Tatsuya Tanida, Tatsuyuki Yoshii, Kazuya Kurotani, Shoji Onogi, Kenji Urayama & Itaru Hamachi


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Soft materials that can undergo a macroscopic change in response to external stimuli may prove useful for a range of biological applications. Now, it has been shown that hydrogels encapsulating active enzymes can undergo a gel–sol transition in the presence of a range of small-molecule triggers and can potentially be used as sensors or drug-delivery systems.

Bioorthogonal cyclization-mediated in situ self-assembly of small-molecule probes for imaging caspase activity in vivo pp519 - 526

Deju Ye, Adam J. Shuhendler, Lina Cui, Ling Tong, Sui Seng Tee, Grigory Tikhomirov, Dean W. Felsher & Jianghong Rao


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Controlling the self-assembly of small molecules within living animals is complicated because of the complex and dynamic nature of the physiological environment. Here, a strategy for directing in situ self-assembly of small molecules into fluorescent nano-aggregates in living mice is demonstrated. The nano-aggregates can be used for imaging caspase-3/7 activity in human tumour xenograft mouse models.

Fatty acid membrane assembly on coacervate microdroplets as a step towards a hybrid protocell model pp527 - 533

T-Y. Dora Tang, C. Rohaida Che Hak, Alexander J. Thompson, Marina K. Kuimova, D. S. Williams, Adam W. Perriman & Stephen Mann


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A hybrid protocell model is described in which a fatty acid membrane spontaneously assembles on the surface of coacervate microdroplets with molecularly crowded interiors. The membrane-enclosed protocells exhibit uptake and exclusion properties that differ from the uncoated droplets. The internal structure can be disassembled at high ionic strength without loss of membrane integrity. This model may help to reconcile alternative mechanisms of prebiotic compartmentalization.

Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups pp534 - 541

Yunju La, Chiyoung Park, Tae Joo Shin, Sang Hoon Joo, Sebyung Kang & Kyoung Taek Kim


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Colloidal inverse bicontinuous cubic mesophases have now been formed by self-assembly of amphiphilic dendritic-linear block copolymers in solution. The internal networks of water channels provide a high surface area with tunable functional groups that can serve as anchoring points for macromolecular guests such as proteins and enzymes.

A mitochondrial pathway for biosynthesis of lipid mediators pp542 - 552

Yulia Y. Tyurina, Samuel M. Poloyac, Vladimir A. Tyurin, Alexander A. Kapralov, Jianfei Jiang, Tamil Selvan Anthonymuthu, Valentina I. Kapralova, Anna S. Vikulina, Mi-Yeon Jung, Michael W. Epperly, Dariush Mohammadyani, Judith Klein-Seetharaman, Travis C. Jackson, Patrick M. Kochanek, Bruce R. Pitt, Joel S. Greenberger, Yury A. Vladimirov, Hülya Bayır & Valerian E. Kagan


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The biosynthesis of lipid mediators has not previously been identified in mitochondria. Here, polyunsaturated cardiolipins are shown to be oxidized in the mitochondria by cytochrome c. Subsequent hydrolysis of these oxygenated species generates a variety of oxygenated fatty acids as well as non-oxygenated and oxygenated lyso-cardiolipins. These reactions represent a new biosynthetic pathway for the production of lipid mediators.



Addendum: Quantitative sequencing of 5-formylcytosine in DNA at single-base resolution p553

Michael J. Booth, Giovanni Marsico, Martin Bachman, Dario Beraldi & Shankar Balasubramanian




Erratum: Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold p553

Cathleen M. Crudden, J. Hugh Horton, Iraklii I. Ebralidze, Olena V. Zenkina, Alastair B. McLean, Benedict Drevniok, Zhe She, Heinz-Bernhard Kraatz, Nicholas J. Mosey, Tomohiro Seki, Eric C. Keske, Joanna D. Leake, Alexander Rousina-Webb & Gang Wu



In Your Element

Thorium lends a fiery hand p554

John Arnold, Thomas L. Gianetti & Yannai Kashtan


John Arnold, Thomas L. Gianetti and Yannai Kashtan look back on thorium's chemistry, and look forward to harnessing its nuclear potential.