Volume 3 Issue 5, May 2011

Volume 3 Issue 5

The cover image shows a surface-confined switch based on an electroactive organic radical (red) that is transformed to the corresponding anion (purple). This bistable system, developed by Jaume Veciana, Concepció Rovira and co-workers, behaves as an extremely robust redox switch in which an electrical input is transduced into an optical and magnetic output. This switch operates at very low voltages, can be patterned and locally addressed, and exhibits an exceptionally high long-term stability and excellent reversibility.

Image by Mateu Marcet/Cover design by Alex Wing, Nature Chemistry

Article p359

Editorial

  • Editorial |

    When it comes to research misconduct, burying one's head in the sand and pretending it doesn't exist is the worst possible plan.

Research Highlights

Blogroll

News and Views

  • News & Views |

    Energetic adsorption of molecules on surfaces is known to either trigger local chemical reactions or initiate the recoil of adsorbates away from the surface. Now, another possible outcome has been observed — the long-range 'cart-wheeling' of energetic molecules across a surface.

    • Joseph W. Lyding
  • News & Views |

    Enzymes that selectively oxidize unactivated C–H bonds are capable of constructing complex molecules with high efficiency. A new member of this enzyme family is RedG, a Reiske-type oxygenase that catalyses chemically challenging cyclizations in the biosynthesis of prodiginine natural products.

    • Steven D. Bruner
  • News & Views |

    There is a long history of gas-phase studies of bimolecular reactions, but the presence of surrounding molecules complicates analogous studies in solution. Now, advances in ultrafast laser technology have enabled the detailed study of vibrational energy release in a reaction in solution.

    • F. Fleming Crim
  • News & Views |

    Heterogeneous catalyst systems comprising metals supported on oxides are widespread. Evidence now suggests that it is the interfacial regions that are most catalytically active, and this has been exploited to create a tandem nanocatalyst system.

    • Peter C. Stair
  • News & Views |

    Keeping the organic and inorganic precursors in separate, immiscible solutions guides the growth of metal-organic frameworks into uniform thin layers that are shaped just like the liquid-liquid interface.

    • Russell E. Morris

Review

  • Review Article |

    Crystalline networks containing empty cavities can host a variety of molecules but also promote reactions between guests. Through robust crystallinity and a pseudo-solution state (dynamic movements) within their pores, these crystalline molecular flasks enable the direct observation of species — including unstable intermediates — during a reaction by in situ X-ray diffraction.

    • Yasuhide Inokuma
    • , Masaki Kawano
    •  & Makoto Fujita

Articles

  • Article |

    The creation of ‘smart surfaces’ that can act as switches or memory devices will rely on systems with bistable states that can be interconverted externally. Now, a low-voltage and robust surface-confined switch that transduces an electrical input into an optical and magnetic output is described.

    • Cláudia Simão
    • , Marta Mas-Torrent
    • , Núria Crivillers
    • , Vega Lloveras
    • , Juan Manuel Artés
    • , Pau Gorostiza
    • , Jaume Veciana
    •  & Concepció Rovira
  • Article |

    The reaction of enols and enolates with electrophiles is used extensively in synthesis. Here, protein engineering — substituting amino acid residues in an enzyme active site — is used to produce biocatalysts for the control of enolate chemistry. The adapted enzymes enable stereoselective C–C bond formation yielding N-heterocycles in high diastereomeric excess by the reaction of trisubstituted-enolates.

    • Refaat B. Hamed
    • , J. Ruben Gomez-Castellanos
    • , Armin Thalhammer
    • , Daniel Harding
    • , Christian Ducho
    • , Timothy D. W. Claridge
    •  & Christopher J. Schofield
  • Article |

    The development of high-performance ‘smart’ catalysts will rely on the rational design of nanoscale metal–metal oxide interfaces. A tandem catalyst that has both CeO2-Pt and Pt-SiO2 interfaces is now reported, and is capable of catalysing sequential reactions to convert methanol into ethylene.

    • Yusuke Yamada
    • , Chia-Kuang Tsung
    • , Wenyu Huang
    • , Ziyang Huo
    • , Susan E. Habas
    • , Tetsuro Soejima
    • , Cesar E Aliaga
    • , Gabor A. Somorjai
    •  & Peidong Yang
  • Article |

    Organolithiums are the prototypical nucleophilic reagent, but the direct use of them as nucleophiles in catalytic asymmetric synthesis has been problematic. Long sought after, conditions have now been identified that allow the highly enantioselective catalytic formation of C–C bonds by a direct SN2′ reaction of organolithiums with allylic halides.

    • Manuel Pérez
    • , Martín Fañanás-Mastral
    • , Pieter H. Bos
    • , Alena Rudolph
    • , Syuzanna R. Harutyunyan
    •  & Ben L. Feringa
  • Article |

    The intrinsically hybrid nature of metal–organic frameworks (MOFs) — microporous crystalline solids composed of metal ions and organic ligands — has been exploited to grow thin MOF films at the aqueous–organic interface of a biphasic reaction mixture. These materials exhibit selective permeability and can also be obtained as hollow capsules that have potential as microreactors.

    • Rob Ameloot
    • , Frederik Vermoortele
    • , Wim Vanhove
    • , Maarten B. J. Roeffaers
    • , Bert F. Sels
    •  & Dirk E. De Vos
  • Article |

    Enzyme-mediated oxidative cyclizations in nature are a powerful demonstration of the utility of selective C–H activation. Here, Rieske oxygenase-like enzymes RedG and McpG are shown to mediate regio- and stereodivergent carbocyclization of undecylprodigiosin to streptorubin B and metacycloprodigiosin, respectively. Understanding these remarkably selective C–H activations could inspire the design of biomimetic catalysts with similar capabilities.

    • Paulina K. Sydor
    • , Sarah M. Barry
    • , Olanipekun M. Odulate
    • , Francisco Barona-Gomez
    • , Stuart W. Haynes
    • , Christophe Corre
    • , Lijiang Song
    •  & Gregory L. Challis
  • Article |

    Crystal growth in nature is controlled by biomolecules to produce precisely engineered crystal shapes. Now, facet-specific peptide sequences that have been rationally selected through a biomimetic evolution process are used as regulating agents for predictable synthesis of platinum nanocrystals with selectively exposed crystal surfaces.

    • Chin-Yi Chiu
    • , Yujing Li
    • , Lingyan Ruan
    • , Xingchen Ye
    • , Christopher B. Murray
    •  & Yu Huang
  • Article |

    The recoil of adsorbates away from and towards surfaces is well-known. Here, long-range recoil in the plane of the surface, which leads to reaction at a distance, is described. Surface reactions are shown to propel their physisorbed ethylenic products across the rough surface of Si(100) by up to 200 Å before re-attachment.

    • K. R. Harikumar
    • , John C. Polanyi
    • , Amir Zabet-Khosousi
    • , Piotr Czekala
    • , Haiping Lin
    •  & Werner A. Hofer
  • Article |

    Macromolecules with antimicrobial properties are promising materials for combating multi-drug-resistant microbes. Now, it has been shown that amphiphilic cationic polycarbonates that are biodegradable can self-assemble into micellar nanoparticles that can kill gram-positive bacteria, MRSA and fungi efficiently, even at low concentrations. Moreover, no significant toxicity is observed during in vivo studies in mice.

    • Fredrik Nederberg
    • , Ying Zhang
    • , Jeremy P. K. Tan
    • , Kaijin Xu
    • , Huaying Wang
    • , Chuan Yang
    • , Shujun Gao
    • , Xin Dong Guo
    • , Kazuki Fukushima
    • , Lanjuan Li
    • , James L. Hedrick
    •  & Yi-Yan Yang

Addendum

In Your Element

  • In Your Element |

    Although it is mainly known for its toxicity, beryllium possesses an array of properties that makes it attractive for a variety of non-industrial purposes. Ralph Puchta discusses why it is not always best avoided.

    • Ralph Puchta

Addendum