Volume 5 Issue 4, April 2013

Volume 5 Issue 4

Andrew Cooper and co-workers have shown that porous solids made from molecular organic cages can separate structural isomers of simple aromatic compounds. The host–guest properties of the discrete organic cages in solution (as illustrated conceptually on the cover in the beaker) correlate with the solid-state behaviour (as shown above the beaker). The shape-sorting selectivity arises from the intrinsic structure of the cage-like building blocks, suggesting that different cages could be designed to separate other feedstocks.

Article p276

IMAGE: KIM JELFS AND SAM CHONG

COVER DESIGN: ALEX WING

Editorial

  • Editorial |

    Nature Chemistry signed up for a Twitter account in March 2009. More than 5,000 tweets later, what have we learned and how do we use it?

Thesis

  • Thesis |

    Bruce Gibb ponders what the future of chemistry research might look like if we take a more data-driven approach.

    • Bruce C. Gibb

Research Highlights

Blogroll

News and Views

  • News & Views |

    Strategies for making sequence-controlled polymers in the laboratory are really quite primitive in comparison with those used in nature. By combining concepts from natural systems and synthetic polymer chemistry, it has now been shown that DNA codes can be translated into non-nucleic-acid polymers with defined sequences.

    • Rachel K. O'Reilly
  • News & Views |

    The study of the reaction of a ground-state O atom with H2 has previously proved difficult because of its high activation barrier. Now, new experiments have revealed unexpected OH product states; but perhaps there is a simple explanation?

    • Millard H. Alexander
  • News & Views |

    Hydrogen–oxygen alkaline fuel cells are promising devices for the 'hydrogen economy' but their oxidation of hydrogen fuel is slow compared with that of acidic fuel cells. More efficient electrocatalysts have now been prepared in which the adsorption of hydroxyl groups onto the electrode surface is controlled through suitable promoters.

    • Marc T. M. Koper
  • News & Views |

    Combined spectroscopic measurements and theoretical calculations bring to light an ultrafast excited-state deactivation process in peptides that may contribute to the ultraviolet photostability of proteins.

    • Wolfgang Domcke
    •  & Andrzej L. Sobolewski
  • News & Views |

    During photosynthesis, the oxygen-evolving complex oxidizes water to produce molecular oxygen. Now, a possible role for the calcium ion in this complex has been proposed based on the electrochemical properties of a series of synthetic heterometallic clusters.

    • Sarah A. Cook
    •  & A. S. Borovik

Review

  • Review Article |

    Two-dimensional materials have recently garnered much interest in the scientific and technology communities. This Review describes how ultrathin transition metal dichalcogenides combine tunable structure and electronic properties, achieved through altering their composition, with versatile chemistry. This makes them attractive in various fields, for example as lithium-ion battery electrodes and electrocatalysts for the hydrogen evolution reaction.

    • Manish Chhowalla
    • , Hyeon Suk Shin
    • , Goki Eda
    • , Lain-Jong Li
    • , Kian Ping Loh
    •  & Hua Zhang

Articles

  • Article |

    A crystalline porous organic cage molecule is shown to have exceptional specificity for separating different structural isomers of C9 aromatics. Uniquely, this solid-state specificity is preconfigured in the discrete molecular building block, which shows an analogous specificity in solution. Both solution and solid-state behaviours can be understood by molecular dynamics simulations.

    • Tamoghna Mitra
    • , Kim E. Jelfs
    • , Marc Schmidtmann
    • , Adham Ahmed
    • , Samantha Y. Chong
    • , Dave J. Adams
    •  & Andrew I. Cooper
  • Article |

    An enzyme-free system that translates DNA into sequence-defined non-nucleic acid polymers including polyethylene glycol, α-(D)-peptides and β-peptides is described. Sequence-defined polymers with molecular weights of 26 kDa containing 16 consecutively coupled building blocks and 90 densely functionalized β-amino acids were translated from DNA templates using this strategy.

    • Jia Niu
    • , Ryan Hili
    •  & David R. Liu
  • Article |

    The presence of Ca2+ is essential for the activity of the oxygen-evolving complex (OEC) of Photosystem II, although its exact role is still unclear. Now, electrochemical measurements of structural mimics of the OEC — based on mixed-metal trimanganese dioxido complexes — reveal a correlation between the Lewis acidity of the redox-inactive metal and the reduction potential of the complex.

    • Emily Y. Tsui
    • , Rosalie Tran
    • , Junko Yano
    •  & Theodor Agapie
  • Article |

    Hydrogen is an attractive alternative to fossil fuels, but the slow rate of the hydrogen oxidation reaction in alkaline fuel cells hinders their development. It is now proposed that bifunctional materials can be devised to offer the optimal balance between hydrogen and hydroxyl adsorption, thus significantly reducing the amount of precious metal on the anode.

    • Dusan Strmcnik
    • , Masanobu Uchimura
    • , Chao Wang
    • , Ram Subbaraman
    • , Nemanja Danilovic
    • , Dennis van der Vliet
    • , Arvydas P. Paulikas
    • , Vojislav R. Stamenkovic
    •  & Nenad M. Markovic
  • Article |

    The heat shock protein Hsp90 is a potential target for cancer and neurodegeneration drugs. Here, the introduction of a substituent into the 19-position of the naturally occurring inhibitor geldanamycin by chemical synthesis is shown to ameliorate toxicity, and also cause a favourable conformational switch that is required for protein binding.

    • Russell R. A. Kitson
    • , Chuan-Hsin Chang
    • , Rui Xiong
    • , Huw E. L. Williams
    • , Adrienne L. Davis
    • , William Lewis
    • , Donna L. Dehn
    • , David Siegel
    • , S. Mark Roe
    • , Chrisostomos Prodromou
    • , David Ross
    •  & Christopher J. Moody
  • Article |

    The reaction O(3P) + H2 → OH(X2Π) + H has, until now, eluded detailed experimental investigation. Now, a laser-induced fluorescence study of the deuterated analogue has revealed product-state distributions that defy the current descriptions of non-Born–Oppenheimer mixing on coupled potential energy surfaces, issuing new challenges to theory.

    • Sridhar A. Lahankar
    • , Jianming Zhang
    • , Kenneth G. McKendrick
    •  & Timothy K. Minton
  • Article |

    Although it is achieved routinely by nitrogenases, the conversion of molecular dinitrogen into ammonia under ambient conditions is proving difficult with synthetic systems. A thiolate-bridged diiron complex has now been developed that produces ammonia from coordinated N2H2 through a sequence of reduction and protonation reactions that may well mimic the biological nitrogen fixation.

    • Yang Li
    • , Ying Li
    • , Baomin Wang
    • , Yi Luo
    • , Dawei Yang
    • , Peng Tong
    • , Jinfeng Zhao
    • , Lun Luo
    • , Yuhan Zhou
    • , Si Chen
    • , Fang Cheng
    •  & Jingping Qu
  • Article |

    The photochemical-induced dimerization of bromine-terminated oligo(ethynylene)s in the solid state is shown to give 1,2-dibromoeneynes on a preparative scale. This single-crystal-to-single-crystal transformation proceeds through a multistep reaction that involves the making and breaking of several bonds in addition to large atom displacements. The reaction represents an atom-efficient and catalyst-free pathway towards functional carbon-rich molecular scaffolds.

    • Tobias N. Hoheisel
    • , Stephen Schrettl
    • , Roman Marty
    • , Tanya K. Todorova
    • , Clémence Corminboeuf
    • , Andrzej Sienkiewicz
    • , Rosario Scopelliti
    • , W. Bernd Schweizer
    •  & Holger Frauenrath
  • Article |

    A strategy to endow vinyl polymers with pseudo-crystalline order has been devised that relies on host–guest cross-polymerization, through functionalization of the channels of a porous coordination polymer with divinyl moieties. Polymerization of vinyl monomers within the channels is accompanied with lateral crosslinking, which ensures the polymer chains remain highly ordered after removal of the host.

    • Gaetano Distefano
    • , Hirohito Suzuki
    • , Masahiko Tsujimoto
    • , Seiji Isoda
    • , Silvia Bracco
    • , Angiolina Comotti
    • , Piero Sozzani
    • , Takashi Uemura
    •  & Susumu Kitagawa
  • Article |

    A ruthenium complex bearing a chemically and redox-non-innocent tetradentate diolefin diazadiene ligand is shown to be an efficient homogeneous catalyst for the conversion of a 1:1 mixture of methanol and water to hydrogen and carbon dioxide. Development of this process is an important step in the production of hydrogen for use as a fuel from biomass.

    • Rafael E. Rodríguez-Lugo
    • , Mónica Trincado
    • , Matthias Vogt
    • , Friederike Tewes
    • , Gustavo Santiso-Quinones
    •  & Hansjörg Grützmacher

In Your Element

  • In Your Element |

    Eric J. Schelter ponders on cerium's rather puzzling redox reactivity, and the varied practical applications that have emerged from it.

    • Eric J. Schelter