Volume 7 Issue 2, February 2015

Volume 7 Issue 2

Metal-organic frameworks (MOFs) have attracted increasing attention for the uptake and separation of hydrocarbon mixtures in an effort to develop more efficient industrial processes and routes to cleaner energy. To better understand how hydrocarbons bind in the pores of a particular MOF (NOTT-300), Sihai Yang, Martin Schröder and co-workers have combined scattering and diffraction studies with computational modelling — a visualization of the mobility and binding dynamics of acetylene, ethylene and ethane guests is shown on the cover. It is found that NOTT-300 selectively binds unsaturated hydrocarbons through cooperative supramolecular interactions, but only interacts weakly with ethane.Article p121IMAGE: HAN XUE AND SIHAI YANGCOVER DESIGN: ALEX WING

Correspondence

Thesis

  • Thesis |

    In the first of two essays that offer a chemistry-themed guided tour around the Solar System, Bruce Gibb looks at what sort of organic molecules are out there and just where you can find them.

    • Bruce C. Gibb

Research Highlights

Blogroll

News and Views

  • News & Views |

    An extracellular ejection of zinc, known as a zinc spark, is triggered by the fertilization of a mammalian egg; however, the origin of this zinc was not clear. Now, a combination of four complementary techniques has revealed the source and provided an unprecedented quantification of the distribution of zinc in a maturing mammalian oocyte.

    • Kyle P. Carter
    •  & Amy E. Palmer
  • News & Views |

    Attempts to create a porous molecular crystal by removing solvent molecules from a solvate usually lead the host to reorganize into a non-porous close-packed structure. The 'virtual porosity' of such an organic cage crystal has now been trapped by introducing a judiciously chosen co-crystal former that prevents rearrangement of the host lattice.

    • Leonard J. Barbour
  • News & Views |

    Previously conspicuous by its absence, a syn-selective dichlorination reaction of alkenes has now been reported, bringing together decades-old stoichiometric chemistry in a useful catalytic process.

    • Brian R. Atwood
    •  & Christopher D. Vanderwal
  • News & Views |

    The synchronous movement of protons and electrons orchestrated by enzymes gives rise to highly efficient catalytic processes in nature, such as photosynthesis. Now, researchers have choreographed similar reactivity for a metal hydride complex, setting the stage for efficient solar fuel production in artificial systems.

    • Jillian L. Dempsey
  • News & Views |

    Mutated enzymes are useful tools for the investigation of the biosynthetic routes to natural products. Now, they are used in a new approach to carry functionalized substrates through the synthesis and produce simplified or modified unnatural compounds with useful properties.

    • Niclas Pryk
    •  & Frank Schulz

Review

  • Review Article |

    Bringing porphyrins in contact with well-defined interfaces generates a rich playground of chemical behaviour and properties for exploration and exploitation. This Review examines our current understanding of surface-confined tetrapyrroles and their embedding in nanoarchitectures - discussing both the structural and functional attributes, and methods by which to manipulate their intramolecular and organizational features.

    • Willi Auwärter
    • , David Écija
    • , Florian Klappenberger
    •  & Johannes V. Barth

Articles

  • Article |

    Gas sorption and separation in porous materials is dependent on the host–guest binding within any given system. Now, the molecular details of cooperative binding between small hydrocarbons and a metal–organic framework, NOTT-300, at multiple sites have been elucidated by complementary scattering and diffraction techniques. This material is also capable of separating C1 and C2 hydrocarbons under ambient conditions.

    • Sihai Yang
    • , Anibal J. Ramirez-Cuesta
    • , Ruth Newby
    • , Victoria Garcia-Sakai
    • , Pascal Manuel
    • , Samantha K. Callear
    • , Stuart I. Campbell
    • , Chiu C. Tang
    •  & Martin Schröder
  • Article |

    The mammalian oocyte cell cycle is regulated by massive zinc fluxes which culminate in coordinated ejections of ~1010 zinc ions at fertilization. Four single-cell physiochemical approaches (live-cell fluorescence imaging, scanning transmission electron microscopy with energy dispersive spectroscopy, X-ray fluorescence microscopy and tomography) reveal that these ‘zinc sparks’ originate from thousands of cortical vesicles which each release ~106 zinc ions.

    • Emily L. Que
    • , Reiner Bleher
    • , Francesca E. Duncan
    • , Betty Y. Kong
    • , Sophie C. Gleber
    • , Stefan Vogt
    • , Si Chen
    • , Seth A. Garwin
    • , Amanda R. Bayer
    • , Vinayak P. Dravid
    • , Teresa K. Woodruff
    •  & Thomas V. O'Halloran
  • Article |

    Proton-coupled electron transfer (PCET) of metal hydrides, in which electrons and protons go to or from different molecular sites, are key steps in catalytic reactions involving solar fuels. Using [(Cp)W(CO)3H] as a model compound, it is now shown that this PCET reaction can occur in a concerted fashion, suggesting a possible low-barrier pathway to catalysis.

    • Marc Bourrez
    • , Romain Steinmetz
    • , Sascha Ott
    • , Frederic Gloaguen
    •  & Leif Hammarström
  • Article |

    The synthetic challenge of constructing arrays of contiguous, chlorinated stereogenic centres in natural products, like the chlorosulfolipids, has sparked recent interest in new methods for stereocontrolled chlorination. Now the first catalytic, syn-stereospecific dichlorination of alkenes, employing a redox-active main group element as a group transfer catalyst is described.

    • Alexander J. Cresswell
    • , Stanley T.-C. Eey
    •  & Scott E. Denmark
  • Article |

    Organic molecular crystals with guest-occupied cavities are often observed, but the cavities tend to collapse when the guests are removed. Now, the porous domain of a crystalline solvate has been stabilized by formation of a cocrystal with a second molecule whose size and shape matches those of the unstable voids.

    • Marc A. Little
    • , Michael E. Briggs
    • , James T. A. Jones
    • , Marc Schmidtmann
    • , Tom Hasell
    • , Samantha Y. Chong
    • , Kim E. Jelfs
    • , Linjiang Chen
    •  & Andrew I. Cooper
  • Article |

    In vitro assembly of out-of-equilibrium enzymatic reaction networks has proved challenging, limiting the development of autonomous synthetic systems. Now, a methodology has been developed to construct an enzymatic reaction network producing oscillations of active trypsin. The modular approach allows amplification or analog-to-digital conversion of the oscillations, and control over a self-assembly process.

    • Sergey N. Semenov
    • , Albert S. Y. Wong
    • , R. Martijn van der Made
    • , Sjoerd G. J. Postma
    • , Joost Groen
    • , Hendrik W. H. van Roekel
    • , Tom F. A. de Greef
    •  & Wilhelm T. S. Huck
  • Article |

    Porous-alumina filter discs typically used to prepare graphene-oxide films are found to corrode during filtration and release aluminium ions that crosslink the negatively charged sheets and make the films insoluble in water. In contrast, aluminium-free graphene-oxide films are significantly weaker and readily disintegrate in water.

    • Che-Ning Yeh
    • , Kalyan Raidongia
    • , Jiaojing Shao
    • , Quan-Hong Yang
    •  & Jiaxing Huang
  • Article |

    A highly enantio- and diastereoselective route to complex indanes via a 5-endo-trig Michael reaction catalysed by a chiral ammonium salt is described. The preference for this formally disfavoured cyclization over a formally favoured alternative shows that geometric and stereoelectronic constraints may not be decisive in the observed outcome of irreversible ring closing reactions.

    • Craig P. Johnston
    • , Abhishek Kothari
    • , Tetiana Sergeieva
    • , Sergiy I. Okovytyy
    • , Kelvin E. Jackson
    • , Robert S. Paton
    •  & Martin D. Smith

In Your Element

  • In Your Element |

    Michael Tarselli reflects on the intriguing characteristics of a rather underrated element, niobium, in its 'missing' and existing forms.

    • Michael A. Tarselli

Erratum

Corrigendum