Volume 2 Issue 10, October 2010

Volume 2 Issue 10

The determination of molecular structure is an important step in the potential applications of naturally occurring organic compounds with interesting biological activity. For a significant fraction of newly isolated natural products, however, standard analytical techniques such as NMR and mass spectrometry cannot provide a definitive structure. Now, Leo Gross and co-workers have used a scanning probe microscopy technique to obtain an atomic-resolution image (shown on the cover) of a single molecule of cephalandole A, thereby enabling an unambiguous assignment of its structure. Image courtesy of Leo Gross, IBM Research-Zurich.

Cover design by Alex Wing/Nature Chemistry.

Article p821

News & Views p799

Editorial

  • Editorial |

    Press embargoes of research articles can serve journals, researchers and journalists — as long as everyone plays by, and understands, the rules.

Thesis

  • Thesis |

    Bruce Gibb finds that time away from the laboratory can help the mind to wander and explore new research ideas — and that inspiration for possible projects can come from somewhat unlikely sources.

    • Bruce C. Gibb

Books and Arts

Research Highlights

Blogroll

News and Views

  • News & Views |

    A series of scanning probe microscopy experiments combined with density functional theory calculations have now been used to unambiguously determine the structure of a marine natural product. Can this method become generally useful for the determination of the structure of natural products?

    • John W. Blunt
  • News & Views |

    Electron transfer between ions and water is of fundamental interest for many processes in biology and chemistry. Now, using core-electron excitation of hydrated iron cations, ultrafast electron transfer to the coordinating water molecules has been detected.

    • Anders Nilsson
  • News & Views |

    A versatile intermediate has been shown to provide access to a wide variety of compounds in the cortistatin family. This approach offers the most efficient total synthesis of the cortistatins reported so far.

    • Richmond Sarpong
  • News & Views |

    The efficient catalytic oxidation of water to dioxygen in the solid state is one of the challenges to be overcome to build sun-driven and/or electrocatalytic water-splitting devices. Now, an effective water-oxidation hybrid catalyst system has been made by attaching a ruthenium-polyoxometallate complex to a carbon nanotube.

    • Antoni Llobet
  • News & Views |

    Identifying the genes responsible for each step of a natural product biosynthesis has allowed the synthesis to be 'hijacked' to make bioactive compounds, and reveals that some suspected transporter enzymes could have other important roles in fungal defence systems.

    • Jason M. Crawford
    •  & Jon Clardy
  • News & Views |

    Taking inspiration from a proposed biosynthetic sequence, a cascade of simple reactions leads to an efficient synthesis of the alkaloid natural product (+)-fastigiatine.

    • Brad M. Loertscher
    •  & Steven L. Castle
  • News & Views |

    The efficiency of photovoltaic materials is compromised by their inability to capture all the energy absorbed when excited by high-energy photons. Such absorption creates 'hot' electrons, and now their transfer from excited lead selenide nanocrystals to an electron acceptor provides a necessary initial step towards tapping their 'lost' energy.

    • Prashant V. Kamat

Review

  • Review Article |

    Most synthetic polymers are made from petroleum and their production is currently not sustainable. RAFT polymerization has emerged as a powerful technique to control the synthesis of such polymers, thus expanding further their applications. This Review discusses the sustainability of RAFT in terms of process and materials.

    • Mona Semsarilar
    •  & Sébastien Perrier

Articles

  • Article |

    The structure of many natural products can often only be confirmed by comparison with a synthetic sample. Here, scanning probe microscopy techniques allow the ultimate discrimination between structures suggested by the standard range of analytical techniques, proving the power of single-molecule imaging for molecular structure determination.

    • Leo Gross
    • , Fabian Mohn
    • , Nikolaj Moll
    • , Gerhard Meyer
    • , Rainer Ebel
    • , Wael M. Abdel-Mageed
    •  & Marcel Jaspars
  • Article |

    Catalytically oxidizing water to produce oxygen is so challenging that even the enzyme that performs the task in nature must be regenerated every 30 mins. Now, stable oxygen-evolving anodes have been made by tethering a polyoxometalate catalyst to a conducting bed of carbon nanotubes.

    • Francesca M. Toma
    • , Andrea Sartorel
    • , Matteo Iurlo
    • , Mauro Carraro
    • , Pietro Parisse
    • , Chiara Maccato
    • , Stefania Rapino
    • , Benito Rodriguez Gonzalez
    • , Heinz Amenitsch
    • , Tatiana Da Ros
    • , Loredana Casalis
    • , Andrea Goldoni
    • , Massimo Marcaccio
    • , Gianfranco Scorrano
    • , Giacinto Scoles
    • , Francesco Paolucci
    • , Maurizio Prato
    •  & Marcella Bonchio
  • Article |

    Monodentate ligands with complementary hydrogen bonding units can self-assemble to form pseudo-bidentate ligands. Here, a combinatorial approach to the synthesis and analysis of reactions using these ligands allows the rapid identification of the most suitable ligand pair for highly selective rhodium-catalysed asymmetric hydrogenation.

    • Joerg Wieland
    •  & Bernhard Breit
  • Article |

    A series of chiral metal–organic frameworks with channels of tunable size have been modified through post-synthetic functionalization to bear catalytic centres along their pore walls. The resulting materials catalyse a carbon–carbon-bond-forming reaction, and the enantioselectivity of the transformation can be altered by changing the size of the channels.

    • Liqing Ma
    • , Joseph M. Falkowski
    • , Carter Abney
    •  & Wenbin Lin
  • Article |

    Kinetic resolution — which relies on the difference in reaction rates of isomers — is most often used in the context of separation of stereoisomers. Here, a self-assembling container molecule is used to protect certain guest molecules from the bulk reaction medium and effect a resolution of constitutional isomers.

    • Simin Liu
    • , Haiying Gan
    • , Andrew T. Hermann
    • , Steven W. Rick
    •  & Bruce C. Gibb
  • Article |

    A detailed understanding of solute–solvent interactions is crucial to appreciating the important role aqueous ions play in various biological and catalytic processes. Now soft X-ray spectroscopy reveals new features in aqueous ion spectra that are due to solute–solvent interaction and electron transfer.

    • Emad F. Aziz
    • , M. Hannelore Rittmann-Frank
    • , Kathrin M. Lange
    • , Sébastien Bonhommeau
    •  & Majed Chergui
  • Article |

    The structural diversity of natural products offers great potential for the identification of new drugs. Here, the gene cluster responsible for the production of a meroterpenoid, pyripyropene, has been identified, and reconstitution of the biosynthetic sequence involved allows the production of analogous synthetic structures with potentially new bioactivity.

    • Takayuki Itoh
    • , Kinya Tokunaga
    • , Yudai Matsuda
    • , Isao Fujii
    • , Ikuro Abe
    • , Yutaka Ebizuka
    •  & Tetsuo Kushiro
  • Article |

    Magnesium hydride is a potential hydrogen-storage material, but its use is hampered by its high stability and slow hydrogen sorption processes. Dimeric magnesium compounds can act as models for these materials, and it is now shown that they can be easily and reversibly hydrogenated across the magnesium–magnesium bond.

    • Simon J. Bonyhady
    • , David Collis
    • , Gernot Frenking
    • , Nicole Holzmann
    • , Cameron Jones
    •  & Andreas Stasch
  • Article |

    Tetrathiafulvalene (TTF)-based [3]catenanes are shown to display multiple stable redox states dominated by TTF···TTF radical dimer interactions occurring within the cavity of what is essentially a ‘molecular flask’. These stabilizing interactions are found to be the basis of a novel recognition motif that can be employed to drive molecular switching under redox control.

    • Jason M. Spruell
    • , Ali Coskun
    • , Douglas C. Friedman
    • , Ross S. Forgan
    • , Amy A. Sarjeant
    • , Ali Trabolsi
    • , Albert C. Fahrenbach
    • , Gokhan Barin
    • , Walter F. Paxton
    • , Sanjeev K. Dey
    • , Mark A. Olson
    • , Diego Benítez
    • , Ekaterina Tkatchouk
    • , Michael T. Colvin
    • , Raanan Carmielli
    • , Stuart T. Caldwell
    • , Georgina M. Rosair
    • , Shanika Gunatilaka Hewage
    • , Florence Duclairoir
    • , Jennifer L. Seymour
    • , Alexandra M. Z. Slawin
    • , William A. Goddard III
    • , Michael R. Wasielewski
    • , Graeme Cooke
    •  & J. Fraser Stoddart
  • Article |

    The phosphoric acid fuel cell is limited by its slow rate of oxygen reduction at the cathode, but now an approach to the rational design of improved catalysts for this process has been developed. Molecular patterning of platinum surfaces with cyanide adsorbates is used to block the adsorption of spectator anions without hindering oxygen reduction, thus improving catalytic activity.

    • Dusan Strmcnik
    • , María Escudero-Escribano
    • , Kensaku Kodama
    • , Vojislav R. Stamenkovic
    • , Angel Cuesta
    •  & Nenad M. Marković
  • Article |

    The cortistatins have attracted a lot of attention in the synthetic community because of their interesting biological activity. Here, four of the cortistatin family are prepared from a common precursor. This efficient synthesis will assist in an investigation of structure–activity relationships and understanding of the biosynthetic route to these compounds.

    • Alec N. Flyer
    • , Chong Si
    •  & Andrew G. Myers
  • Article |

    Discrete metal–organic polyhedra are usually prepared from metal ions and organic linkers by a direct self-assembly approach in solution. Now, using the polyhedra themselves as starting materials, it has been shown that a wider variety of structures can be obtained through the partial or complete substitution of their linkers.

    • Jian-Rong Li
    •  & Hong-Cai Zhou

In Your Element

  • In Your Element |

    Although reports on the use of nickel can be traced back to 3,500 BC, Catherine Drennan points to a resurgence of interest in nickel-based chemistry in the energy and environmental areas.

    • Catherine L. Drennan