Chemistry articles within Nature Chemistry

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  • In Your Element |

    Herbert Roesky relates how the small, highly electronegative fluorine atom unveiled the chemical reactivity of noble gases and found many practical applications. but it can also render organic compounds highly toxic or pollutants.

    • Herbert W. Roesky

  • News & Views |

    Monomers that contain masked ketene groups provide new opportunities for facile crosslinking and post-synthetic modification of polymers in a wide variety of materials applications.

    • Steve Rimmer

  • Commentary |

    Traditional scientific conferences can be costly and time-consuming, and certainly aren't 'green', with participants travelling long distances to attend. Are there advantages to meetings held in the virtual world, and can they really offer equally satisfying — or even better — experiences compared with the real world?

    • Christopher J. Welch
    • , Sanjoy Ray
    •  & Martin Leach

  • Article |

    Stepwise deuteration of protonated methane CH5+ — a fluxional structure that undergoes ‘hydrogen scrambling’ — leads to dramatic changes in the infrared spectra of the isotopologues. The spectra can be assigned using ab initio quantum simulations that account for the non-classical occupation — by H and D atoms — of topologically different sites within the molecule.

    • Sergei D. Ivanov
    • , Oskar Asvany
    •  & Stephan Schlemmer

  • Article |

    Steric, torsion, stereoelectronic and polar effects are widely used to explain and predict the stereochemical outcome of synthetic organic reactions. Here, the asymmetric distortion of the reactant is considered and used to explain the observed stereoselectivity where these accepted models are unable to provide a clear prediction.

    • Robert V. Kolakowski
    •  & Lawrence J. Williams

  • Article |

    Formic acid fuel cells require nanosized intermetallic nanoparticles as anode catalysts, but current techniques are poor at producing the small size required. Now, surface-modified ordered mesoporous carbons have been used to produce nanocrystallites as small as 1.5 nm that are extremely active catalysts.

    • Xiulei Ji
    • , Kyu Tae Lee
    •  & Linda F. Nazar

  • Article |

    A triflimide-catalysed rearrangement of N-allylhydrazones has been developed that allows for the generation of a sigma bond between two unfunctionalized sp3 carbons such that no clear marker remains for how the bond was formed. This traceless bond construction offers new avenues for convergent fragment coupling in synthetic strategies.

    • Devon A. Mundal
    • , Christopher T. Avetta Jr
    •  & Regan J. Thomson

  • Research Highlights |

    The slow oxidation of tellurium in semiconductor cadmium telluride nanoparticles, accompanied by the replacement of tellurium by sulfur, has led to CdS/CdTe nanoparticles that self-assemble under visible light into twisted nanoribbons.

    • Anne Pichon

  • Research Highlights |

    The motion of a molecule on a hot surface is investigated using molecular dynamics, revealing a regime of fast rolling and vibrational excitation.

    • Gavin Armstrong

  • Article |

    Fullerene cages that break the isolated pentagon rule are rare and often unstable. Now a range of fullerenes that feature three sequentially fused pentagons of carbon have been stabilized by chlorination.

    • Yuan-Zhi Tan
    • , Jia Li
    •  & Lan-Sun Zheng

  • Article |

    Polytheonamide B is a large non-ribosomal peptide with very high bioactivity. The synthesis described here includes the first preparation of several non-proteinogenic amino acids and a general coupling strategy for large non-natural peptides. The synthesis is a key step necessary to understand and utilize the bioactivity of this and similar compounds.

    • Masayuki Inoue
    • , Naoki Shinohara
    •  & Shigeru Matsuoka

  • Research Highlights |

    The reversible conversion between guanine-based extended ribbons and macrocyclic G-quartets has been directly observed at a liquid–solid interface by scanning tunnelling microscopy.

    • Anne Pichon

  • Research Highlights |

    Positive charges lower, and negative charges raise the freezing temperature of supercooled water on a pyroelectric surface, as well as affecting at which interface nucleation takes place.

    • Gavin Armstrong

  • Review Article |

    The field of organocatalysis has grown rapidly in the past decade to become, along with metal catalysis and biocatalysis, a third pillar of asymmetric catalysis. Here, progress in the use of organocatalytic cascade reactions for total synthesis is reviewed. The elegance and efficiency of such cascades mean that they have emerged as a powerful tool in synthetic organic chemistry.

    • Christoph Grondal
    • , Matthieu Jeanty
    •  & Dieter Enders

  • Research Highlights |

    A Brønsted acid co-catalyst is the key to the synthesis of furans by alkene cross-metathesis.

    • Laura Croft

  • Research Highlights |

    Exposing supramolecular filaments to X-rays results in spontaneous and reversible crystalline ordering.

    • Neil Withers

  • News & Views |

    A linear molecule containing three bipyridine ligands can be wrapped around a single metal-ion template to form an open-knot complex. The loose ends of the knot can be 'tied' together through esterification or olefin-metathesis reactions to form closed knots that do not unravel when the metal template is removed.

    • Edward E. Fenlon

  • Article |

    The movement of oxygen ions through materials is important in electrolytes and separation membranes, but is rare at lower temperatures. Two different low-temperature diffusion pathways are revealed during the reduction process of CaFeO2.5 to CaFeO2. The two pathways are significantly different, resulting in anisotropy.

    • Satoru Inoue
    • , Masanori Kawai
    •  & Yuichi Shimakawa

  • Article |

    The uptake of ammonia by a covalent–organic framework (COF) containing a high density of Lewis-acidic boron sites has been found to be significantly greater than that exhibited by other state-of-the-art porous materials. The ammonia can be removed by heating under vacuum and the structural integrity of the COF is maintained during adsorption/desorption cycles.

    • Christian J. Doonan
    • , David J. Tranchemontagne
    •  & Omar M. Yaghi

  • Article |

    The synthesis of interlocked compounds such as catenanes and rotaxanes has undergone much development in recent years, but molecular knots are still relatively hard to make. It has now been shown that a linear bipyridine oligomer can fold around a single zinc-ion template to form a complex that can be cyclized to give a molecular trefoil knot.

    • Jun Guo
    • , Paul C. Mayers
    •  & Christopher A. Hunter

  • Article |

    A methodology for describing local electronic transmission through bridging molecules between metallic electrodes is presented. Its application to simple alkane, phenyl and cross-conjugated systems highlights an unexpected number of cases whereby ‘through space’, rather than ‘through bond’ terms dominate and that interference effects coincide with the reversal of ring currents.

    • Gemma C. Solomon
    • , Carmen Herrmann
    •  & Mark A. Ratner

  • Research Highlights |

    Silicon-based polymers have been assembled into honeycomb films that exhibit good flexibility, stability and thermal conductivity, showing great promise for industrial applications.

    • Anne Pichon

  • Research Highlights |

    Replacing readily hydrolysable ester linkages with amides in a natural adjuvant has resulted in not only more stable, but significantly more active and less toxic analogues.

    • Georgia Tsoukala

  • News & Views |

    Yttrium-based catalysts can be used to stitch together two different lactone monomers in an alternating fashion to produce polyesters with well-defined primary structures. The ability to control the sequence of building blocks in polymers with increasing levels of precision offers new opportunities for tailoring the properties of designer synthetic macromolecules.

    • Jean-François Lutz

  • News & Views |

    The stereochemical lability of cycloalkylzinc reagents combined with a large difference in reactivity between epimers has been exploited to form a wide variety of interesting organic compounds with both high yields and diastereoselectivities.

    • Frank Glorius

  • News & Views |

    Quantum tunnelling can at times be the cause of kinetic isotope effects, and in these cases conventional wisdom has been that molecules with isotopes of larger mass will react more slowly. New calculations, however, predict that sometimes the reverse should be true.

    • Barry K. Carpenter

  • News & Views |

    An enzyme that is unusually tolerant of a truly broad range of substrates can catalyse aldol-type chemistry on sugars in which the various hydroxyl groups are protected. The new methodology combines some of the most important advantages of enzyme and small-molecule catalysis.

    • Benjamin G. Davis

  • News & Views |

    The use of conventional computers to calculate molecular properties is hindered by the exponential increase in computational cost on increasing the size of the molecules studied. Using quantum computers could be the solution and the initial steps are now being taken.

    • Kenneth R. Brown

  • Editorial |

    The financial crisis that continued to grip the world in 2009 has brought the question of who should pay for scientific research — and what it should set out to achieve — into sharper focus than ever.

  • Thesis |

    Michelle Francl wonders why people almost inevitably draw scientists as men with weird hair and glasses, and why there is no such thing as a 'draw a lawyer' test.

    • Michelle Francl

  • In Your Element |

    In the search for superheavy elements, element 112 was a stepping stone towards the 'islands of stability'. Sigurd Hofmann now relates the steps that led to its 'creation' and detection.

    • Sigurd Hofmann

  • News & Views |

    Chemical reactions of fullerenes and metallofullerenes lined up inside single-walled carbon nanotubes can be monitored at the atomic scale inside an aberration-corrected transmission electron microscope.

    • Mauricio Terrones

  • News & Views |

    A molecular 'walker' can be made to move up and down a molecular 'track' by alternately locking and unlocking the two different types of covalent bonds that join the two components together. By changing the conditions under which one of the bond-forming/bond-breaking processes occurs, a directional bias for walking can be achieved.

    • Sijbren Otto

  • Article |

    Chlorine-activation reactions on polar stratospheric cloud (PSC) particles are crucial to ozone depletion in the winter/spring polar stratosphere and their rates depend on the phase state of the PSC particle surface. Now experiments show that, on particle formation, a phase separation into pure ice with a residual solution coating takes place.

    • Anatoli Bogdan
    • , Mario J. Molina
    •  & Thomas Loerting

  • Article |

    The ability to rapidly functionalize polymers is vital for application development. Here, a method for the introduction of masked ketenes into monomers for both ring-opening metathesis and radical-type polymerizations is described. These ketenes — a group previously underexploited in polymer chemistry — allow both crosslinking and post-polymerization functionalization of the polymers.

    • Frank A. Leibfarth
    • , Minhyuk Kang
    •  & Craig J. Hawker

  • Article |

    The selective construction of multiple adjacent stereocentres is an important challenge for synthetic organic methodology, and only a handful of catalytic methods exist that can forge adjacent quaternary and tertiary stereocentres. Here, a palladium-catalysed multiple-bond-forming cascade leads to the construction of such systems in high yield, diastereomeric ratio and enantiomeric excess.

    • Jan Streuff
    • , David E. White
    •  & Brian M. Stoltz

  • Article |

    A method for observing the photodynamics of single molecules, without having to immobilize them to a surface or confine them within vesicles, has been used to study the important photosynthetic antenna protein, allophycocyanin. Light-induced conformational changes and a complex relationship between fluorescence intensity and lifetime have been observed.

    • Randall H. Goldsmith
    •  & W. E. Moerner

  • Research Highlights |

    Insertion of tungsten into a carbon–carbon bond of a heterocyclic ligand is a rare example of C–C bond activation and could provide new opportunities for the functionalization of aromatic molecules.

    • Stephen Davey

  • Research Highlights |

    Details of how an ion's reactivity is affected by the size and shape of the water network surrounding it have been elucidated using infrared spectroscopy.

    • Gavin Armstrong

  • Article |

    A combined theoretical and experimental approach has been used to investigate the structure and bonding of an all-boron cluster (B19−). Calculations suggest that the minimum energy structure is a near-planar one — in which a pentagonal B6 unit is encircled by a larger B13 ring — possessing two concentric aromatic π systems.

    • Wei Huang
    • , Alina P. Sergeeva
    •  & Alexander I. Boldyrev

  • Research Highlights |

    Arrays of silicon microwires grown by a vapour–liquid–solid method point the way to more efficient photocathodes.

    • Neil Withers

  • Research Highlights |

    A very mild method for the selective functionalization of tyrosine residues in proteins provides an attractive new option for bioconjugation.

    • Stephen Davey

  • Research Highlights |

    An unusual pathway in the reaction of various transition metal atoms with methanol leads to the direct production of hydrogen.

    • Gavin Armstrong

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