Chemistry articles within Nature Chemistry

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  • Article |

    Porous coordination polymers — PCPs, also known as metal–organic framework materials — have been widely investigated for their useful properties, but controlling their size and shape in a nanocrystalline form is difficult. Now, a rapid method of preparing porous crystalline nanosized PCPs that uses a microemulsion system under ultrasonic irradiation has been reported.

    • Daisuke Tanaka
    • , Artur Henke
    •  & Juergen Groll

  • Research Highlights |

    A rationally designed highly electrophilic iridium complex excels at catalysing the formation of five-membered carbocycles.

    • Stephen Davey

  • Research Highlights |

    The water molecules surrounding a protein can be dissolved in an organic solvent to form dry, glassified microbeads of controllable size that preserve the protein's activity.

    • Anne Pichon

  • Article |

    N-heterocyclic carbenes have been shown to be versatile ligands for metal catalysts and even catalysts in their own right. Here, bulky N-heterocyclic carbenes are shown to stabilize paramagnetic and electron-poor species sufficiently for their crystallographic characterization.

    • Olivier Back
    • , Bruno Donnadieu
    •  & Guy Bertrand

  • Research Highlights |

    Microporous crystals formed by hydrogen-bonded dipeptides show different permeabilities for argon, nitrogen and oxygen.

    • Anne Pichon

  • Research Highlights |

    Strontium-doped lanthanum perovskite oxides can help to remove harmful NOx pollution from diesel exhaust.

    • Neil Withers

  • Article |

    Although the triiodide/iodide redox couple works efficiently in dye-sensitized solar cells it restricts functionality by absorbing visible light. Now, a disulfide/thiolate redox couple that has negligible absorption in the visible spectral range is presented, which in conjunction with a sensitized heterojunction, displays an efficiency of 6.4% under standard illumination test conditions.

    • Mingkui Wang
    • , Nathalie Chamberland
    •  & Michael Grätzel

  • Article |

    Identifying the best catalyst for a particular reaction traditionally involves testing a wide variety of metal and ligand combinations in standard reactions. Here, the best catalyst is found by using mass spectrometry to identify the least stable — and thus most reactive — intermediate in a dynamic mixture of complexes.

    • Jeroen Wassenaar
    • , Eveline Jansen
    •  & Joost N. H. Reek

  • Research Highlights |

    A double-reductive alkylation of amides with two different organometallic compounds allows the direct formation of a tertiary alkylamines in one pot.

    • Stephen Davey

  • Research Highlights |

    An efficient heterogeneous catalyst for the conversion of glucose into fructose has been prepared by incorporating tin centres into the framework of a zeolite.

    • Anne Pichon

  • In Your Element |

    Ram Mohan looks at how bismuth — a remarkably harmless element among the toxic heavy metals in the periodic table — has sparked interest in areas varying from medicinal to industrial chemistry.

    • Ram Mohan

  • News & Views |

    The convergent total synthesis of the pore-forming polytheonamide B — a linear peptide natural product — pokes holes through perceived limitations in de novo peptide synthesis, and provides access to novel synthetic membrane channels.

    • Craig J. Forsyth

  • News & Views |

    Macrocyclic compounds can serve as hosts for smaller organic molecules, but precise control over the uptake and release of the guests remains challenging. Now, a host–guest system has been built that responds to the addition of metal ions, showing promise for drug-delivery applications.

    • Werner M. Nau

  • News & Views |

    A strong acid catalyst and a small change to one reactant have transformed a 37-year-old 'curiosity' into a useful chemical reaction that has great potential in organic synthesis.

    • Sarah E. Steinhardt
    •  & Christopher D. Vanderwal

  • Editorial |

    Is any experiment worth your health — or your life?

  • Thesis |

    In the sink-or-swim world of academia, Bruce C. Gibb considers what support structures should be put in place for those who have only just entered the water.

    • Bruce C. Gibb

  • News & Views |

    Electrochemistry has so far been mostly centred around measuring factors and coefficients. Through the reversible reduction and oxidation of an electrode coating formed from three-dimensional hybrid aniline–gold nanoparticles, it has now moved on to controlling the pH of a solution, thus triggering specific reactions.

    • Reginald M. Penner

  • Article |

    Helium is a reluctant participant when it comes to chemical reactions and bonding and it is one of only two stable elements for which there are currently no known crystalline derivatives. Now, based on a computational investigation, compounds containing helium atoms that form charge-shift, rather than covalent bonds have been proposed.

    • Henry S. Rzepa

  • Article |

    Interfaces between organic molecules and metal surfaces have a key role in determining the performance of many emerging technologies. Now an intensive experimental study — supported by calculations — of tetracyano-p-quinodimethane molecules on a copper surface, reveals structural rearrangement of both the organic molecules and the surface atoms after charge transfer across the interface.

    • Tzu-Chun Tseng
    • , Christian Urban
    •  & Rodolfo Miranda

  • Research Highlights |

    A stable water-oxidation catalyst containing a cobalt oxide core has been made.

    • Neil Withers

  • Research Highlights |

    The sliding movement of the actin–myosin protein conjugate responsible for contracting muscles can be inhibited using a dendrimer that glues them together.

    • Gavin Armstrong

  • Review Article |

    Rare-earth metal dialkyl complexes can be readily transformed into the corresponding cationic monoalkyl species — which have been shown to catalyse a range of (co)polymerization processes — as well as into polyhydride complexes that have unique structures and a rich reaction chemistry.

    • Masayoshi Nishiura
    •  & Zhaomin Hou

  • Article |

    The reactivity of organoaluminium reagents makes them particularly attractive nucleophiles for a wide range of organic reactions. Here, the use of metal halide catalysts provides access to functionalized organoaluminium reagents directly from the metal. The utility of these organoaluminium reagents is then demonstrated by their reaction with a wide variety of electrophilic coupling partners.

    • Tobias Blümke
    • , Yi-Hung Chen
    •  & Paul Knochel

  • Article |

    Gold nanoparticles can catalyse oxidation reactions in remarkably mild conditions and have excited much interest in recent years. With experimental studies disagreeing over the size of the most active nanoparticles, density functional calculations have now shown that limiting the particle size to below two nanometres is crucial.

    • Olga Lopez-Acevedo
    • , Katarzyna A. Kacprzak
    •  & Hannu Häkkinen

  • Article |

    Viruses are ideal templates for engineering multifunctional materials. They can exhibit multiple copies of surface ligands and encapsulate inorganic and organic materials. Here, viruses are assembled into well-defined micrometre-sized objects by the addition of dendritic linkers. The linkers are designed to decompose on irradiation, which results in the release of the original virus particles.

    • Mauri A. Kostiainen
    • , Oksana Kasyutich
    •  & Roeland J. M. Nolte

  • Article |

    Macrocyles capable of hosting other molecules inside their hollow interiors have been used extensively to make threaded complexes and interlocked molecules. Now, a relatively large and flexible tetracationic macrocycle has been shown to bind anionic guests to form pseudorotaxanes that form extended structures in solution and the solid state.

    • Han-Yuan Gong
    • , Brett M. Rambo
    •  & Jonathan L. Sessler

  • Article |

    Single-molecule magnets are clusters of metal ions linked together by organic bridges, with properties typically arising from exchange coupling of unpaired metal electrons. In mixed-valence systems, another magnetic mechanism involving itinerant electrons can also occur and induce a high-spin ground state. Now, such electron delocalization has been observed through an imidazolate bridge — a common linker in metal-organic architectures — which may enable the construction of higher spin clusters or three-dimensional magnets.

    • Bettina Bechlars
    • , Deanna M. D'Alessandro
    •  & Jeffrey R. Long

  • Article |

    Although enzymes are known to use diiron centres to cleave carbon–hydrogen bonds, preparing synthetic compounds that can break these strong, stable bonds has remained notoriously difficult. Now, converting a low-spin ‘diamond core’ iron–oxo biomimetic complex into its high-spin ‘open core’ counterpart has enhanced its C–H bond cleavage ability by over a million times.

    • Genqiang Xue
    • , Raymond De Hont
    •  & Lawrence Que Jr

  • Research Highlights |

    The intercalation of potassium into a simple aromatic hydrocarbon results in a new class of organic superconductors.

    • Neil Withers

  • Article |

    A wide range of porous framework materials has been assembled with a modular approach that takes advantage of prefabricated structural building units (SBUs). Now, it has been shown that functional all-inorganic frameworks can be made from a macrocyclic polyoxometalate SBU — that has a built-in aperture approximately 1 nm in diameter — linked together with redox-switchable metal ions.

    • Scott G. Mitchell
    • , Carsten Streb
    •  & Leroy Cronin

  • Article |

    Chiral thiols and organosulfur compounds are important in many areas of chemistry but there are relatively few methods available for their efficient enantioselective synthesis. Here, a kinetic resolution of chiral thiols is reported along with a demonstration that a concomitant desymmetrization of the acylating agent is beneficial for the selectivity of both processes.

    • Aldo Peschiulli
    • , Barbara Procuranti
    •  & Stephen J. Connon

  • Article |

    Nanotubular structures made from different materials are being investigated for applications ranging from sensing to drug delivery, but controlling how they interact with ‘cargo’ molecules has proved challenging. Now, the selective uptake, precise positioning and triggered release of gold nanoparticles has been achieved with nanotubes assembled from triangular DNA building blocks.

    • Pik Kwan Lo
    • , Pierre Karam
    •  & Hanadi F. Sleiman

  • Research Highlights |

    Molecular dynamics simulations have revealed important mechanistic details about how carbamate is transported from one active site to another within in an enzyme.

    • Gavin Armstrong

  • Research Highlights |

    Charge transport through electron hopping has been observed between π–π stacked perylene derivatives incorporated into DNA hairpin scaffolds.

    • Anne Pichon

  • News & Views |

    The interactions of electrons and water molecules are not just of great fundamental interest but are also studied to understand the role electrons have in damaging biomolecules. Now using ultrafast photoelectron spectroscopy, key details about the energy and lifetime of the hydrated electron in bulk and at an interface have been determined.

    • Daniel M. Neumark

  • Article |

    The existence of solvated electrons bound at the liquid/water surface has not, until now, been proved experimentally. Here, using ultrafast photoelectron spectroscopy, the existence, vertical binding energies and lifetimes of solvated electrons bound at the water-surface/vacuum interface, and in bulk solution, have been revealed.

    • Katrin R. Siefermann
    • , Yaxing Liu
    •  & Bernd Abel

  • Research Highlights |

    Thermally stable stereoisomers can be interconverted by the application of a mechanical force using ultrasound irradiation.

    • Stephen Davey

  • Research Highlights |

    A krypton difluoride coordination compound — where it acts as a ligand to a bromine atom — has been synthesized and studied.

    • Neil Withers

  • News & Views |

    The long-awaited first total synthesis of the structurally intriguing natural product palau'amine has now been achieved. The synthesis features cascade reactions and an 'across ring' stitching of a 'macropalau'amine', and sets the bar for future efforts towards an enantioselective variant.

    • Daniel Romo

  • News & Views |

    Public acceptance of the expansion of nuclear power may hinge on the safe disposal of nuclear waste. Ion exchangers that remove radioactive metals — such as caesium ions — from the waste could provide part of the answer, so a flexible-framework material that selectively grab them from solution is a step in the right direction.

    • Abraham Clearfield

  • News & Views |

    Monitoring the dynamics of a single molecule is impeded by their motion in solution, and immobilizing them without changing their properties is problematic. By using a trapping method that counteracts a molecule's Brownian motion, the complex dynamics of a fluorescent protein, allophycocyanin, have been investigated.

    • Peter Dedecker
    •  & Johan Hofkens

  • News & Views |

    Electromerism is an unfamiliar concept to many chemists and refers to molecules that are not conventional isomers but instead differ in how the electrons are distributed across their structure. A novel example of such electromers has now been demonstrated.

    • Thomas Bally

  • News & Views |

    Supramolecular gels, which rely on non-covalent interactions, are typically fragile. Now, hydrogels that possess remarkable mechanical strength combined with the ability to rapidly self-heal have been built through multiple non-covalent interactions.

    • David K. Smith

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