Articles in 2018

  • Article |

    A small-molecule manganese-based catalyst has been developed for the selective oxidation of strong methylene C–H bonds in the presence of more oxidatively labile aromatic functionality. This reaction enables the late-stage oxidative derivatization of medicinally relevant compound scaffolds and may also prove useful for diversifying aromatic drugs and natural products, as well as helping to quickly identify their metabolites.

    • Jinpeng Zhao
    • , Takeshi Nanjo
    • , Emilio C. de Lucca Jr
    •  & M. Christina White
  • Article |

    The concept of ‘interrupted transfer hydrogenation’ is presented, allowing the reductive hydroxymethylation of pyridinium and quinolinium salts at the C3 position. Mechanistic studies show the reaction occurs through an initial reversible iridium hydride reduction, followed by trapping of an enamine generated in situ before a final irreversible iridium-hydride reduction.

    • Alexandru Grozavu
    • , Hamish B. Hepburn
    • , Philip J. Smith
    • , Harish K. Potukuchi
    • , Peter J. Lindsay-Scott
    •  & Timothy J. Donohoe
  • News & Views |

    One goal of synthetic biologists is to develop artificial systems to help study biological processes. Now, cell communication and differentiation have been demonstrated using spatiotemporal patterns created in artificial multicellular compartments.

    • Yi Li
    •  & Rebecca Schulman
  • News & Views |

    Gold nanomaterials are attractive for a variety of applications, including in medicine, but need to be made stable enough to operate in biological systems. Now, gold nanorods have been stabilized for photothermal therapy by sequential surface anchoring, using a bidendate PEG-based ligand that features a thiolate moiety and an Au–NHC moiety.

    • Guillaume Médard
    •  & Anthoula C. Papageorgiou
  • Comment |

    Let’s flip over the periodic table to peek at its dark side.

    • Michelle Francl
  • Comment |

    The periodic table as we know it now seems complete, its current 118 elements nicely fitting in the seven familiar rows. How many more can be synthesized — and how will the table expand to accommodate them? The search for ever-heavier elements is pointing towards new periods, though perhaps not as neatly ordered as the first seven.

    • Hiromitsu Haba
  • Editorial |

    The United Nations has declared 2019 to be the International Year of the Periodic Table to coincide with this iconic chemical chart turning 150 years old. We join in with the celebrations by publishing a collection of articles that explore the edges of the periodic system and look at some of the elements that do — and don’t — make up the table.

  • Comment |

    Scientists and non-scientists alike have long been dreaming of elements with mighty properties. Perhaps the fictional materials they have conjured up are not as far from reality as it may at first seem.

    • Suze Kundu
  • In Your Element |

    Yuri Oganessian relates the story of the formation and decay of a doubly odd moscovium nucleus.

    • Yuri Oganessian
  • Comment |

    At its inception, the periodic table sorted elements by weight, so it may be surprising that the heaviest natural element on Earth remains controversial, or at best, nebulous. In the strange, perhaps-unfinished search for this weightiest nucleus, the only definitive conclusion is that it lies somewhere beyond uranium.

    • Brett F. Thornton
    •  & Shawn C. Burdette
  • Article |

    Intersystem crossing (ISC) is a radiationless process that is important in many photophysical systems. It has now been observed to take place in the exit channel for the reaction of ground-state atomic oxygen with alkylamines.

    • Hongwei Li
    • , Alexander Kamasah
    • , Spiridoula Matsika
    •  & Arthur G. Suits
  • Article |

    Preparation of well-defined N-glycans is very demanding, which hampers progress in glycoscience. Now, a biomimetic synthetic approach has been developed in which a readily available bi-antennary glycan can be converted in ten or fewer steps into multi-antennary N-glycans. This approach enables each arm to be uniquely extended by glycosyltransferases to give complex branched N-glycans.

    • Lin Liu
    • , Anthony R. Prudden
    • , Chantelle J. Capicciotti
    • , Gerlof P. Bosman
    • , Jeong-Yeh Yang
    • , Digantkumar G. Chapla
    • , Kelley W. Moremen
    •  & Geert-Jan Boons
  • Article |

    Rapamycin and FK506 are macrocycles that contain an FKBP-binding domain and an effector domain responsible for interacting with their respective targets, mTOR and calcineurin. Now, a 45,000-compound macrocycle library has been synthesized by fusing oligopeptides with synthetic FKBP-binding domains. Screening and subsequent optimization yielded a highly potent FKBP-dependent inhibitor of hENT1.

    • Zufeng Guo
    • , Sam Y. Hong
    • , Jingxin Wang
    • , Shahid Rehan
    • , Wukun Liu
    • , Hanjing Peng
    • , Manisha Das
    • , Wei Li
    • , Shridhar Bhat
    • , Brandon Peiffer
    • , Brett R. Ullman
    • , Chung-Ming Tse
    • , Zlatina Tarmakova
    • , Cordelia Schiene-Fischer
    • , Gunter Fischer
    • , Imogen Coe
    • , Ville O. Paavilainen
    • , Zhaoli Sun
    •  & Jun O. Liu
  • Article |

    Widely used palladium-mediated cross-couplings typically operate via a handful of fundamental reaction steps. Now, the reactivity between palladium and C–C σ-bonds has been described. This carbopalladation enables the coupling of organoboronic esters and aryl triflates across a C–C σ-bond of a bicyclo[1.1.0]butane to form disastereomerically pure trisubstituted cyclobutanes.

    • Alexander Fawcett
    • , Tobias Biberger
    •  & Varinder K. Aggarwal
  • Article |

    In native photosystem II (PSII), multi-chromophore antennas surround the reaction centre, capturing light and triggering the quantized (four-flashes) photo-oxidation of water to oxygen. The PSII ‘quantasome’ is the most efficient photo-electrolyser built so far. An artificial quantasome has now been developed; it is specifically designed for oxygen evolution by self-assembling light-harvesting-perylene bisimides with a ruthenium polyoxometalate water-oxidation catalyst.

    • Marcella Bonchio
    • , Zois Syrgiannis
    • , Max Burian
    • , Nadia Marino
    • , Erica Pizzolato
    • , Konstantin Dirian
    • , Francesco Rigodanza
    • , Giulia Alice Volpato
    • , Giuseppina La Ganga
    • , Nicola Demitri
    • , Serena Berardi
    • , Heinz Amenitsch
    • , Dirk M. Guldi
    • , Stefano Caramori
    • , Carlo Alberto Bignozzi
    • , Andrea Sartorel
    •  & Maurizio Prato
  • Article |

    The creation of a viable technology that enables precise control over the monomer sequence in synthetic polymers remains a significant challenge. High-purity sequence-defined polyethers with readily tailored side-chain functionalities have now been made through liquid-phase iterative synthesis combined with size-exclusion molecular sieving and real-time monitoring.

    • Ruijiao Dong
    • , Ruiyi Liu
    • , Piers R. J. Gaffney
    • , Marc Schaepertoens
    • , Patrizia Marchetti
    • , Christopher M. Williams
    • , Rongjun Chen
    •  & Andrew G. Livingston
  • Article |

    Some porous coordination polymers (PCPs) are known to be flexible and guest-responsive. Now, the guest-induced sharp, reversible structural transformation of the surface of a single-crystalline PCP has been visualized by in situ liquid-phase atomic force microscopy. This local response occurred at a guest concentration that was too low to trigger changes to the bulk crystal.

    • Nobuhiko Hosono
    • , Aya Terashima
    • , Shinpei Kusaka
    • , Ryotaro Matsuda
    •  & Susumu Kitagawa
  • Article |

    The SN2 reaction, a fundamental process associated with ionic chemistry, can be incorporated into a photochemical approach to creating radicals from alkyl electrophiles. This method occurs readily under visible-light irradiation, exhibits broad functional-group tolerance, and enables the formation of open-shell intermediates from substrates that are incompatible with traditional radical-generating strategies.

    • Bertrand Schweitzer-Chaput
    • , Matthew A. Horwitz
    • , Eduardo de Pedro Beato
    •  & Paolo Melchiorre
  • Article |

    Synthetic gene circuits encapsulated in lipid membrane compartments are often employed as artificial cell mimics, but these lack the complex behaviour of biological tissues. Now, spatial information based on chemical gradients has been used to engineer non-trivial dynamics such as signal propagation and differentiation in an artificial multicellular system.

    • Aurore Dupin
    •  & Friedrich C. Simmel
  • News & Views |

    Covalent organic frameworks (COFs), whose heterogeneous backbones can be easily tuned at the molecular level, are promising photocatalysts for artificial photosynthesis. Sulfone-rich crystalline, wettable COFs have now been shown to exhibit high photocatalytic hydrogen evolution rates with platinum nanoparticles as co-catalysts.

    • Tanmay Banerjee
    •  & Bettina V. Lotsch
  • In Your Element |

    Stuart Cantrill explains why looking to the heavens for element 61 — named after the Titan who stole fire from the gods — could extend the periodic table.

    • Stuart Cantrill
  • News & Views |

    Superoxide dismutase mimics can help regulate the levels of O2•− in the body, but typically rely on redox-active metals that are toxic in their free form. Now, a complex featuring a redox-active quinol moiety complexed to a redox-inactive zinc centre has been shown to catalyse O2•− dismutation.

    • Diane E. Cabelli
  • News & Views |

    Magnetic or electric fields have long been used to align or orient atomic or molecular species in a molecular beam. Now, experiments in a merged beam apparatus show that an external magnetic field can be used to favour one particular reaction path.

    • Astrid Bergeat
    •  & Christian Naulin
  • Article |

    Heteromultivalency, which involves the simultaneous interactions of more than one type of ligand with more than one type of receptor, is common in biological systems but challenging to engineer artificially. Now, a heteromultivalent platform prepared by co-assembling cyclodextrin and calixarene amphiphiles has shown self-adaptive peptide binding with high affinity. The platform was used to sequester amyloid β-peptides, reducing amyloid cytotoxicity.

    • Zhe Xu
    • , Shaorui Jia
    • , Wei Wang
    • , Zhi Yuan
    • , Bart Jan Ravoo
    •  & Dong-Sheng Guo
  • Article |

    Solid acid heterogeneous catalysts are widely used in industrial chemical processes, but understanding the exact molecular structures responsible for catalytic activity has proved difficult. Now, the structure of the strong Brønsted acid site for a sulfated zirconium-based metal–organic framework has been shown to consist of a specific arrangement of adsorbed water and sulfate moieties on the zirconium clusters.

    • Christopher A. Trickett
    • , Thomas M. Osborn Popp
    • , Ji Su
    • , Chang Yan
    • , Jonathan Weisberg
    • , Ashfia Huq
    • , Philipp Urban
    • , Juncong Jiang
    • , Markus J. Kalmutzki
    • , Qingni Liu
    • , Jayeon Baek
    • , Martin P. Head-Gordon
    • , Gabor A. Somorjai
    • , Jeffrey A. Reimer
    •  & Omar M. Yaghi
  • Article |

    Typical methods for the enantioselective α-functionalizations of ketones join ketone enolate nucleophiles with carbon or heteroatom electrophiles. We report an umpolung strategy to achieve this transformation with masked ketone electrophiles and a wide range of conventional heteroatom and carbon nucleophiles catalysed by a metallacyclic iridium catalyst in high yield and enantioselectivity.

    • Zhi-Tao He
    •  & John F. Hartwig
  • Article |

    The use of Li or Na as electrodes in Li-Na alloy–O2 batteries creates formidable challenges for both safety and stability because of their oxidative corrosion and the growth of dendrites and cracks on their surface. Now, an aprotic bimetal Li-Na alloy–O2 battery with high cycling stability has been developed using a Li-Na eutectic alloy anode and an electrolyte additive.

    • Jin-ling Ma
    • , Fan-lu Meng
    • , Yue Yu
    • , Da-peng Liu
    • , Jun-min Yan
    • , Yu Zhang
    • , Xin-bo Zhang
    •  & Qing Jiang
  • Article |

    Nitrogen fixation—the direct conversion of dinitrogen into ammonia or other nitrogen-containing products—is notoriously difficult to promote under mild conditions. Now, the reactivity of a multimetallic diuranium(iii) complex recently found capable of reducing and functionalizing N2 has been explored, replacing its nitride bridge with an oxo bridge, which resulted in a markedly different reactivity.

    • Marta Falcone
    • , Luciano Barluzzi
    • , Julie Andrez
    • , Farzaneh Fadaei Tirani
    • , Ivica Zivkovic
    • , Alberto Fabrizio
    • , Clemence Corminboeuf
    • , Kay Severin
    •  & Marinella Mazzanti
  • Article |

    Synthetic receptors can be used to help understand biological systems, but rarely compete in terms of affinity or selectivity. Now, a glucose-binding compound has been prepared that, despite its symmetry and simplicity, can match all but the strongest glucose-binding proteins. The high binding affinity and outstanding selectivity of this receptor may translate into biomedical applications.

    • Robert A. Tromans
    • , Tom S. Carter
    • , Laurent Chabanne
    • , Matthew P. Crump
    • , Hongyu Li
    • , Johnathan V. Matlock
    • , Michael G. Orchard
    •  & Anthony P. Davis
  • Article |

    N-heterocyclic carbenes (NHCs) are valuable surface anchors, but their use has remained limited to either spherical or planar nanomaterials. Now, they have been grafted onto gold nanorods through a bidentate ligand featuring a thiolate and a NHC–gold complex. The resulting nanorods are robust towards a wide range of harsh conditions and show promise for photothermal therapy.

    • Michelle J. MacLeod
    • , Aaron J. Goodman
    • , Hong-Zhou Ye
    • , Hung V.-T. Nguyen
    • , Troy Van Voorhis
    •  & Jeremiah A. Johnson
  • Article |

    The preparation of conjugates between proteins and small molecules is often challenging and requires several synthetic steps to functionalize each component for conjugation. Now, a conjugation methodology that leverages an electrophilic Se–S bond of selenocysteine to create bioconjugates between polypeptides and complex small molecules has been described.

    • Daniel T. Cohen
    • , Chi Zhang
    • , Colin M. Fadzen
    • , Alexander J. Mijalis
    • , Liana Hie
    • , Kenneth D. Johnson
    • , Zachary Shriver
    • , Obadiah Plante
    • , Scott J. Miller
    • , Stephen L. Buchwald
    •  & Bradley L. Pentelute
  • News & Views |

    The structural features and catalytic performances of catalyst particles have now been correlated using a fluorescence microscopy approach, by tracking nanoprobes as well as fluorescent reaction products. Such mapping enables exploration of structure–function relationships, which is essential for the design of better catalysts.

    • Wei Wang
  • Article |

    A 27 kDa photosensitizer protein (PSP) has now been developed and used to design a miniature photocatalytic CO2-reducing enzyme. Visible light drives the PSP efficiently to the long-lived triplet excited state (PSP*), and then to a super-reducing radical (PSP), which is strong enough to reduce many CO2-reducing catalysts. The 3D structure of PSP at 1.8 Å resolution was determined by X-ray crystallography.

    • Xiaohong Liu
    • , Fuying Kang
    • , Cheng Hu
    • , Li Wang
    • , Zhen Xu
    • , Dandan Zheng
    • , Weimin Gong
    • , Yi Lu
    • , Yanhe Ma
    •  & Jiangyun Wang
  • Article |

    The accessibility of materials’ porous domains is typically explored through bulk, and often non-visual, measurements. Now, an integrated fluorescence microscopy approach has established a direct visual relationship between pore architecture (which depends on pore sizes and interconnectivity), molecular transport, and in turn catalytic performance in industrial-grade catalyst particles.

    • Gareth T. Whiting
    • , Nikolaos Nikolopoulos
    • , Ioannis Nikolopoulos
    • , Abhishek Dutta Chowdhury
    •  & Bert M. Weckhuysen
  • Article |

    Catalytic activation of non-polar unstrained C−C bonds remains challenging. Now, the C(aryl)−C(aryl) bonds in 2,2′-biphenols can be cleaved using phosphinites as a recyclable directing group through a rhodium-based spirocyclic intermediate. In particular, the biaryl linkage found in softwood lignin could be cleaved using this method.

    • Jun Zhu
    • , Jianchun Wang
    •  & Guangbin Dong
  • Article |

    Limitations associated with the primary amination of aryl C–H bonds include the poor control of regioselectivity with electron-rich substrates and the challenging nature of the reaction in the case of electron-deficient arenes. Now, site-directed C–C bond primary amination of simple alkylarenes and benzyl alcohols provides a route for the direct and efficient preparation of anilines.

    • Jianzhong Liu
    • , Xu Qiu
    • , Xiaoqiang Huang
    • , Xiao Luo
    • , Cheng Zhang
    • , Jialiang Wei
    • , Jun Pan
    • , Yujie Liang
    • , Yuchao Zhu
    • , Qixue Qin
    • , Song Song
    •  & Ning Jiao
  • Article |

    Establishing a fundamental understanding of the electronic structure of actinides remains a challenging task for both experiment and theory. Now, it is shown that for the uranium dimer, relativity and electron correlation affects not only the nature of the electronic ground state, but also lowers the bond multiplicity in comparison to previous studies.

    • Stefan Knecht
    • , Hans Jørgen Aa. Jensen
    •  & Trond Saue
  • Article |

    A series of in vitro and in vivo studies has now shown that 5fC is linked to increased nucleosome occupancy and stability. Moreover, there is evidence that Schiff base formation between histones and 5fC impacts RNA polymerase II transcription activity in mouse embryonic stem cells.

    • Eun-Ang Raiber
    • , Guillem Portella
    • , Sergio Martínez Cuesta
    • , Robyn Hardisty
    • , Pierre Murat
    • , Zhe Li
    • , Mario Iurlaro
    • , Wendy Dean
    • , Julia Spindel
    • , Dario Beraldi
    • , Zheng Liu
    • , Mark A. Dawson
    • , Wolf Reik
    •  & Shankar Balasubramanian
  • News & Views |

    The applicability of metal-organic frameworks (MOFs) — in spite of their obvious potential — is hindered by stability issues, in particular towards water. Now, a ‘crumple zone’ concept has been proposed in which the presence of sacrificial bonds protects a MOF without significantly altering its structure or functionality.

    • Jürgen Senker
  • Thesis |

    Bruce Gibb focuses on fatty acids and wonders whether we’ll all be eating cyanobacteria before too long.

    • Bruce C. Gibb
  • In Your Element |

    Liz Williams explores the synthesis of tennessine, a story in which elements in supporting roles play a crucial part.

    • Elizabeth Williams
  • Article |

    So far, monosubstituted carbenes have only been spectroscopically characterized at very low temperatures. Now, it has been shown that a bulky, chemically inert, amino substituent is enough to tame the intrinsic tendency of carbenes towards dimerization, enabling their isolation at room temperature.

    • Ryo Nakano
    • , Rodolphe Jazzar
    •  & Guy Bertrand
  • Article |

    Steric effects in a fundamental energy-transfer reaction at collision energies from over 1,000 K down to 20 mK have now been studied. At high energies a pronounced dependence of the reactivity on the reactant orientation is observed, but this effect is not present at the lowest energies because of dynamic reorientation.

    • Sean D. S. Gordon
    • , Juan J. Omiste
    • , Junwen Zou
    • , Silvia Tanteri
    • , Paul Brumer
    •  & Andreas Osterwalder
  • Article |

    A chemical proteomic strategy has now been developed for profiling pyridoxal-phosphate dependent enzymes (PLP-DEs) in cells. Pyridoxal-based probes are phosphorylated in situ and bind to cellular PLP-DEs as cofactor mimics. The method accessed 73% of the Staphylococcus aureus PLP-dependent proteome and annotated uncharacterized proteins as novel PLP-DEs.

    • Annabelle Hoegl
    • , Matthew B. Nodwell
    • , Volker C. Kirsch
    • , Nina C. Bach
    • , Martin Pfanzelt
    • , Matthias Stahl
    • , Sabine Schneider
    •  & Stephan A. Sieber
  • Article |

    A direct conversion of carboxylic acids to alpha-olefins without the need for a stoichiometric additive has now been reported. The transformation is enabled by a dual cobalt/iridium proton-reduction–photoredox catalyst system, and can proceed on abundant fatty acids as well as on complex carboxylic acids.

    • Xiang Sun
    • , Junting Chen
    •  & Tobias Ritter
  • Article |

    Inhibiting the interaction between amyloid-β (Aβ) and a neuronal cell surface receptor, LilrB2, could offer a potential route for treating Alzheimer’s disease. Now, binding sites between Aβ and LilrB2 have been discovered and computational selection has identified inhibitors that block this binding site. Cell-penetrating inhibitors were found to block the Aβ–LilrB2 interaction and limit Aβ-induced cytotoxicity.

    • Qin Cao
    • , Woo Shik Shin
    • , Henry Chan
    • , Celine K. Vuong
    • , Bethany Dubois
    • , Binsen Li
    • , Kevin A. Murray
    • , Michael R. Sawaya
    • , Juli Feigon
    • , Douglas L. Black
    • , David S. Eisenberg
    •  & Lin Jiang
  • Article |

    Binding interactions, whether between a biological receptor and ligand or between a synthetic host and guest, are frequently stronger for larger molecules than for smaller ones. This is commonly believed to arise from increased dispersion interactions, but it has now been shown that cavitation energies—always required to dissolve molecules in solution—can be more important.

    • Suhang He
    • , Frank Biedermann
    • , Nina Vankova
    • , Lyuben Zhechkov
    • , Thomas Heine
    • , Roy E. Hoffman
    • , Alfonso De Simone
    • , Timothy T. Duignan
    •  & Werner M. Nau