Browse Articles

  • Article |

    Single-molecule force spectroscopy reveals that maleimide–thiol adducts can be stabilized by stretching through a force-dependent kinetic control mechanism. This unconventional use of mechanochemistry enabled us to produce stable polymer–protein conjugates by simply applying a mechanical force to the maleimide–thiol adducts through mild ultrasonication.

    • Wenmao Huang
    • , Xin Wu
    • , Xiang Gao
    • , Yifei Yu
    • , Hai Lei
    • , Zhenshu Zhu
    • , Yi Shi
    • , Yulan Chen
    • , Meng Qin
    • , Wei Wang
    •  & Yi Cao
  • Article |

    Heterometallic clusters have shown promise in catalysis and small-molecule activation, but species comprising uranium–metal bonds have remained difficult to synthesize. Now, facile reactions between uranium and nickel precursors have led to nickel-bridged diuranium clusters supported by a heptadentate N4P3 scaffold. Computational analysis points to an unusual electronic configuration for uranium, U(iii)-5f26d1.

    • Genfeng Feng
    • , Mingxing Zhang
    • , Dong Shao
    • , Xinyi Wang
    • , Shuao Wang
    • , Laurent Maron
    •  & Congqing Zhu
  • Article |

    Conjugated mesopolymers can combine the advantages of polymers and oligomers, but have received less attention as semiconducting materials. Now, such compounds have been synthesized by direct arylation polycondensation that exhibit high molecular regularity, solubility and solution processability. These mesopolymers also show electron mobilities that are significantly better than those of their polymer counterparts.

    • Zhenjie Ni
    • , Hanlin Wang
    • , Huanli Dong
    • , Yanfeng Dang
    • , Qiang Zhao
    • , Xiaotao Zhang
    •  & Wenping Hu
  • News & Views |

    Strained boronate complexes have now been shown to enable an unprecedented cross-coupling reaction across a C–C σ-bond. Using this approach, highly functionalized cyclobutanes can be prepared with excellent stereocontrol from readily available reagents.

    • Alejandro Parra
    •  & Mariola Tortosa
  • Thesis |

    The elements of the periodic table are more integral to our daily lives now than they have ever been before. Bruce C. Gibb takes a look at the factors used to decide just how critical the supply of any given mineral is.

    • Bruce C. Gibb
  • In Your Element |

    Lanthanum is the first lanthanide — or the last. Or it’s not a lanthanide at all. In any case, Brett Thornton and Shawn Burdette are sure that it’s an element that might or might not be in group three of the periodic table.

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

    Michelle Francl suggests that we should expand our view of the periodic table to new dimensions.

    • Michelle Francl
  • News & Views |

    Most compounds form crystals so small that scientists cannot experimentally determine their atomic structures using X-ray crystallography. Microcrystal electron diffraction now provides a unique solution for this challenge.

    • Oleg Sitsel
    •  & Stefan Raunser
  • News & Views |

    Intersystem crossing plays a role in the mechanism of many reactive collisions between atomic species and organic molecules, and has been generally observed when the reactants are still approaching one another. Now, intersystem crossing has been observed to also occur after their initial interaction.

    • Luis Bañares
  • Article |

    Anchored single-atom catalysts have recently been shown to be very active for various processes, however, a catalyst that features two adjacent copper atoms—which we call an atom-pair catalyst—is now reported. The Cu10–Cu1x+ pair structures work together to carry out the critical bimolecular step in CO2 reduction.

    • Jiqing Jiao
    • , Rui Lin
    • , Shoujie Liu
    • , Weng-Chon Cheong
    • , Chao Zhang
    • , Zheng Chen
    • , Yuan Pan
    • , Jianguo Tang
    • , Konglin Wu
    • , Sung-Fu Hung
    • , Hao Ming Chen
    • , Lirong Zheng
    • , Qi Lu
    • , Xuan Yang
    • , Bingjun Xu
    • , Hai Xiao
    • , Jun Li
    • , Dingsheng Wang
    • , Qing Peng
    • , Chen Chen
    •  & Yadong Li
  • Article |

    Despite their huge potential in medicinal chemistry, current approaches for the synthesis of fluorinated piperidines are often impractical. A straightforward process for the rhodium-catalysed dearomatization–hydrogenation of fluoropyridines has now been described. This strategy enables the highly diastereoselective formation of a variety of all-cis-(multi)fluorinated piperidines and the study of their conformational behaviour.

    • Zackaria Nairoukh
    • , Marco Wollenburg
    • , Christoph Schlepphorst
    • , Klaus Bergander
    •  & Frank Glorius
  • Article |

    Developing a stable metallic lithium anode is necessary for next-generation batteries; however, lithium is prone to corrosion, a process that must be better understood if practical devices are to be created. A Kirkendall-type mechanism of lithium corrosion has now been observed. The corrosion is fast and is governed by a galvanic process.

    • Dingchang Lin
    • , Yayuan Liu
    • , Yanbin Li
    • , Yuzhang Li
    • , Allen Pei
    • , Jin Xie
    • , William Huang
    •  & Yi Cui
  • Article |

    A two-coordinate monovalent gold complex that features a highly polarized aluminium–gold covalent bond, Alδ+–Auδ−, has been synthesized using a very strongly electron-donating aluminyl ligand. In solution, the complex reacts as a nucleophilic source of gold towards heteroallenes such as carbodiimides and CO2.

    • Jamie Hicks
    • , Akseli Mansikkamäki
    • , Petra Vasko
    • , Jose M. Goicoechea
    •  & Simon Aldridge
  • Article |

    One-dimensional diffusive binding represents an important mechanism used by nature to facilitate many fundamental biochemical processes. Now, a completely synthetic system with similar capabilities has been constructed. The system was exploited to significantly speed up bimolecular reactions and to catalytically transport molecular cargo in solution and within physically separated compartments.

    • Lifei Zheng
    • , Hui Zhao
    • , Yanxiao Han
    • , Haibin Qian
    • , Lela Vukovic
    • , Jasmin Mecinović
    • , Petr Král
    •  & Wilhelm T. S. Huck
  • Article |

    Symmetrical protein oligomers perform key structural and catalytic functions in nature, but engineering such oligomers synthetically is challenging. Now, oppositely supercharged synthetic variants of normally monomeric proteins have been shown to assemble via specific, introduced electrostatic contacts into symmetrical, highly well-defined oligomers.

    • Anna J. Simon
    • , Yi Zhou
    • , Vyas Ramasubramani
    • , Jens Glaser
    • , Arti Pothukuchy
    • , Jimmy Gollihar
    • , Jillian C. Gerberich
    • , Janelle C. Leggere
    • , Barrett R. Morrow
    • , Cheulhee Jung
    • , Sharon C. Glotzer
    • , David W. Taylor
    •  & Andrew D. Ellington
  • 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
  • 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
  • In Your Element |

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

    • Yuri Oganessian
  • 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
  • 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
  • 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
  • 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 |

    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 |

    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 |

    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 |

    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 |

    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 |

    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 |

    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 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