Volume 11 Issue 3, March 2019

Volume 11 Issue 3

Supercharging protein self-assembly

The biological function of many proteins requires their assembly into a specific multi-protein structure. Designing artificial protein assemblies is difficult, however, and often relies on the precise redesign of protein–protein interfaces. Now, David W. Taylor, Andrew D. Ellington and colleagues have shown that supercharging green fluorescent protein enables variants of alternating net charge to assemble into a variety of well-defined architectures. The front cover shows a symmetrical 16-mer structure composed of two stacked rings of octamers.

See Simon et al

IMAGE: Jens Glaser, University of Michigan. COVER DESIGN: Tulsi Voralia.

Editorial

Comment

  • Comment |

    By expanding the scope of sustainability to the entire lifecycle of chemical products, the concept of circular chemistry aims to replace today’s linear ‘take–make–dispose’ approach with circular processes. This will optimize resource efficiency across chemical value chains and enable a closed-loop, waste-free chemical industry.

    • Tom Keijer
    • , Vincent Bakker
    •  & J. Chris Slootweg

Thesis

  • Thesis |

    After a PhD in Canada, a post-graduate career in the USA and fellowships in Japan and Austria, Reuben Hudson discusses how a universal language enables the meaningful pursuit of chemistry across cultures.

    • Reuben Hudson

News & Views

  • News & Views |

    Gold — long presumed to be an inert metal — has been increasingly shaking this image over the past couple of decades, mostly through electrophilic behaviour. Now, a two-coordinate gold complex has been shown to exhibit nucleophilic reactivity, with the insertion of CO2 into its polarized Auδ−–Alδ+ bond.

    • Didier Bourissou
  • News & Views |

    Finely tuned interactions in the second coordination sphere of enzymes or homogeneous catalysts can be essential for their function. Now, this concept has been applied to the surface of a catalytic material, utilizing pairs of Cu atoms for the selective electrochemical fixation of CO2.

    • Benjamin S. Natinsky
    •  & Chong Liu
  • News & Views |

    Enzymatic approaches to synthesize oligosaccharides offer an alternative to chemical syntheses for the production of homogeneous glycans; however, enzyme-based routes typically require lengthy processes. Now, the design of a water-soluble affinity tag has enabled the automation of multistep enzymatic syntheses of mammalian oligosaccharides.

    • Nicola L. B. Pohl

Articles

  • 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 |

    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 |

    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 |

    An automated platform that can synthesize a wide range of complex glycans could greatly facilitate progress in glycoscience. Now, a fully automated process for enzyme-mediated oligosaccharide synthesis has been developed. This process uses glycosyltransferase-catalysed reactions performed in solution, with product purification being accomplished by solid phase extraction using a sulfonate tag.

    • Tiehai Li
    • , Lin Liu
    • , Na Wei
    • , Jeong-Yeh Yang
    • , Digantkumar G. Chapla
    • , Kelley W. Moremen
    •  & Geert-Jan Boons
  • 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 |

    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 |

    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 |

    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 |

    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 |

    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

Amendments & Corrections

In Your Element

  • In Your Element |

    The first element to be identified one atom at a time was named after the main architect of the modern periodic table. This seemingly straightforward etymological choice illustrates how scientific recognition can eclipse geopolitical tensions, says Anne Pichon.

    • Anne Pichon