Polymerization mechanisms articles within Nature Chemistry

Featured

  • Article |

    Sterically demanding 2′-modified nucleotides used in antisense therapeutics have thus far been challenging to synthesise enzymatically. Now, it has been shown that mutation of two gatekeeper residues in an archaeal DNA polymerase unlocks efficient synthesis of the modified nucleic acid oligomers 2′-O-methyl-RNA and 2′-O-(2-methoxyethyl)-RNA and enables the evolution of 2′-O-methyl-RNA enzymes.

    • Niklas Freund
    • , Alexander I. Taylor
    •  & Philipp Holliger

  • Article |

    Two phosphine-based reagents can be used to prepare aromatic acid chlorides in the presence of either primary or secondary amines. This approach enables the living polycondensation of aromatic amino acids under mild conditions and can be used to make block copolymers as well as helical aromatic amide foldamers.

    • Subhajit Pal
    • , Dinh Phuong Trinh Nguyen
    •  & Andreas F. M. Kilbinger

  • Article |

    Oxygen is a potent inhibitor of radical polymerization reactions, but the facultative bacterium Shewanella oneidensis has now been shown to facilitate aerobic radical polymerizations by first consuming dissolved oxygen and then directing extracellular electron flux to a metal catalyst. Aerobic polymerization activity is dependent on the S. oneidensis genotype and can be initiated using lyophilized or spent cells.

    • Gang Fan
    • , Austin J. Graham
    •  & Benjamin K. Keitz

  • News & Views |

    A heterodinuclear MgCo catalyst has been shown to be highly active for the copolymerization of CO2 and epoxides under low (atmospheric) CO2 pressures. Its performance arises from the intramolecular synergy between the two metals, which adopt distinct roles and mediate each other’s reactivity during catalysis.

    • Xiao-Bing Lu

  • Article |

    The copolymerization of CO2 with epoxides is an attractive approach for valorizing waste products and improving sustainability in polymer manufacturing. Now, a heterodinuclear Mg(ii)Co(ii) complex has been shown to act as a highly active and selective catalyst for this reaction at low CO2 pressure. The synergy between the two metals was investigated using polymerization kinetics.

    • Arron C. Deacy
    • , Alexander F. R. Kilpatrick
    •  & Charlotte K. Williams

  • Article |

    In a ruthenium-catalysed living ring-opening metathesis polymerization, one metal centre is required for each polymer chain, and this requires high catalyst loadings when aiming for short polymer chains. Now, it has been shown that a degenerative reversible chain-transfer process enables the synthesis of ring-opened metathesis polymers with controlled molecular weight, using only catalytic amounts of a ruthenium complex.

    • Mohammad Yasir
    • , Peng Liu
    •  & Andreas F. M. Kilbinger

  • Article |

    Many properties of polymers are dictated by topology. However, the topology of a macromolecule is typically a static feature after synthesis. Now, an approach to dynamic and transformable macromolecular architecture has been developed. When triggered by an external stimulus, macromolecular topology can be triggered to transform via thermodynamic control.

    • Hao Sun
    • , Christopher P. Kabb
    •  & Brent S. Sumerlin

  • Article |

    The secondary and tertiary structure of a protein has profound implications on function and catalysis. Now, both the secondary and tertiary structures of a synthetic polymer have been utilized to catalyse the polymerization of N-carboxyanhydrides. Both the folding of the resulting polypeptides into α-helices and their macromolecular organization dramatically enhance the polymerization rate.

    • Ryan Baumgartner
    • , Hailin Fu
    •  & Jianjun Cheng

  • Article |

    Ring-opening metathesis polymerization (ROMP) offers good control over dispersity, but the requirement of one initiator per chain can be expensive and problematic for purification. Now, a reversible cyclohexenyl-containing chain-transfer agent is described, thus allowing a catalytic living ROMP process to produce narrow dispersity polymers and block copolymers.

    • Amit A. Nagarkar
    •  & Andreas F. M. Kilbinger

  • Review Article |

    Two-dimensional polymers, which exhibit periodic bonding in two orthogonal directions, offer mechanical, electronic and structural properties distinct from their linear or irregularly crosslinked polymer counterparts. Their potential is largely unexplored because versatile and controlled synthetic strategies are only now emerging. This Review describes recent developments in two-dimensional polymerization methods.

    • John W. Colson
    •  & William R. Dichtel

  • Article |

    A strategy to endow vinyl polymers with pseudo-crystalline order has been devised that relies on host–guest cross-polymerization, through functionalization of the channels of a porous coordination polymer with divinyl moieties. Polymerization of vinyl monomers within the channels is accompanied with lateral crosslinking, which ensures the polymer chains remain highly ordered after removal of the host.

    • Gaetano Distefano
    • , Hirohito Suzuki
    •  & Susumu Kitagawa

  • Article |

    The site-selective initiation and propagation of an atom-transfer radical polymerization reaction forms an addressable crosslinked polymer constrained within the interior cavity of a virus-like particle derived from the bacteriophage P22. This protein–polymer hybrid is useful as a new vehicle for high-density delivery of small-molecule cargos.

    • Janice Lucon
    • , Shefah Qazi
    •  & Trevor Douglas

  • Article |

    Nature synthesizes proteins and nucleic acids by polymerization methods that use well-regulated and segregated templates. Now, synthetic block-copolymer templates have been designed to assemble in a biomimetic fashion to segregate, and thus control, the synthetic radical polymerization of complementary nucleobase-containing vinyl monomers, to yield high-molecular-weight, low-polydispersity polymer chains.

    • Ronan McHale
    • , Joseph P. Patterson
    •  & Rachel K. O'Reilly

  • Article |

    The bottom-up construction of covalently linked molecular architectures on surfaces has recently been demonstrated, but only rather simple structures can be obtained in such one-step connection processes. A sequential approach has now been used to induce the selective connection of molecules with a programmed reactivity, enabling network formation with high selectivity.

    • L. Lafferentz
    • , V. Eberhardt
    •  & L. Grill

  • News & Views |

    Autonomous propulsion of microparticles using catalytic olefin polymerization, and directional rotation of a molecule on a metal surface using electrons from the tip of a scanning tunnelling microscope.

    • Ben Feringa

  • Review Article |

    Most synthetic polymers are made from petroleum and their production is currently not sustainable. RAFT polymerization has emerged as a powerful technique to control the synthesis of such polymers, thus expanding further their applications. This Review discusses the sustainability of RAFT in terms of process and materials.

    • Mona Semsarilar
    •  & Sébastien Perrier

  • Article |

    In analogy to classical living polymerizations, the controlled formation of highly monodisperse cylindrical micelles — ranging from approximately 200 nm to 2 µm in length — has been demonstrated using very small and uniform crystallite seeds as initiators for the crystallization-driven living self-assembly of block copolymers with a crystallizable, core-forming metalloblock.

    • Joe B. Gilroy
    • , Torben Gädt
    •  & Ian Manners

  • 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

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