Polymer chemistry articles within Nature Chemistry

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  • 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 |

    Lustrous flexible thin films of semiconducting cyclic polyacetylene (c-PA) have been synthesized and characterized. Rapid and efficient tungsten-catalysed acetylene polymerization conditions produce temporarily soluble c-PA, enabling the in situ derivatization of this typically insoluble polymer. Compelling evidence for the cyclic topology—and its influence on the physical properties of the polymer—are presented.

    • Zhihui Miao
    • , Stella A. Gonsales
    •  & Adam S. Veige

  • Article |

    Single crystals of a helical covalent polymer have been obtained from an achiral monomer through spiroborate formation. Polymerization and crystallization occur simultaneously to give a network of pairs of entwined helical strands of the same handedness. No strong non-covalent interactions were observed between the two helical polymers forming a pair; instead, each interacts with neighbouring pairs through hydrogen bonding.

    • Yiming Hu
    • , Simon J. Teat
    •  & Wei Zhang

  • Article |

    The metathesis of carbon–carbon double bonds is an important tool in organic synthesis and now a similar reshuffling has been carried out with heavier alkene analogues featuring unsymmetrically substituted Ge=Ge double bonds. This reaction enables the synthesis of symmetric molecular digermenes as well as a polymer based on Ge=Ge repeat units.

    • Lukas Klemmer
    • , Anna-Lena Thömmes
    •  & David Scheschkewitz

  • News & Views |

    Sophisticated drug delivery systems are as essential to modern medicine as drugs themselves. Now, polymer mechanochemistry in sonicated solutions has been used to activate drugs in three different systems. These results offer a promising approach that can be tailored to diverse molecular structures of modern pharmaceuticals.

    • Roman Boulatov

  • Article |

    Stimuli-responsive control of drug activation can mitigate issues caused by poor drug selectivity. Now, it has been shown that mechanical force—induced by ultrasound—can be used to activate drugs in three different systems. This approach has enabled the activation of antibiotics or a cytotoxic anticancer agent from synthetic polymers, polyaptamers and nanoparticle assemblies.

    • Shuaidong Huo
    • , Pengkun Zhao
    •  & Andreas Herrmann

  • Article |

    Iron-catalysed [2+2] cycloaddition/oligomerization of neat butadiene affords (1,n′-divinyl)oligocyclobutane—a telechelic, crystalline material consisting of 1,3-enchained cyclobutyl units. This oligocyclobutane can be chemically recycled to pure butadiene using the same iron catalyst employed in its synthesis, demonstrating design principles for next-generation plastic materials that can be returned to pristine monomer.

    • Megan Mohadjer Beromi
    • , C. Rose Kennedy
    •  & Paul J. Chirik

  • Article |

    Fluorinated polyacetylene has typically proven to be inaccessible using traditional polymer synthesis, but there is much interest in its predicted properties. Now, a mechanochemical unzipping strategy has succeeded in the synthesis of a gold-coloured, semiconducting fluorinated polyacetylene with improved stability in air compared to polyacetylene.

    • Benjamin R. Boswell
    • , Carl M. F. Mansson
    •  & Noah Z. Burns

  • Article |

    Metallocenes are attractive mechanophores because they are stable in the absence of force, yet reactive under tension. Now, covalently bridging the two cyclopentadienyl (Cp) ligands of ferrocenes embedded in a polymer has been shown to alter their mechanochemical reactivity, leading to a faster dissociation of the Fe–Cp bond, which occurs through a peeling mechanism rather than a shearing one.

    • Yudi Zhang
    • , Zi Wang
    •  & Stephen L. Craig

  • News & Views |

    Artificial photosynthesis represents a promising method of generating hydrogen for our clean and sustainable energy needs. Now, photocatalytic nanofibres have been developed that incorporate photosensitizers and catalysts into well-defined self-assembled structures for efficient hydrogen production.

    • Gregory I. Peterson
    • , Sanghee Yang
    •  & Tae-Lim Choi

  • Article |

    Artificial systems capable of photocatalytic hydrogen production are not typically based on precisely controlled scaffolds. Now, statistical seeded crystallization of block copolymers—bearing either a pendant cobalt catalyst or a photosensitizer—from solution has been shown to yield recyclable, colloidally stable nanofibres that can be tailored to promote photocatalytic hydrogen production from water.

    • Jia Tian
    • , Yifan Zhang
    •  & Ian Manners

  • Article |

    The majority of discrete structures obtained by self-assembly possess high symmetry, and thus low complexity: all subunits relate to their neighbours in a similar manner. Now, the spontaneous formation of complex low-symmetry assemblies produced from a single building block has been demonstrated using a systems chemistry approach. The single building block oligomerizes to form specific homomeric cyclic macromolecules that adopt a folded conformation.

    • Charalampos G. Pappas
    • , Pradeep K. Mandal
    •  & Sijbren Otto

  • News & Views |

    The manner in which adjacent sheets stack in layered covalent organic frameworks largely influences their material properties, including chemical stability, crystallinity and porosity. The layer stacking of a COF has now been probed locally, showing disorder that is not detected through long-range characterization.

    • Andre Mähringer
    •  & Dana D. Medina

  • Article |

    Chemical reactions usually proceed through either a radical, concerted or ionic mechanism; transformations in which all three mechanisms occur are rare. Now, the mechanical dissociation of an N-heterocyclic carbene precursor has been shown to proceed with the rupture of a C–C bond through concomitant heterolytic, concerted and homolytic pathways.

    • Robert Nixon
    •  & Guillaume De Bo

  • News & Views |

    The potential applications of smart photoswitchable porous materials are currently limited by incomplete switching. Now, efficient bulk switching has been achieved by embedding a photoisomerizable overcrowded alkene in a highly porous aromatic framework, creating a material capable of photomodulated gas uptake.

    • Jet-Sing M. Lee
    •  & Hiroshi Sato

  • Article |

    Despite numerous potential applications, the development of light-responsive solid materials based on molecular photoswitches is impeded by the low efficiency of photoisomerization in the solid environment. Now a robust, solid porous material made from tetraphenylmethane and a photoswitchable overcrowded alkene exhibits nearly quantitative photoisomerization in the bulk and in photomodulation of gas uptake.

    • Fabio Castiglioni
    • , Wojciech Danowski
    •  & Ben L. Feringa

  • 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

  • Review Article |

    Cyclic polymers have a ring-like architecture and one of the most important consequences of this topology is the absence of any chain ends, which typically have a substantial impact on the physical properties of macromolecules. This Review Article discusses advances in the synthesis, purification and characterization of cyclic polymers and the potential applications they may prove useful for.

    • Farihah M. Haque
    •  & Scott M. Grayson

  • News & Views |

    Hydrogels that can respond to multiple external stimuli are typically prepared as a single or interpenetrated polymer network material. Now, water-in-oil droplet networks have been used to precisely pattern different stimuli-responsive materials into well-ordered, continuous hydrogel structures.

    • Abigail O. Delawder
    •  & Jonathan C. Barnes

  • 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 |

    Responsive hydrogels are of interest for a range of potential applications, including microscale soft robotic and biomedical devices. Now, a versatile fabrication approach has been developed to prepare patterned, multi-material and multi-responsive hydrogels. Pre-gel droplets are connected through lipid bilayers in predetermined architectures and photopolymerized to yield continuous hydrogel structures that respond to a variety of stimuli.

    • Florence G. Downs
    • , David J. Lunn
    •  & Hagan Bayley

  • News & Views |

    Although the application of force to induce chemical transformations is an active area of research, detailed understanding of these mechanochemical pathways is still lacking. Now, the mechanochemical activation of [4]-ladderane has been studied and found to exhibit unique non-equilibrium dynamic effects.

    • Vincenzo Lordi

  • News & Views |

    Monoclonal antibodies have shown tremendous success in cancer treatment; however, humanization for clinical applications is expensive and not straightforward. Now, molecularly imprinted polymer nanogels have been developed that can block cell-surface proteins and disrupt tumour spheroids.

    • Alessandra Maria Bossi

  • Review Article |

    Growing polymers directly on surfaces has emerged as a powerful tool because it can provide a route to otherwise inaccessible structures such as defect-free linear chains, graphene nanoribbons and two-dimensional networks. This Review Article describes general principles and key aspects of this method from the perspectives of surface science and polymer chemistry.

    • Leonhard Grill
    •  & Stefan Hecht

  • Article |

    The mechanochemical activation of [4]-ladderane/ene has been studied and found to exhibit cascade unzipping and a consistent stereochemical distribution of products under various conditions and in different polymer backbones. Ab initio steered molecular dynamics simulations revealed unique non-equilibrium dynamic effects in the mechanochemistry of ladderane, cascade activation and reaction pathway bifurcation.

    • Zhixing Chen
    • , Xiaolei Zhu
    •  & Yan Xia

  • Article |

    Ring-opening metathesis polymerization of norbornene-based (macro)monomers produces macromolecules with diverse compositions and complex architectures that cannot be degraded easily. Now, it has been shown that a class of eight-membered cyclic bifunctional silyl ether-based monomers copolymerize efficiently with norbornene-based (macro)monomers, providing a range of copolymers with tunable degradability under mildly acidic aqueous conditions.

    • Peyton Shieh
    • , Hung V.-T. Nguyen
    •  & Jeremiah A. Johnson

  • Article |

    It is difficult to prepare 2D polymers that are crystalline over large areas. Now, few-layer 2D polyimides and polyamides with good crystallinity on the micrometre scale have been synthesized on a water surface. A surfactant monolayer is used to organize amine monomers before their polymerization with anhydride moieties.

    • Kejun Liu
    • , Haoyuan Qi
    •  & Xinliang Feng

  • Article |

    Polyacetylene is an ideal system to probe to gain a better understanding of the nature of charge transport in conducting polymers. Now, individual atomically precise polyacetylene chains have been synthesized on a copper surface and characterized using a range of techniques, revealing a doping-induced semiconductor-to-metal transition.

    • Shiyong Wang
    • , Qiang Sun
    •  & Wei Xu

  • News & Views |

    The longstanding ‘polyelectrolyte theory of the gene’ proposes that a multiply charged backbone is the universal signature of all genetic polymer systems that support life. Now, the first tenable challenge to this theory has been mounted, through the successful engineering of enzymes which can synthesize and reverse-transcribe from an artificial, uncharged nucleic acid analogue.

    • Asha Brown
    •  & Tom Brown

  • Thesis |

    Bruce C. Gibb explains why plastic isn’t always fantastic.

    • Bruce C. Gibb

  • Article |

    It is difficult to recover materials for re-manufacturing and re-use from plastics that are compounded with colourants, fillers and flame retardants. Now, it has been shown that alternative plastics based on dynamic covalent poly(diketoenamine)s depolymerize in strong aqueous acids and enable triketone and amine monomers to be isolated and upcycled into new plastics.

    • Peter R. Christensen
    • , Angelique M. Scheuermann
    •  & Brett A. Helms

  • Article |

    A strategy for directly synthesizing unnatural polymers in cells through radical polymerization has now been developed. This approach provides a platform to manipulate, track and control cellular behaviour by the in cellulo generation of macromolecules and a variety of nanostructures.

    • Jin Geng
    • , Weishuo Li
    •  & Mark Bradley

  • 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 |

    The development of porous, crystalline materials with high chemical stability is crucial for their practical uses. Now, polyarylether-based covalent organic frameworks (PAE-COFs) have been synthesized that show high crystallinity and porosity, as well as good stability against harsh chemical environments including boiling water and strong acids and bases.

    • Xinyu Guan
    • , Hui Li
    •  & Shilun Qiu

  • Article |

    Synthetic dissipative systems, formed by out-of-equilibrium self-assembly processes, can mimic some of the properties of biological systems, but often show poor mechanical performance. Now, a shear-induced transient hydrogel has been prepared that is also highly stretchable. The system is based on coordination interactions between Cu(ii) centres and the pendant carboxylate groups of a pseudopolyrotaxane.

    • Hua Ke
    • , Liu-Pan Yang
    •  & Wei Jiang

  • 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
    •  & Yi Cao

  • 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
    •  & Wenping Hu

  • 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
    •  & Andrew G. Livingston

  • Article |

    On-surface polymerization is a promising technique to prepare organic functional nanomaterials, but it has remained difficult to carry out on insulating surfaces. Now, the photoinitiated radical polymerization of dimaleimide on KCl, initiated from a two-dimensional gas phase and guided by molecule–substrate interactions, has led to polymer fibres up to 1 μm long.

    • Franck Para
    • , Franck Bocquet
    •  & Matthew B. Watkins

  • Article |

    Membranes with high selectivity and high permeance that allows rapid passage of solvent molecules are desirable for efficient separation processes. Microporous conjugated-polymer membranes have now been fabricated through surface-initiated polymerization. These membranes are capable of ultrafast organic-solvent nanofiltration because of the high porosity and pore interconnectivity originating from the rigid skeleton.

    • Bin Liang
    • , Hui Wang
    •  & Zhiyong Tang

  • Article |

    Biological systems are made up of complex networks that can respond to stimuli and function across relatively long distances in molecular terms. Now, it has been shown that a local disruption (the isomerization of just a single azobenzene unit) at the interface of supramolecular glassy polymersomes can immediately spread through over 500 bonds, significantly changing membrane permeability and enabling controllable release of guest molecules.

    • Mijanur Rahaman Molla
    • , Poornima Rangadurai
    •  & S. Thayumanavan

  • News & Views |

    Ribosomes have now been shown to accept certain initiator tRNAs acylated with aromatic foldamer–dipeptides thereby enabling the translation of a peptide or protein with a short aromatic foldamer at the N-terminus. Some foldamer–peptide hybrids could be cyclized to generate macrocycles that present conformationally restricted peptide loops.

    • Alanna Schepartz

  • Article |

    A method to produce sequence-defined, diversely functionalized nucleic acid polymers that bind to proteins of biomedical interest has been developed. The method is based on a ligase-mediated, DNA-templated polymerization system and in vitro selection. The selected polymers are shown to bind their targets in a manner that is strongly dependent on specific side chains at certain polymer positions.

    • Zhen Chen
    • , Phillip A. Lichtor
    •  & David R. Liu

  • News & Views |

    Using infrared light to control the outcome of a chemical reaction is problematic in solution because of numerous interactions and non-specific sample heating. Now, condensed-phase results showing the vibrational enhancement of an otherwise thermally driven reaction may reinvigorate discussion of the practical applications of vibrational control.

    • Amanda S. Case

  • Article |

    Biomaterials that respond to precise combinations of environmental cues represent an important technology for tissue engineering and next-generation drug delivery systems. Now, a modular framework to programme material degradation following Boolean logic has been demonstrated by specifying the molecular architecture and connectivity of orthogonal stimuli-labile moieties within hydrogel cross-linkers.

    • Barry A. Badeau
    • , Michael P. Comerford
    •  & Cole A. DeForest

  • Article |

    A practical realization of selective IR-driven reaction-rate control has been hampered by competing processes leading to sample heating. Now, the acceleration of a bimolecular ground-state reaction in solution using the IR excitation of a vibration connected to the reaction coordinate is demonstrated. The behaviour is monitored and understood using a combination of femtosecond IR-pump IR-probe spectroscopy and theoretical calculations.

    • Till Stensitzki
    • , Yang Yang
    •  & Karsten Heyne

  • News & Views |

    The use of mechanical force to break and build chemical bonds in polymers can enable transformations that cannot be conducted using stimuli such as light and heat. Now, an insulating polymer has been mechanically unzipped to create a semiconducting polymer with extended regions of conjugation.

    • Stephen L. Craig

  • Article |

    An attractive feature of supramolecular polymers is their reversibility — they typically depolymerize upon heating. Now, in the presence of a scavenger molecule, a metalloporphyrin derivative bearing eight amide-containing side chains has been shown to undergo supramolecular polymerization on heating as well as cooling through π-stacking and multivalent hydrogen-bonding interactions.

    • Kotagiri Venkata Rao
    • , Daigo Miyajima
    •  & Takuzo Aida

  • Article |

    Ultrafast-scanning fluorescence correlation spectroscopy has now been used to measure the molecular interactions underlying the phase behaviour of disordered proteins. Sequence-encoded conformational fluctuations of these proteins are shown to give rise to phase-separated droplets of surprisingly low concentrations. These results provide insight into how the structural features of the droplets affect the properties of liquid-phase intracellular organelles.

    • Ming-Tzo Wei
    • , Shana Elbaum-Garfinkle
    •  & Clifford P. Brangwynne

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