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  • Molecular geometry can influence chemical reactivity through several opposing effects. By selecting individual conformers of hydroquinone in the chemi-ionization reaction with metastable neon, it is now shown that reaction pathways can be governed by molecular alignment due to geometry-dependent forces that are, however, countered by molecular rotation.

    • L. Ploenes
    • P. Straňák
    • S. Willitsch
  • Lysine ubiquitination, catalysed by E3 ubiquitin ligases, is pivotal for regulating protein stability and cell signalling. Using protein semisynthesis, the roles of the C-terminal carboxylate and conformational interconversion in HECT-domain E3 catalysis are now characterized, revealing evolutionary plasticity in side chain versus backbone utilization.

    • Hanjie Jiang
    • Bryant D. Miller
    • Philip A. Cole
  • Although natural terpenoid cyclases generate polycyclic structures through cationic intermediates, alternative radical cyclization pathways are underexplored. Now an artificial radical cyclase has been prepared by anchoring a biotinylated cobalt Schiff-base complex within a chimeric streptavidin scaffold. Chemogenetic optimization of the catalytic performance affords enantioenriched terpenoids via a metal-catalysed H-atom transfer mechanism.

    • Dongping Chen
    • Xiang Zhang
    • Thomas R. Ward
  • Weaving purely organic molecular threads into two-dimensional patterns remains a formidable challenge. Now, driven by the formation of dative B–N bonds, a purely organic, two-dimensional and flawless woven polymer network has been prepared. In addition, free-standing monolayers of woven polymer nanosheets have been obtained through mechanical exfoliation.

    • Ding Xiao
    • Zhitong Jin
    • Feihe Huang
    ArticleOpen Access
  • Selection mechanisms were critical at the emergence of life and will also be important for the synthesis of life. Now, it has been shown that template-based copying controls the selection of unstable molecules in a chemically fuelled dynamic combinatorial library. Moreover, when encapsulated inside coacervate droplets, these mechanisms change the coacervate’s physical properties.

    • Christine M. E. Kriebisch
    • Ludwig Burger
    • Job Boekhoven
    ArticleOpen Access
  • The mechanism of collagen heterotrimer folding is difficult to recapitulate synthetically. Now an ABC collagen mimetic heterotrimer has been designed that employs pairwise amino acid interactions, validated by X-ray crystallography, to promote composition- and register-specific assembly. The high specificity of its assembly leads to an increased rate of folding compared with similar collagen heterotrimers.

    • Carson C. Cole
    • Douglas R. Walker
    • Jeffrey D. Hartgerink
  • Conventional Li-ion battery electrolytes often show sluggish kinetics and severe degradation due to high Li+ desolvation energies and poor compatibility. Now, a molecular-docking strategy between solvents and inducers has been shown to enable dynamic Li+ coordination that promotes fast, stable and high-voltage lithium battery chemistries.

    • Baochen Ma
    • Haikuo Zhang
    • Xiulin Fan
  • Phosphinidene oxides are intermediates in the combustion of organic phosphorus compounds; however, they are highly unstable and their observation requires ultralow temperatures. Now it has been shown that a combination of steric bulk and electronic stabilization enables the isolation and manipulation of a two-coordinate phosphorus(III) oxide compound at room temperature.

    • Chenyang Hu
    • Nicolas H. Rees
    • Jose M. Goicoechea
  • Most lipid nanoparticles are structurally simplistic, existing as single-compartment assemblies. Now, a microfluidic technology to create liposomes-in-liposomes—with full control over particle features, such as the composition of each membrane, the intermembrane distance and payload of each compartment—has been developed. These particles are exploited for multi-stage release and in situ enzymatic synthesis within the particle’s attolitre volume.

    • Colin P. Pilkington
    • Ignacio Gispert
    • Yuval Elani
    ArticleOpen Access
  • A class of cationic—amidine-based degradable—lipids can now be readily synthesized through a tandem multi-component amine–thiol–acrylate conjugation reaction. Mechanistic studies provided key insights, from which the observed lead lipid enabled mRNA delivery to multiple organs, highlighting the potential for developing mRNA vaccines and therapeutics to treat various diseases.

    • Xuexiang Han
    • Mohamad-Gabriel Alameh
    • Michael J. Mitchell
  • Expanded use of earth-abundant chromophores for excited-state chemistry requires the ability to increase the energy content of excited states while simultaneously lengthening their lifetimes. It has now been shown that this goal can be achieved in Co(III)-based chromophores by virtue of their photophysical dynamics occurring in the Marcus inverted region.

    • Atanu Ghosh
    • Jonathan T. Yarranton
    • James K. McCusker
  • Living anionic polymerization generally requires stringent conditions and one metal initiator per polymer chain. Now it has been shown that a weakly acidic compound serves as the initiator or chain-transfer agent in the presence of a potassium base catalyst to produce a polymer chain through a proton transfer anionic polymerization mechanism.

    • Mineto Uchiyama
    • Natsumi Ohira
    • Masami Kamigaito
  • Unlike homo-dihalogenation, selective hetero-dihalogenation reactions are underdeveloped. Now an oxidative alkene hetero-dihalogenation reaction adds chloride and fluoride ions over unactivated alkenes with high regio-, chemo- and diastereoselectivity. A switch in the mechanism triggers a reversal of the diastereoselectivity to promote either anti- or syn-addition.

    • Sayad Doobary
    • Andrew J. D. Lacey
    • Alastair J. J. Lennox
    ArticleOpen Access
  • The oxidative addition of the H–H bond to a single main-group centre in a metallomimetic fashion and its further use in catalysis is challenging. Now the oxidative addition of the H–H bond to a single phosphorus centre is shown and used for the catalytic hydrogenation of unsaturated compounds.

    • Deependra Bawari
    • Donia Toami
    • Roman Dobrovetsky
  • The characterization of surface ligands around nanoparticles is challenging and often limited to static studies. Now, the structure of the ligand shell around gold nanoparticles, and at the ligand–gold interface, has been investigated by transmission electron microscopy in a liquid environment by using high-quality graphene liquid cells.

    • Adrián Pedrazo-Tardajos
    • Nathalie Claes
    • Sara Bals
  • De novo syntheses of 1,2-arylheteroaryl ethanes, key scaffolds in drug discovery, are challenging, typically relying on pre-functionalized synthons, harsh conditions and multi-step processes. Now a modular assembly of arenes, ethylene and heteroarenes yields diverse drug-like 1,2-arylheteroaryl ethanes, highlighting the importance of radical polarity matching in selective multi-component couplings.

    • Tao Liu
    • Talin Li
    • Jie Wu
  • Thermal generation of free carbenes with 100% atom economy is rare. Now, it has been shown that this can be achieved by the net [3+2] cycloaddition between many classes of 2-alkynyl iminoheterocycles and electrophilic alkynes. Together with a host of carbene trapping reactions, this method provides facile and versatile access to diverse heterocycle scaffolds.

    • Qian Xu
    • Thomas R. Hoye
  • Nitrogen-rich Ruddlesden–Popper nitrides are notoriously difficult to stabilize. Now a high-pressure high-temperature synthesis method has enabled the preparation of Pr2ReN4, Nd2ReN4 and Ce2TaN4. Neutron diffraction analysis reveals fully nitrided materials and intricate magnetic structures.

    • M. Weidemann
    • D. Werhahn
    • Simon D. Kloß
  • Hydroxyl radicals are reactive species capable of water purification and disinfection, although their generation, particularly through renewable approaches, is challenging. Now, low-valent Au on potassium-incorporated carbon nitride has been shown to produce hydroxyl radicals upon solar illumination and to provide high water disinfection rates.

    • Zhenyuan Teng
    • Hongbin Yang
    • Bin Liu
  • Whereas bonds that strengthen under mechanical stress occur frequently in nature, all synthetic bonds weaken under force. Now, an artificial supramolecular catch bond has been shown to strengthen the particle–surface interface under increasing shear flow in a rolling adhesion assay, thereby mimicking biological adhesion processes.

    • Martijn van Galen
    • Annemarie Bok
    • Joris Sprakel
    ArticleOpen Access