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  • Intersystem crossing in reaction entrance channels usually arises from ‘heavy-atom’ effects. Now molecular-beam experiments show that even without heavy atoms, the O(3P) + pyridine reaction leads to spin-forbidden pyrrole + CO products. Theoretical calculations reveal efficient intersystem crossing before the entrance barrier for O-atom addition to the N-atom lone pair, which dominates reactivity at low to moderate temperatures.

    • Pedro Recio
    • Silvia Alessandrini
    • Vincenzo Barone
    Article
  • Decisions, decisions. There’s a lot to think about when moving on from a postdoctoral position and Shira Joudan takes us through the considerations that led to her ultimately taking a tenure-track position in a new city.

    • Shira Joudan
    Thesis
  • Noyori-type catalysts and inorganic bases are frequently used together for homogeneous hydrogenation, but key intermediates have not yet been isolated. Now, the structure and reactivity of a long-postulated intermediate — the alkali metal amidate complex — have been reported through experimental and computational studies.

    • Pavel A. Dub
    News & Views
  • Madison Knapp and Jennifer Bridwell-Rabb explore the functions of chlorophyll and explain how our understanding of this green pigment has changed over time.

    • Madison Knapp
    • Jennifer Bridwell-Rabb
    In Your Element
  • General synthetic methods to access pleuromutilin antibiotics are limited due to their complex carbocyclic skeleton. Now, a synthetic platform has been developed to access structurally diverse pleuromutilins with variations at the quaternary C12 position and hydrindanone cores. Seventeen structurally distinct derivatives were prepared and evaluated against a panel of Gram-positive and -negative bacteria.

    • Olivia Goethe
    • Mikaela DiBello
    • Seth B. Herzon
    Article
  • Alkyl and aryl polycyanurate networks have now been prepared through polymerization of diols and substituted triazines via a dynamic SNAr reaction. When treated with excess mono alcohol or phenol, the polycyanurate networks can be depolymerized into the starting monomers, which can be separated and reused, thus achieving closed-loop recycling.

    • Zepeng Lei
    • Hongxuan Chen
    • Wei Zhang
    Article
  • On-surface synthesis enables highly reactive structures to be produced under vacuum, but they need to be passivated to be incorporated into practical devices. Here, the facile protection of air-sensitive chiral graphene nanoribbons has been shown, by either hydrogenation or synthesis of an oxidized form. The chemically stable forms can subsequently be deprotected.

    • James Lawrence
    • Alejandro Berdonces-Layunta
    • Dimas G. de Oteyza
    Article
  • Aqueous organic redox flow batteries are promising for low-cost and large-scale energy storage, but the redox-active molecules they rely on degrade prematurely. Now, a facile electrochemical protocol to regenerate them has been proposed, resulting in extended battery lifetimes.

    • Antoni Forner-Cuenca
    News & Views
  • Quantitatively studying the partitioning of biomolecules and reaction equilibria in cellular systems is an enormous challenge. Now, a multiphase coacervate model system provides insight into this complex biological problem, illustrating how coexisting phases influence RNA partitioning and duplex dissociation.

    • Shuqi Wu
    • Liangfei Tian
    News & Views
  • Proteins rich in phenylalanine-glycine (FG) repeats can phase separate through FG–FG interactions. The molecular interactions of an important FG-repeat protein, nucleoporin 98, have now been studied in liquid-like transient and amyloid-like cohesive states. These interactions underlie the behaviour of FG-repeat proteins and their function in physiological and pathological cell activities.

    • Alain Ibáñez de Opakua
    • James A. Geraets
    • Markus Zweckstetter
    Article Open Access
  • A method has been developed to identify RNA transcript isoforms at the single-molecule level using solid-state nanopore microscopy. In this method, target RNA is refolded into RNA identifiers with designed sets of complementary DNA strands. Each reshaped molecule carries a unique sequence of structural (pseudo)colours that enables identification and quantification using solid-state nanopore microscopy.

    • Filip Bošković
    • Ulrich Felix Keyser
    Article
  • The principal mid-visible light-harvesting system in cyanobacteria is the phycobilisome. Now, using broadband multidimensional spectroscopy, delocalized vibronic excitations and sub-picosecond excitation transfer pathways have been observed in the rods of intact phycobilisomes. An observed kinetic bottleneck in the phycobilisome’s core arises from the intramolecular charge-transfer character of the bilin chromophores, enabling photoregulatory processes to operate on the >10-ps timescale.

    • Sourav Sil
    • Ryan W. Tilluck
    • Warren F. Beck
    Article
  • The total synthesis and complete stereochemical assignment of the cyclic peptide natural product SR-A3—which has potential as a cancer therapeutic—has now been reported. Single-molecule biophysical and cellular experiments reveal a crucial, stereospecific role for a side-chain hydroxyl in SR-A3, which confers enhanced target residence time and efficacy in a mouse tumour model.

    • Hao-Yuan Wang
    • Haojun Yang
    • Jack Taunton
    Article
  • Noyori-type hydrogenation catalysts consist of an N–H moiety coordinated to a metal centre. Now, a metal-hydride amidate complex (HMn–NLi) has been isolated and found to have superior reactivity and catalytic performance compared with the corresponding HMn–NH complex, highlighting the superiority of M/NM′ bifunctional catalysis over the classic M/NH bifunctional catalysis for hydrogenation reactions.

    • Yujie Wang
    • Shihan Liu
    • Qiang Liu
    Article
  • The reduction of nitrite (NO2) to nitric oxide (NO), relevant to the biogeochemical nitrogen cycle as well as radioactive waste, typically occurs at redox-active metal centres. Now, a Lewis acid-capped nitrite has been reduced to the nitrite dianion (NO22−), a nitrogen-centred radical that connects three redox levels in the global nitrogen cycle through NO2, NO and N2O.

    • Valiallah Hosseininasab
    • Ida M. DiMucci
    • Timothy H. Warren
    Article
  • In silico chemical prediction of a polyketide synthase gene cluster in the bacterium Gynuella sunshinyii has led to the discovery of a class of natural products called janustatins. The absolute configuration of the stereocentres in these compounds was determined by a combination of techniques including DFT calculations and 2D NMR experiments—and finally confirmed by total synthesis. Janustatins were found to cause delayed, synchronized cell death at subnanomolar concentrations.

    • Reiko Ueoka
    • Philipp Sondermann
    • Jörn Piel
    Article
  • Cyclic polymers are topologically interesting and envisioned as a lubricant material, but methods for the scalable synthesis of pure cyclic polymers are currently elusive. Now, a scalable process has been developed by leveraging heterogeneity of the catalysts with the help of compartmentalized custom glassware, namely, a cyclic polymer dispenser.

    • Ki-Young Yoon
    • Jinkyung Noh
    • Robert H. Grubbs
    Article
  • Oligonucleotide catalysts such as ribozymes and DNAzymes can cleave RNA efficiently and specifically but are typically dependent on high concentrations of divalent cations, limiting their biological applications. A modular XNAzyme catalyst composed of 2′-deoxy-2′-fluoro-β-d-arabino nucleic acid (FANA) has now been developed that can cleave long (>5 kb), highly structured mRNAs under physiological conditions and enables allele-specific catalytic RNA knockdown inside cells.

    • Alexander I. Taylor
    • Christopher J. K. Wan
    • Philipp Holliger
    Article