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  • The installation of difluoromethylene groups into bio-relevant molecules allows access to important scaffolds, but existing methods to do so often rely on oxidative chemical species that can hamper reactivity. Here, radical hydrodifluoromethylation with a wide range of unsaturated C–C bonds is achieved via an electroreductive two-pronged approach, granting access to a variety of difluoromethylated organic molecules.

    • Seonyoung Kim
    • Keon Ha Hwang
    • Hyunwoo Kim
    Article Open Access
  • Efficient electron-hole separation and carrier utilization are key factors in photosynthetic systems. Here, the authors achieve efficient charge separation following a photogenerated hole-transfer band-trap pathway in the ternary composite Pt@NH2-UiO-66/CdS, resulting in photocatalytic hydrogen evolution with good stability and a quantum efficiency of 40.3% at 400 nm irradiation.

    • Zichao Lian
    • Zhao Li
    • Weiwei Yang
    Article Open Access
  • Photoinduced conjugation has been broadly used for functionalization of molecules but is limited by possible photodegradation. Here, the authors report a robust amide bond formation method based on the photoreaction of 3-acylindolizines with amines triggered via red-light irradiation in nearly quantitative yields within less than 5 min.

    • Kenji Watanabe
    • Asuka Kuratsu
    • Takamitsu Hosoya
    Article Open Access
  • Photo-mediated radical dearomatization involving 5-exo-trig cyclizations has proven to be an important route to accessing spirocyclic compounds, whereas 6-exo-trig spirocyclization has been much less explored. Here, a dearomative annulation cascade is realized through a photoredox-mediated C–O bond activation of aromatic carboxylic acids to produce two kinds of spirocyclic frameworks, whereby the spirocyclizations are triggered by acyl radical formation from benzoic acids leading to spiro-chromanones via a direct intramolecular 6-exo-trig cyclization or spirocyclic lactams via an intermolecular addition/5-exo-trig cyclization cascade.

    • Chao Zhou
    • Andrey Shatskiy
    • Peter Dinér
    Article Open Access
  • In situ illumination of liquid-state NMR samples allows to characterise light-dependent chemical and biological phenomena, but, in practice, the position of an NMR sample deep within the bore of a spectrometer magnet renders such illumination challenging. Here, the authors demonstrate the working principles of a sample illumination device, with an LED array positioned directly at the top of special sample tube, which is inserted into the NMR spectrometer.

    • Jack E. Bramham
    • Alexander P. Golovanov
    Article Open Access
  • Methoxy polyethylene glycol (mPEG) is widely attached to drug molecules to improve their therapeutic efficacy, however mPEG can induce anti-PEG antibodies that negatively impact their therapeutic effects. Here, the authors determine the co-crystal structure of the humanized 15-2b anti-mPEG antibody with mPEG, providing insights into understanding mPEG-binding specificity and antigenicity of anti-mPEG antibodies.

    • Minh-Tram T. Nguyen
    • Yu-Chien Shih
    • Yu-Cheng Su
    Article Open Access
  • The RquA protein is required for rhodoquinone biosynthesis; however, its exact function is not yet known. Here, the authors demonstrate that RquA is homologous to SAM-dependent methyltransferases but functions as an aminotransferase using Mn2+ as cofactor to convert ubiquinone to rhodoquinone.

    • Trilok Neupane
    • Lydia R. Chambers
    • David N. Langelaan
    Article Open Access
  • Caprazamycin is a nucleoside antibiotic that can interrupt bacterial peptidoglycan biosynthesis, but the biosynthesis of caprazamycin is not fully understood yet. Here, the authors characterize five key enzymes from caprazamycin/muraymycin gene cluster, particularly nonheme αKG-dependent enzyme Cpz10 as a β-hydroxylase that recruits two iron atoms and leads to caprazamycin formation.

    • Saeid Malek Zadeh
    • Mei-Hua Chen
    • Tsung-Lin Li
    Article Open Access
  • Current crystal structure prediction methods for anticipating polymorphism are lacking in their ability to provide information on the depth of each energy minimum and the possible transition paths and energy barriers between polymorph structures. Here, a Monte Carlo threshold algorithm is applied to four polymorphic organic systems to estimate the energy barriers that separate the different polymorph structures and characterise the global structure of the energy landscapes of their molecular crystal structures.

    • Shiyue Yang
    • Graeme M. Day
    Article Open Access
  • Adiabatic state preparation (ASP) can generate correlated wave functions for quantum chemical calculations, but is inherently unsuitable for studying strongly correlated systems. Here, the authors perform numerical simulations of ASP for the ground state wave functions of molecules with strongly correlated electrons and propose practical conditions for preparation of close-to-exact correlated wave functions.

    • Kenji Sugisaki
    • Kazuo Toyota
    • Takeji Takui
    Article Open Access
  • Understanding the mechanisms of virus-induced cell modifications is critical for the development of diagnostics and antiviral treatments. Here, confocal Raman microspectroscopy is demonstrated to be a useful tool to study biochemical modifications in cells caused by SARS-CoV-2 infection.

    • Hamideh Salehi
    • Anuradha Ramoji
    • Frederic Cuisinier
    Article Open Access
  • Given their low cost and diverse nature, coupling of amine and carboxylic acid building blocks provides an opportunity to expand the accessible chemical space. Here, a copper-catalyzed deaminative esterification of aryl amines with carboxylic acids is developed and its use in library synthesis with high-throughput experimentation is demonstrated.

    • Yuning Shen
    • Babak Mahjour
    • Tim Cernak
    Article Open Access
  • Defects and disordered local domains in soft, self-assembled aggregates determine their dynamic and adaptive properties, and enable communication between entities, but characterizing and classifying such intricate dynamic behaviors is highly complex. Here, the authors report on a data-driven workflow to identify objective criteria for the comparison of complex dynamic features in soft supramolecular materials, deriving a data-driven ’defectometer’ that allows to classify soft self-assembled materials based on the structural dynamics of the ordered/disordered molecular environments that statistically emerge within them.

    • Andrea Gardin
    • Claudio Perego
    • Giovanni M. Pavan
    Article Open Access
  • Bringing enzymes and substrates together in confined compartments within porous systems can offer enhanced catalytic efficiency and increased lifetimes for the encapsulated enzymes. Here, the authors construct enzymatic compartments by spatiotemporal control of the self-assembly of catalytic peptide TPE-Q18H in hollow glucan particles, and demonstrate enhanced substrate-binding affinity and reaction kinetics as well as increased thermostability and resistance to hydrolysis.

    • Yaling Wang
    • Tiezheng Pan
    • Chunqiu Zhang
    Article Open Access
  • Nitrene transfer chemistry is an effective strategy for introducing C–N bonds, but inexpensive reaction systems for tunable, intermolecular chemoselective nitrene transfer for late-stage amination of unsaturated natural products remains a challenge. Here, the authors report copper catalysed chemoselective allylic C–H amination and catalyst-free visible-light induced aziridination of alkenes through nitrene transfer.

    • Qi Xing
    • Ding Jiang
    • Zhendong Zhu
    Article Open Access
  • Benzoazepine is a well-known pharmacophore presented in several marketed drugs. Here, the authors report the isolation and total syntheses of asperazepanones A and B from coral-derived Aspergillus candidus, two novel pyrrolinone-fused benzoazepine alkaloids with potent anti-inflammatory activities.

    • Li Xu
    • Feng-Wei Guo
    • Chang-Lun Shao
    Article Open Access
  • Aryldifluoromethyl aryl ethers (ArCF2OAr’) are powerful structural motifs to improve druggability, however, their targeted synthesis remains challenging. Here, the authors report the efficient synthesis of ArCF2OAr’ motifs via nickel-catalyzed aryloxydifluoromethylation with arylboronic acids, and their application in the total synthesis of a difluoromethylated PD-1/PD-L1 immune checkpoint inhibitor with enhanced antitumor efficacy over the non-fluoro congener.

    • Heng Lu
    • Ruo-Xuan Xiao
    • Ao Zhang
    Article Open Access
  • Heterogeneous nucleation of metal oxyhydroxides on mineral surfaces is key to environmentally relevant crystal growth and dissolution, but the cation dimerization steps remain largely unexplored. Here, the authors use ab initio molecular dynamics calculations to examine the coordination structure of hydroxide-bridged Cu(II) dimers, and the free energy changes associated with Cu(II) dimerization on silica surfaces.

    • Kevin Leung
    • Jeffery A. Greathouse
    Article Open Access
  • Mutations to oncogenic protein KRAS are responsible for some of the deadliest cancers, and KRAS is thus a key target for new antitumour agents. Here, a short bis-histidine peptide derived from the αH helix of the cofactor SOS1 is designed and shown to reversibly bind to KRAS with high affinity upon coordination to Pd(II), inhibiting KRAS-activated pathways in live cells.

    • Soraya Learte-Aymamí
    • Pau Martin-Malpartida
    • M. Eugenio Vázquez
    Article Open Access