Chemistry

  • Article
    | Open Access

    Aqueous solutions under nanoscale confinement exhibit interesting physicochemical properties. This work reports evidence on the spontaneous formation of two-dimensional alkali chloride crystalline/non-crystalline nanostructures in dilute aqueous solution under nanoscale confinement by computer simulations.

    • Wenhui Zhao
    • , Yunxiang Sun
    •  & Xiao Cheng Zeng
  • Article
    | Open Access

    Machine learning has the potential to significantly speed-up the discovery of new materials in synthetic materials chemistry. Here the authors combine unsupervised machine learning and crystal structure prediction to predict a novel quaternary lithium solid electrolyte that is then synthesized.

    • Andrij Vasylenko
    • , Jacinthe Gamon
    •  & Matthew J. Rosseinsky
  • Article
    | Open Access

    The development of anode-free batteries requires fundamental investigations at the current collector/electrolyte interface. Here, the authors report an atomically defective carbon current collector to improve the electrochemical behaviour of an anode-free Li-based cell.

    • Hyeokjin Kwon
    • , Ju-Hyuk Lee
    •  & Hee-Tak Kim
  • Article
    | Open Access

    Isopropenyl ethers (IPPEs) are essential intermediates for obtaining ketal-based prodrugs and biomaterials, but traditional approaches for their synthesis are limited by poor functional group compatibility and harsh reaction conditions. Here, the authors report an organocatalytic transisopropenylation approach for IPPE synthesis in mild reaction conditions and with wide range of substrates, and use it to prepare acid-sensitive ketal-linked prodrugs and biomaterials.

    • Na Yu
    • , Yang Xu
    •  & Shutao Guo
  • Article
    | Open Access

    Transfer of scarce phosphate to organic molecules is a significant challenge for prebiotic chemistry. Here authors show a prebiotic physicochemical cycle to activate orthophosphate and via a kinetically stable, thermodynamically activated molecule phosphorylate all of life’s basic building blocks.

    • Oliver R. Maguire
    • , Iris B. A. Smokers
    •  & Wilhelm T. S. Huck
  • Article
    | Open Access

    The development of robust and efficient catalysts for CO2 hydrogenation to value-added chemicals is an urgent task. Here the authors report two-dimensional carbide catalyst based on earth-abundant molybdenum that hydrogenates CO2 with high activity, stable performance and tunable selectivity.

    • Hui Zhou
    • , Zixuan Chen
    •  & Christoph R. Müller
  • Article
    | Open Access

    Organic cluster-triggered emission (CTE) displays promising application in bioimaging, chemical sensing, and multicolor luminescence but circular polarize luminescence derived from CTE remains less studied. Here, the authors demonstrate CTE based CPL emission from a supramolecular film derived from solid phase molecular self-assembly.

    • Peilong Liao
    • , Shihao Zang
    •  & Yun Yan
  • Article
    | Open Access

    High-nitrogen content polyhedral molecules are of fundamental interest for theory and for synthesis applications. The authors, using isomer selective, tunable soft photoionization reflectron time-of-flight mass spectrometry, identify the formation of a hitherto elusive prismatic P3N3 molecule during sublimation of PH3 and N2 ice mixtures exposed to energetic electrons.

    • Cheng Zhu
    • , André K. Eckhardt
    •  & Ralf I. Kaiser
  • Article
    | Open Access

    Detection of the tumour boundary in prostate cancer is required for surgery. Here the authors present a fluorescent molecular rotor probe to target a prostate cancer marker, prostate-specific membrane antigen (PSMA), which they use in a xenograft mouse model to show it can be used for in vivo imaging.

    • Jingming Zhang
    • , Anastasia Rakhimbekova
    •  & Xing Yang
  • Article
    | Open Access

    Efficient oxygen activation is crucial for catalytic oxidation reaction, but highly depends on the construction of active sites. Here, dual adjacent Fe atoms anchored on MnO2 can assemble into a diatomic site, which activates molecular oxygen to form an active intermediate species Fe(O = O)Fe for CO oxidation.

    • Huayu Gu
    • , Xiao Liu
    •  & Lizhi Zhang
  • Article
    | Open Access

    Ultrafast diffraction is fundamental in capturing the structural dynamics of molecules. Here, the authors establish a variant of quantum state tomography for arbitrary degrees of freedom to characterize the molecular quantum states, which will enable the reconstruction of a quantum molecular movie from diffraction data.

    • Ming Zhang
    • , Shuqiao Zhang
    •  & Zheng Li
  • Article
    | Open Access

    Understanding the catalysts’ structure evolution under working conditions is challenging. Here the authors use a multiscale simulation approach and machine learning to study the structures and nucleation of CeO2-supported Pd clusters and single atoms at various catalyst loadings, temperatures, and exposures to CO.

    • Yifan Wang
    • , Jake Kalscheur
    •  & Dionisios G. Vlachos
  • Article
    | Open Access

    Deep eutectic solvents (DES) are intriguing green reaction media for biomass processing, however, undesired lignin condensation is a typical drawback. Here the authors develop a tunable ternary DES system that allows for stabilization of reactive intermediates for efficient lignocellulose fractionation.

    • Yongzhuang Liu
    • , Noemi Deak
    •  & Katalin Barta
  • Article
    | Open Access

    Here, Broszeit et al. show that circulating A/H3N2 viruses have evolved binding specificity to α2,6-sialosides on extended LacNAc moieties and therefore cannot agglutinate erythrocytes. Applying glycan remodeling allows to install functional receptors on erythrocytes and promotes identification of newly circulating variants to facilitate vaccine design.

    • Frederik Broszeit
    • , Rosanne J. van Beek
    •  & Geert-Jan Boons
  • Article
    | Open Access

    Commonly, large π-conjugated systems facilitate low-energy electronic transitions. Here, the authors demonstrate that the relief of excited-state antiaromaticity of the benzene core leads to large Stokes shifts, and allows the construction of emitters covering the entire visible spectrum without the need of extending π-conjugation.

    • Heechan Kim
    • , Woojin Park
    •  & Dongwhan Lee
  • Article
    | Open Access

    The “anti-branching rule”, introduced in 1950, excludes branched polyphosphates from biological relevance due to their supposedly rapid hydrolysis. Here, the authors synthesize monodisperse branched polyphosphates and demonstrate their unexpected stability in water, as well as provide evidence for their competence in phosphorylation.

    • Tobias Dürr-Mayer
    • , Danye Qiu
    •  & Henning J. Jessen
  • Article
    | Open Access

    The generation of alkyl radicals through deoxygenation of abundant alcohols via photoredox catalysis is of interest. In this study, the authors report a one-pot strategy for visible-light-promoted photoredox coupling of alcohols with electron-deficient alkenes, assisted by carbon disulfide and triphenylphosphine.

    • Hong-Mei Guo
    •  & Xuesong Wu
  • Article
    | Open Access

    Photosynthetic Complex I (PS-CI) is proposed to couple ferredoxin oxidation and plastoquinone reduction to proton pumping across thylakoid membranes. Here the authors determine the reduction potentials of the iron-sulphur clusters of PS-CI and thus the bioenergetics of the electron transfer relay.

    • Katherine H. Richardson
    • , John J. Wright
    •  & Maxie M. Roessler
  • Article
    | Open Access

    The long-term cycling of Li-S batteries depends on the polysulfides shuttling regulation. Here, the authors present a saccharide-based binder system to control the polysulfides migration and improve the cycle life of a Li-S pouch cell.

    • Yingyi Huang
    • , Mahdokht Shaibani
    •  & Mainak Majumder
  • Article
    | Open Access

    At the nanoscale, elastic strain and crystal defects largely influence the properties and functionalities of materials. Here, the authors report an unusual twin boundary migration process in a single platinum nanoparticle during carbon monoxide oxidation using Bragg coherent diffraction imaging.

    • Jérôme Carnis
    • , Aseem Rajan Kshirsagar
    •  & Marie-Ingrid Richard
  • Article
    | Open Access

    Borosins are ribosomally encoded and posttranslationally modified peptide (RiPP) natural products featuring amide-backbone α-N-methylation. Here, the authors report the discovery and characterization of type IV borosin ‘split’ pathways encoding distinct, separate α-N-methyltransferases and precursor peptide substrates.

    • Fredarla S. Miller
    • , Kathryn K. Crone
    •  & Michael F. Freeman
  • Article
    | Open Access

    Unlike other halogen atoms, the ability for fluorine to exist in a [C–X–C]+ connectivity pattern has only been shown in spectroscopic studies. Here the authors present a single crystal structure of a fluoronium cation, characterized by X-ray diffraction.

    • Kurt F. Hoffmann
    • , Anja Wiesner
    •  & Sebastian Riedel
  • Article
    | Open Access

    Enantiomeric bridged [2,2,1] bicyclic lactone skeletons and their ring-opening products are important scaffolds widely occurring in both pharmaceutics and biology active compounds. Here the authors show an efficient method for enantioselective construction of these compounds bearing a quaternary stereocenter via Rh-catalyzed asymmetric hydroformylation/intramolecular cyclization/ pyridinium chlorochromate oxidation.

    • Shuailong Li
    • , Zhuangxing Li
    •  & Hui Lv
  • Article
    | Open Access

    Here, the authors use solid-state NMR and EPR measurements to characterise the ATP hydrolysis transition state of the oligomeric bacterial DnaB helicase from Helicobacter pylori, which was trapped by using aluminium fluoride as a chemical mimic. They identify protein protons that coordinate to the phosphate groups of ADP and DNA and observe that the aluminium fluoride unit is highly mobile and fast-rotating.

    • Alexander A. Malär
    • , Nino Wili
    •  & Thomas Wiegand
  • Article
    | Open Access

    Machine learning faces challenges in catalyst design due to its black-box nature. Here, the authors develop a theory-infused neural network approach that integrates deep learning algorithms with the well-established d-band theory of chemisorption for reactivity prediction of transition-metal surfaces.

    • Shih-Han Wang
    • , Hemanth Somarajan Pillai
    •  & Hongliang Xin
  • Article
    | Open Access

    Multistep nucleation phenomena are of considerable fundamental interest. Here the authors combine molecular dynamics, machine learning and molecular cluster analysis to investigate the multistep nucleation of smectic clusters from a nematic fluid that cannot be accounted for by the classical nucleation theory.

    • Kazuaki Z. Takahashi
    • , Takeshi Aoyagi
    •  & Jun-ichi Fukuda
  • Article
    | Open Access

    Electrochemical conversion of CO2 to fuels is a promising strategy to reduce the ever-increasing CO2 emission. Here, the authors developed graphene quantum dots (GQDs) catalysts to efficiently convert CO2 to CH4 and revealed the significance of electron-donating functional groups in regulating the reactivity of GQDs.

    • Tianyu Zhang
    • , Weitao Li
    •  & Jingjie Wu
  • Article
    | Open Access

    Sulfinyl radicals are an underexplored synthon in organic chemistry due to the fact that they reversibly add to pi systems and undergo homodimerization. Here the authors synthesize sulfonyl sulfones, previously thought to be unstable, and demonstrate their broad use as sulfinyl radical precursors in disulfurizations of alkenes and alkynes.

    • Zikun Wang
    • , Zhansong Zhang
    •  & Xihe Bi
  • Article
    | Open Access

    It is still challenging to engineer single-atom catalysts for electrocatalytic methanol oxidation. Here, the authors design Pt single atom supported on RuO2 for highly active methanol oxidation in contrast to the inert Pt single atom supported on carbon.

    • Zhiqi Zhang
    • , Jiapeng Liu
    •  & Francesco Ciucci
  • Article
    | Open Access

    By now a plethora of ultrathin hydrophobic coatings are available but their durability are not well developed. Here, the authors present a thin, durable and fluorine-free PDMS-based vitrimer coating that implements many desirable aspects like energy efficiency, durability and sustainability.

    • Jingcheng Ma
    • , Laura E. Porath
    •  & Christopher M. Evans
  • Article
    | Open Access

    The analysis of NMR spectra of complex biochemical samples with respect to individual resonances is challenging but critically important. Here, the authors present a deep learning-based method that accelerates this process also for crowded NMR data that are non-trivial to analyze, even by expert NMR spectroscopists.

    • Da-Wei Li
    • , Alexandar L. Hansen
    •  & Rafael Brüschweiler
  • Article
    | Open Access

    Shock-wave driven reactions of organic molecules may have played a key role in prebiotic chemistry, but their mechanisms are difficult to investigate. The authors, using time-resolved x-ray diffraction and small-angle x-ray scattering experiments, observe the transformation of liquid benzene during a shock, identifying carbon and hydrocarbon solid products.

    • D. M. Dattelbaum
    • , E. B. Watkins
    •  & R. L. Sandberg
  • Article
    | Open Access

    The transformation of planar aromatic molecules into non-planar structures is a challenging task and has not been realized by mechanochemistry before. Here, the authors demonstrate that mechanochemical forces can transform a planar polyarene into a curved geometry by creating new C-C bonds along the rim of the molecular structure.

    • Teoh Yong
    • , Gábor Báti
    •  & Mihaiela C. Stuparu
  • Article
    | Open Access

    Encapsulating large and contorted nanographenes inside artificial receptors remain challenging. This work reports the synthesis, characterization and binding properties of a trigonal prismatic cage compound that can serve as a receptor for contorted nanographene derivatives.

    • Huang Wu
    • , Yu Wang
    •  & J. Fraser Stoddart
  • Article
    | Open Access

    Asymmetric transamination of α-keto amides could provide an efficient strategy to synthesise peptides, but has not been well developed yet. Here, the authors design chiral pyridoxamine catalyst and realize the asymmetric biomimetic transamination of α-keto amides, providing access to various peptides with excellent enantiopurities.

    • Weiqi Cai
    • , Xuelong Qiao
    •  & Baoguo Zhao