Browse Articles

  • Article
    | Open Access

    Organophosphorous zwitterions are important intermediates in organic synthesis but can be unstable and difficult to characterise. Here, two analogues of such intermediates stabilised by conjugation to an open-cage fullerene derivative allow for characterisation by single-crystal X-ray diffraction, with mechanistic implications.

    • Yoshifumi Hashikawa
    • , Shu Okamoto
    •  & Yasujiro Murata
  • Article
    | Open Access

    Water ligands found in the oxygen-evolving Mn4CaO5 cluster in photosystem II are thought to be important during photosynthesis, but the nature of the proton-releasing substrate water molecules is disputed. Here the pKa values of four key water molecules are estimated, with implications for the mechanism of water oxidation.

    • Keisuke Saito
    • , Minesato Nakagawa
    •  & Hiroshi Ishikita
  • Article
    | Open Access

    Acomplete account of the structural evolution occurring during photopolymerisation is lacking. Here the physical changes occurring on the nanometer scale during photopolymerisation of acrylates are followed over time by FTIR, X-ray reflectometry, AFM, and GISAXS, offering insight into the mechanism by which initial composition influences the final morphology.

    • C. J. Brett
    • , S. Montani
    • , M. Schwartzkopf
    • , R. A. T. M. van Benthem
    • , J. F. G. A. Jansen
    • , G. Griffini
    • , S. V. Roth
    •  & M. K. G. Johansson
  • Article
    | Open Access

    For the geological disposal of radionuclides through immobilization within minerals, naturally aerobic conditions need to be considered. Here the authors report a quantitative reduction of Tc7+ and partial structural incorporation of Tc4+ into in situ formed nonstochiometric magnetite under ambient conditions.

    • Daria Boglaienko
    • , Jennifer A. Soltis
    • , Ravi K. Kukkadapu
    • , Yingge Du
    • , Lucas E. Sweet
    • , Vanessa E. Holfeltz
    • , Gabriel B. Hall
    • , Edgar C. Buck
    • , Carlo U. Segre
    • , Hilary P. Emerson
    • , Yelena Katsenovich
    •  & Tatiana G. Levitskaia
  • Article
    | Open Access

    Microwave irradiation allows for direct and focused heating of solid catalysts, however, temperature control remains a major challenge. Here the local temperatures of platinum nanoparticles on γ-Al2O3 and SiO2 supports are elucidated with in situ XAFS and operando XANES spectroscopy.

    • Taishi Ano
    • , Shuntaro Tsubaki
    • , Anyue Liu
    • , Masayuki Matsuhisa
    • , Satoshi Fujii
    • , Ken Motokura
    • , Wang-Jae Chun
    •  & Yuji Wada
  • Article
    | Open Access

    Nurr1 is a promising therapeutic target for neurodegenerative diseases, but mechanistic understand of its modulation is limited and Nurr1 modulators as tools are lacking. Here, non-steroidal anti-inflammatory drugs are shown to act as inverse Nurr1 agonists, and their interactions with the NR4A family are characterised.

    • Sabine Willems
    • , Whitney Kilu
    • , Xiaomin Ni
    • , Apirat Chaikuad
    • , Stefan Knapp
    • , Jan Heering
    •  & Daniel Merk
  • Article
    | Open Access

    The properties of carboxyl compounds depend on their conformations, but characterising each conformation can be challenging. Here, femtosecond spectroscopy reveals that the carboxyl group of N-acetylproline preferentially adopts a syn conformation in water, but in apolar environments an intramolecular hydrogen favours an anti conformation.

    • Giulia Giubertoni
    • , Oleksandr O. Sofronov
    •  & Huib J. Bakker
  • Article
    | Open Access

    Modern NMR methods such as chemical shift imaging and mobility ordered spectroscopy offer direct insight into the spatial distribution of chemical species within heterogeneous systems. Here, spatial molecular-dynamically ordered spectroscopy (SMOOSY) is developed and used to characterise the spatial distribution and diffusion behavior of small molecules within a heterogeneous biological sample.

    • Kengo Ito
    • , Yuuri Tsuboi
    •  & Jun Kikuchi
  • Article
    | Open Access

    Rhodamine derivatives are useful spirocyclic fluorescent probes, but tuning their properties can involve laborious synthesis and screening. Here quantum chemical modeling of the equilibrium between open and closed forms allows prediction of the pK of cyclisation and rational tailoring of properties of interest.

    • Ryo Tachibana
    • , Mako Kamiya
    • , Satoshi Suzuki
    • , Keiji Morokuma
    • , Aika Nanjo
    •  & Yasuteru Urano
  • Article
    | Open Access

    Liquid-liquid phase separation occurs in cells and can be induced in artificial systems, but the mechanism of the effect of molecular crowders is unclear. Here dehydration entropy-driven phase separation of model charged polymers lacking any chemical complexity or hydrophobicity is shown to be enhanced by polyethylene glycol.

    • Sohee Park
    • , Ryan Barnes
    • , Yanxian Lin
    • , Byoung-jin Jeon
    • , Saeed Najafi
    • , Kris T. Delaney
    • , Glenn H. Fredrickson
    • , Joan-Emma Shea
    • , Dong Soo Hwang
    •  & Songi Han
  • Article
    | Open Access

    Degradation of heterogeneous catalysts limits their cost efficiency and sustainability. Here a hydrogenation catalyst that is stable over a hundred cycles of reuse is reported, with stability attributed to the formation of an agglomeration at the palladium/silicon interface.

    • Yoichi M. A. Yamada
    • , Heeyoel Baek
    • , Takuma Sato
    • , Aiko Nakao
    •  & Yasuhiro Uozumi
  • Article
    | Open Access

    Ferrihydrite nanoparticles have many hydroxyl sites which can react with environmental contaminants and nutrients, but the surface structure of this common mineral is still not fully understood. Here, a combination of vibrational spectroscopy and molecular simulations identify hydroxyl groups exposed along rows at the edges of sheets of iron octahedra.

    • Jean-François Boily
    •  & Xiaowei Song
  • Article
    | Open Access

    Formaldehyde is known to react with nucleophilic amino acids in solution but its in vivo nonenzymatic reactivity is poorly understood. Here LC/MS and isotopic labeling studies suggest nonenzymatic formaldehyde metabolism may occur in living mice through the direct reactivity of formaldehyde with amino acids, including a possible role of timonacic, a product of formaldehyde and cysteine, as a reservoir.

    • Matthias Pietzke
    • , Guillermo Burgos-Barragan
    • , Niek Wit
    • , Jacqueline Tait-Mulder
    • , David Sumpton
    • , Gillian M. Mackay
    • , Ketan J. Patel
    •  & Alexei Vazquez
  • Comment
    | Open Access

    Science disengagement amongst school children remains a global challenge, leading to calls for more scientists to engage with the public. Here the authors discuss how a voluntary, flexible program can enhance graduate attributes in addition to addressing barriers to public engagement.

    • Sean M. Mackay
    • , Eng Wui Tan
    •  & David S. Warren
  • Article
    | Open Access

    Inserting membrane proteins into networks of droplet interface bilayers is important for building biomimetic minimal tissues. Here this is achieved using a chemically activatable mutant of the mechanosensitive channel of large conductance (MscL), where translocation of the activator through the channel defines the overall network flux.

    • Stuart Haylock
    • , Mark S. Friddin
    • , James W. Hindley
    • , Enrique Rodriguez
    • , Kalypso Charalambous
    • , Paula J. Booth
    • , Laura M. C. Barter
    •  & Oscar Ces
  • Article
    | Open Access

    Lectin-like oxidised LDL receptor 1, LOX-1, is implicated in cardiovascular diseases and cancer. Here a small molecule inhibitor of LOX-1 is introduced, which in a unique mode of action stabilises dimers of LOX-1 to prevent LOX-1 mediated signalling.

    • Gisela Schnapp
    • , Heike Neubauer
    • , Frank H. Büttner
    • , Sandra Handschuh
    • , Iain Lingard
    • , Ralf Heilker
    • , Klaus Klinder
    • , Jürgen Prestle
    • , Rainer Walter
    • , Michael Wolff
    • , Markus Zeeb
    • , Francois Debaene
    • , Herbert Nar
    •  & Dennis Fiegen
  • Article
    | Open Access

    Characterising ensembles and populations of disordered structures is a challenge in structural biology. Here a Bayesian model allows solution data from NMR, fluorescence, and SAXS experiments to be synthesised in order to quantify the conformational distribution of disordered protein states.

    • James Lincoff
    • , Mojtaba Haghighatlari
    • , Mickael Krzeminski
    • , João M. C. Teixeira
    • , Gregory-Neal W. Gomes
    • , Claudiu C. Gradinaru
    • , Julie D. Forman-Kay
    •  & Teresa Head-Gordon
  • Article
    | Open Access

    Hydrogenated BiOCl shows high performance as a semiconductor photocatalyst, but the mechanism and synergetic effects of hydrogenation are hard to study. Here interactions of oxygen vacancies and hydrogen atoms in BiOCl nanosheets show a modulation of energy dispersion, which leads to both improvements in charge separation and photocatalytic activity.

    • Dandan Cui
    • , Kang Xu
    • , Xingan Dong
    • , Dongdong Lv
    • , Fan Dong
    • , Weichang Hao
    • , Yi Du
    •  & Jun Chen
  • Article
    | Open Access

    Ultrafast laser pump-probe methods allow chemical reactions to be followed in real-time, but to directly show the rearrangement of nuclear frameworks is challenging. Here an improved real-time-resolved 3D covariance-map Coulomb explosion imaging technique for ultrafast gas-phase reactions is presented.

    • Jason W. L. Lee
    • , Hansjochen Köckert
    • , David Heathcote
    • , Divya Popat
    • , Richard T. Chapman
    • , Gabriel Karras
    • , Paulina Majchrzak
    • , Emma Springate
    •  & Claire Vallance
  • Article
    | Open Access

    C60 is a highly efficient singlet oxygen (1O2) photosensitizer, but its oxidation by self-sensitized 1O2 has not been reported. Here, the authors uncover a single-photon oxidation mechanism via self-sensitized 1O2 in solvents above an excitation energy of 3.7 eV.

    • Linqi Zhang
    • , Chong Wang
    • , Jiming Bao
    •  & A. Kaan Kalkan
  • Article
    | Open Access

    In microbial fuel cells direct electron transfer offers high energy conversion efficiency, but low concentrations of redox centers on bacterial membranes result in low power density. Here nitrogen-doping is fine tuned to match Flavin reaction sites, converting diffusive mediators to anchored redox centers toward direct electrochemistry.

    • Xiaoshuai Wu
    • , Yan Qiao
    • , Chunxian Guo
    • , Zhuanzhuan Shi
    •  & Chang Ming Li
  • Article
    | Open Access

    Lysine trimethylation is a key post-translational modification, which some epigenetic reader proteins detect through binding to aromatic cages involving cation-π interactions. Here systematic modification of the aromatic cage reveals that weaker cation-π interactions do not correlate with weaker binding owing to a compensating release of bound water molecules.

    • Bas J. G. E. Pieters
    • , Maud H. M. Wuts
    • , Jordi Poater
    • , Kiran Kumar
    • , Paul B. White
    • , Jos J. A. G. Kamps
    • , Woody Sherman
    • , Ger J. M. Pruijn
    • , Robert S. Paton
    • , Thijs Beuming
    • , F. Matthias Bickelhaupt
    •  & Jasmin Mecinović
  • Article
    | Open Access

    Selective functionalisation of the N-terminus of peptides and proteins may offer a useful tool for single-site modification. Here a general method for selective N-terminal labeling of peptides is reported, based on cyclisation of ethynylbenzaldehyde to form stable isoquinolinium salts.

    • Jie-Ren Deng
    • , Nathanael Chun-Him Lai
    • , Karen Ka-Yan Kung
    • , Bin Yang
    • , Sai-Fung Chung
    • , Alan Siu-Lun Leung
    • , Man-Chung Choi
    • , Yun-Chung Leung
    •  & Man-Kin Wong
  • Article
    | Open Access

    Low-temperature manganese-based denitrification catalysts require a balance between high reduction reactivity and selectivity. Here aluminium in a mesoporous molecular sieve induces the growth of manganese oxide to obtain an iron-manganese catalyst which achieves high efficiency at temperatures of 150–300 °C.

    • Ge Li
    • , Baodong Wang
    • , Ziran Ma
    • , Hongyan Wang
    • , Jing Ma
    • , Chunlin Zhao
    • , Jiali Zhou
    • , Dehai Lin
    • , Faquan He
    • , Zhihua Han
    • , Qi Sun
    •  & Yun Wang
  • Article
    | Open Access

    The microscopic evolution of elementary chemical reactions remains challenging to describe, as a plethora of parallel channels often determines reaction dynamics. Here the authors propose a theoretical approach to formulate the optical potential for Ne*(3P2,0) chemi-ionizations as a prototype gas-phase oxidation process.

    • Stefano Falcinelli
    • , Franco Vecchiocattivi
    •  & Fernando Pirani
  • Article
    | Open Access

    Sequence-defined macromolecules are a synthetic challenge but offer opportunities for high-density data storage. Here, Passerini three-component reactions yield dual sequence-defined oligomers via an iterative reaction cycle in which both the backbone and side-chains are independently varied, allowing more than 33 bits to be stored in a pentamer.

    • Katharina S. Wetzel
    • , Maximiliane Frölich
    • , Susanne C. Solleder
    • , Roman Nickisch
    • , Philipp Treu
    •  & Michael A. R. Meier
  • Article
    | Open Access

    Radionuclide pairs 44Sc/47Sc and 86Y/90Y possess great promise in the development of theranostic agents, but realizing the full potential of these isotopes necessitates improving rare-earth chelation chemistry. Here the authors show that a hydroxypyridinone-based ligand is a promising candidate for applications in this arena.

    • Korey P. Carter
    • , Gauthier J.-P. Deblonde
    • , Trevor D. Lohrey
    • , Tyler A. Bailey
    • , Dahlia D. An
    • , Katherine M. Shield
    • , Wayne W. Lukens Jr.
    •  & Rebecca J. Abergel
  • Article
    | Open Access

    Tyrosinases are an industrially significant class of polyphenol oxidase. Here, two tyrosinases are shown to cleave a specific peptide bond in a carboxylesterase, yielding a truncated product with higher catalytic activity than the full-length enzyme.

    • A. Biundo
    • , V. Braunschmid
    • , M. Pretzler
    • , I. Kampatsikas
    • , B. Darnhofer
    • , R. Birner-Gruenberger
    • , A. Rompel
    • , D. Ribitsch
    •  & G. M. Guebitz
  • Article
    | Open Access

    Acyl fluorides are useful synthetic intermediates, but their preparation may involve toxic or unstable reagents. Here the authors use 2-(difluoromethoxy)-5-nitropyridine as a bench-stable reagent for the one pot palladium-catalysed conversion of aryl and vinyl iodides to the corresponding acyl fluorides.

    • Yumeng Liang
    • , Zhengyu Zhao
    •  & Norio Shibata
  • Article
    | Open Access

    The catalytic mechanism in non-oxidative methane coupling becomes complicated at high temperatures, making informed catalyst design challenging. Here, microkinetic modelling and experiments on a single-atom iron catalyst show how optimizing the reaction conditions can increase the C2 hydrocarbon yield.

    • Seok Ki Kim
    • , Hyun Woo Kim
    • , Seung Ju Han
    • , Sung Woo Lee
    • , Jungho Shin
    •  & Yong Tae Kim
  • Article
    | Open Access

    Hyperpolarised water is an attractive alternative to metal-containing contrast agents in magnetic resonance imaging, but generating usefully persistent hyperpolarised water protons is challenging. Here dissolution dynamic nuclear polarisation using UV-generated radicals is used to obtain substantial water signal enhancement.

    • Arthur C. Pinon
    • , Andrea Capozzi
    •  & Jan Henrik Ardenkjær-Larsen
  • Article
    | Open Access

    Ionic liquids are used as solvents in biocatalysis but how they interact with the structures of proteins is imperfectly understood. Here the effect of three common ionic liquids on the structure of green fluorescent protein is studied using a suite of experimental techniques, finding a complex relationship which is poorly captured by any single technique.

    • Liem Bui-Le
    • , Coby J. Clarke
    • , Andreas Bröhl
    • , Alex P. S. Brogan
    • , James A. J. Arpino
    • , Karen M. Polizzi
    •  & Jason P. Hallett
  • Article
    | Open Access

    The conformational flexibility of monoribonucleotides can make interpreting their vibrational spectra challenging. Here a combination of classical and ab initio molecular dynamics is used to calculate the contributions of different monoribonucleotide conformers to experimental Raman spectra.

    • Alex L. Wilson
    • , Carlos Outeiral
    • , Sarah E. Dowd
    • , Andrew J. Doig
    • , Paul L. A. Popelier
    • , Jonathan P. Waltho
    •  & Andrew Almond
  • Meeting Report
    | Open Access

    In celebration of International Women’s Day, on 6 March 2020 the University of Nottingham hosted its second Women in Chemistry conference. Or, as branded by a security guard at the host building, a ‘chemical ladies’ meeting’. Victoria Richards recounts the event and shares key take-home messages from the speakers.

    • Victoria Richards
  • Article
    | Open Access

    Organic molecules that exhibit thermally activated delayed fluorescence allow for high efficiencies in OLEDs, but their operational stability remains a challenge to their commercialization. Here the molecular factors that govern the stability of various dyads based on a cycloamino donor–acceptor platform are studied.

    • Sanju Hwang
    • , Yu Kyung Moon
    • , Ho Jin Jang
    • , Sinheui Kim
    • , Hyein Jeong
    • , Jun Yeob Lee
    •  & Youngmin You
  • Article
    | Open Access

    Hypoxia-inducible factor (FIH) is an oxygenase which post-translationally hydroxylates proteins and is implicated in a range of biological processes. Here a wide substrate tolerance for FIH is demonstrated, including for d-amino acids, where double hydroxylation of d-leucine is observed.

    • Hwanho Choi
    • , Adam P. Hardy
    • , Thomas M. Leissing
    • , Rasheduzzaman Chowdhury
    • , Yu Nakashima
    • , Wei Ge
    • , Marios Markoulides
    • , John S. Scotti
    • , Philip A. Gerken
    • , Helen Thorbjornsrud
    • , Dahye Kang
    • , Sungwoo Hong
    • , Joongoo Lee
    • , Michael A. McDonough
    • , Hwangseo Park
    •  & Christopher J. Schofield
  • Article
    | Open Access

    Molecular crowding such as that which may occur in model protocells is known to reduce the rate and fidelity of RNA replication. Here diffusion NMR and NMR relaxation studies of RNA monomers under crowded conditions show that purines stack more efficiently than pyrimidines, reducing their availability for polymerization.

    • Niraja V. Bapat
    • , Harshad Paithankar
    • , Jeetender Chugh
    •  & Sudha Rajamani
  • Article
    | Open Access

    The mechanism of formation of H3+ cations during double ionisation of methanol is debated. Here a combination of spectroscopic and molecular dynamics studies support a mechanism involving abstraction of a proton from the double cation by roaming neutral hydrogen molecules within 100 femtoseconds.

    • Ester Livshits
    • , Itamar Luzon
    • , Krishnendu Gope
    • , Roi Baer
    •  & Daniel Strasser
  • Article
    | Open Access

    Dienes are useful reagents for cross-couplings in the synthesis of unsaturated natural products, but decarboxylative Heck reactions of dienes are limited by facile E/Z isomerism. Here configurationally stable divinyldicarboxylic acid is used as a coupling reagent in which the carboxylates direct the Heck reaction prior to decarboxylation.

    • Lei Ke
    •  & Zhilong Chen
  • Article
    | Open Access

    Dilute alloy nanoparticles are a promising class of heterogeneous catalysts, but how their composition and structure affects performance is imperfectly understood. Here dilute PdAu catalysts are shown to be highly dynamic, which enables systematic tuning of their structure and composition to maintain an active state.

    • Mathilde Luneau
    • , Erjia Guan
    • , Wei Chen
    • , Alexandre C. Foucher
    • , Nicholas Marcella
    • , Tanya Shirman
    • , David M. A. Verbart
    • , Joanna Aizenberg
    • , Michael Aizenberg
    • , Eric A. Stach
    • , Robert J. Madix
    • , Anatoly I. Frenkel
    •  & Cynthia M. Friend
  • Article
    | Open Access

    The restrained electrostatic potential (RESP) is a widely used method for assigning partial charges to organic molecules for molecular dynamics simulations, but it imperfectly accounts for self-polarization in solution. Here, RESP is updated by co-optimizing the polarity of the charges it generates, along with atomic Lennard-Jones parameters, to yield an improved model of non-bonded interactions.

    • Michael Schauperl
    • , Paul S. Nerenberg
    • , Hyesu Jang
    • , Lee-Ping Wang
    • , Christopher I. Bayly
    • , David L. Mobley
    •  & Michael K. Gilson
  • Article
    | Open Access

    Enantioselective dicarbofunctionalization of tethered alkenes typically relies on facially selective arylmetalation as a key step. Here, a nickel-catalyzed reductive carboacylation of alkenes and alkyl iodides which features acylnickelation as the enantiodetermining step is reported.

    • Yun Lan
    •  & Chuan Wang