Latest Research

  • Article |

    Natural hydrogenases exclusively utilize Ni and/or Fe to activate or produce hydrogen. Now, a catalytically active [Mn]-hydrogenase has been prepared by incorporating a synthetic Mn complex into the apoenzyme of [Fe]-Hydrogenase. The semi-synthetic [Mn]-hydrogenase shows higher activity than the corresponding Fe analogue.

    • Hui-Jie Pan
    • , Gangfeng Huang
    • , Matthew D. Wodrich
    • , Farzaneh Fadaei Tirani
    • , Kenichi Ataka
    • , Seigo Shima
    •  & Xile Hu
  • Article |

    Structural defects are known to exist in metal–organic frameworks (MOFs), and to affect the materials’ properties, but their exact structures have remained difficult to determine. Now, missing-linker and missing-cluster defects have been observed in a MOF using low-dose transmission electron microscopy, enabling their distributions, evolutions during crystallization and effects on the material’s catalytic activity to be explored.

    • Lingmei Liu
    • , Zhijie Chen
    • , Jianjian Wang
    • , Daliang Zhang
    • , Yihan Zhu
    • , Sanliang Ling
    • , Kuo-Wei Huang
    • , Youssef Belmabkhout
    • , Karim Adil
    • , Yuxin Zhang
    • , Ben Slater
    • , Mohamed Eddaoudi
    •  & Yu Han
  • Article |

    A set of stereochemically complex and structurally diverse compounds were created from the diterpene natural product pleuromutilin using the complexity-to-diversity strategy. Phenotypic screening identified a compound that induces rapid ferroptotic death of cancer cells. Experiments to probe the mechanism revealed the compound to be an inhibitor of thioredoxin.

    • Evijola Llabani
    • , Robert W. Hicklin
    • , Hyang Yeon Lee
    • , Stephen E. Motika
    • , Lisa A. Crawford
    • , Eranthie Weerapana
    •  & Paul J. Hergenrother
  • Article |

    Gas sorption studies in porous materials typically reflect their overall gas uptake. Now, using a ‘gas adsorption crystallography’ method, the gas adsorption isotherms of two metal–organic frameworks (MOFs) have been quantitatively decomposed into sub-isotherms that reflect the pore-filling behaviour of various guests in the different types of pores present in the MOFs.

    • Hae Sung Cho
    • , Jingjing Yang
    • , Xuan Gong
    • , Yue-Biao Zhang
    • , Koichi Momma
    • , Bert M. Weckhuysen
    • , Hexiang Deng
    • , Jeung Ku Kang
    • , Omar M. Yaghi
    •  & Osamu Terasaki
  • Article |

    Secondary-sphere interactions serve a fundamental role in controlling the reactivity and selectivity of organometallic and enzyme catalysts, but their study in organocatalytic systems is scarce. Now, it has been shown that the in situ secondary-sphere modification of organocatalysts combined with machine-learning techniques can uncover reaction mechanisms and streamline catalyst optimization.

    • Vasudevan Dhayalan
    • , Santosh C. Gadekar
    • , Zayed Alassad
    •  & Anat Milo
  • Article |

    The reaction between an excited atom and a charged molecule has now been studied at low temperature and a reaction blockading effect has been observed that differs significantly from what is expected from standard chemical capture theory.

    • Prateek Puri
    • , Michael Mills
    • , Ionel Simbotin
    • , John A. Montgomery Jr
    • , Robin Côté
    • , Christian Schneider
    • , Arthur G. Suits
    •  & Eric R. Hudson
  • Article |

    Bacteria communicate through excretion of minute amounts of chemical signalling molecules that affect virulence, biofilm formation and colonization. In staphylococci, these molecules, called autoinducing peptides, are macrocyclic thiolactone-containing peptides. Now, a simple enrichment method, based on chemoselective capture on polymer beads, has been developed that enables the identification of previously unknown autoinducing peptides.

    • Bengt H. Gless
    • , Martin S. Bojer
    • , Pai Peng
    • , Mara Baldry
    • , Hanne Ingmer
    •  & Christian A. Olsen
  • Article |

    Nucleic acid nanotechnology offers a promising route towards the design and synthesis of reconfigurable biomolecular materials. Now, the combination of dynamic and structural DNA nanotechnology has enabled the dynamic control of the assembly and disassembly of DNA nanotubes. The process involves minimal synthetic gene systems, including an autonomous molecular oscillator.

    • Leopold N. Green
    • , Hari K. K. Subramanian
    • , Vahid Mardanlou
    • , Jongmin Kim
    • , Rizal F. Hariadi
    •  & Elisa Franco
  • Article |

    The synthesis of aryl amines is traditionally achieved through aromatic nitration or transition metal-catalysed cross coupling. Now, photocatalysis provides a route for the direct and selective C–H amination of aromatics with alkyl amines, without the need for pre-functionalization. This reaction tolerates a variety of functional groups and can be used for late-stage modification.

    • Alessandro Ruffoni
    • , Fabio Juliá
    • , Thomas D. Svejstrup
    • , Alastair J. McMillan
    • , James J. Douglas
    •  & Daniele Leonori
  • Article |

    The highly charged phosphodiester chemistry of the natural nucleic acids DNA and RNA has been widely considered to be indispensable for their function as informational molecules. Now, synthetic genetic polymers with an uncharged alkyl phosphonate backbone chemistry have been shown to enable genetic information transfer and evolution.

    • Sebastian Arangundy-Franklin
    • , Alexander I. Taylor
    • , Benjamin T. Porebski
    • , Vito Genna
    • , Sew Peak-Chew
    • , Alexandra Vaisman
    • , Roger Woodgate
    • , Modesto Orozco
    •  & Philipp Holliger
  • Article |

    It is difficult to recover materials for re-manufacturing and re-use from plastics that are compounded with colourants, fillers and flame retardants. Now, it has been shown that alternative plastics based on dynamic covalent poly(diketoenamine)s depolymerize in strong aqueous acids and enable triketone and amine monomers to be isolated and upcycled into new plastics.

    • Peter R. Christensen
    • , Angelique M. Scheuermann
    • , Kathryn E. Loeffler
    •  & Brett A. Helms
  • Article |

    Conventional regioselectivity in Pd-catalysed C(sp3)–H activation is dictated by the formation of a five-membered palladacycle. Now, it has been shown that the combination of a simple directing group and a 2-pyridone ligand favours six-membered cyclopalladation, demonstrating the feasibility of using geometric strain to reverse conventional site selectivity in these reactions.

    • Guoqin Xia
    • , Jiang Weng
    • , Luoyan Liu
    • , Pritha Verma
    • , Ziqi Li
    •  & Jin-Quan Yu
  • Article |

    The photochemical electrocyclic ring-opening of 1,3-cyclohexadiene is a textbook organic chemistry reaction. Now, using ultrafast electron diffraction its reaction pathway has been resolved on the level of atomic distances and on its natural femtosecond timescale. Furthermore, coherent isomerization dynamics of the photoproduct 1,3,5-hexatriene were observed.

    • T. J. A. Wolf
    • , D. M. Sanchez
    • , J. Yang
    • , R. M. Parrish
    • , J. P. F. Nunes
    • , M. Centurion
    • , R. Coffee
    • , J. P. Cryan
    • , M. Gühr
    • , K. Hegazy
    • , A. Kirrander
    • , R. K. Li
    • , J. Ruddock
    • , X. Shen
    • , T. Vecchione
    • , S. P. Weathersby
    • , P. M. Weber
    • , K. Wilkin
    • , H. Yong
    • , Q. Zheng
    • , X. J. Wang
    • , M. P. Minitti
    •  & T. J. Martínez
  • Article |

    Magic-number Au11 clusters containing N-heterocyclic carbene (NHC) ligands are prepared by ligand exchange on known phosphine clusters and the introduction of even a single NHC results in improved cluster stability. The use of NHC-containing clusters in the electrocatalytic reduction of CO2 to CO is described and correlates with cluster stability.

    • Mina R. Narouz
    • , Kimberly M. Osten
    • , Phillip J. Unsworth
    • , Renee W. Y. Man
    • , Kirsi Salorinne
    • , Shinjiro Takano
    • , Ryohei Tomihara
    • , Sami Kaappa
    • , Sami Malola
    • , Cao-Thang Dinh
    • , J. Daniel Padmos
    • , Kennedy Ayoo
    • , Patrick J. Garrett
    • , Masakazu Nambo
    • , J. Hugh Horton
    • , Edward H. Sargent
    • , Hannu Häkkinen
    • , Tatsuya Tsukuda
    •  & Cathleen M. Crudden
  • Review Article |

    Biochemical and cellular assays are often plagued by false positive readouts elicited by nuisance compounds. A significant proportion of those compounds are aggregators. This Review discusses the basis for colloidal aggregation, experimental methods for detecting aggregates and analyses recent progress in computer-based systems for detecting colloidal aggregation with particular emphasis on machine learning [In the online version of this Review originally published, the graphical abstract image was incorrectly credited to ‘Reven T.C. Wurman / Alamy Stock Photo’ this has now been corrected].

    Oleksii Telnov / Alamy Stock Photo

    • Daniel Reker
    • , Gonçalo J. L. Bernardes
    •  & Tiago Rodrigues
  • Article |

    A strategy for directly synthesizing unnatural polymers in cells through radical polymerization has now been developed. This approach provides a platform to manipulate, track and control cellular behaviour by the in cellulo generation of macromolecules and a variety of nanostructures.

    • Jin Geng
    • , Weishuo Li
    • , Yichuan Zhang
    • , Neelima Thottappillil
    • , Jessica Clavadetscher
    • , Annamaria Lilienkampf
    •  & Mark Bradley
  • Article |

    While much effort has been devoted to understanding how nanoparticle morphology can be leveraged to improve catalytic activity, engineering their microstructure from first principles to this end has remained difficult. Now a methodology for designing the optimal structure of a solid catalyst with the aim of achieving the highest possible activity for surface-sensitive reactions has been developed.

    • M. Núñez
    • , J. L. Lansford
    •  & D. G. Vlachos
  • Article |

    The development of porous, crystalline materials with high chemical stability is crucial for their practical uses. Now, polyarylether-based covalent organic frameworks (PAE-COFs) have been synthesized that show high crystallinity and porosity, as well as good stability against harsh chemical environments including boiling water and strong acids and bases.

    • Xinyu Guan
    • , Hui Li
    • , Yunchao Ma
    • , Ming Xue
    • , Qianrong Fang
    • , Yushan Yan
    • , Valentin Valtchev
    •  & Shilun Qiu
  • Article |

    In a ruthenium-catalysed living ring-opening metathesis polymerization, one metal centre is required for each polymer chain, and this requires high catalyst loadings when aiming for short polymer chains. Now, it has been shown that a degenerative reversible chain-transfer process enables the synthesis of ring-opened metathesis polymers with controlled molecular weight, using only catalytic amounts of a ruthenium complex.

    • Mohammad Yasir
    • , Peng Liu
    • , Iris K. Tennie
    •  & Andreas F. M. Kilbinger
  • Article |

    Two chemical probes, YnF and YnGG, that enable the identification of prenylated peptides and global analysis of protein prenylation using quantitative chemical proteomics have now been developed. Prenylation dynamics in response to pharmacological inhibition of prenyl-transferase enzymes were also studied. As a final demonstration, defective Rab prenylation in a model of the retinal degenerative disease choroideremia was also quantified.

    • Elisabeth M. Storck
    • , Julia Morales-Sanfrutos
    • , Remigiusz A. Serwa
    • , Nattawadee Panyain
    • , Thomas Lanyon-Hogg
    • , Tanya Tolmachova
    • , Leandro N. Ventimiglia
    • , Juan Martin-Serrano
    • , Miguel C. Seabra
    • , Beata Wojciak-Stothard
    •  & Edward W. Tate
  • Article |

    Synthetic dissipative systems, formed by out-of-equilibrium self-assembly processes, can mimic some of the properties of biological systems, but often show poor mechanical performance. Now, a shear-induced transient hydrogel has been prepared that is also highly stretchable. The system is based on coordination interactions between Cu(ii) centres and the pendant carboxylate groups of a pseudopolyrotaxane.

    • Hua Ke
    • , Liu-Pan Yang
    • , Mo Xie
    • , Zhao Chen
    • , Huan Yao
    •  & Wei Jiang
  • Article |

    RNA is usually considered to be the first genetic polymer, with DNA a product of a biochemical pathway that arose after the origin of life. Now, studies into the prebiotic phosphorylation of an RNA nucleoside reveal pathways for the synthesis of DNA building blocks, providing experimental support for a prebiotic link between RNA and DNA.

    • Jianfeng Xu
    • , Nicholas J. Green
    • , Clémentine Gibard
    • , Ramanarayanan Krishnamurthy
    •  & John D. Sutherland
  • Article |

    Nitriles are widely used in chemistry and are found in many bioactive compounds but, despite recent advances, there are no broadly applicable approaches for the synthesis of di- or tri-substituted alkenyl nitriles. New catalytic cross-metathesis strategies now allow direct access to a wide range of Z- or E-di-substituted cyano-substituted alkenes and their tri-substituted variants.

    • Yucheng Mu
    • , Thach T. Nguyen
    • , Ming Joo Koh
    • , Richard R. Schrock
    •  & Amir H. Hoveyda
  • Perspective |

    Spins in molecules provide a simple platform with which to encode a quantum bit (qubit), the elementary unit of future quantum computers. This Perspective discusses how chemistry can contribute to designing robust spin systems based, in particular, on mononuclear lanthanoid complexes.

    • A. Gaita-Ariño
    • , F. Luis
    • , S. Hill
    •  & E. Coronado
  • Article |

    Pharmacophore-directed retrosynthesis targets a potential pharmacophore from early on in a natural product synthesis and incremental increases in the complexity of this minimal structure enable a SAR profile to develop over the course of the campaign. The method is applied to gracilin A, finding simplified derivatives displaying potent immunosuppressive effects or selective neuroprotective effects in cell-based assays.

    • Mikail E. Abbasov
    • , Rebeca Alvariño
    • , Christian M. Chaheine
    • , Eva Alonso
    • , Jon A. Sánchez
    • , Michael L. Conner
    • , Amparo Alfonso
    • , Marcel Jaspars
    • , Luis M. Botana
    •  & Daniel Romo
  • Article |

    Helical structures play important roles in biological processes, yet their aggregation into fibres—which can in turn form gels—is poorly understood. Now, the self-assembly of a linear pentakis (urea) peptidomimetic compound into helices that further intertwine into well-defined braided structures has been described and analysed through braid theory. Homochiral gels may be formed by exposing the precursor sol to a chiral material.

    • Christopher D. Jones
    • , Henry T. D. Simmons
    • , Kate E. Horner
    • , Kaiqiang Liu
    • , Richard L. Thompson
    •  & Jonathan W. Steed
  • Article |

    Introducing fluorine into organic compounds enables their electronic properties to be tuned and can also significantly alter their function. Now, the α-fluorination of amides has been achieved using nucleophilic fluorinating agents using a polarity reversal strategy. This new method has been used to synthesize a fluorinated analogue of the blockbuster antidepressant drug, citalopram.

    • Pauline Adler
    • , Christopher J. Teskey
    • , Daniel Kaiser
    • , Marion Holy
    • , Harald H. Sitte
    •  & Nuno Maulide
  • Article |

    The structure and dynamics of hydrogen bonds in ion hydration shells are not yet fully understood, however, small ion–dihydrate molecular complexes represent ideal model systems with which to investigate the interplay between ion–water and water–water interactions. Now, state-of-the-art quantum dynamics simulations have provided evidence for tunnelling in hydrogen-bond rearrangements in the iodide–dihydrate complex.

    • Pushp Bajaj
    • , Jeremy O. Richardson
    •  & Francesco Paesani
  • Article |

    Gold–thiol contacts are ubiquitous across the physical and biological sciences, connecting organic molecules to surfaces. Now, conductance measurements of different sulfur-bound single-molecule junctions show that thiols—in contrast to the prevailing view—are not chemisorbed on gold, which strongly suggests that the thiol hydrogen is retained.

    • Michael S. Inkpen
    • , Zhen–Fei Liu
    • , Haixing Li
    • , Luis M. Campos
    • , Jeffrey B. Neaton
    •  & Latha Venkataraman
  • Article |

    Biosynthesis of peptidoglycan requires carefully orchestrated transpeptidation reactions to maintain the structural integrity of this essential component of the bacterial cell wall. Now, rotor-fluorescent d-amino acids have been shown to enable real-time tracking of these transpeptidation reactions in live bacterial cells. These powerful tools allow visualization of peptidoglycan biosynthesis with high spatiotemporal resolution.

    • Yen-Pang Hsu
    • , Edward Hall
    • , Garrett Booher
    • , Brennan Murphy
    • , Atanas D. Radkov
    • , Jacob Yablonowski
    • , Caitlyn Mulcahey
    • , Laura Alvarez
    • , Felipe Cava
    • , Yves V. Brun
    • , Erkin Kuru
    •  & Michael S. VanNieuwenhze
  • Article |

    An automated platform that can synthesize a wide range of complex glycans could greatly facilitate progress in glycoscience. Now, a fully automated process for enzyme-mediated oligosaccharide synthesis has been developed. This process uses glycosyltransferase-catalysed reactions performed in solution, with product purification being accomplished by solid phase extraction using a sulfonate tag.

    • Tiehai Li
    • , Lin Liu
    • , Na Wei
    • , Jeong-Yeh Yang
    • , Digantkumar G. Chapla
    • , Kelley W. Moremen
    •  & Geert-Jan Boons
  • Article |

    Amphiphilic self-assembly is ubiquitous both in nature and synthetic systems, yet the underlying mechanisms governing the transition from molecules to assemblies have not yet been fully resolved. Now, the role of liquid–liquid phase separation prior to the assembly process has been explored through the detailed analysis of a model block-copolymer system.

    • Alessandro Ianiro
    • , Hanglong Wu
    • , Mark M. J. van Rijt
    • , M. Paula Vena
    • , Arthur D. A. Keizer
    • , A. Catarina C. Esteves
    • , Remco Tuinier
    • , Heiner Friedrich
    • , Nico A. J. M. Sommerdijk
    •  & Joseph P. Patterson
  • Article |

    A concise strategy for engineering functional, supramolecular protein complexes has now been developed based on single-mutation-mediated covalent tethering. Metalloproteins designed with this method can sustain large alterations to the metal coordination environment, bind small molecules, exhibit reversible redox activity and sustain large alterations to the protein structure.

    • Jonathan Rittle
    • , Mackenzie J. Field
    • , Michael T. Green
    •  & F. Akif Tezcan
  • Article |

    Single-molecule force spectroscopy reveals that maleimide–thiol adducts can be stabilized by stretching through a force-dependent kinetic control mechanism. This unconventional use of mechanochemistry enabled us to produce stable polymer–protein conjugates by simply applying a mechanical force to the maleimide–thiol adducts through mild ultrasonication.

    • Wenmao Huang
    • , Xin Wu
    • , Xiang Gao
    • , Yifei Yu
    • , Hai Lei
    • , Zhenshu Zhu
    • , Yi Shi
    • , Yulan Chen
    • , Meng Qin
    • , Wei Wang
    •  & Yi Cao
  • Article |

    Heterometallic clusters have shown promise in catalysis and small-molecule activation, but species comprising uranium–metal bonds have remained difficult to synthesize. Now, facile reactions between uranium and nickel precursors have led to nickel-bridged diuranium clusters supported by a heptadentate N4P3 scaffold. Computational analysis points to an unusual electronic configuration for uranium, U(iii)-5f26d1.

    • Genfeng Feng
    • , Mingxing Zhang
    • , Dong Shao
    • , Xinyi Wang
    • , Shuao Wang
    • , Laurent Maron
    •  & Congqing Zhu
  • Article |

    Conjugated mesopolymers can combine the advantages of polymers and oligomers, but have received less attention as semiconducting materials. Now, such compounds have been synthesized by direct arylation polycondensation that exhibit high molecular regularity, solubility and solution processability. These mesopolymers also show electron mobilities that are significantly better than those of their polymer counterparts.

    • Zhenjie Ni
    • , Hanlin Wang
    • , Huanli Dong
    • , Yanfeng Dang
    • , Qiang Zhao
    • , Xiaotao Zhang
    •  & Wenping Hu
  • Article |

    Anchored single-atom catalysts have recently been shown to be very active for various processes, however, a catalyst that features two adjacent copper atoms—which we call an atom-pair catalyst—is now reported. The Cu10–Cu1x+ pair structures work together to carry out the critical bimolecular step in CO2 reduction.

    • Jiqing Jiao
    • , Rui Lin
    • , Shoujie Liu
    • , Weng-Chon Cheong
    • , Chao Zhang
    • , Zheng Chen
    • , Yuan Pan
    • , Jianguo Tang
    • , Konglin Wu
    • , Sung-Fu Hung
    • , Hao Ming Chen
    • , Lirong Zheng
    • , Qi Lu
    • , Xuan Yang
    • , Bingjun Xu
    • , Hai Xiao
    • , Jun Li
    • , Dingsheng Wang
    • , Qing Peng
    • , Chen Chen
    •  & Yadong Li
  • Article |

    Despite their huge potential in medicinal chemistry, current approaches for the synthesis of fluorinated piperidines are often impractical. A straightforward process for the rhodium-catalysed dearomatization–hydrogenation of fluoropyridines has now been described. This strategy enables the highly diastereoselective formation of a variety of all-cis-(multi)fluorinated piperidines and the study of their conformational behaviour.

    • Zackaria Nairoukh
    • , Marco Wollenburg
    • , Christoph Schlepphorst
    • , Klaus Bergander
    •  & Frank Glorius
  • Article |

    Developing a stable metallic lithium anode is necessary for next-generation batteries; however, lithium is prone to corrosion, a process that must be better understood if practical devices are to be created. A Kirkendall-type mechanism of lithium corrosion has now been observed. The corrosion is fast and is governed by a galvanic process.

    • Dingchang Lin
    • , Yayuan Liu
    • , Yanbin Li
    • , Yuzhang Li
    • , Allen Pei
    • , Jin Xie
    • , William Huang
    •  & Yi Cui
  • Article |

    A two-coordinate monovalent gold complex that features a highly polarized aluminium–gold covalent bond, Alδ+–Auδ−, has been synthesized using a very strongly electron-donating aluminyl ligand. In solution, the complex reacts as a nucleophilic source of gold towards heteroallenes such as carbodiimides and CO2.

    • Jamie Hicks
    • , Akseli Mansikkamäki
    • , Petra Vasko
    • , Jose M. Goicoechea
    •  & Simon Aldridge
  • Article |

    One-dimensional diffusive binding represents an important mechanism used by nature to facilitate many fundamental biochemical processes. Now, a completely synthetic system with similar capabilities has been constructed. The system was exploited to significantly speed up bimolecular reactions and to catalytically transport molecular cargo in solution and within physically separated compartments.

    • Lifei Zheng
    • , Hui Zhao
    • , Yanxiao Han
    • , Haibin Qian
    • , Lela Vukovic
    • , Jasmin Mecinović
    • , Petr Král
    •  & Wilhelm T. S. Huck
  • Article |

    Symmetrical protein oligomers perform key structural and catalytic functions in nature, but engineering such oligomers synthetically is challenging. Now, oppositely supercharged synthetic variants of normally monomeric proteins have been shown to assemble via specific, introduced electrostatic contacts into symmetrical, highly well-defined oligomers.

    • Anna J. Simon
    • , Yi Zhou
    • , Vyas Ramasubramani
    • , Jens Glaser
    • , Arti Pothukuchy
    • , Jimmy Gollihar
    • , Jillian C. Gerberich
    • , Janelle C. Leggere
    • , Barrett R. Morrow
    • , Cheulhee Jung
    • , Sharon C. Glotzer
    • , David W. Taylor
    •  & Andrew D. Ellington