Physical sciences articles within Nature Chemistry

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  • Article |

    Photon-driven dinitrogen reduction to ammonia is a promising but challenging reaction. Now it has been shown that lithium hydride undergoes photolysis upon ultraviolet illumination to yield long-lived photon-generated electrons residing in hydrogen vacancies, favouring the activation of the N≡N bond and achieving photocatalytic ammonia synthesis.

    • Yeqin Guan
    • , Hong Wen
    •  & Ping Chen

  • Article |

    The synthesis, structure and reactivity of room-temperature-stable [Cp(C6F5)5]+[Sb3F16]− is presented. Coordination of the cyclopentadienyl cation by [Sb3F16]− or C6F6 stabilizes the antiaromatic singlet state in the solid state. Calculated hydride and fluoride ion affinities of the [Cp(C6F5)5]+ cation are higher than those of the tritylium cation [C(C6F5)3]+.

    • Yannick Schulte
    • , Christoph Wölper
    •  & Stephan Schulz

  • Article
    | Open Access

    The organization of electrolytes at the air/water interface affects the structure of interfacial water and therefore numerous natural processes. It has now been demonstrated that the surface of an electrolyte solution is stratified and consists of an ion-depleted outer surface and an ion-enriched subsurface layer, jointly determining the water interfacial structure.

    • Yair Litman
    • , Kuo-Yang Chiang
    •  & Mischa Bonn

  • Article |

    The activation of dioxygen at metal centres, and subsequent functionalization of unactivated C‒H bonds, requires the generation of high-energy radical intermediates that often result in undesirable side reactions. Now an elusive oxygen-derived reactive iron(II)–radical intermediate is spectroscopically characterized as part of a strategy to stabilize phenoxyl radical cofactors during substrate oxidation reactions.

    • Dustin Kass
    • , Virginia A. Larson
    •  & Kallol Ray

  • Article |

    Selectivity of photochemical reactions is notoriously difficult to model. Now it has been shown that by employing an analogy to ground-state reactions with post-transition-state bifurcations, selectivity for a complex photochemical denitrogenation reaction can be captured and rationalized, and its dynamical origins understood.

    • Zhitao Feng
    • , Wentao Guo
    •  & Dean J. Tantillo

  • Article
    | Open Access

    Natural products discovery remains an ongoing challenge. Now, halide depletion offers a complementary approach to discover natural products whose biosynthesis requires halides, including products of cryptic halogenation. Halide depletion reveals that nostochlorosides, the products of an orphan biosynthetic gene cluster in Nostoc punctiforme, are polymerized by a halide-displacing etherifying enzyme.

    • Nathaniel R. Glasser
    • , Dongtao Cui
    •  & Emily P. Balskus

  • Research Briefing |

    Trans–cis photoisomerization is a fundamental photochemical reaction that is thought to proceed through an intermediate with a perpendicular conformation. However, unambiguous identification of this state has proved challenging. The combination of state-of-the-art ultrafast spectroscopy and quantum chemical calculations now provides evidence for its structural observation in stilbene photoisomerization.

  • News & Views |

    Tetracoordinate boron molecules are the key intermediates in many organoboron-related chemical transformations. Now, using alkynyl tetracoordinate boron species, a nickel-catalysed asymmetric 1,3-metallate shift towards axial chirality has been developed, giving access to various axially chiral alkenes in high efficiency.

    • Li-Qing Ren
    •  & Chuan He

  • Perspective |

    The self-assembly of stimuli-responsive building blocks yields functional nano-systems and smart materials. This Perspective discusses how the integration of photoswitches into discrete coordination cages enables control over their assembly, guest binding and systems behaviour. Four scenarios are drawn to highlight the relationship between the photoswitching and dynamic assembly equilibria.

    • Elie Benchimol
    • , Jacopo Tessarolo
    •  & Guido H. Clever

  • Article |

    Enantioselective transformations based on tetracoordinate borons are elusive. Now, an enantioselective nickel-catalysed strategy for the construction of axially chiral alkenes has been reported, via a 1,3-metallate shift of alkynyl tetracoordinate boron species. The reaction uses readily accessible starting materials and a cheap transition-metal catalyst, and the chemoselectivity, regioselectivity and atroposelectivity could be well controlled.

    • Xingxing Ma
    • , Mengwei Tan
    •  & Qiuling Song

  • Article |

    The prototypical trans–cis photoisomerization of stilbenes is thought to occur via a transient intermediate with a perpendicular conformation—often called ‘the phantom state’—but its unambiguous identification has thus far proved difficult. Now, using ultrafast ultraviolet Raman spectroscopy and ab initio molecular dynamics simulation, evidence for its existence and its perpendicular conformation has been obtained.

    • Hikaru Kuramochi
    • , Takuro Tsutsumi
    •  & Tahei Tahara

  • Article
    | Open Access

    High-throughput experimentation (HTE) has great utility for chemical synthesis. However, robust interpretation of high-throughput data remains a challenge. Now, a flexible analyser has been developed on the basis of a machine learning-statistical analysis framework, which can reveal hidden chemical insights from historical HTE data of varying scopes, sizes and biases.

    • Emma King-Smith
    • , Simon Berritt
    •  & Alpha A. Lee

  • Article |

    The heterogeneous catalytic dehydrogenation of hydrocarbons usually suffers from a negative pressure dependence on H2. Now it has been shown that for propane dehydrogenation on gallium oxide-based catalysts, a positive activity dependence on H2 partial pressure arises from a metastable hydride-mediated catalysis in which gallium hydrides promote C–H activation.

    • Guodong Sun
    • , Zhi-Jian Zhao
    •  & Jinlong Gong

  • News & Views |

    Liquid–liquid phase separation (LLPS) within cells is a captivating phenomenon known to aid the organization of cellular components; however, its complex kinetics have remained a puzzle. Now, a new study elucidates the crosstalk between the phase state of an encapsulating membrane and LLPS dynamics.

    • Rumiana Dimova

  • Thesis |

    Given the fraught history of fluorine, Michelle Francl wonders what made medicinal chemists consider fluorine derivatives?

    • Michelle Francl

  • Article
    | Open Access

    Cysteine bioconjugation is an important method to modify biomolecules, but synthetic efforts to diversify reactive warheads and the low reactivity of introducible linchpins often impede application in biological laboratories. Now, a thianthrenium-based reagent permits site-selective installation of episulfonium on biomacromolecules, enabling one-step addition of bioorthogonal nucleophiles and further applications in quantitative proteomics and cross-linking.

    • Philipp Hartmann
    • , Kostiantyn Bohdan
    •  & Tobias Ritter

  • Article |

    In contrast to photothermal therapy requiring high powers over extended times and photodynamic therapy being abrogated by inhibitors of reactive oxygen species, actuation of vibronic modes in single molecules—molecular jackhammers—can now induce efficient cancer cell death. Here, the mechanical disassembly of cell membranes is characterized as the underlying mechanism by which this vibronic-driven action promotes necrotic cell death.

    • Ciceron Ayala-Orozco
    • , Diego Galvez-Aranda
    •  & James M. Tour

  • News & Views |

    As the need for specific fluorescent probes that enable high sensitivity and super-resolution imaging experiments continues to grow, it is imperative to develop new, well-characterized methods to modulate the emission of fluorophores. Now, a general platform affords visible-to-NIR fluorogenic fluorophores by engineering a simple cyclization event into cyanine dyes.

    • Quintashia D. Wilson
    •  & Ellen M. Sletten

  • Article |

    Current proteolysis-targeting chimeras can promote the ubiquitination and subsequent degradation of both target and off-target proteins by inducing their respective proximity with the cereblon ubiquitin ligase. Now, by developing and deploying an off-target profiling platform, ‘bumped proteolysis-targeting chimeras’ can maintain on-target degradation efficacy with reduced off-targets.

    • Tuan M. Nguyen
    • , Vedagopuram Sreekanth
    •  & Amit Choudhary

  • News & Views |

    The study of disordered materials poses numerous challenges, and computational approaches have proved useful to supplement and support structural experiments. Now, an abstract computational model has been used to study the structure of amorphous calcium carbonate, providing mechanistic insights into the emergence of the disordered phase as well as its atomic-level configurations.

    • Julia Dshemuchadse

  • Article |

    Robust protocols for the synthesis of chiral α-tertiary amino acids remain scarce due to the challenge of constructing congested tetrasubstituted stereocentres. Now a cobalt-catalysed enantioselective aza-Barbier reaction of ketimines with various unactivated alkyl halides has been developed, forming diverse chiral α-tertiary amino esters with high enantioselectivity and excellent functional group tolerance.

    • Xianqing Wu
    • , Hanyu Xia
    •  & Yifeng Chen

  • Article |

    The umpolung functionalization of imines bears vast synthetic potential, but polarity inversion is less efficient compared with the carbonyl counterparts. Now, an alternative strategy exploiting chiral phosphoric acid catalytic aromatization has been developed, affording structures possessing a central chirality or a stereogenic C–N axis with high efficiency and enantiocontrol.

    • Ye-Hui Chen
    • , Meng Duan
    •  & Bin Tan

  • Article |

    Methods for transition-metal-catalysed enantioselective C(sp3)–S bond construction are underdeveloped. Now, by taking advantage of the biomimetic radical homolytic substitution manifold, the copper-catalysed enantioconvergent C(sp3)–S cross-coupling of racemic secondary and tertiary alkyl halides with highly transformable sulfur nucleophiles has been realized. This reaction provides access to an array of α-chiral alkyl organosulfur compounds.

    • Yu Tian
    • , Xi-Tao Li
    •  & Xin-Yuan Liu

  • Article |

    Activation of H2 by a metal–olefin complex is characterized experimentally and computationally using a nickel pincer complex, showing that the reaction proceeds via a direct ligand-to-ligand hydrogen transfer mechanism. An application of this cooperative H2-activation mechanism is demonstrated in the nickel-catalysed semihydrogenation of diphenylacetylene.

    • María L. G. Sansores-Paredes
    • , Martin Lutz
    •  & Marc-Etienne Moret

  • Article |

    Borenium ions have traditionally served as main group (pre-)catalysts, and their use in materials-related applications have been limited by their instability. Now, a series of fully π-conjugated azaboraacenium ions derived from carbodicarbene have been developed that exhibit high air and moisture stability with full colour-tunable luminescence. Furthermore, these azaboraacene cations mimic the electronic structures of higher-order carbonaceous acenes while featuring enhanced resistance to photo-oxidation.

    • Chun-Lin Deng
    • , Akachukwu D. Obi
    •  & Robert J. Gilliard Jr.

  • Article |

    Light-induced azobenzene cis/trans isomerization has been extensively investigated, but the mechanical strength of its cis/trans structure is not well understood. Now it has been shown that cis azobenzene is mechanically less stable than the trans isomer due to its regiochemical structure, as revealed by single-molecule force spectroscopy.

    • Yiran Li
    • , Bin Xue
    •  & Yi Cao

  • Article
    | Open Access

    Enzyme-initiated polymerization-induced self-assembly has been used to generate various biomimetic structures. Now, myoglobin’s activity is used for biocatalytic polymerization-induced self-assembly to generate vesicular artificial cells. As various cargoes can be encapsulated during polymerization, these artificial cells are capable of protein expression and can act as microreactors for distinct enzymatic reactions.

    • Andrea Belluati
    • , Sètuhn Jimaja
    •  & Nico Bruns

  • Article |

    Many natural products are produced by non-ribosomal peptide synthetases in an assembly-line fashion. How these molecular machines orchestrate the biochemical sequences has remained elusive. It is now understood that an extended-conformation ensemble is needed to coordinate chemical-transformation steps whereas the biosynthesis directionality is driven by the enzyme’s innate conformational free energies.

    • Xun Sun
    • , Jonas Alfermann
    •  & Haw Yang

  • News & Views |

    Fluoroalkyl fragments are ubiquitous motifs in pharmaceuticals and agrochemicals, but their introduction to a given molecule typically involves expensive or difficult-to-handle reagents. Now, the photocatalysed hydrofluoroalkylation of alkenes has been achieved using simple and readily available fluoroalkyl carboxylic acids.

    • Fabio Juliá

  • News & Views |

    Stereoselective decarboxylative protonation can produce diverse chiral molecules from widely available carboxylic acids. However, general and practical strategies are lacking. Now, a chiral spirocyclic phosphoric acid-catalysed decarboxylation of aminomalonic acids has enabled the modular synthesis of α-amino acids.

    • Xufeng Lin
    •  & Alemayehu Gashaw Woldegiorgis

  • Article |

    The synthesis of two-dimensional (2D) organic lateral heterostructures with desirable properties from organic single crystals remains challenging. Now, 2D organic lateral heterostructures have been produced by using a liquid-phase growth approach and vapour-phase growth method, enabling the structural inversion of organic lateral heterostructures via a two-step strategy.

    • Qiang Lv
    • , Xue-Dong Wang
    •  & Liang-Sheng Liao

  • Article
    | Open Access

    Polymethine dyes are bright and red-shifted fluorophores that lack an intrinsic turn-on mechanism, which leads to non-specific staining when applied to biological samples. Now the fluorescence of polymethine dyes was masked through an intracellular cyclization strategy that gets reversed upon binding an intended macromolecular target, providing specificity for live-cell imaging.

    • Annabell Martin
    •  & Pablo Rivera-Fuentes

  • Article
    | Open Access

    Late-stage functionalization of complex drug molecules is challenging. To address this problem, a discovery platform based on geometric deep learning and high-throughput experimentation was developed. The computational model predicts binary reaction outcome, reaction yield and regioselectivity with low error margins, enabling the functionalization of complex molecules without de novo synthesis.

    • David F. Nippa
    • , Kenneth Atz
    •  & Gisbert Schneider

  • Research Briefing |

    Ribonucleoprotein granules are ubiquitous in living organisms with the protein and RNA components having distinct roles. In the absence of proteins, RNAs are shown to undergo phase separation upon heating. This transition is driven by desolvation entropy and ion-mediated crosslinking and is tuned by the chemical specificity of the RNA nucleobases.

  • Article |

    The inherent rigidity of the azaarene ring structure has made it challenging to achieve remote stereocontrol through asymmetric catalysis on these substrates. Now, through a photoenzymatic process, an ene-reductase system facilitates the production of diverse azaarenes with distant γ-stereocentres, highlighting the potential of biocatalysts for stereoselectivity at remote sites.

    • Maolin Li
    • , Wesley Harrison
    •  & Huimin Zhao

  • Article |

    Asymmetric decarboxylation can transform abundant carboxylic acids into valuable chiral molecules but faces major limitations due to the challenging enantiocontrol of proton transfer. Now the use of Brønsted acid catalysis in conjunction with an anchoring group strategy has enabled the decarboxylative protonation of aminomalonic acids to access diverse amino acids.

    • Wei-Feng Zheng
    • , Jingdan Chen
    •  & Zhongxing Huang

  • Article
    | Open Access

    Long polyynes have fascinating properties but they are difficult to synthesize as a consequence of their high reactivity. Now, it has been shown that cobalt carbonyl complexes can be used as masked alkyne equivalents, enabling the preparation of stable polyyne polyrotaxanes with up to 34 contiguous triple bonds.

    • Connor W. Patrick
    • , Yueze Gao
    •  & Harry L. Anderson

  • Article |

    Alkene hydrofluoroalkylation offers a promising route to diverse fluoroalkylated compounds but current methods have limitations, such as needing expensive fluoroalkylating reagents. Now, leveraging iron photocatalysis and hydrogen-atom-transfer catalysis, a hydrofluoroalkylation method has been developed that utilizes feedstock chemicals such as trifluoroacetic acid as direct fluoroalkyl radical precursors, providing a redox-neutral, general protocol to introduce fluoroalkyl moieties.

    • Kang-Jie Bian
    • , Yen-Chu Lu
    •  & Julian G. West

  • Research Briefing |

    To develop covalent inhibitors with high potency and low off-target effects, combinatorial approaches that search for candidates from large libraries are desired. Here, sulfur(VI) fluoride exchange (SuFEx) in vitro selection is established for the evolution of covalent aptamers from trillions of SuFEx-modified oligonucleotides. Through this technique, covalent aptamers with optimally balanced selectivity and reactivity are identified.

  • Article |

    Sequences of synthetic polymers are generally heterogeneous and dictate many of their physiochemical properties, but are challenging to determine. Now an imaging method, termed CREATS (coupled reaction approach toward super-resolution imaging), can count, localize and identify each monomer of single polymer chains during (co)polymerization.

    • Rong Ye
    • , Xiangcheng Sun
    •  & Peng Chen

  • Article |

    The synthesis of optically enriched atropisomers has so far been limited to molecules containing aryl groups. Now a variant of non-aryl atropisomerism has been identified in vinyl sulfoxonium ylides, and an organocatalytic method has been developed to produce these molecules. This type of axial chirality is characterized by restricted rotation of the central C(sp2)–C(sp2) bond.

    • Fengjin Wu
    • , Yichi Zhang
    •  & Yong Huang

  • Article |

    Radium complexes are of interest for use as cancer therapeutic agents, but the structure and bonding are poorly understood. Here, the synthesis of a Ra2+ complex is reported, and the structure and bonding characteristics are elucidated using single-crystal X-ray diffraction.

    • Frankie D. White
    • , Nikki A. Thiele
    •  & Samantha K. Cary

  • Article |

    The physicochemical driving forces of protein-free, RNA-driven phase transitions were previously unclear, but it is now shown that RNAs undergo entropically driven liquid–liquid phase separation upon heating in the presence of magnesium ions. In the condensed phase, RNAs can undergo an enthalpically favourable percolation transition that leads to arrested condensates.

    • Gable M. Wadsworth
    • , Walter J. Zahurancik
    •  & Priya R. Banerjee

  • Article |

    Bottom-up assembly of protocells into networking superstructures represents a further key step towards rudimentary formation of life. Now it has been shown that a pool of biomolecules can self-organize into an interactive binary population of protocell coacervates with a self-sorting chain-like configuration, allowing for biomolecular extraction, translocation and macroscale separation.

    • Wenjing Mu
    • , Liyan Jia
    •  & Yan Qiao

  • News & Views |

    Open-shell organic molecules with properties that can be modulated by external stimuli are of interest for spintronics applications. Now, an overcrowded alkene with open-shell tetraradical character has been synthesized in which the interaction between the π-conjugated subunits depends on the charge and spin state.

    • Yoshito Tobe

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