Chemistry

  • Article
    | Open Access

    Neural Networks are known to perform poorly outside of their training domain. Here the authors propose an inverse sampling strategy to train neural network potentials enabling to drive atomistic systems towards high-likelihood and high-uncertainty configurations without the need for molecular dynamics simulations.

    • Daniel Schwalbe-Koda
    • , Aik Rui Tan
    •  & Rafael Gómez-Bombarelli
  • Article
    | Open Access

    Rapid growth of highly crystalline Covalent organic framework (COF) materials remains challenging. Here, the authors accelerate single-crystal polymerization using supercritical CO2 and realize the fabrication of two-dimensional COF single crystals within several minutes.

    • Lan Peng
    • , Qianying Guo
    •  & Dacheng Wei
  • Article
    | Open Access

    Understanding the structure and dynamics of enzymes is important for a number of applications. Here, the authors report on the crystal structure of vanillic acid decarboxylase, and show how the dynamics of the UbiD superfamily enzymes relate to the covalent catalysis of aromatic (de)carboxylation.

    • Stephen A. Marshall
    • , Karl A. P. Payne
    •  & David Leys
  • Article
    | Open Access

    The morphology of semicrystalline plastics on the 1-100 μm scale, such as spherulites, strongly affect mechanical and other properties of the material but currently only 2D imaging techniques are available. Here, the authors use fluorescence labels and confocal microscopy to visualize the internal structure of neat polymers and composites in 3D and reveal unsuspected morphologies.

    • Shu-Gui Yang
    • , Zhen-Zhen Wei
    •  & Goran Ungar
  • Article
    | Open Access

    Synthesizing complex structures of high enantiomeric excess from racemic feedstock is an enduring challenge. Here, the authors couple racemic secondary alcohols with pyrroles to form enantioenriched 2-substituted heteroarenes, via a borrowing hydrogen mechanism using the combination of an iridium catalyst and chiral phosphoric acid.

    • Yongbing Liu
    • , Ran Tao
    •  & Yu Zhao
  • Article
    | Open Access

    Tetrel bonds are noncovalent interactions between electron donors and group 14 elements; in these situations, C(sp3) atoms can act as Lewis acids, accepting electron density. Here, the authors show that methyl groups, when bound to atoms less electronegative than carbon, can participate in noncovalent interactions as electron density donors.

    • Oliver Loveday
    •  & Jorge Echeverría
  • Article
    | Open Access

    Developments in the field of two-dimensional van der Waals materials offer big promise for device applications. This study reports a first-principle investigation on the dielectric properties of 32 exfoliable two-dimensional layered dieletrics for assessing the prospects of these materials in devices.

    • Mehrdad Rostami Osanloo
    • , Maarten L. Van de Put
    •  & William G. Vandenberghe
  • Article
    | Open Access

    Radiationless relaxation is ubiquitous in natural processes and often involves excited states that are difficult to observe. Here the authors, combining X-ray transient absorption spectroscopy and computations, provide insight into the photoinduced dynamics in pyrazine and the involvement of an optically dark 1Au(nπ*) state.

    • Valeriu Scutelnic
    • , Shota Tsuru
    •  & Stephen R. Leone
  • Article
    | Open Access

    The authors introduce an analytical approach for quantitative analysis of 3D atom dynamics during electron microscopy. They image a Co-Mo-S nanocrystal with 1.5 Å resolution, and observe chemical transformations caused by beam-stimulated vibrations.

    • Fu-Rong Chen
    • , Dirk Van Dyck
    •  & Stig Helveg
  • Article
    | Open Access

    Sonodynamic therapy has therapeutic promise due to its safety and good tissue penetration, but is currently bottlenecked due to a lack of efficient and safe sonosensitizers. Here the authors show that [Ru(bpy)3]2+ can produce singlet oxygen and sonooxidize NADH in deep tissue, and destroy mouse tumors effectively.

    • Chao Liang
    • , Jiaen Xie
    •  & Pingyu Zhang
  • Article
    | Open Access

    Spatiotemporal dynamic of charge carriers is commonly studied with optical or photoconductivity measurements, yet these techniques come with their own limitations. To circumvent these limits, the authors probe the free-carrier diffusion dynamics of microsecond lifetimes via laser-illuminated microwave impedance microscopy.

    • Xuejian Ma
    • , Fei Zhang
    •  & Keji Lai
  • Article
    | Open Access

    In comparison to their neutral or anionic counterparts, examples of cationic boron clusters remain scarce. Here, the authors prepare a variety of cationic polyhedral boranes by reacting closo-10-vertex carboranes with N-heterocyclic carbenes; the resulting open-cage cationic nido- arachno- or closo- derivatives are water soluble, which may enable unprecedented applications.

    • Jan Vrána
    • , Josef Holub
    •  & Aleš Růžička
  • Article
    | Open Access

    Establishing a structure-property relationship for nanoclusters and the link with their catalytic performance remain challenging. Here the authors show palladium nanocluster with a core of 2 nm surrounded by a diffuse dynamic shell of Pd atoms exhibit features of heterogeneous and homogenous catalyst at the same time.

    • Israel Cano
    • , Andreas Weilhard
    •  & Jesum Alves Fernandes
  • Article
    | Open Access

    Dissipative self-assembly, which requires a continuous supply of fuel to maintain the assembled states far from equilibrium, is the foundation of biological systems but it remains a challenge to introduce light as fuel into artificial dissipative self-assemblies. Here, the authors report an artificial dissipative self-assembly system that is constructed from light-induced amphiphiles.

    • Xu-Man Chen
    • , Xiao-Fang Hou
    •  & Quan Li
  • Article
    | Open Access

    Controlling localization of multiple metal nanoparticles on a single support is at the cutting edge of designing innovatory cascade catalysts. Here, the authors report a multicompartmentalized mesoporous organosilica to spatially position different metal nanoparticles in intimate proximity for efficient sequential hydrogenation reactions.

    • Houbing Zou
    • , Jinyu Dai
    •  & Hengquan Yang
  • Article
    | Open Access

    2-Fluoroindoles are an important structural scaffold in many bioactive or therapeutic agents, but efficient constructions of 2-fluoroindole derivatives are very sparce. Here the authors report an efficient and general strategy for the construction of 2-fluoroindoles in which a wide variety of 2-fluoroindoles were accessed with high efficiency and chemoselectivity.

    • Jianke Su
    • , Xinyuan Hu
    •  & Qiuling Song
  • Article
    | Open Access

    Converting a carboxylic acid into a boronic acid, which makes a useful chemical handle from a feedstock chemical, currently relies on decarboxylation and requires metal catalysts and prior functionalization. Here the authors show a simplified procedure via deoxygenation, using diboron and free carboxylic acids.

    • Jianbin Li
    • , Chia-Yu Huang
    •  & Chao-Jun Li
  • Article
    | Open Access

    The preparation of chiral monolayer-protected metal clusters is interesting for their potential applications in a variety of fields, including catalysis. Here, the authors synthesize chiral Ag14 nanoclusters in an all-achiral environment, and decipher the origin of chirality at the molecular level; the solvent choice is key to achieve homochiral crystallization.

    • Xiao-Qian Liang
    • , Ying-Zhou Li
    •  & Di Sun
  • Article
    | Open Access

    General and stereoselective synthesis of tetracyclic isochroman-containing polyketide oligomers is challenging. Here, the authors report on an Au(I)/chiral Sc(III) bimetallic catalyst for a biomimetic asymmetric hetero-Diels–Alder reaction for in-situ generation of isochromene and ortho-quinonemethide.

    • Xiangfeng Lin
    • , Xianghui Liu
    •  & Can Li
  • Article
    | Open Access

    Fabricating materials with simultaneously spontaneous magnetic and electrical polarisations is challenging due to contradictory electronic features. Here, the authors report a synthesis path toward a perovskite MnSrTa2O7 by performing low-temperature cation-exchange reactions on Li2SrTa2O7.

    • Tong Zhu
    • , Fabio Orlandi
    •  & Michael A. Hayward
  • Article
    | Open Access

    5-Hydroxymethylfurfural (HMF) can be transformed to a range of industrially useful derivatives, such as 2,5-diformylfuran (DFF), but the reactions needed for efficient industrial production are hindered by several issues. Here, the authors perform reaction and enzyme engineering resulting in a galactose oxidase variant with high activity towards HMF, improved oxygen binding and high productivity.

    • William R. Birmingham
    • , Asbjørn Toftgaard Pedersen
    •  & Nicholas J. Turner
  • Article
    | Open Access

    Photoreduction of CO2 into energy-rich products is a sustainable solution to lessen the global energy and environmental crisis. Here the authors show that Mn ions in Mn, C-codoped ZnO hollow spheres function as “ionized cocatalyst” to promote the CO2 adsorption and light harvesting to boost the CO2 photoreduction activity.

    • Mahmoud Sayed
    • , Feiyan Xu
    •  & Jiaguo Yu
  • Article
    | Open Access

    Polymer electrolyte fuel cells are promising but suffer from low performance. Here, the authors use a combination of electrochemical measurements and molecular dynamics simulations to reveal the role of the highly oxygen permeable ionomer in polymer electrolyte fuel cells that enhances the oxygen transport and catalytic activity.

    • Ryosuke Jinnouchi
    • , Kenji Kudo
    •  & Akihiro Shinohara
  • Article
    | Open Access

    Nematic liquid crystals with polar order bear great potential for many applications but their rational design is difficult. Mandle et al. outline a set of design principles for this new phase of matter, guided by experiments and simulation, showing polar order to be driven by steric interactions.

    • Richard J. Mandle
    • , Nerea Sebastián
    •  & Alenka Mertelj
  • Article
    | Open Access

    C-Glycosyl peptides/proteins are metabolically stable mimics of the native glycopeptides/proteins of great therapeutic potential, but their chemical synthesis is challenging. Here, the authors report a protocol for the synthesis of vinyl C-glycosyl amino acids and peptides, via a Ni-catalyzed reductive hydroglycosylation reaction of alkyne derivatives of amino acids and peptides with glycosyl bromides.

    • Yan-Hua Liu
    • , Yu-Nong Xia
    •  & Biao Yu
  • Article
    | Open Access

    The only known animal polyketide-nonribosomal peptides, the nemamides, are biosynthesized by two megasynthetases in the canal-associated neurons (CANs) of C. elegans. Here, the authors map the biosynthetic roles of individual megasynthetase domains and identify additional enzymes in the CANs required for nemamide biosynthesis.

    • Likui Feng
    • , Matthew T. Gordon
    •  & Rebecca A. Butcher
  • Article
    | Open Access

    Catalytic asymmetric dearomatization is a powerful tool for the rapid construction of diverse chiral cyclic molecules from cheap and easily available arenes. Here the authors show an organocatalytic enantioselective dearomatization of substituted thiophenes in the context of a rare remote asymmetric 1,10-conjugate addition.

    • Xingguang Li
    • , Meng Duan
    •  & Jianwei Sun
  • Article
    | Open Access

    Suppressing phase transitions is crucial for the layered lithium/sodium transition metal oxide cathodes in batteries. Here, the authors report a water-mediated strategy to mitigate the phase transitions and boost electrochemical performances of manganese-based layered cathodes for cost-effective Na-ion batteries.

    • Wenhua Zuo
    • , Xiangsi Liu
    •  & Yong Yang
  • Article
    | Open Access

    Aggregation-induced emission (AIE) fluorescence probes are indispensable for biomedical imaging, however, interference with tissue autofluorescence results in low signal-to-noise ratio limiting the development of bioimaging with AIE materials. Here the authors develop AIEgen room-temperature phosphors with long emission lifetimes efficiently eliminating intereference with the background signal in imaging.

    • Jianhui Yang
    • , Yahui Zhang
    •  & Xin Zhang
  • Article
    | Open Access

    Broad-band emission of self-trapped exciton in low-dimensional perovskite is prospective for white LED, yet rational design new white perovskite remains challenge. Here, the authors develop an atom-substituting strategy to trigger exciton self-tapping in perovskites and reveal the mechanism behind.

    • Mingming Zhang
    • , Lili Zhao
    •  & Jun Xing
  • Article
    | Open Access

    Biobased poly(γ-methyl-α-methylene-γ-butyrolactone) (PMMBL) has attracted interest because it is biorenewable and exhibits superior properties to petroleum-based linear analog poly(methyl methacrylate) (PMMA). Here the authors report the synthesis of well-defined PMMBL-based ABA tri-block copolymers, enabled by dual-initiating and living frustrated Lewis pairs, which have superior mechanical properties compared to those of PMMA-based tri-BCPs.

    • Yun Bai
    • , Huaiyu Wang
    •  & Eugene Y.-X. Chen
  • Article
    | Open Access

    Quantum mechanical calculations of molecular ionized states are computationally quite expensive. This work reports a successful extension of a previous deep-neural networks approach towards transferable neural-network models for predicting multiple properties of open shell anions and cations.

    • Roman Zubatyuk
    • , Justin S. Smith
    •  & Olexandr Isayev
  • Article
    | Open Access

    Various strategies to assemble protein building blocks into one-, two- and three-dimensional hierarchical nanostructures were described, but controlling the transformation between those different assemblies is largely uninvestigated. Here, the authors describe a protein interface redesign strategy and use it for the self-assembly transformation of dimeric building blocks from hollow protein nanocage to filament, nanorod and nanoribbon.

    • Xiaorong Zhang
    • , Yu Liu
    •  & Guanghua Zhao
  • Article
    | Open Access

    Deactivation of supported metal catalysts via thermally induced sintering is a major concern in the catalysis community. Here, the authors demonstrate that enlarging particle distance to over the critical distance could suppress the particle coalescence greatly up to 900 °C.

    • Peng Yin
    • , Sulei Hu
    •  & Hai-Wei Liang
  • Article
    | Open Access

    The concept of delocalization, resonance and aromaticity are commonly discussed within electronic structure frameworks relying on specific wave function expansions. Here the authors propose a redefinition of these concepts from first-principles by investigating saddle points of the all-electron probability density.

    • Leonard Reuter
    •  & Arne Lüchow
  • Article
    | Open Access

    Selective cleavage of C-C bonds is very important in organic chemistry, but remains challenging because of their inert chemical nature. Here, the authors report that Zn2+ coordinated with N species on N-doped carbon catalysts can catalyze the aerobic oxidative cleavage and esterification of C(CO)-C bonds with high efficiency and activity.

    • Chao Xie
    • , Longfei Lin
    •  & Buxing Han
  • Article
    | Open Access

    Disproportion of uranium(IV) is rare, as it is usually the stable product of uranium(III) or (V) disproportionation. Here, the authors report uranium(IV) disproportionation to uranium(III) and (V) revealing ligand and solvent control over a key thermodynamic property of uranium

    • Jingzhen Du
    • , Iskander Douair
    •  & Stephen T. Liddle