Research articles

Berberine is a plant-derived benzylisoquinoline alkaloid with diverse pharmaceutical activities, however, the production of berberine from medicinal plants and organic synthesis remains unsustainable. Here, the authors report the complete biosynthesis of berberine in yeast by engineering genes from plants and bacteria.

Copper doping of atomically precise gold nanoclusters is a useful strategy to tune their chemical and physical properties, but Au–Cu nanocluster alloys tend to exhibit poor stability. Here, a [Au₁₂Cu₁₃(Ph₃P)₁₀I₇](SbF₆)₂ cluster is prepared and shown to display enhanced stability and fluorescence in comparison to homonuclear cluster [Au₂₅(PPh₃)₁₀Br₇](SbF₆)₂, in addition to promising photocatalytic activity for methanol oxidation.

Atomically precise gold nanoclusters display useful photoluminescence properties, but limitations in synthetic methods and characterization techniques have hindered their detailed exploration. Here, a Au₃₈(PET)₂₆ nanocluster is found to exhibit fluorescence, phosphorescence, and thermally activated delayed fluorescence emissions, with a significant enhancement in photoluminescence intensity at cryogenic temperatures owing to the suppression of nonradiative pathways.

Electrospray ionization (ESI) mass spectrometry is invaluable for studying complex biological systems, and although lipid nanodiscs are a powerful tool for the study of membrane proteins, a lack of clear understanding of the ESI mechanism presents a challenge for spectral interpretation and assignments. Here, the authors study the release behavior of lipid nanodiscs from charged nano-droplets in the ESI process using microsecond atomistic molecular dynamics simulations.

The atomic structures of metallic nanoparticles dictate their chemical and physical properties, making their structural study under different chemical environments of importance. Here, electron microscopy finds that silver nanoparticles primarily adopt an icosahedron structure under air exposure, while previous reports showed that the face-centred cubic isomer is favoured when the nanoparticles are kept in vacuum.

Polyetheretherketone (PEEK) is an important super engineering plastic utilized in industries owing to its thermal stability and mechanical strength, however, its robustness hinders chemical recycling. Here, the authors report the depolymerization of insoluble PEEK using sulfur nucleophiles via carbon–oxygen bond cleavage and then treatment with organic halides to form various dithiofunctionalized benzophenones and hydroquinone monomers.

The spherulite morphology is common among crystalline materials and melt-crystallized products, however, the structural determination of spherulites by X-ray diffraction remains difficult due to their polycrystalline nature. Here, the authors report the direct structure determination of the polymorphism of vemurafenib in compact spherulite form using 3D electron diffraction.

Photocatalytic methane conversion under ambient conditions holds immense promise for sustainable use of methane resources, but incomplete knowledge of reaction mechanisms hampers the development of engineering strategies for methane photocatalysis. Here, combining real-time mass spectrometry and operando infrared absorption spectroscopy with ab initio molecular dynamics simulations, the authors explore the role of interfacial water in C–H activation during the photocatalytic conversion of methane.

Lawsones and indenopyrazoles harbor an interesting benzo-fused cyclic ketone scaffold as an essential structural motif in diverse bioactive molecules, however, their synthesis remains challenging. Here, the authors report an efficient synthesis of lawsones and indenopyrazolones via the solvent-controlled regioselective ring-expansion of indantriones involving a 1,2-carbonyl shift.

Singlet fission excited-state relaxation, as observed in covalently linked dimers, could allow energy-conversion efficiencies in photovoltaic devices beyond the Shockley–Queisser limit. Here, the authors study the effect of the molecular configuration of two covalently ortho-linked pyrene dimers on singlet fission dynamics using steady-state and time-resolved spectroscopies.

Lipid peroxidation plays an important role in cell signaling and disease as well as therapy, however, the effect on the membrane structure and mechanical behavior remains poorly understood. Here, the authors report the direct and quantitative measurement of the bilayer’s structure and viscoelastic properties upon peroxidation of lipid membranes.

Formaldehyde is a potent toxic electrophile at high concentrations; however its potential regulatory roles remain unknown. Here, the authors report that formaldehyde can react with terminal proline-containing proteins to generate stable 5,5-bicyclic aminal termini that modulate protein function.

Machine learning algorithms are widely employed for molecular simulations, but there are likely many yet unexplored routes for the prediction of structural and energetic properties of biologically relevant systems. Here, the authors develop a hypergraph representation and message passing method for transferring knowledge obtained from simple molecular systems onto more complex ones, demonstrated by transfer learning from tri-alanine to the deca-alanine system.

The description of full singlet-triplet-quintet dynamics is challenging due to the need for simultaneous treatment of disparate spin states, as well as multidimensional dynamics. Here the authors report a branching mechanism for the Fe(II) polypyridine complex [Fe(terpy)₂]²⁺ by full-dimensional simulation of singlet-triplet-quintet dynamics, showing that the quintet (⁵MC) state is populated on the sub-ps timescale by two sequential ³MLCT→³MC→⁵MC pathways involving the two ³MC components ³T_1g and ³T_2g.

Dual-atom catalysts (DACs) pose several advantages such as uniformity in the active sites and high atom utilization efficiency supported by a synergy of the two catalyst metal atoms. Here, the authors use spin-polarized density functional theory with van der Waals corrections to derive surface Pourbaix diagrams of an Fe–Ni–N_x–C model, showing that the surface states of DACs generally differ from a pristine surface at electrocatalytic operating conditions due to the strong adsorption capacity of a DAC’s unique metal–metal bridge site.

While stimuli-responsive metal-organic frameworks have been widely investigated, much less is understood about structural flexibility in their covalent counterparts. Here, 3D diamondoid covalent-organic frameworks are studied via dynamic free energy simulations, revealing key insight into how the nature of the building blocks and the degree of interpenetration contribute to framework flexibility.

Techniques capable of measuring adsorption processes in solution typically rely on indirect methods. Here, a magnetic sustentation technique is shown to rapidly and directly measure the mass of adsorbates in four paramagnetic metal–organic framework materials in solution.

The generation of stationary patterns is often studied under constant experimental conditions, but in biological systems parameters such as chemical flow are not stationary. Here, the authors use experiments and numerical analyses to elucidate the mechanisms controlling Turing patterns under periodic variations in chemical feed concentration.