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Alkenes are essential functional groups in organic chemistry, featuring well-defined geometries and bond orders of 2. In this study, cubene and 1,7-quadricyclene are calculated to possess unusual hyperpyramidalized geometries and low alkene bond orders near 1.5. Their resultant high reactivities ultimately permit access to intricate scaffolds and new chemical space.

Spiropyran and merocyanine systems are useful due to the photoswitching properties, but do have some limitations. Here, the authors report pyridine-substituted merocyanines as photochromic compounds, with a photoinitiated C-N bond formation.

Spatiotemporal insight into photoactivation of the prototypical B₁₂ photoreceptor CarH is revealed across nine orders of magnitude in time, identifying a transient adduct that distinguishes it from thermally activated B₁₂ enzymes.

New methods for targeted covalent protein modification at low reactivity aspartates and glutamates are of high interest. Here, the authors report a technique inspired by the HaloTag technology, which employs a covalent conjugation reaction between ligands with a reactive chloroalkane linker and a specific aspartic acid, and use it to covalently modify lipoprotein chaperone PDEδ at a binding site glutamic acid.

Investigation of the reaction process at the single-bond interface is key to understanding the catalytic reaction mechanism. Here, the authors develop a STM-BJ method to monitor the catalytic process from the perspective of single-bond energy.

Conventional methods for forming C(sp3)−C(sp3) bonds via radical-radical coupling pathways often suffer from poor selectivity, limiting their practicality in synthetic applications. Herein, the authors report a single electron transfer strategy that enables the cleavage of amine α-C − H bonds and heterobenzylic C − O bonds to form C(sp3)−C(sp3) bonds.

This study highlights an emergent mechanism in non-natural biocatalysis, showcasing the role of protein engineering in addressing challenges in chemical synthesis.

The coexistence of frustrated magnetism and bond order is demonstrated in a family of antiferromagnets. Layers of dual frustrated orders are interleaved in the same crystal lattice, which presents an exciting possibility for engineering new responses.

The mismatched bilateral bond strength between NiO_x and perovskite hinders the development of inverted perovskite solar cells. Here, authors adsorb 1-(benzothiaxole-2-ylthio)succinic acid on NiO_x surface for passivating bilateral defects and achieve maximum efficiency close to 27% in stable devices.

Methylthio-alkane reductases are recently discovered enzymes that can produce methanethiol and small hydrocarbons from methylated sulfur compounds. Now the cryo-EM structure of a methylthio-alkane reductase complex is solved, revealing large metalloclusters previously observed only within nitrogenases.

The homocatenation of electron-deficient Group 13 metals to form metal-metal multiple bonds through covalent self-assembly remains extremely challenging. Here, the authors demonstrate the synthesis and characterization of N-heterocyclic carbene-stabilized digallyl digallenes which exhibit unsaturated Ga-Ga=Ga-Ga chains with trans-bent geometries.

The ability to selectively break a chemical bond in a molecule is indispensable to chemical synthesis. Here, the authors show that a hundred-fold bond selectivity can be obtained in electron-induced surface reaction due simply to different bond alignments at the surface.

Although derived from feedstock chemicals and therefore in principle abundant, ketones are not widely used as cross-coupling partners in organic synthesis. Herein, the authors use ketone derivatives as one-electron handles for forging C(sp3) architectures via dual photo- and nickel catalysis.

Endosomal sequestration of lipid-based nanoparticles is a barrier to delivery of nucleic acids. Here the authors test an array of cholesterol variants and perform in-depth investigation of nanoparticle shape, internal structure and intracellular trafficking.

π-Conjugated polymers are useful commodities as they are used in the fabrication of organic photovoltaic devices, light-emitting diodes and field effect transistors. Here the authors describe the polycondensation of bifunctional aryl ethers or aryl ammonium salts with aromatic dimetallic compounds through cleavage of inert C–O/C–N bonds.

Deep learning-based generative tools are used to design protein building blocks with well-defined directional bonding interactions, allowing the generation of a variety of scalable protein assemblies from a small set of reusable subunits.

Nylon-11 is a common and durable polymer but possess low piezoelectric properties. Here, the authors use mechanical accelerations and strong electric fields to induce crystallization, hydrogen-bonding and dipole alignment in Nylon-11 films, achieving high piezoelectricity.

Sperm–egg adhesion is crucial for mammalian reproduction. Here, authors report the human Izumo1:Juno complex, a key regulator of sperm-egg adhesion, forms an unusually strong bond through a secondary binding site, which is impaired in an infertility-associated Juno mutant.

ATF6α activation in human and preclinical models of hepatocellular carcinoma is significantly associated with an aggressive tumour phenotype characterized by reduced survival, glycolytic reprogramming and local immunosuppression.

Macrocyclization typically proceeds via thioesterase mediation in type I polyketide synthases. Now, using genome mining and crystallographic analysis, an alternative mechanism for stereoselective macrocyclization in the akaeolide biosynthetic pathway is reported. The mechanism is proposed to proceed via an iminium-catalysed tandem Michael addition and Knoevenagel condensation, using nuclear transport factor 2-like enzymes.

Cross-coupling processes without the use of transition metals are challenging to achieve. Here, the authors show a transition-metal-free cross-coupling utilizing aryl(heteroaryl) methyl sulfoxides and alcohols to afford alkyl aryl(heteroaryl) ethers and propose a nucleophilic addition mechanism based on experiments and theory.

Controlled breaking of a chemical bond by mechanical forces can provide key insight into reaction mechanisms. Here the authors, using atomic force microscopy and computations, measure the forces involved in breaking a single dative bond between a CO molecule and a ferrous phthalocyanine complex.

Macroscopic mechanical systems typically respond linearly to external force, and generating nonlinearity is challenging. Here, the authors generate nonlinearity in a macroscopic mechanical resonator by linking it to a gold contact and exploiting the anharmonicity in the chemical bonding interactions.

Adaptive microwave surfaces can dynamically adjust their electromagnetic transmission to meet specific needs, being potentially useful in reconfigurable communication systems. Here, the authors use temperature induced break and reconstruction of hydrogen bonds to drive the orientational motion and charge mobility of an ionic liquid in a polymer leading to the controllable modulation of dielectric properties at microwave frequencies.

Per- and polyfluoroalkyl substances (PFAS) have substantial environmental and health hazards, but their persistence and stability challenge remediation efforts. Now, a lithium-metal-mediated electroreduction strategy has been developed to effectively degrade PFAS with a high defluorination efficiency across different functional end groups while allowing for upcycling of the released fluoride.

Decarboxylative azidation is a valuable transformation in organic chemistry, but a biocatalytic equivalent remained elusive. Now merging photoredox with metalloenzymatic catalysis enables the enantioselective decarboxylative radical azidation and thiocyanation of N-hydroxyphthalimide esters.

The force required to break a chemical bond is related both to the bond strength and the rate at which force is applied, however recent experiments on gold nanowires have challenged this view. Here, the authors perform breaking experiments on single gold-gold bonds and propose a solution to the apparent paradox.

Experimental realizations of discrete time crystals have mainly involved 1D models with Ising-like couplings. Here, the authors realize a 2D discrete time crystal with anisotropic Heisenberg coupling on a quantum simulator based on superconducting qubits, uncovering a rich phase diagram.

The selective dissociation and formation of different functional groups in a single organic molecule may prove useful for making nanoscale devices and offer new opportunities for studying changes in electronic structure. It has now been shown that bond-selective chemistry can be induced and visualized at the submolecular level in a complex thiol-based molecule using a scanning tunnelling microscope.

Iron–sulfur minerals play critical roles in regulating nitrogen cycling under anoxic conditions. This study shows that pyrrhotite with abundant iron vacancies promotes electron transfer and microbial nitrate reduction to dinitrogen.

Controlling the hydrothermal reaction kinetics during the fabrication of Sb₂(S,Se)₃ solar cells is challenging. Chen Qian et al. show that sodium sulfide buffers the pH and allows a controlled release of Se, enabling a certified efficiency of 10.7%.

Electrochemical CO reduction to multi-carbon products offers a carbon-negative approach to produce chemicals, but the intricate reaction pathways lead to a broad spectrum of products. Now it has been shown that alkali cations alter the mechanistic pathways that govern the reaction selectivity involved in the formation of hydrocarbons versus oxygenates.

The coupling of carbon monoxide molecules is an attractive prospect for organic synthesis, but only a few metal complexes are known to do this. A compound containing a boron–boron triple bond has now been shown to induce the coupling of four CO molecules, through an intermediate with a single CO.

Manipulating the chemical composition of proteins and peptides has been central to the development of polypeptide-based therapeutics and to help address fundamental biological questions. This Review describes how nature-inspired protein ligation strategies have been repurposed as chemical biology tools.

Natural products inspire the development of pseudo-natural products through combinations of fragments of compound classes that are chemically and biologically distinct. Here, the authors report a library of 244 pseudo-natural products, evaluate them in the cell painting essays and identify the phenotypic role of individual fragments.

Studying many-body quantum chaos on current quantum hardware is hindered by noise and limited scalability. Now it is shown that a superconducting processor, combined with error mitigation, can accurately simulate dual-unitary circuit dynamics.

The concept of resonant valence bond phases has inspired many areas of condensed matter physics, but few realistic models have been identified. Now an analytical solution of such a phase has been found for pyrochlore and related lattices.

Natural products populate areas of chemical space not occupied by average synthetic molecules. Here, an analysis of more than 180,000 natural product structures results in a library of 2,000 natural-product-derived fragments, which resemble the properties of the natural products themselves and give access to novel inhibitor chemotypes.

Native top-down proteomics reveals epidermal growth factor receptor–estrogen receptor-alpha (EGFR–ER) signaling crosstalk in breast cancer cells and dissociation of nuclear transport factor 2 (NUTF2) dimers to modulate ER signaling and cell growth.

The mechanism of the multiple-q charge density wave phase in the antiferromagnetic kagome metal FeGe is not fully understood. Here the authors reveal dimerization-driven hexagonal charge-diffuse precursor and identify the fraction of dimerized/undimerized states as the key order parameter of the phase transition.

The chemical recycling of polyurethane through catalytic hydrogenation to recover anilines and polyols has attracted increasing attention. Here, the authors demonstrate that polyurethane can be broken down into aniline monomers using CeO₂ nanoparticles as a catalyst to cleave carbamate bonds.

The structure of layered oxides dictates their properties as positive electrodes in sodium-ion batteries, but its rational design remains challenging. Here, authors employ electronegativity and configurational entropy as a design descriptor to guide the synthesis of a sodium-deficient layered oxide with an O3 stacking sequence, rendering good thermal and air stability.

Many chemical reactions rely on the preference of copper for positive oxidation states. In this work, the authors report that the reaction of an N-heterocyclic carbene ligated copper alkoxide with a dimeric magnesium(I) compound results in a stable compound with a Cu-Mg bond which acts as a nucleophilic source copper in the formal oxidation state of Cu(-I).

Fracto-mechanoluminescence is the emission of light from fracturing solids. Here, the authors show that this emission in Mn halides arises from elastic stiffness, electromechanical coupling, and trap states that activate Mn²⁺ d−d transitions.

Researchers mapped how the plant enzyme FUT11 adds fucose to N-glycans. Microarrays, crystal structures and simulations indicate the enzyme can distort the acceptor sugar during catalysis, informing glycoprotein engineering.