The conversion of methane driven by solar energy offers a promising approach to directly transform methane into valuable energy sources under mild conditions, but remains a great challenge. This Review highlights recent advances in the photocatalytic conversion of methane and gives insights into the design of effective semiconductor-based photocatalysts and classifies the photooxidations according to the oxidants in the reaction system.

A classification of copper sulfides based on crystallographic features has been proposed from investigation of the structure–property relationships reported on their phases in dozens of publications from the fields of crystallography and materials for energy conversion. This classification reveals systematic trends that can be explained and exploited for the design and engineering of new environmentally friendly materials.

A liquid-phase method has been developed for the synthesis of highly conjugated covalent organic frameworks (COFs). Vacuum filtration leads to the formation of a uniform conducting film of the COFs and COF-GO hybrid materials on a variety of substrates. The overpotential of one of the materials was as low as 45 mV in 0.5 m H₂SO₄ and reached a current density of 10 mA cm⁻², which is better than all the metal-free catalysts currently available.

We describe a rapid light-activated C(sp³)–C(sp³) bond-forming reaction that enables installation of N^ϵ-modified sidechains into peptides and proteins at defined positions. Selective for cysteine residues, the method proceeds via interception of free-radical-mediated desulfurization. The chemistry is operationally simple, tolerant to ambient atmosphere, and retains the native stereochemistry at the modified residue.

Supramolecular confinement effect facilitates cyclic polymerization of a telechelic cyanostilbene macromonomer via [2+2] photo-cycloaddition, in stark contrast to Z-E photo-isomerization in the monomeric state.

A flexible alteration of an 2 e⁻/4 e⁻ oxygen reduction reaction (ORR) pathway was discovered by tuning the coordination environment of Zn single sites derived from MOF-5 by varying the functional group of ligands within the metal–organic framework (MOF) precursors. The formed ZnN₄ follows a 4 e⁻ ORR pathway, while ZnO₃C achieves a maximum H₂O₂ production rate of 340 mmol g⁻¹ h⁻¹.

An iron-superoxide corrole has been generated from a ferrous corrole and dioxygen, and was found to be capable of indole dioxygenation and H-atom transfer reactions.

Substrate-induced generation of a transient catalytic microphase was shown in presence of a single amino acid functionalized fatty acid and a cofactor hemin. The transient state exhibited acceleration of catalytic potential resulting in degradation of the substrate. Furthermore, latent catalytic function was displayed to hydrolyze a precursor to yield the same substrate suggesting promiscuous activity.

We developed a macrobicyclic olefin system bearing a sacrificial silyloxide bridge on the α,β′-positions of the double bond as a new sequence-defined monomer for regio-selective ring-opening metathesis polymerization. The monomeric sequence information is implanted in the macro-ring, while the small ring with a substantial ring tension can provide not only narrow polydispersity, but also high regio-/stereospecificity.

A general and selective synthesis of amines via hydroaminomethylation of olefins in the presence of the specific Co-tert-BuPy-Xantphos catalyst is presented. This novel system is complementary to previously known noble metal catalysts and constitutes one of the most general catalysts for HAM.

The coupling of (electro-)chemically driven, reductive N₂ splitting with nitrogen atom transfer to NO is reported. Nitrous oxide generation directly from dinitrogen and nitric oxide defines a new strategy for direct oxidative nitrogen fixation. Initial coordination of an activating NO ligand prepares the chemically robust Re^V nitride for Re≡N/NO radical coupling.

A fully condensed poly (triazine imide) crystal, which features extended π-conjugation and deficient structural defects, decorated with Pt and CoO_x as redox cocatalysts efficiently drives the one-step excitation overall water splitting for H₂ and O₂ production with a record apparent quantum efficiency of 12 % at 365 nm.

Au₁₈S₂(SR)₁₂, a new gold cluster that can be viewed as an interlocked dimer of Au₉S(SR)₆ cages, was synthesized using a bulky thiol ligand. Theoretical calculation demonstrated that the Au₆ core can be interpreted as a face-to-face dimer of Au₃ superatoms.

The lithiation front region of one β-MnO₂ nanowire analyzed by in situ TEM, where the MnO₂/LiMnO₂ interface features arrow-headed disordered regions, is disclosed with its atomic structure clearly captured. The findings have a bearing on MnO₂ open-framed electrode materials for reversible energy storage.

Fumarate to maleate (E→Z) isomerization was investigated to validate n_O→ π_C=O* interactions as a driving force for contra-thermodynamic isomerization. A general protocol based on selective energy transfer catalysis was developed with inexpensive thioxanthone as a sensitizer for the conversion of diverse fumarate derivatives, including tetrasubstituted alkenes. The involvement of n_O→π_C=O* interactions was confirmed by X-ray crystallography.

Cell membrane-coated nanoparticles are engineered to express a viral fusion protein, thus enabling them to exhibit improved endosomal escape properties. It is demonstrated that these virus-mimicking nanocarriers are able to deliver mRNA payloads to the cytosolic compartment after cellular uptake, enhancing expression of the encoded proteins both in vitro and in vivo.

We developed a novel HTS engineering platform to optimize photoenzymatic activity. The improvements in variants were correlated to an increase in enzymatic photon efficiency. Transient absorption spectroscopy revealed a shift from a stepwise to a concerted mechanism. The platform was expanded to improve the synthesis of γ, δ, ϵ-lactams, and acyclic amides.

Multiblock core–shell MOFs heterojunctions were prepared through an epitaxial growth process, in which the shell exhibits both persistent luminescence and photochromic properties. The bright yellow afterglow in MOFs shell can be detected before irradiation but almost disappears after coloration upon continuous UV irradiation.

Pronounced fluorescence enhancement could be shown for a weakly fluorescent merocyanine dye in hetero-folda-trimer architectures. This folding-induced fluorescence enhancement (FIFE) for specific sequences of π-stacked dyes points at a viable strategy towards improved fluorophores that relates to the approach used by nature in the green fluorescent protein (GFP).

Molecular sensors for plant polyphenol imaging based on near-infrared (NIR) fluorescent single-wall carbon nanotubes (SWCNTs) are presented. These sensors probe the polyphenol content in complex biological systems such as the plant rhizosphere. In summary, this approach enables real-time spatiotemporal visualization of plant defense via polyphenols release.

The self-assembly of anisotropic nanoparticles into large superstructures is a key component in the research of novel metamaterials. While the formation of mono-phase mesocrystals has been achieved in recent years, the self-assembly of binary structures from such particles remained highly challenging. A simple method enables the formation of binary mesocrystals from anisotropic iron oxide and platinum nanocubes in two and three dimensions.

A method is described for theory-based catalyst optimization of CoCu alloys in CO₂ hydrogenation. Moderate Co surface segregation, boosted ethanol production, and suppressed methane generation suggest that theory-guided catalyst optimization could be beneficial in similar alloy systems.

NIR-II hydrogen-bonded organic frameworks (HOFs) were devised to oxidize β-amyloid spatiotemporally and noninvasively. The well-designed photocatalyst shows an inhibitory effect of Aβ aggregation and recovery of memory deficits in triple-transgenic AD model mice upon the NIR-II irradiation.

Use of synthetic fluorescent ceramide molecules allows the discovery of the first selective drug-like small molecule inhibitors for alkaline ceramidase 3, an intra-membrane enzyme involved in sphingolipid metabolism in health and disease. These inhibitors represent a new paradigm for controlling lipid metabolism with drug-like small molecules targeting conformationally dynamic membrane proteins.

A new simple hybrid salt has been synthesized that exhibits reversible multistep phase transitions and an unprecedented thermally induced three-step “silent-medium-low-high” second-harmonic-generation switching behavior. This behavior arises from complex and stepwise molecular dynamic changes of the polar organic cations.

An unexpected new type of cooperativity of the two silicon(II) atoms in a 1,4-terphenyl-bridged bis(silylene) towards CS₂ is reported and the results are compared with that of related mono-silylenes. While a dearomatization occurs with the bis-silylene, a novel mesoionic five-membered Si₂S₂C heterocyclic compound, among other new products, results from stepwise degradation of CS₂ with mono-silylenes.

We propose a general gelation strategy for the construction of highly processible covalent organic framework (COF)-Gel materials through side-chain engineering. The COF-Gel is compatible with electronic devices with diverse functionality, including in lithium-ion batteries.

Electrokinetic and surface-enhanced infrared spectroscopic results indicate that the C−C coupling is unlikely to be the rate-determining step (RDS) in the formation of C₂₊ products in the electrochemical CO reduction reaction. Electrochemical hydrogenation of CO with adsorbed water as the proton donor is proposed as the RDS.

The third way: the umpolung of nucleophilic [1.1.1]propellane into an electrophilic halogen bond complex enables the synthesis of nitrogen-substituted bicyclo[1.1.1]pentanes (BCP) after attack of anilines and azoles. DFT calculations show that the halogen bond interaction helps avoiding the decomposition of the BCP cage. This approach opens a third avenue to access functionalised BCPs besides the better explored radical and anionic strategies.

A S-HKUST-1 precatalyst with stable isolated Cu−S motifs was prepared by the strategy of local sulfur doping. The precatalyst can be in situ reconstructed to obtain a Cu(S) matrix with active biphasic copper/copper sulfide interfaces, which delivers a current density of 400 mA cm⁻² with Faradaic efficiency of ethylene to 57.2 % in the flow cell.

The binding of intercalating dyes such as thiazole orange (TO) to polynucleotides allows for a simple method to load RNA-rich virus-like particles with molecular cargo, and then to release that cargo by diffusion. TO-labeled molecules come out much slower than they go in because of the high RNA concentration inside the shell; the surprise is how much cargo these easily produced nanocontainers can carry.

A Weyl semimetal Co₃Sn₂S₂ cathode was applied in aqueous Zn-ion batteries with a discharge plateau around 1.5 V. Co₃Sn_1.8S₂ activates Sn²⁺ and provides active sites with impressive charge-storage capabilities and fast kinetic processes. The material has high structural stability and conductivity, and an ionic diffusion rate that achieves appreciable cycling stability and capacity retention.

Varied excited-state relaxation dynamics observed in the primary photoreaction of microbial rhodopsins are the ground-state heterogeneity arising from the acid-base equilibrium of the amino acid residue acting as the counterion of a protonated retinal Schiff base chromophore.

We developed a method for imaging aqueous proton transport with spatial resolution and observed the lateral transport of protons along the nanofluidic interface. The dynamics of proton transport can be further captured by quantitative analysis, thanks to the temporal resolution of this optical imaging technique.

The reaction selectivity of a nanozyme system was enhanced by screening and channeling of substrates. A catalytic cascade incorporating N-doped carbon nanocages with oxidase-like activity, and Prussian blue nanoparticles with peroxidase-like activity, improved reaction selectivity by more than 2000 times.

We present a new type of MIM comprised by two “open” U-shaped metallotweezers. The dissociation into its two components is hampered by mechanical bonds, as the presence of bulky tert-butyl groups provides the mechanical coercion required for avoiding the slippage that would otherwise produce the disassembly.

Zr(OH)₄ can catalyze the selective oxidation of anilines to azoxybenzenes, symmetric/unsymmetric azobenzenes and nitrosobenzenes for a wide range of substrates. Control experiments and DFT calculations reveal that the activation of H₂O₂ and O₂ can be attributed to the bridging hydroxyl and terminal hydroxyl groups of Zr(OH)₄, respectively.

α-Ketoglutaric acid (α-KG) has an exceptionally high free radical yield under photo-irradiation at cryogenic temperature. This radical can be used as a universal polarizing agent to hyperpolarize ¹³C-molecules such as [1-¹³C]lactate, a promising alternative to pyruvate for in vivo metabolic studies by ¹³C magnetic resonance.

A Ni/C hybrid nanosheet array with dual-active nanoisland sites is reported. One type of island represents the bare Ni particle surface, the other consists of core–shell Ni@C structures (denoted as Ni-C HNSA). The catalyst achieves efficient hydrogen production in an overall hydrazine splitting, showing its potential for practical applications.

Here, we discovered a novel crystallized Zn²⁺ conductor based on inducing crystallization of high-entropy, charge-separated eutectic liquids. To the best of our knowledge, it is the first introduction of the concept of a crystallized eutectic material to achieve dramatically enhanced multivalent-ion transport properties. This facile strategy may also open up opportunities for designing a wide variety of new solid ionic conductors.

Sterically wrapped multiple resonance (MR) dopants with the MR-core sandwiched by bulk substituents have been developed to suppress molecular interactions, realizing organic light-emitting diodes with remarkably high maximum external quantum efficiencies of 36.3–37.2 %, identical small FWHMs of 24 nm and alleviated efficiency roll-offs over a wide range of dopant concentrations (1–20 wt %).

While the reaction of the [Cu₁₁H₂{S₂P(OⁱPr)₂}₆(C≡CPh)₃] template with Cu⁺ or Ag⁺ produces Cu₁₂H₂ and AgCu₁₄H₂ species in which the hydrides behave as Lewis bases, in the reaction with Au⁺, the hydrides act as reducing agents, leading to a luminescent, two-electron Au@Cu₁₁ superatom, whose metal core has a defect fcc structure.

Three 2D robust COFs with controllable hydrophobicity and processability were synthesized by introducing mixed hydrophobic substituents. After coating on a stainless-steel net (SSN) substrate, the superhydrophobic COF@SSN coating exhibits an excellent oil/water separation efficiency (>99.5 %), high oil-permeation flux (2.84±0.08)×10⁵ L m⁻² h⁻¹, high water-pressure resistance (>15 kPa), and a high degree of reusability (>50 cycles).

N-sulfonylhydrazones of cyclic ketones are readily transformed into NH-free spirocyclic pyrrolidines and isoindolines by reaction with γ-azidoboronic acids. The transition-metal-free transformation is widely applicable and represents a new disconnection towards spirocyclic pyrrolidines. The application of the reaction in the modification of natural steroids and other biorelevant molecules highlights the synthetic usefulness of the methodology.

The outer membrane of Gram-negative bacteria is an asymmetric bilayer. The effect of this asymmetry on protein structure and dynamics remains elusive. The β-barrel assembly machinery (BAM) mediates the folding and insertion of proteins into the outer membrane. Using in situ electron spin resonance spectroscopy, we show that the native outer membrane significantly enhances the dynamics of the BamA insertase of the BAM complex.

A two-dimensional fused aromatic network with a honeycomb lattice constituted of 90-ring hexagons, the largest yet reported, was obtained by solvothermal synthesis.

By incorporating intramolecular S⋅⋅⋅O noncovalent interactions (INIs) for boosting the intrinsic hole mobilities, two simple-structured dopant-free hole-transporting materials (HTMs) were designed and delivered a remarkable efficiency of 21.10 % with decent device stability in inverted perovskite solar cells, demonstrating the great promise of the INI strategy for accessing high-performance dopant-free HTMs.

X⋅⋅⋅X (X=Cl, Br, I) type weak halogen bonds induce the formation of supramolecular helical structures both in solid and solution state. The halogen bonds could further influence the helical nanoarchitectures in mono- and multiple-component coassemblies with melamine, providing a flexible route to prepare chiral functional materials.

A series of highly crystalline 3D COFs with variable loadings of ethynyl groups were designed and synthesized. Remarkably, these alkyne-tagged 3D COFs provide a platform for targeted anchoring various organic groups onto the pore walls via click reactions, which can accordingly change their properties, e.g., the obtained click products exhibited higher CO₂/N₂ selectivity.

The development of a nonlinear kinetic model for crystal reactions allows us to quantify for the first time how the kinetics depend on sample morphology. Furthermore, the quantitative connection between molecular reaction kinetics and mechanical response in well-defined single crystals provides a new benchmark for analyzing these photomechanical materials.

Through covalent modification of the nicotinamide adenine dinucleotide mimics and Ce^III-OEt moieties in a metal–organic framework, a new multiphoton excitation approach was developed. This new strategy enables step-by-step triggering of the photoinduced electron transfer, ligand-to-metal charge transfer and hydrogen atom transfer processes for activation of inert C(sp³)−H bonds and oxygen.