Phosphine-functionalized MOFs (P-MOFs) offer novel opportunities in heterogeneous catalysis. In this Minireview, we summarize the synthetic strategies, characterization and catalytic reactions based on the reported P-MOFs. In particular, we remark the current obstacles and possible solutions, including new reaction types and techniques as the perspectives for the development of P-MOF catalysts, highlighting the opportunities behind challenges.

This Minireview summarizes developments in degradable block copolymer nanoparticles, including shell-degradable, core-degradable and all-degradable nanoparticles, synthesized by polymerization-induced self-assembly (PISA). The high production efficiency of PISA coupled with degradability provides the next generation of particulate materials that can better serve the need for sustainability.

Progress, challenges, and opportunities for designing and engineering atomic metal catalysts are discussed from single to dual metal sites for CO₂ to CO conversion. In particular, designing optimal dual metal site catalysts could offer additional sites to break the scaling relationship limitation and activity-stability trade-off. Challenges and solutions of CO₂RR electrolysis in flow reactors are highlighted for improved CO₂ utilization, reaction kinetics, and mass transport.

It has by now been realized that London dispersion (LD) interactions, the main contributor to the attractive part of the van der Waals potential, are ubiquitously present and need to be taken into consideration in structures and dynamics of chemical reactions. This review highlights recent experimental and theoretical advances in utilizing LD interactions as a design element.

Sortase-mediated ligation (SML) is extensively employed in site-specific bioconjugations. This review presents an overview of recent advancements in sortase engineering and the resulting innovative in vitro and in vivo SML applications. Moreover, we explore the potential future impact of integrating SML with cutting-edge techniques, such as click chemistry, unnatural amino acid incorporation, and CRISPR-Cas9, for interdisciplinary research.

Nucleic acid-based sensors unveil the DNA binding mechanisms of platinum(II) complexes. Based on signals generated at dual frequencies of square wave voltammetry upon introduction of platinum(II) antineoplastics, the sensors can resolve formation of monovalent adducts and bivalent adducts on the purine-rich DNA sequences.

An asymmetric nickel/metallaphotoredox catalyzed C(sp³)−H benzylic carbamoylation employing alkylarenes and isocyanates is described. A broad array of 2-arylamides can be prepared in one pot under mild reaction conditions. Mechanistic studies, including control experiments and DFT calculations, shed light on the rate and stereodetermining step of this transformation.

Molecular assembly can be designed by fusing binding domains. A precise optimization of the level of compaction of the assembly using linker of different lengths or compositions can provide a simple strategy to program their assembly properties (e.g., midpoint, dynamic range, and inhibition). The thermodynamic and mechanistic principles demonstrated herein also shine light behind the evolution of biological molecular assembly.

A biohybrid system (LMP vaccine) that is based on living cancer cells and a manganese-phenolic nanocloak is developed for synergistic immunotherapy. The nanocloak affords an immunoactive exoskeleton by integrating the toll-like receptor ligand to enhance dendritic cell engulfment and Mn²⁺ ions to sensitize the stimulator of the interferon genes (STING) pathway, leading to superior therapeutic efficacy against melanoma.

We for the first time report the copolymerization of formaldehyde and cyclic anhydride, which is fast and chemo-selective under mild conditions using common acids as catalysts. The versatile method yields a series of sustainable polymers with tunable AB/ABB units, which can be completely degraded into valuable diacids in water or seawater at ambient temperature.

Pulse potential electrolysis bolsters the methane selectivity on N-confused copper (II) tetraphenylporphyrin by 3-fold through promoted water dissociation, aggrandized OH⁻ consumption and thereby populated protons at high anodic bias.

By choosing the solvent accessible surface area as the critical parameter for predicting relative drug release and hence cytotoxicity of polymer prodrug nanoparticles, an optimized polymer-drug linker with enhanced hydrophilicity and solvation has been developed. This hypothesis was experimentally validated by the synthesis of the corresponding polymer prodrugs based on two different drugs, which demonstrated greater drug release and cytotoxicity on two cancer cell lines.

Manipulating defects within a highly symmetric iodide crystal has successfully yielded a remarkable ionic conductivity exceeding 1 mS cm⁻¹ at room temperature in a novel Li₄YI₇ solid-state electrolyte. This achievement not only demonstrates its promising compatibility with lithium metal but also enables the realization of high-performance iodide-based all-solid-state lithium batteries.

The small molecule RBS-10 exploits a novel synthetic lethal vulnerability in cancer cells that show widespread resistance to degraders.

Lysine-reactive activity-based probes based on aryl fluorosulfates (ArOSO₂F) are reported, enabling successful profiling of >300 endogenous kinases and providing a global landscape of ligandable catalytic lysines of the human kinome. Introduction of these aminophiles into a noncovalent Aurora A kinase inhibitor led to novel lysine-reactive inhibitors that exhibited excellent in vitro potency and cellular activities with prolonged residence time.

The successful implementation of an entropy-regulation approach is proposed by using PBAs as cathode for aqueous AIBs, resulting in excellent electrochemical performance. As-designed medium-entropy cathode could deliver a high capacity for reversible Al³⁺ storage, which is attributed to the activation of numerous redox centres and low strain, further enabling ultra-high rates of ion storage and an exceptionally long lifespan.

The electrostatic repulsion effect between the surface negative charges and the active anions (AlCl₄⁻) hinders the intercalation of AlCl₄⁻. Here, we propose a charge regulation strategy for MXene cathodes to overcome this challenge, which is a breakthrough for achieving ultrahigh-energy-density aluminum-ion batteries and other rechargeable batteries by tuning surface charge of electrode materials.

Biodegradable monometallic Al is used for the first time as a pyroptosis biotuner for tumor therapy. Al reacts with H⁺ to form H₂ and Al³⁺, which not only remodels the TME but also enables its degradation. H₂ and Al³⁺ disrupt redox balance and ionic homeostasis, inducing the generation of abundant ROS, which activates ROS-responsive prodrugs, ultimately achieving efficient tumor therapy.

Two 60-metal lanthanide nanocages (Ln₆₀, Ln=Eu and Tb) constructed from Schiff base ligands were used as molecular drug delivery agents (DOX@Ln₆₀, DOX=doxorubicin). They provided for effective tumor therapy in a murine model with negligible side effects. Moreover, DOX@Ln₆₀ proved luminescent and efficiently internalized by breast cancer cells, allowing these cells to be readily visualized.

Specific substitutions in the omega loop (R164-D179) of Klebsiella pneumoniae carbapenemase 2 (KPC-2) alter its structure and function and can lead to increased resistance to antibiotics. Accelerated rare-event sampling well-tempered metadynamics simulations have now revealed that in D179 variants of KPC-2 β-lactamase, the N170 side chain can rotate away from the active site, allowing the binding of antibiotics such as moxalactam and ceftazidime.

A stress dissipation strategy driven by multi-interface BEFs and architected structure, is proposed to achieve compatibility between fast kinetics and structural stability in an anode. Based on this strategy, desert-rose-like HMI-MFS NRs with multiple interfaces and a staggered cantilever configuration at micro- and macro-scales are fabricated, which display ultrafast and superior long-term sodium ion storage in half/full SIBs.

A general skeletal ring expansion strategy for the direct conversion of aziridines into 2-vinyl azetidines via one-carbon insertion using vinyl-N-triftosylhydrazones is described. The method is scalable, tolerates diverse functional groups, and is amenable to the synthesis of medicinally relevant molecules.

Boron-containing species were threaded through macrocycles bearing a 2,2’-biphenol unit. The new threaded species exhibited interesting fluorescence features with quantum yields up to 91 % and an enhanced photostability. Their properties were rationalized with quantum chemistry to unravel the vibronic contributions. This methodology was used to synthesize a rotaxane.

This work presents the phase transfer of hydrophobic clusters into the aqueous phase with maintained emission intensities via the supramolecular recoupling of emissive Ag₂₉ nanoclusters with atomic precision.

While the irreversible thermal transformation of electrolytes is typically attributed to solvent boiling, which disrupts solvent intermolecular interactions, our research revealed that hygroscopic solutes shift the determining factor to solute decomposition, breaking solute intramolecular bonds. As intramolecular bonds are much stronger, it enables ultrahigh thermal tolerance of non-van der Waals solute-in-air electrolytes.

Operando mobile catalysis enables the formation of mobile metal species during the reaction and enhances the catalytic efficiency by increasing the collision probability with the intermediates.

Asymmetric acceptor DT-C8Cl with functional haloalkyl chains was designed and synthesized, where noncovalent interactions induced by haloalkyl chains could effectively optimize the morphology and suppress unfavorable morphology evolutions, leading to simultaneously enhanced efficiency and morphology stability of organic solar cells.

We report an approach of photo-induced disproportionation for preparation of Type-I photodynamic agents capable of simultaneously oxidizing tetrahydrobiopterin and generating superoxide radicals.

Cyanopiperazines as covalent enzyme inhibitors are disclosed. Extending on cyanopyrrolidines, reported cyanamides made of 6-membered rings display context-dependent reversibility and exquisite specificity for the deubiquitinating enzyme UCHL1 among human DUBs and the protein deglycase DJ-1/PARK7. Their mechanism of specificity is rationalized by a crystal structure, highlighting how protein reactivity of electrophilic compounds can be finetuned.

The development of alkyne addition to the aziridine moiety of aziridinoquinoxalines using dual Ir(III)/Cu(I) catalysts under green light-emitting diode (LED) photolysis (λ_max=525 nm), is described. The experimental and quantum chemical explorations suggest a triplet energy transfer mechanism followed by a ring-opening reaction ultimately leading to the formation of azomethine ylide intermediates that are trapped with copper(I) acetylides.

The introduction of Ni into the octahedral site of Co₃O₄ effectively induced a low-to-high spin-state transition, thereby enhancing the activity of ¹O₂ generation. We further explored the spin-related charge transfer and orbital interactions between the catalysts and intermediates, leading to a more comprehensive understanding of the ¹O₂ generation. This work deepens the understanding about orbital interactions and spin states.

Carbocation-based rearrangements are vital for terpene versatility. AacSHC triterpene cyclase from Alicyclobacillus acidocaldarius acted as a promiscuous catalyst for multiple monoterpene rearrangements. Tailored AacSHC variants directed the specific isomerization of pinene with exceptional selectivities. Success involved restructuring the aromatic active pocket and reorganizing water clusters to stabilize demanding carbocationic intermediates.

Understanding the mechanism of spreading depolarization (SD) is essential for the therapy of SD associated diseases. We report a potentiometric dual-channel microsensor for simultaneous detection of H₂S and pH, enabling the first observation of H₂S fluctuation induced by SD in vivo. Our work provides the direct experimental evidence that the H₂S release during SD in rat cortex is less pH-dependent, possibly by modulating enzyme-dependent pathways.

Purely organic luminescent material TBBU does not show room temperature phosphorescence (RTP) in the solid state even under N₂. When doped with 0.1 mol % DTBU, a persistent yellowish green afterglow can be observed from this binary system in N₂ atmosphere. This induced phosphorescence is quite sensitive to oxygen, making the material a candidate for oxygen sensing.

The direct, triisopropy silyl triflate (TIPSOTf)-mediated, regioselective and stereodivergent Michael additions of thioimides to α,β-unsaturated aldehydes catalyzed by chiral nickel complexes give any of the potential syn and anti diastereomers, at will, with good to high yields. The resultant adducts can be easily transformed into a wide array of enantiomerically pure intermediates ready to participate in the asymmetric synthesis of biologically active compounds.

Molecular crystals with polar molecular cages were firstly proposed as a promising system for exploring superior IR NLO materials and a representative system, the binary chalcogenide family P₄S_n (n=3–9), is introduced. As a member of the system, α-P₄S₅ possesses a robust SHG response (1.1×AGS), a broad band gap (3.02 eV), ample birefringence (0.134@2050 nm), a wide optical transmission range (0.41–14.7 μm), and exceptional water-resistance.

The dual stimuli-responsiveness of novel [2]rotaxanes endows them with both tunable vibration-induced emission and switchable circularly polarized luminescence, providing a novel platform for the construction of smart chiral luminescent materials for practical use.

A key polymer material, nitrile-butadiene rubber (NBR), is converted under mild conditions via a one-pot catalytic sequence to bio-based polyesters with highly modulable structure and properties. The overall process operates with high atom-economy, formally redistributing the NBR monomers into new difunctional monomers as well as a single valuable small molecule by-product.

We propose an effective strategy for achieving circularly polarized organic ultralong room-temperature phosphorescence (CP-OURTP) with a high dissymmetry factor based on a bilayered soft helical superstructure doped with a light-driven molecular motor and room-temperature polymer layer. This enables the significant modulation of reflection across a wide spectral range and the dynamic controlling the dissymmetry factor of CP-OURTP from 1.38 to 0.60.

A metal–phenolic-mediated assembly approach is presented whereby a library of functional small molecules, encompassing anticancer drugs, latency reversal agents, and fluorophores, are assembled into functional metal–phenolic network nanoparticles (FSM-MPN NPs) under ambient conditions. These FSM-MPN NPs have potential use in a range of biological applications.

The electrocrystallization of hetera-buckybowl trichalcogenasumanenes (TCSs) has afforded radical cation salts with excellent stability under ambient conditions. The resulting salts are mostly polar crystals, where the TCSs are partially charged and form columnar stacks. A reversible semiconductor-to-semiconductor phase transition is observed, which is caused by a negative thermal expansion of the unit cell.

An artificial LiF-rich solid electrolyte interface formed by a fluorinated carbon nanotube macrofilm endows stable Li-metal batteries with long lifetimes.

Upon extended cycling, the presence of microcracks and resulting internal degradation lead to the hindered kinetics during the (de)intercalation of Li⁺ ions. While these issues were not problematic during charging at low currents, fast charging conditions induce electrochemically unreactive regions in the cathodes owing to increased resistance and polarization, which lead to the loss of fast charging.

Hierarchical porous aromatic chiral cage-based πOF with spring-like structure presents outstanding elasticity and reversible pressure-dependent emission with high-contrast emission difference over a wide pressure range.

Standard research paradigm proposed to uncover the structure-property-activity relationships for the electrochemical CO₂ reduction reaction (CO₂RR) over SnO₂, illustrating the surface reconstruction induced by oxygen vacancies (1/1 ML coverage) and surface-active species (Sn layer) accountable for selective HCOOH production. This proposed methodology validated by the experimental CO₂RR is appliable to other electrocatalytic systems.

We developed a method for the N-terminal-specific dual modification of peptides through a three-component [3+2] cycloaddition with aldehydes and maleimides under mild copper catalysis. This approach enables exclusive functionalization at the glycine N-terminus of peptides, regardless of the presence of lysine ϵ-amine, affording the chemically robust pyrrolidine ring in excellent yields with complete exo-diastereoselectivity.

A platform has been established for the exploration of didemnin-based drugs, combining microbial synthesis of didemnin B through genetic engineering of Tistrella mobilis and semisynthesis for the production of plitidepsin for drug purposes, didemnin derivatives for studying structure–activity relationships, and didemnin B probes for targeted protein profiling. This sustainable approach holds potential for investigating other marine natural products.

A multifunctional additive, tin trifluoromethanesulfonate (Sn(OTf)₂), is proposed to engineer a non-flammable triethyl phosphate (TEP)-based electrolyte, aiming to regulate the solvation environment of Na⁺, facilitate uniform Na deposition, and suppress the shuttling of sodium polysulfides for safe and efficient room-temperature sodium-sulfur (RT Na-S) batteries.

A sequence of novel VIA group elements (O, S, Se)-bridged 1D COFs with typical 4-c sql topology were synthesized and applied as catalysts in the photosynthesis of H₂O₂. Thanks to their 1D configurations, more active sites are accessible, the proton interlaminar shuttle are accelerated, and the directional transfer of electrons is also improved. The bridge-atoms (O, S, Se) in the 1D COFs play a crucial role for the catalytic activity and selectivity.

A unimolecular self-locked allosteric DNAzyme biosensor (named SPOT) is developed to enable sensitive detection (LOD: fM-aM) of low-abundance nucleic acids in a one-pot, one-step, preamplification-free, isothermal detection manner. SPOT exhibits potent performance on miRNA-based detection for cancer diagnostics and viral RNA-based detection for SARS-CoV-2 infection diagnostics.

Strong covalent bonding between metal monolayer and graphene driven by the sp and d orbital hybridization, 2D metal/graphene (M/G) system is investigated. The charge transfer from metal to graphene allows for the electrodeposition of another metal film, thus forming metal/graphene/metal (M/G/M) system. These 2D hybrid systems exhibit excellent activity and selectivity toward formic acid production over competitive hydrogen evolution reaction.

A strong built-in electric field (BIEF) resulted in a strong asymmetrical charge distribution on the Ru cluster, which accelerated water dissociation. However, strong hydrogen adsorption on the interfacial Ru atoms created a high energy barrier for hydrogen desorption and spillover, resulting in unsatisfactory activity at low potentials. As the potential became more negative, the barrier for hydrogen spillover from the interfacial Ru to the Co site, which had a near-zero hydrogen adsorption energy, significantly decreased, thus accelerating the entire alkaline hydrogen evolution reaction (HER) process.

Tightly packed and well-faceted single-crystal microwires of tert-butylcarbazole difluoroboron β-diketonate (DtCzBF2) enabled thermally activated delayed fluorescence (TADF) and low-threshold microlasers. In contrast, its guest-host amorphous thin-films exhibited organic room-temperature phosphorescence (ORTP) with a PLQY up to 61 %, leading to solution-processed OLEDs with external quantum efficiency approaching 18.6 %. This study opens possibilities of low-cost ORTP emitters for high performance OLEDs and future low-threshold electrically injected organic semiconductor lasers (OSLs).

PolyHOF membrane, constructed via covalently copolymerizing nanoscale HOFs into polymeric network, not only exhibits customizable mechanical properties, but also shows excellent functional compatibility, proven by the benchmark luminescent temperature sensing behavior of lanthanide anchored polyHOF membrane even under harsh conditions.

The first activator-based photoswitchable proteolysis-targeting chimera (PS-PROTAC) was developed for the optical control of NAMPT and NAD⁺ in biological systems. The novel PS-PROTAC enabled the reversible regulation of NAMPT and NAD⁺, resulting in a significant reduction in target-related toxicity compared to conventional NAMPT degraders or inhibitors. Furthermore, PS-PROTAC allowed for the in vivo optical manipulation of antitumor activity, NAMPT, and NAD⁺.

Machine-learning force field molecular dynamics simulations reveal the superionic Li⁺ transport in glassy LiTaCl₆ via the dynamic monkey bar mechanism–the high density and dynamics of the vibrating Cl⁻ ions (the dynamic bars) allow Li ions to hold on to them while moving fast through the lattice.

A cascade electrocatalytic and thermocatalytic reaction Scheme is demonstrated to convert CO₂ to propionaldehyde. By individually optimizing and efficiently coupling the upstream and downstream processes, this hybrid system achieves a propionaldehyde selectivity of ~38 %, considerably higher than the best electrochemical systems alone or other hybrid systems reported earlier.

The facile and cost-effective hybridization strategy for proton exchange membranes (PEMs) design by blending 1 nm metal oxide clusters and polyvinyl butyral. The fuel cells equipped with the PEM show promising power densities and excellent durability that is on par with Nafion® and surpass the previously reported non-fluorinated PEMs.

Asymmetric deprotonation of N-benzyl urea derivatives of nitrogen heterocycles leads to enantioselective insertion of the benzylic substituent into an aromatic C−N bond. Treatment of the ring-expanded products induces a stereospecific ring-contraction that results in an overall asymmetric enantioselective one-carbon enlargement of the heterocycle.

A single-atom Cu-decorated WO₃ photocatalyst has achieved a high conversion rate and excellent selectivity in the process of visible light-driven oxidation of glycerol to trioses. The critical role of single Cu atoms is to attract photogenerated holes, thereby improving charge transfer and activating glycerol molecules.

Making anionic zirconium-organic cage and cationic boron-imidazolate cage into a tightly ordered structure achieves an efficient optical limiting response.

A first reversible thiyl radical addition-fragmentation chain transfer (SRAFT) polymerization strategy has been developed, which could directly control the thiyl radical chain polymerizations to afford polymers with a controlled molecular weight and high chain-end fidelity.

Amino-λ³-iodanes enable the electrophilic amination of arylboronic acids and boronates. Iodine(III) reagents with transferable amino groups, including one with an NH₂ group, were synthesized and used in the amination, allowing the synthesis of a wide range of primary and secondary (hetero)arylamines.

This study shows that a two-hole oxidation process such as TEMPO catalyzed alcohol oxidation is a viable reaction to couple with reduction reaction to eliminate SED and generate two added-value chemicals in dye-sensitized photocatalytic systems.

An enzyme and a peptide catalyze—in an aqueous buffer—a two-step cascade reaction with high chemo- and stereoselectivity in one pot. The optimization of the modular peptide catalyst and the identification of common reaction conditions were key for bringing the two worlds of enzyme and peptide catalysis together.

The symmetry of ultrasmall Ru nanoparticles is compromised by embedding Co single atoms, leading to the release of Ru single atoms and the formation of a Co₁Ru_1,n/rGO structure, which regulates the interaction between active sites and enhances the hydrogen oxidation reaction kinetics, mass activity and excellent durability.

A palladium-catalyzed deuteration of arylketone oxime ethers has been realized. Regioselective deuteration of some biologically important drugs and natural products is showcased via Friedel–Crafts acylation and subsequent deacylative deuteration. Vicinal difunctionalization of electro-rich arenes is achieved by using the ketone as both directing group and leaving group.

C(sp³)-rich mono- and bicyclic heterocycles can be assembled on DNA from readily available ketochlorohydrins through a reductive amination and cyclization process. The resulting hydroxypyrrolidine-containing DNA encoded libraries occupy a unique region of pharmaceutically relevant chemical space.

The metabolic capacity of Clostridium sporogenes ATCC 15579 against small molecules was predicted by using an in silico machine learning platform, MoleculeX, followed by experimental evaluation in vivo. Bioinformatics and in vitro biochemical assays were further utilized to identify an enzyme EvoB3 for everolimus modification through ketoreduction.

A chiral cyclopentadienyl-rhodium(III) catalyzed highly enantioselective aziridination of challenging unactivated terminal alkenes and N-pivalolyloxy sulfonamides has been developed. This catalytic system demonstrated outstanding catalytic activity and broad functional group tolerance, yielding synthetically important and highly valuable chiral aziridines with good to excellent yields and enantioselectivities (up to 99% yields, 93% ee).

The conditions under which orthohydrogen with a unique Partial Negative Line (PNL) can be observed were determined by one of the essential Nuclear Magnetic Resonance (NMR) hyperpolarization methods, called Signal Amplification by Reversible Exchange (SABRE). A transient species exists during the preliminary SABRE activation processes, and is responsible for the generation of PNL.

Ni-catalyzed decarboxylative C(sp³)−N cross-coupling of redox active ester and oxime esters was realized through electrochemical cathodic reduction. Mechanistic studies unveil a high-valent nickel species-driven reductive elimination pathway, rather than direct radical-radical coupling. The utility of this methodology was demonstrated through a broad scope (1°, 2°, 3° carboxylic acids) and late-stage functionalization of complex molecules.

The α-/β-C−H functionalization of E styrenes with simple alkenes and alkynes is presented. The process involves α C−H functionalization via a six-membered exo-palladacycle to afford tri- and tetrasubstituted 1,3-dienes and β C−H functionalization via a seven-membered endo-palladacycle to produce tetra- and pentasubstituted 1,3,5-trienes, both enabled by the chelation assistance of pyrazinamide.