A scalable synthesis of trifluorovinyl hypervalent iodine reagent [ArI(CF = CF2)OTf] (TrFVI) has been successfully developed using bulk chemical HFC-134a. Light-induced radical C(sp2)–H trifluorovinylation of (hetero)arenes with TrFVI reagent is achieved and exhibits good functional group compatibility. Detailed mechanism studies show a plausible radical chain pathway.

Trifluorovinyl group is an emerging and valuable motif in drug discovery and material science, especially in polymer-related researches. However, the practical and efficient synthesis of trifluorovinylated compounds with broad structural diversity still remains a challenging task. Herein, we report the scalable synthesis of a trifluorovinyl hypervalent iodine(III) reagent, ArI(CF ═ CF2)OTf (TrFVI), from a bulk chemical, HFC-134a. The first C(sp2)─H trifluorovinylation of (hetero)arenes is achieved using TrFVI reagent via photoredox catalysis, which shows good functional group compatibility. Furthermore, late-stage trifluorovinylation of highly modified substrates, including drug candidates, is achieved to illustrate the powerfulness of our method. A possible radical pathway is proposed according to the mechanism study.

A CO2-assisted Pb/Pb7Bi3 catalytic system enables efficient and selective electrochemical glycine synthesis from oxalic acid and nitrogen sources. The PbBi-II catalyst achieves a high glycine Faradaic efficiency of 91.8% via a cyclic hydrogen-donation pathway and maintains stable performance over 120 h, highlighting the effectiveness of heterointerface engineering and CO2 co-catalysis in facilitating C─N bond formation.

Electrochemical synthesis has emerged as a sustainable platform in constructing C─N bonds for amino acid production. Glycine, a particularly valuable target compound, continues to experience escalating global demand, yet achieving simultaneous high efficiency and operational stability remains a persistent challenge. Herein, we demonstrate a CO2-mediated strategy for glycine electrosynthesis using oxalic acid and N2/nitrate as feedstocks. By using Pb/Pb7Bi3-CO2 catalytic system, a very high glycine Faradaic efficiency (FE) of 91.8% with durable stability over 120 h could be achieved. Moreover, when using nonthermal plasma-activated N2 as the nitrogen source, the glycine production rate could maintain at 94.4 µmol h−1 cm−2 with N-selectivity as high as 93.2%. Mechanistic investigations combining experiments and theoretical calculations reveal that CO2 undergoes facile protonation on the Pb/Pb7Bi3 heterointerfaces to form *OCOH intermediate, which donates hydrogen for the reduction of oxalic acid and nitrate into glyoxylic acid and NH2OH, respectively, while CO2 is simultaneously regenerated. Notably, hydrogenation via the *OCOH intermediate significantly lowers the energy barriers compared to direct protonation, thereby promoting the subsequent spontaneous C─N bond formation and enabling highly efficient electrosynthesis of glycine.

Monodisperse Zn1N3O3 and Ir4+ synergistically modulate substrate and active sites for high-performance ammonia oxidation. Atomically dispersed Zn single atoms in an N,O-doped carbon support serve as dedicated *OH-adsorption sites, while Ir-modulated Pt(100) nanocubes selectively activate NH3.

A rationally designed, bifunctional ammonia-oxidation catalyst spatially decouples NH3 activation and *OH adsorption to overcome the intrinsic trade-off of single-component systems. Atomically dispersed Zn single atoms in an N,O-doped carbon support (Zn1/NOC) serve as dedicated *OH-adsorption sites, while Ir-modulated Pt(100) nanocubes selectively activate NH3. Comprehensive structural characterization (AC HAADF-STEM, XPS, XANES, EXAFS) confirms Zn-N3O3 coordination and atomically isolated Zn centers. Electrochemical-kinetic analysis, mechanistic spectroscopy, and DFT calculations reveal that Zn1/NOC lowers the *OH-adsorption energy by 0.84 eV (to −0.98 eV versus −0.14 eV on Pt), facilitating the dehydrogenation steps and reducing surface poisoning. Simultaneously, traces of stabilized Ir4+-decorated Pt cubes enhance NH3 dissociation kinetics to form N2. The catalyst demonstrates a specific activity of 3.80 mA cm−2 PGMs, exceeding the state-of-the-art benchmarks. When deployed in a membrane-electrode-assembly direct ammonia fuel cell, the catalyst achieves a maximum current density of 200 mA cm−2 and a peak power density of 18 mW cm−2, representing a significant improvement over previously reported systems, with ∼250% increase over Ptnp–C || Pt/C and more than double monofunctional systems. This work demonstrates a generalizable strategy for engineering spatially decoupled active sites in multistep electrochemical reactions, paving the way for high-performance ammonia fuel cells and beyond.

The potassium aluminyl K[Al(NON)] reacts with Ge[N(SiMe3)2]2 by a sequential reductive deamination pathway. The initially formed aluminacyclodigermene contains Ge(I) centres and may be considered as a η 2-coordinated digermyne at aluminium. Further reduction leads to compounds containing a μ,η 2,η 2-[Ge(0)]2 unit coordinated to two Al(NON) groups, or a Ge4-cluster containing species with oxidation state Ge(-I). DFT analysis indicates reduced Al centres and Ge─Ge multiple bonding in both the [RGeGeR] and [Ge2] groups.

The reaction of the potassium aluminyl K[Al(NON)] ([NON]2− = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3) with the diaminogermylene Ge[N(SiMe3)2]2 afforded [K(C6H6)][Al(NON){(Me3Si)2NGeGeN(SiMe3)2}] containing an AlGe2 ring. Structural and computational analysis confirm an aluminacyclodigermene complex that can be considered as an η 2-coordinated digermyne at aluminium with Ge(I) centres. This compound is an intermediate on the reduction pathway to K3[(Ge4){Al(NON)}2{N(SiMe3)2}], which contains a distorted tetrahedral cluster of Ge(-I) centres. Characterisation of the dialumane (NON)Al─Al(NON) from this reaction is indicative of sequential one electron redox processes initiated by the aluminyl anion. Repeating the reaction in methylcyclohexane afforded K2[{Al(NON)}2(Ge2)], containing a formally digermanium(0) unit with an exceptionally long Ge═Ge double bond.

This study introduces redox-switchable poly-Lewis acids (PLAs) based on dibenzo[a,e]cyclooctatetraene, whose reduction leads to planarisation, π$\upi$-system extension, and weakened Lewis acidity, enabling controlled guest release. The reversible switching of these PLAs and their coordination polymers highlights their potential for applications in catalysis, electronics, and functional materials.

Presently, there is a notable interest in poly-Lewis acids (PLAs), their host-guest chemistry and their application in catalytic processes. The present study combines PLAs with redox-active dibenzo[a,e]cyclooctatetraene (dbCOT) units. dbCOT-based PLAs can be planarised by a two-electron reduction. The molecular structures of the reduced PLAs, studied by sc-XRD experiments and DFT calculations, show the formation of extended π$\upi$-systems. This π$\upi$-system extends to the Lewis acid functions and reduces their acidity. This allows a controlled release of complexed guest molecules. Oxidation regenerates the original Lewis acidity. Such reduction/oxidation cycles were also applied to an Al─P coordination polymer. sc-XRD shows the connectivity of the coordination polymer to remain unchanged, so that the polymer is stable in the neutral and reduced state. The possibility of switching such dbCOT-based PLAs and their adducts as well as the formed coordination polymers between two states with different structures and electronic compositions is of interest for the development of functional materials in the fields of electronics, optics and magnetism as well as for the development of switchable catalysts.

In this work, a planar conjugated molecule, 1,8-naphthyridin-2-amine (2-NA), is introduced as a multifunctional interfacial modifier in CsPbI3-xBrx perovskite solar cells. It enhances hole extraction and passivates undercoordinated Pb2+ defects, boosting carrier dynamics and reducing recombination. Furthermore, a hydrophobic interfacial layer also improves moisture resistance, ultimately enabling a record 22.49% efficiency.

Rational molecular design at the perovskite/hole transport layer (HTL) interface presents a viable strategy to suppress nonradiative recombination in CsPbI3-xBrx-based perovskite solar cells (PSCs). However, simultaneously achieving efficient defect passivation and rapid charge extraction with a single molecular modifier remains challenging. Herein, we employ a planar conjugated molecule, 1,8-naphthyridin-2-amine (2-NA), as a multifunctional interfacial modifier that concurrently enhances charge extraction and suppresses interfacial recombination in CsPbI3-xBrx PSCs. Combined density functional theory (DFT) calculations and experimental analyses reveal that 2-NA forms a dense protective layer via noncovalent interactions (e.g., π-π stacking and hydrogen bonding), effectively passivating undercoordinated Pb2+ while inhibiting ion migration. Remarkably, 2-NA incorporation facilitates hot-carrier extraction, reducing the carrier cooling time from 515 to 240 fs and quadrupling the carrier diffusion length, thereby improving charge transport. As a result, the optimized device achieves a power conversion efficiency (PCE) of 22.49%, the highest reported value for this class of PSCs to date. Furthermore, the device retains 93.6% of its initial PCE after 1008 h under ambient conditions, demonstrating exceptional stability. This work offers a promising molecular engineering approach for enhancing the performance and durability of inorganic PSCs through interfacial modification.

An efficient and versatile metallaphotoredox catalyst system has been developed to promote highly selective C(sp2)─C(sp3) cross-electrophile couplings of aryl chlorides and alkyl halides. The design and development of a unique PyIm ligand was crucial in tuning the reactivity of the less reactive aryl chlorides. The strength of the protocol has been demonstrated through peptide diversification and direct functionalization of drugs, such as fenofibrate, indomethacin, and etoricoxib.

Cross-electrophile coupling (XEC) reactions that forge C(sp2)─C(sp3) bonds have received considerable attention due to the vast libraries of commercially available organohalides. However, the incorporation of ubiquitous aryl chlorides remains a challenge due to the slow rate of oxidative addition of metal catalysts to these electrophiles relative to iodide and bromide derivatives. This study reports a simple metallaphotoredox-catalyzed C(sp2)─C(sp3) cross-electrophile coupling (XEC) method for the selective coupling of a broad range of aryl chlorides and alkyl halides. By design, this methodology exploits the enabling interplay of a bidentate 2-(1H-imidazol-2-yl)pyridine ligand, incorporating the strong σ-donor capacity of a 1H-imidazole moiety with the moderate π-acceptor capacity of a pyridine unit. The synergy provided by these modular components allowed for the electronic requirements of elementary steps to be accommodated, such as the synchronous integration of alkyl radical generation (typically relatively fast) and oxidative addition of low valent nickel species to aryl chlorides (often relatively slow). This protocol enabled the efficient late-stage diversification of the drugs Me-fenofibrate, indomethacin, and etoricoxib to enhance their sp3-rich complexity. Using an equimolar ratio of substrates, this methodology facilitated a decagram XEC in continuous flow, showcasing the applicability of the method for large scale synthesis.

A formal cyclopropylation of imines with cyclopropanols enables stereoselective access to cyclopropane-embedded γ-amino alcohols bearing three contiguous stereocenters. The transformation proceeds through a sequence of Mannich-type addition and ring closure involving enolized zinc homoenolate, and is applicable to both N-sulfonyl and chiral N-sulfinyl trifluoromethyl imines, providing building blocks diversifiable to various aminocarbonyl compounds.

γ-Amino alcohols are essential motifs in bioactive compounds and chiral catalysts, yet the synthesis of their conformationally constrained variants remains challenging due to the lack of suitable methodologies. Here, we report a formal cyclopropylation of imines with cyclopropanols, enabling the construction of previously inaccessible cyclopropane-embedded γ-amino alcohols. This transformation leverages the unique reactivity of enolized zinc homoenolates, which effectively act as a β-hydroxycyclopropyl anions and engage imines through a sequence of Mannich addition and ring closure. The key to this reactivity lies in the use of bulky N-heterocyclic carbene (NHC) ligands, which promote efficient coupling with N-sulfonyl aldimines as well as chiral N-sulfinyl trifluoromethyl-ketimines while ensuring excellent diastereocontrol over three contiguous stereocenters. Furthermore, the resulting γ-amino alcohols can be transformed into β- or γ-aminofunctionalized ketones via homoenolate or β-keto radical intermediates, offering versatile platforms for downstream derivatization.

From radical to diradical cation. Photoionization (PI) of the thermally generated pentafluorophenyl radical yields the pentafluorophenyl cation in the gas phase. This cation is found to be a diradical with nearly degenerate open-shell singlet and triplet ground states, and it is even more unstable than the parent phenyl cation by ∼40 kcal mol−1.

We report the first direct observation of the pentafluorophenyl cation in the gas phase via vacuum ultraviolet (VUV) photoionization (PI) of the thermally generated pentafluorophenyl radical. The reactive intermediates and stable reaction products were characterized utilizing photoelectron photoion coincidence (PEPICO) spectroscopy with synchrotron radiation. Electron removal from the pentafluorophenyl radical yields the cation with an adiabatic ionization energy (AIE) of 9.84 ± 0.02 eV. Threshold photoelectron spectra combined with high-level ab-initio calculations show that the cation is described as a π5σ1 diradical with an open-shell singlet (1A2) ground state, while the triplet (3A2) state lies only 1.5 ± 0.4 kcal mol−1 higher in energy. The closed-shell singlet (1A) state is highly distorted and lies >4 kcal mol−1 above the ground state. This unique aryl carbenium ion exhibits a ∼40 kcal mol−1 higher hydride affinity (HA) as compared to the parent phenyl cation, explaining its high reactivity and elusive character. In addition, the radical's reactivity was investigated upon hydrogen abstraction and unimolecular decomposition, forming tetrafluoro ortho-benzyne as well as smaller fluorinated species.

High-entropy Prussian blue with great mechanochemical compatibility is proposed as cathode material for sodium-ion batteries, contributing high reversible specific capacity, great rate capability and long-term lifespan over 9000 cycles due to the suppressed Jahn–Teller lattice distortion as well as the enhanced electron/ion transfer kinetics benefited from high-entropy effect.

High-entropy Prussian blue analogues (PBAs) have considered as high-performance cathodes for sodium-ion batteries (SIBs). However, the impact of high-entropy component compatibility on electrodes’ lattice stress and kinetics remains underexplored. Herein, a series of high-entropy PBAs are served as cathode materials for SIBs. The tailoring Na2Mn0.2Fe0.2Co0.2Ni0.2Cu0.2[Fe(CN)6] (HE-Cu) with superior mechanochemical compatibility shows superior phase stability without obvious lattice stress and faster electron/ion transfer kinetics. Intrinsic and accumulated lattice stresses can be obtained by ion-incompatible Sn-based high-entropy PBA (HE-Sn) and valence-electron mismatched Ti-based high-entropy PBA (HE-Ti), thereby exhibiting poor structure stability and dynamics. Serious Jahn–Teller structural distortion and unstable octahedron, observed in Na2Mn[Fe(CN)6] with complicated Na-ion storage phase evolution (monoclinic ↔ cubic ↔ tetragonal), can be entirely suppressed by high-entropy effect, appearing a zero-strain solid-solution reaction mechanism for HE-Cu employing Mn, Fe, and Co-ions as redox centers to involve in charge compensation. Consequently, HE-Cu presents high initial specific capacity of 120.4 mAh·g−1, superior rate capability and outstanding cyclability with ultra-long cycling life of 9000 cycles with the lowest capacity-decay-rate of 0.0042% per cycle. Na-ion full cell demonstrates high initial energy density of 397.0 Wh·kg−1 and perfect cycling stability with long lifespan over 2000 cycles.

First examples of Pd(II)-catalyzed Wacker oxidation of trisubstituted alkenes, coupled with electrophilic fluorination, enable a one-carbon ring expansion of exocyclic α,β-unsaturated carbonyls to 2-fluoro-2-acyl-cycloalkanones.

The Wacker oxidation is a powerful synthetic method widely employed for the transformation of monosubstituted alkenes into methyl ketones. Its substrate scope has progressively expanded to include internal disubstituted and, more recently, gem-disubstituted alkenes. Herein, we report the first examples of Wacker-type oxidation of trisubstituted alkenes under Pd(II)/Pd(IV) catalysis. In the presence of Selectfluor (2.3 equiv) and a catalytic amount of Pd(MeCN)4(BF4)2 (10 mol%), exocyclic trisubstituted α,β-unsaturated carbonyl compounds undergo a fluorinative one-carbon ring expansion to deliver 2-fluoro-1,3-dicarbonyl compounds in good yields. The reaction displays broad functional group tolerance, including alkyl halide, aryl halide, alkyl tosylate, hydroxyl, carboxylic acid, ester, secondary amide, ketone, cyano, and N-phthalimide. While a semi-pinacol rearrangement of the Pd(IV) intermediate is a plausible mechanistic pathway given the excellent nucleofugality of the Pd(IV) atom, preliminary studies suggest that a 1,2-alkyl/Pd(IV) dyotropic rearrangement is operative in product formation.

A three-dimensional mixed-valence bimetallic metal-organic framework (MOF) features unique tubular and sinuous channels alongside ligand-provided active sites, and exhibits exceptional colorimetric selectivity for detecting cysteine or cysteine residues. This specific synergistic interaction enables the MOF to function as a highly promising sensor for monitoring thiolase enzyme activity, underscoring its significant potential for biomedical applications.

We have successfully designed and synthesized a mixed-valence bimetallic metal-organic framework (MOF), denoted ZnCoBTCHx, featuring periodic tubular and sinuous channels along with active sites provided by the ligands. This MOF demonstrates exceptional colorimetric selectivity toward cysteine (Cys). X-ray photoelectron spectroscopy, solid-state 13C NMR, UV-Vis absorption spectra, electrochemical analysis, and density functional theory calculations complementarily validate the valence state switching of cobalt centers in ZnCoBTCHx, the host–guest interactions and significant electron transfer between Cys and the framework. Additionally, isothermal titration calorimetry data suggest potential adsorption occurring within the channels of ZnCoBTCHx. In contrast, the mixed-valence CdCoBTCHx possesses a monoporous architecture wherein all potential N/O donor atoms of the ligands are engage in metal coordination. CdCoBTCHx displays a colorimetric response not only to Cys but also to other sulfur-containing amino acids. Notably, ZnCoBTCHx represents the first reported MOF that exhibits the ability to selectively recognize Cys residues in polypeptides and enzymes. This distinctive property enables ZnCoBTCHx to serve as a promising sensor for thiolase activity, underscoring its significant potential for biomedical applications.

Three self-assembled polyoxometalate superstructures with ultrathin graphene-like morphologies exhibit enhanced conductivity and increased exposure of activity sites, leading to a significant improvement in catalytic activity toward the oxygen evolution reaction.

Superstructures assembled from nanoscale polyoxometalates (POMs) attract considerable interest due to their well-defined architectures and outstanding physicochemical properties. However, the targeted synthesis of self-assembled POM-based superstructures with high-efficiency electrocatalytic performance remains a significant challenge. Herein, we report the rational design and construction of three POM-based superstructures with ultrathin graphene-like morphologies and well-organized frameworks via a simple self-assembled method, in which transition metals (TMs) bridge POMs into graphene-like planes, while cetyltrimethylammonium bromide (CTAB) serves as an intercalation agent, endowing the structures with high surface area and enhanced electronic conductivity. Among the resulting materials (denote as POM-CTAB-TM, TM═Co, Ni, or Cu), POM-CTAB-Co exhibits the highest catalytic activity toward oxygen evolution reaction (OER), achieving a low overpotential of 292 mV at a current density of 10 mA cm−2. In situ electrochemical spectroscopy and theoretical calculations underscore that the Co atoms within the POM serve as active sites and facilitate the rate-determining step of *OOH formation. Moreover, an anion exchange membrane water electrolyzer employing POM-CTAB-Co as the anode and Pt/C as the cathode demonstrates exceptional performance, delivering a current density of 2 A cm−2 at a cell voltage of 2.247 V, along with remarkable durability exceeding 2000 h at an industrial-grade current density of 500 mA cm−2. This study develops a simple and efficient method for synthesizing supramolecular POM-based nanosheets as OER electrocatalysts.

A spatially integrated Nb2C/Nb2O5/ZnO heterostructure couples Schottky and S-scheme interfaces to promote directional charge separation and photothermal-assisted CO2 activation, enabling efficient photoreduction without molecular cocatalysts or sacrificial agents through synergistic interfacial engineering and carrier dynamic control.

Photocatalytic CO2 reduction into solar fuels presents a promising strategy for carbon mitigation and sustainable energy conversion. However, single-component photocatalysts suffer from inefficient charge separation, while binary heterojunctions—even with cocatalysts assistance—often undergo rapid Coulombic recombination due to timescale mismatches between ultrafast charge transfer and slower surface reaction kinetics. To overcome these limitations, a spatially engineered Nb2C/Nb2O5/ZnO ternary heterostructure is developed by anchoring ZnO quantum dots (QDs) onto Nb2O5 nanorods grown in situ from Nb2C MXene. This architecture integrates an Nb2O5/ZnO S-scheme heterojunction and an Nb2C/Nb2O5 Schottky junction, sharing Nb2O5 as a central mediator, thereby establishing bidirectional interfacial electric fields (IEFs) that direct photogenerated electrons toward ZnO and holes toward Nb2C. In situ irradiated X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS), and femtosecond transient absorption spectroscopy (fs-TAS) reveal interface-specific electronic interactions and time-resolved carrier dynamics, confirming efficient and spatially resolved charge migration across the decoupled interfaces. This spatial charge separation effectively suppresses Coulombic recombination and prolongs carrier lifetimes. Additionally, the photothermal effect of Nb2C MXene enhances CO2 chemisorption and activation at defective ZnO QDs. These synergistic effects collectively enable high-efficiency CO2 photoreduction without molecular cocatalysts or sacrificial agents, providing a mechanistically distinct and scalable approach for artificial photosynthesis.

Nanofluidics has garnered significant attention due to the designability and unique transport features at the nanoscale. With the development of nanofabrication, nanofluidic devices are systematically developed for ultrasensitive molecular recognition and physical perception, paving the way for intelligent recognition applications in the fields of bioscience, food safety, medical diagnostics, and so on.

Nanofluidics has garnered significant attention as the ultra-sensitive method for molecular recognition and physical perception that are not easily accessible through the traditional methods. The development of nanofluidic devices necessitates the integrated solid-state nanochannels/nanopores with versatile surface modification strategies using precise nanofabrication techniques. This review systematically summarizes the development of the solid-state nanochannels and nanopores, nanofabrication methods, sensing principles, transport characteristics, and the strategies employed to perceive molecules and physical stimuli. The discussion also emphasizes promising research directions and explores how the interaction between interface chemistry influenced by molecular recognition and physical stimuli, in conjunction with the exceptional ion transport properties of nanofluidic devices, significantly impacts the sensing performance of the nanofluidics. Lastly, we present the vision for the future prospects of biomimetic nanofluidic devices in ionic sensing applications.

Introduce π-conjugated cation as a universal paradigm to equilibrate bandgap, birefringence, and SHG-responsible constraints. Enable an NLO crystal (GUPO) that exhibits full-wavelength PM ability (down to 215 nm) and outperforms the traditional commercial KDP's PM wavelength limit by 43 nm blueshift.

While birefringence phase-matching (PM) remains the most practical approach for nonlinear optical (NLO) frequency conversion, conventional phosphate crystals suffer from intrinsically low birefringence (Δn < 0.05) that hinders PM behavior in the solar-blind ultraviolet (UV) region (λ < 280 nm). Herein, we demonstrate a π-conjugated cation engineering strategy to break this limitation, reporting two phosphite-based NLO crystals: (C2N4OH7)H2PO3 (GUPO) and C(NH2)3H2PO3 (GPO). The synergistic alignment of π-conjugated guanidinium cations and [H2PO3]⁻ anions enables record-breaking optical anisotropy (Δn = 0.19 @ 589.3 nm for GUPO), surpassing all known inorganic phosphates. Crucially, GUPO is the first phosphate to realize full-wavelength PM, in which the PM wavelength fully covers its optical transparency range down to 215 nm. Concurrently, GUPO exhibits exceptional second-harmonic generation (SHG) response (2.2 × KDP at 1064 nm and 1.0 × β-BBO at 532 nm), which may enable direct 266 nm laser generation. Mechanistic studies reveal that the giant birefringence originates from oriented π–π interactions between cations, while the SHG response stems from the cooperative polarization of cations. This work establishes π-conjugated cation engineering as a paradigm for designing UV NLO materials, with GUPO crystal emerging as a cheap, efficient alternative to conventional UV NLO crystals.

DNA duplex-programmed presentation of two different (cyclo)peptides provides bispecific agents that recognize unique fingerprints of cells through improved avidity and specificity. Bispecific DNA-cyclopeptide complexes enabled a cell-specific targeting and internalization of cytotoxic payload.

Chemical modification and nucleic acid self-assembly can be used to make protein receptor ligands form specific arrangements. While this property has been extensively exploited for probing of homomultivalent interactions, there has been comparatively little attention paid to the exploration of heteromultivalent interactions. In this study, we investigated the use of readily assemblable DNA duplexes for programming bispecific targeting of specific cell types. In contrast to previous bispecific agents, we leverage the potential of peptide-based high-affinity binders of cell surface proteins used in diagnostics/therapeutics. Systematic spatial screening revealed the optimal distance between two (cyclo)peptides required for selectively recognizing cells expressing unique combinations of receptors. The VGFR2/αVβ3 receptor system on HUVECs was tolerant to changes of the distance between two cyclopeptides (L and cyclo(-RGDf(N-Me)K-)) and required that the distance exceeded the equivalent of 20 nucleotides distance. A different distance-affinity landscape was observed for recognition of EGFR and MET on A549 cells (through GE11 and bicyclic peptide GE-137). The DNA-programmed bispecific binders demonstrated specificity and efficient internalization into target cells. Auristatin-loaded DNA enabled a selective targeting of cytotoxic payload. Of note, the distance-optimized bispecific DNA-peptide probes have much lower molecular weight than previously used agents based on DNA nanostructures or antibodies.

exTTF[10]CPP, featuring shape-persistent architecture and curved conjugation, exhibits tunable Kasha/anti-Kasha dual emissions. Meanwhile, exTTF[10]CPP not only exhibits reversible redox responsiveness but also shows redox-dependent tunability in its binding interaction with C60. Moreover, its complex with C60 displays exceptional charge-transfer property, enhancing the photocurrent in C60⊂exTTF[10]CPP-based cast film.

Developing functionalized cycloparaphenylenes (CPPs) that respond to various stimuli, particularly redox, remains challenging yet crucial for advanced nanocarbon applications. Here, we report the exploration of the synergy between the concave π-extended tetrathiafulvalene (exTTF) and the curved CPP scaffold for constructing the rigid, conjugated nanohoop exTTF[10]CPP. X-ray analysis reveals a unique spherical packing arrangement in which six adjacent nanohoops interlock through concave and convex interactions. Interestingly, fluorescence studies revealed that exTTF[10]CPP exhibited unexpected anti-Kasha emissions originating from higher excited states, along with Kasha emission from S1 excited state in toluene and THF. However, in a PMMA film, it displayed a redshifted Kasha emission. The unique Kasha/anti-Kasha dual-emission behavior represents a rarely explored photophysical phenomenon within exTTF derivatives and nanocarbon-based systems. Ultraviolet-Visible (UV–vis) absorption investigations showed that exTTF[10]CPP demonstrated reversible redox responsiveness with tunable binding affinity for C60 up to 1.92 × 106 M−1. Notably, femtosecond transient absorption measurements further revealed a prolonged lifetime of the charge-separated state, C60 •−/exTTF[10]CPP•+ , which provides sufficient time for charge utilization. This exceptional charge-transfer property enhances the photocurrent in C60⊂exTTF[10]CPP-based cast film, which is 2.43 times higher than that of exTTF[10]CPP alone, highlighting its potential in photoelectronic device.

Conventional Pt/Al2O3 catalysts are prone to sintering into larger particles under high-temperature oxidation. In contrast, a La2O3-modified Pt/Al2O3 catalyst undergoes a transformation to the formation of Al2O3-Pt1-La2O3 structure via strong oxide-support interaction (SOSI)—driven interfacial reconstruction during calcination, markedly improving CO oxidation performance and thermal durability.

Supported metal nanoparticle catalysts often suffer from sintering-induced size-dependent deactivation, limiting their high-temperature applications. Although high-temperature redispersion offers a potential solution, this strategy remains restricted to reducible support materials, severely limiting the selection of catalyst supports with versatile compositions and tunable functionalities. Here, we engineer cationic vacancies at Al2O3-La2O3 interface via strong oxide-support interaction (SOSI)—driven interfacial reconstruction during calcination. The vacancy-mediated confinement effect dynamically intercepts migrating Pt species, enabling the construction of Al2O3-Pt1-La2O3 structure with precisely defined coordination environments. The resulting catalyst achieves complete CO conversion at 145 °C and maintains stability with minimal decline after a 6-h treatment at 1100 °C in air with 10% steam. This interfacial engineering strategy proves universal, as demonstrated by ZrO2-La2O3 counterparts. Our findings break the reducibility dependency in traditional single-atom catalysts (SACs) stabilization by establishing oxide–oxide interface as universal anchoring platforms, which expands the design space of industrial-grade SACs beyond conventional reducible oxides.

Mitochondria-targeted single-molecule drugs, nanodrugs, and polymeric drugs have become important molecular tools in tumor therapy. In this review, we systematically summarize the latest advances in molecular tools for mitochondria-targeted precision tumor therapy, providing valuable references to facilitate the clinical translation of precision medicine.

Precise therapy for tumors faces challenges associated with traditional methods, such as low targeting efficiency, substantial side effects, and drug resistance. As the core regulators of cellular energy metabolism and apoptosis, mitochondria exhibit considerable advantages through targeted molecular tools that precisely deliver drugs, interfere with key pathways, and activate immune responses. This article reviews the latest advancements in mitochondria-targeted molecular tools for precision tumor therapy. Modifying molecular structures or designing functionalized carriers, small molecular drugs, metal complexes, nanodrugs, and polymeric drugs can be precisely enriched in mitochondria, disrupting the mitochondrial membrane, interfering with the respiratory chain, or activating immune pathways, thereby significantly enhancing antitumor efficacy and reducing systemic toxicity. However, further optimization of the design of mitochondria-targeted molecular tools is required, and their synergistic potential with immunotherapy metabolic regulation, and mitochondrial DNA targeting warrants further exploration. The rational design of mitochondria-targeted molecular tools holds great promise for achieving precise, personalized, and low-toxicity tumor therapy.