Pseudo-2D Layered Organic-Inorganic Manganese Bromide with a Near-Unity Photoluminescence Quantum Yield for White Light-Emitting Diode and X-Ray Scintillator

Eco-friendly lead-free organic–inorganic manganese halides (OIMHs) have attracted considerable attention in various optoelectronic applications because of their superior optical properties and flexible solution processibility. Herein, we report a novel pseudo-2D layered OIMH (MTP)₂MnBr₄ (MTP: methyltriphenylphosphonium), which exhibits intense green emission under UV/blue or X-ray excitation, with a near-unity photoluminescence quantum yield, high resistance to thermal quenching (I_{150 °C}=84.1 %) and good photochemical stability. These features enable (MTP)₂MnBr₄ as an efficient green phosphor for blue-converted white light-emitting diodes, demonstrating a commercial-level luminous efficiency of 101 lm W⁻¹ and a wide color gamut of 116 % NTSC. Moreover, these (MTP)₂MnBr₄ crystals showcase outstanding X-ray scintillation properties, delivering a light yield of 67000 photon MeV⁻¹, a detection limit of 82.4 nGy s⁻¹, and a competitive spatial resolution of 6.2 lp mm⁻¹ for X-ray imaging. This work presents a new avenue for the exploration of eco-friendly luminescent OIMHs towards multifunctional light-emitting applications.     

Overcoming Cancer Resistance to Platinum Drugs by Inhibiting Cholesterol Metabolism

Drug resistance is a serious challenge for platinum anticancer drugs. Platinum complexes may get over the drug resistance via a distinct mechanism of action. Cholesterol is a key factor contributing to the drug resistance. Inhibiting cellular cholesterol synthesis and uptake provides an alternative strategy for cancer treatment. Platinum(IV) complexes FP and DFP with fenofibric acid as axial ligand(s) were designed to combat the drug resistance through regulating cholesterol metabolism besides damaging DNA. In addition to producing reactive oxygen species and active platinum(II) species to damage DNA, FP and DFP inhibited cellular cholesterol accumulation, promoted cholesterol efflux, upregulated peroxisome proliferator-activated receptor alpha (PPARα), induced caspase-1 activation and gasdermin D (GSDMD) cleavage, thus leading to both apoptosis and pyroptosis in cancer cells. The reduction of cholesterol significantly relieved the drug resistance of cancer cells. The double-acting mechanism gave the complexes strong anticancer activity in vitro and in vivo, particularly against cisplatin-resistant cancer cells.     

Balancing the Crystallinity and Film Formation of Metal–Organic Framework Membranes through In Situ Modulation for Efficient Gas Separation

Polycrystalline metal–organic framework (MOF) layers hold great promise as molecular sieve membranes for efficient gas separation. Nevertheless, the high crystallinity tends to cause inter-crystalline defects/cracks in the nearby crystals, which makes crystalline porous materials face a great challenge in the fabrication of defect-free membranes. Herein, for the first time, we demonstrate the balance between crystallinity and film formation of MOF membrane through a facile in situ modulation strategy. Monocarboxylic acid was introduced as a modulator to regulate the crystallinity via competitive complexation and thus concomitantly control the film-forming state during membrane growth. Through adjusting the ratio of modulator acid/linker acid, an appropriate balance between this structural “trade-off” was achieved. The resulting MOF membrane with moderate crystallinity and coherent morphology exhibits molecular sieving for H₂/CO₂ separation with selectivity up to 82.5.     

A Strategy for Controlling the Polymerizations of Thiyl Radical Propagation by RAFT Agents

The ability to extend the polymerizations of thiyl radical propagation to be regulated by existing controlled methods would be highly desirable, yet remained very challenging to achieve because the thiyl radicals still cannot be reversibly controlled by these methods. In this article, we reported a novel strategy that could enable the radical ring-opening polymerization of macrocyclic allylic sulfides, wherein propagating specie is thiyl radical, to be controlled by reversible addition–fragmentation chain transfer (RAFT) agents. The key to the success of this strategy is the propagating thiyl radical can undergo desulfurization with isocyanide and generate a stabilized alkyl radical for reversible control. Systematic optimization of the reaction conditions allowed good control over the polymerization, leading to the formation of polymers with well-defined architectures, exemplified by the radical block copolymerization of macrocyclic allylic sulfides and vinyl monomers and the incorporation of sequence-defined segments into the polymer backbone. This work represents a significant step toward directly enabling the polymerizations of heteroatom-centered radical propagation to be regulated by existing reversible-deactivation radical polymerization techniques.     

Cooperative Ni(Co)-Ru-P Sites Activate Dehydrogenation for Hydrazine Oxidation Assisting Self-powered H2 Production

Water electrolysis for H₂ production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru₁−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm⁻², respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm⁻² at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru₁−NiCoP optimize H* adsorption, and enhance adsorption of *N₂H₂ to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H₂ production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h⁻¹ m⁻².     

Superparamagnetic Composite Nanobeads Anchored with Molecular Glues for Ultrasensitive Label-free Proteomics

Mass spectrometry has emerged as a mainstream technique for label-free proteomics. However, proteomic coverage for trace samples is constrained by adsorption loss during repeated elution at sample pretreatment. Here, we demonstrated superparamagnetic composite nanoparticles functionalized with molecular glues (MGs) to enrich proteins in trace human biofluid. We showed high protein binding (>95 %) and recovery (≈90 %) rates by anchor-nanoparticles. We further proposed a Streamlined Workflow based on Anchor-nanoparticles for Proteomics (SWAP) method that enabled unbiased protein capture, protein digestion and pure peptides elution in one single tube. We demonstrated SWAP to quantify over 2500 protein groups with 100 HEK 293T cells. We adopted SWAP to profile proteomics with trace aqueous humor samples from cataract (n=15) and wet age-related macular degeneration (n=8) patients, and quantified ≈1400 proteins from 5 μL aqueous humor. SWAP simplifies sample preparation steps, minimizes adsorption loss and improves protein coverage for label-free proteomics with previous trace samples.     

Directing the Selectivity of CO Electrolysis to Acetate by Constructing Metal-Organic Interfaces

Electrochemically converting CO₂ to valuable chemicals holds great promise for closing the anthropogenic carbon cycle. Owing to complex reaction pathways and shared rate-determining steps, directing the selectivity of CO₂/CO electrolysis to a specific multicarbon product is very challenging. We report here a strategy for highly selective production of acetate from CO electrolysis by constructing metal-organic interfaces. We demonstrate that the Cu-organic interfaces constructed by in situ reconstruction of Cu complexes show very impressive acetate selectivity, with a high Faradaic efficiency of 84.2 % and a carbon selectivity of 92.1 % for acetate production, in an alkaline membrane electrode assembly electrolyzer. The maximum acetate partial current density and acetate yield reach as high as 605 mA cm⁻² and 63.4 %, respectively. Thorough structural characterizations, control experiments, operando Raman spectroscopy measurements, and density functional theory calculation results indicate that the Cu-organic interface creates a favorable reaction microenvironment that enhances *CO adsorption, lowers the energy barrier for C−C coupling, and facilitates the formation of CH₃COOH over other multicarbon products, thus rationalizing the selective acetate production.     

Nano Proteolysis Targeting Chimeras (PROTACs) with Anti-Hook Effect for Tumor Therapy

Proteolysis targeting chimera (PROTAC) is an emerging pharmacological modality with innovated post-translational protein degradation capabilities. However, off-target induced unintended tissue effects and intrinsic “hook effect” hinder PROTAC biotechnology to be maturely developed. Herein, an intracellular fabricated nano proteolysis targeting chimeras (Nano-PROTACs) modality with a center-spoke degradation network for achieving efficient dose-dependent protein degradation in tumor is reported. The PROTAC precursors are triggered by higher GSH concentrations inside tumor cells, which subsequently in situ self-assemble into Nano-PROTACs through intermolecular hydrogen bond interactions. The fibrous Nano-PROTACs can form effective polynary complexes and E3 ligases degradation network with multi-binding sites, achieving dose-dependent protein degradation with “anti-hook effect”. The generality and efficacy of Nano-PROTACs are validated by degrading variable protein of interest (POI) such as epidermal growth factor receptor (EGFR) and androgen receptor (AR) in a wide-range dose-dependent manner with a 95 % degradation rate and long-lasting potency up to 72 h in vitro. Significantly, Nano-PROTACs achieve in vivo dose-dependent protein degradation up to 79 % and tumor growth inhibition in A549 and LNCap xenograft mice models, respectively. Taking advantages of in situ self-assembly strategy, the Nano-PROTACs provide a generalizable platform to promote precise clinical translational application of PROTAC.     

Porous Cyclodextrin Polymer Enables Dendrite-Free and Ultra-Long Life Solid-State Zn-I2 Batteries

Zn-I₂ batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD-Si) by nucleophilic reaction of β-cyclodextrin with SiCl₄, and CD-Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD-Si) to solve above-mentioned problems. Through the anchoring of the CD-Si, a conductive network with dual transmission channels was successfully constructed. Due to the non-covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10⁻³ S cm⁻¹ at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite-free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm⁻² and 1200 h at 20 mA cm⁻²). The solid-state Zn-I₂ battery shows an ultra-long life of over 35,000 cycles at 2 A g⁻¹. Molecular dynamics simulations are performed to elucidate the working mechanism of CD-Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn-I₂ batteries.     

Palladium and Ruthenium Dual-Single-Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

Heterogeneous single-metal-site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd₁−Ru₁ single-atom-sites supported on porous ionic polymers (Pd₁−Ru₁/PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd- or Ru-site catalyst, the dual single-atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single-Ru site exhibited a strong CO adsorption energy of −1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd₁−Ru₁/PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd₁/PIPs for the rate-determining step. The synergetic effect between neighboring single sites Pd₁ and Ru₁ not only enhanced the overall activity, but also stabilized Pd^II active sites. The discovery of synergetic effects between single sites can deepen our understanding of single-site catalysts at the molecular level.