Liang Feng

Developing advanced adsorbents with both high selectivity and low regeneration energy remains a central challenge in realizing energy-efficient CO 2 capture technologies. In this work, we report an ultramicroporous metal–organic framework, PCP-IPAN, designed with CO 2 -philic electrostatic cavities to promote strong yet thermally tunable interactions with CO 2 molecules. Notably, the framework exhibits highly temperature-sensitive adsorption profiles, characterized by a sharp reduction in CO 2 uptake within a narrow temperature range (273–323 K). This significant thermal sensitivity enables a large working capacity and ensures facile desorption at mild temperatures, which is a key requirement for reducing the energy penalty in pressure- and temperature-swing adsorption (P/TSA) processes. Single-component adsorption measurements reveal that PCP-IPAN-Co achieves high CO 2 capacities of 4.60 and 3.32 mmol g –1 at 273 and 298 K (1.0 bar), respectively. Furthermore, it delivers CO 2 /N 2 (15/85) IAST selectivities of 71.6 and 99.3, alongside CO 2 /CH 4 (50/50) IAST selectivities of 39.8 and 19.6 at these temperatures. Dynamic column breakthrough experiments for CO 2 /N 2 and CO 2 /CH 4 binary mixtures confirm the material’s excellent separation selectivity, and vacuum pressure swing adsorption (VPSA) simulations demonstrate its efficient separation energy consumption during cyclic operation. These findings highlight PCP-IPAN as an efficient platform for carbon capture.

Porous solid adsorbents are a promising class of materials for carbon dioxide (CO 2 ) capture owing to their structural tunability, high surface area, and low regeneration energies. Amine-functionalized sorbents offer strong CO 2 affinity under humid and low-concentration conditions. However, grafting and impregnation often lead to amine loss and poor durability, and covalent polyamine incorporation typically requires complex multistep syntheses with limited scalability. Herein, we present a defect-driven polyamine growth strategy in zirconium-based metal−organic frameworks (MOFs) that enables uniform and dense polyamine incorporation. Selective linker-vacancy formation in tetracarboxylate-linker-based Zr-MOFs generates abundant coordinatively unsaturated Zr sites that initiate efficient in-pore polyamine polymerization while preserving framework stability. The resulting polyamine-rich MOFs display markedly enhanced low-pressure CO 2 adsorption, and the best-performing material exhibits a 1881-fold increase in uptake at 0.4 mbar compared to the pristine framework. This simple and broadly applicable approach provides a powerful route for constructing polyamine-functionalized MOFs for advanced applications in energy and environmental technologies.

Developing strategies that address both the plastic pollution crisis and climate change is increasingly urgent yet technically challenging. Porous materials are promising candidates for direct air capture (DAC) of CO 2, but their efficiency is severely impeded by coadsorption of atmospheric water, which incurs substantial energy penalties during regeneration. In this work, we demonstrate an effective and low-cost method for upcycling polystyrene (PS) into a robust hydrophobic shield on the surface of metal–organic framework (MOF) nanoparticles, thereby creating core–shell adsorbents (MOF@PS). This strategy dramatically enhances surface hydrophobicity, yielding water contact angles exceeding 125° (compared to 0° before encapsulation), and reduces water uptake by around 70% compared to pristine MOF. Notably, this hydrophobic gating does not impede CO 2 penetration and allows limited access of water vapor to the amine-functionalized core that facilitates amine-mediated chemisorption. The resulting material with amine loading exhibits an exceptional DAC breakthrough capacity of approximately 3.06 mmol g –1 under ambient air and maintains excellent stability over 10 cycles. This work provides innovative insights into the interconnection between PS upcycling, hydrophobic engineering, and DAC.

Living systems achieve precise control over macromolecular synthesis within the confined pockets of enzymes. Reproducing such spatial regulation in artificial systems remains a significant challenge in molecular engineering. Although artificial nanoconfinement has been explored to regulate polymerization, tunable and length-specific peptide growth has yet to be realized. Here, we present a highly stable metal–organic framework (MOF) as an artificial oligomerization platform that enables confined N -carboxyanhydride (NCA) ring-opening polymerization (ROP) with dynamically tunable short peptide growth. Reaction kinetics and NMR analyses reveal a confined oligomerization process within one-dimensional channels segmented by Zr 6 clusters. Compared with unconfined solution NCA polymerization showing nearly no chain-length selectivity in short-chain growth, these regularly repeating subcompartments provide defined reaction pockets that achieve pronounced chain-length selectivity and remarkably high peptide loading while maintaining framework integrity. The short peptide chain length can be dynamically tuned by monomer size and reaction kinetics, converting confinement from a template limitation into an active design principle. Moreover, pre-coordination of amino acids at Zr 6 clusters modifies the pocket microenvironment, accelerating NCA-ROP by over 30-fold. Selecting suitable monomers further enables the formation of A–(B) n sequence peptides. This work establishes a robust MOF-based platform inspired by natural biosynthetic machinery, advances understanding of confined oligomerization and polymerization, and provides a versatile platform for creating functional peptide–MOF materials with potential application in biomimetic catalysis.

Osteoarthritis (OA) is a multifactorial degenerative joint disease with increasing evidence implicating environmental pollutants as underrecognized contributors to its pathogenesis. This review EditedbyDr.CaterinaFaggiostematically synthesizes in vitro, animal, computational, and human epidemiological studies to elucidate the mechanistic and population-level effects of chemical exposures on OA. Airborne pollutants, including PM2.5, PM10, NO2, O3, and trihalomethanes, are associated with increased OA incidence, promoting cartilage degradation through oxidative stress, inflammatory cytokine overproduction, and epigenetic or developmental programming. Heavy metals such as cadmium, lead, arsenic, mercury, and copper induce reactive oxygen species (ROS), chondrocyte apoptosis, extracellular matrix (ECM) breakdown, and systemic inflammation, with both experimental and epidemiological studies demonstrating dose-dependent relationships. Persistent organic pollutants, including polychlorinated biphenyls (PCBs) and per-/polyfluoroalkyl substances (PFAS), disrupt autophagy, endocrine signaling, and cartilage homeostasis, with evidence of bioaccumulation in synovial fluid and modulation of gene expression relevant to bone-cartilage metabolism. Endocrine-disrupting chemicals, including phthalates, brominated flame retardants, and acetyl tributyl citrate, further exacerbate OA susceptibility via MAPK and NF-κB pathway activation, ROS generation, and ECM dysregulation. Epidemiological data consistently demonstrate associations between these exposures and OA prevalence, incidence, and symptom severity, often showing additive or synergistic effects for multiple pollutants. Despite these advances, research is limited by cross-sectional designs, high-dose experimental models, incomplete assessment of pollutant mixtures, and geographic and joint-specific biases. Future studies should prioritize longitudinal cohort designs, repeated biomonitoring, mechanistic exploration of mixture effects, and inclusion of emerging pollutants such as microplastics. Integrating environmental exposure assessment with advanced imaging, omics technologies, and computational modeling will enhance understanding of pollutant-induced OA mechanisms. Collectively, this evidence underscores the need for environmental interventions, public health strategies, and preventive approaches aimed at mitigating pollutant-driven joint degeneration, highlighting environmental exposures as a critical, yet modifiable, determinant of OA risk.

As an emerging class of porous supports, metal–organic frameworks (MOFs) can host multifarious guests to realize diverse applications. Among the guest-introducing approaches, the in situ encapsulation method is unique in its ability to incorporate a diverse range of guests, from small organic molecules and metal clusters to proteins and even more complicated guests. Previous investigations have focused on guests that are either neutral or negatively charged. The realization of the in situ encapsulation of cationic catenanes in MOFs under mild conditions, however, has rarely been investigated. Herein, we have accomplished in situ encapsulation of a cationic catenane (DA[2]C) within UiO-66-F 4 ─a MOF consisting of Zr 6 nodes and tetrafluoroterephthalic acid ligands─at room temperature using H 2 O as a green solvent. Theoretical calculations elaborated that tetrafluoroterephthalic acid ligands interact strongly with the cationic DA[2]C. This observation is a result of electrostatic interactions between carboxylate anions and DA[2]C cations as well as the attraction of electronegative F atoms in tetrafluoroterephthalic acid to the cations. As a proof-of-concept application, the DA[2]C·4Cl/UiO-66-F 4 composite demonstrated heterogeneous catalytic detoxification of 2-chloroethyl ethyl sulfide to the sulfoxide with a complete conversion rate (>99%) and high selectivity (>97%). This method could also be extended to other organic cationic molecules, including dibenzyl benzoimidazoloimidazole chloride and a pyrene-functionalized cyclobis(paraquat- p -phenylene), rendering it as a universal platform for constructing host–guest MOF systems with various applications.

Cytology screening has lower cervical precancer sensitivity than HPV DNA testing, which lacks specificity. To overcome this limitation, we assessed the diagnostic performance of E6/E7 mRNA, P16, and Ki-67, both alone and in combination, in detecting cervical intraepithelial neoplasia grade 2 or higher (CIN2+). A total of 403 cervical samples were collected from the First People's Hospital of Nanning between January 2019 and January 2024, and each biomarker was evaluated for its diagnostic accuracy. E6/E7 mRNA showed moderate performance, with 68.2% sensitivity and 61.8% specificity in detecting CIN2+ lesions. P16 exhibited superior performance, achieving 82.2% sensitivity and 90.1% specificity. Although Ki-67 showed the highest sensitivity at 95%, it had the lowest specificity at 27.2%. The combination of P16 and Ki-67 yielded the best diagnostic results, with 90% sensitivity and 79.8% specificity for CIN2+, representing a significant enhancement over individual biomarkers. These findings highlight the superior accuracy of P16, especially when combined with Ki-67, in detecting both CIN2+ and CIN3+ lesions. This approach improves high-risk lesion detection by reducing false negatives. Incorporating P16/Ki-67 biomarkers enhances screening sensitivity/specificity and clinical outcomes.

One of the hallmarks of multicomponent metal-organic frameworks (MOFs) is to finely tune their active centers to achieve product selectivity. In particular, obtaining bimetallic MOF hollow structures with precisely tailored redox centers under the same topology is still challenging despite a recent surge of such efforts. Herein, we present an engineering strategy named "cluster labilization" to generate hierarchically porous MOF composites with hollow structures and tunable active centers. By partially replacing zirconium with cerium in the hexanuclear clusters of UiO-66, unevenly distributed yolk-shell structures (YSS) were formed. Through acid treatment or annealing of the YSS precursor, single-shell hollow structures (SSHS) or double-shell hollow structures (DSHS) can be obtained, respectively. The active centers in SSHS and DSHS differ in their species, valence, and spatial locations. More importantly, YSS, SSHS, and DSHS with distinct active centers and microenvironments exhibit tunable catalytic activity, reversed selectivity, and high stability in the tandem reaction and the photoreaction.

High Resolution Image Download MS PowerPoint Slide A linker design strategy is developed to attain novel polynuclear rare-earth (RE) metal–organic frameworks (MOFs) with unprecedented topologies. We uncover the critical role of ortho-functionalized tricarboxylate ligands in directing the construction of highly connected RE MOFs. The acidity and conformation of the tricarboxylate linkers were altered by substituting with diverse functional groups at the ortho position of the carboxyl groups. For instance, the acidity difference between carboxylate moieties resulted in forming three hexanuclear RE MOFs with novel (3,3,3,10,10)-c wxl, (3,12)-c gmx, and (3,3,3,12)-c joe topologies, respectively. In addition, when a bulky methyl group was introduced, the incompatibility between the net topology and ligand conformation guided the co-appearance of hexanuclear and tetranuclear clusters, generating a novel 3-periodic MOF with a (3,3,8,10)-c kyw net. Interestingly, a fluoro-functionalized linker prompted the formation of two unusual trinuclear clusters and produced a MOF with a fascinating (3,8,10)-c lfg topology, which could be gradually replaced by a more stable tetranuclear MOF with a new (3,12)-c lee topology with extended reaction time. This work enriches the polynuclear clusters library of RE MOFs and unveils new opportunities to construct MOFs with unprecedented structural complexity and vast application potential.

Stable metal–organic frameworks (MOFs) with mesopores (2–50 nm) are promising platforms for immobilizing nanosized functional compounds, such as metal-oxo clusters, metal-sulfide quantum dots, and coordination complexes. However, these species easily decompose under acidic conditions or high temperatures, hindering their in situ encapsulation in stable MOFs, which are usually synthesized under harsh conditions involving excess acid modulators and high temperatures. Herein, we report a route for the room-temperature and acid-modulator-free synthesis of stable mesoporous MOFs and MOF catalysts with acid-sensitive species encapsulated: (1) we initially construct a MOF template by connecting stable Zr 6 clusters with labile Cu-bipyridyl moieties; (2) Cu-bipyridyl moieties are subsequently exchanged by organic linkers to afford a stable version of Zr-MOFs; (3) acid-sensitive species, including polyoxometalates (POMs), CdSeS/ZnS quantum dots, and Cu-coordination cages, can be encapsulated in situ into the MOFs during step 1. The room-temperature synthesis allows the isolation of mesoporous MOFs with 8-connected Zr 6 clusters and reo topology as kinetic products, which are inaccessible by traditional solvothermal synthesis. Furthermore, acid-sensitive species remain stable, active, and locked within the frameworks during MOF synthesis. We observed high catalytic activity for VX degradation by the POM@Zr-MOF catalysts as a result of the synergy between redox-active POMs and Lewis-acidic Zr sites. The dynamic bond-directed method will accelerate the discovery of large-pore stable MOFs and offer a mild route to avoid the decomposition of catalysts during MOF synthesis.

High Resolution Image Download MS PowerPoint Slide While trinuclear [Fe x M 3– x (μ 3 -O)] cluster-based metal–organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [Fe x M 3– x (μ 3 -O)]-based MOFs (PCN-250, M = Ni 2+, Co 2+, Zn 2+, Mg 2+ ) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe 3+ sites was observed along with the transformation of Fe 3+ coordination geometries from octahedron to square pyramid. Furthermore, the effect of divalent metals in heterometallic PCN-250 was studied for the purpose of reducing the activation temperature and increasing the number of open metal sites. The metal site structures were corroborated by X-ray absorption and infrared spectroscopy. These results will not only guide the pretreatment of [Fe x M 3– x (μ 3 -O)]-based MOFs but also corroborate spectral and computational studies on these materials.

Abstract Rotaxanes with well‐defined ring sequences are attractive synthetic goals in the construction of functional materials associated with molecular shuttles and switches, molecular electronics, and information storage. Sequence‐controlled synthesis of oligo‐ and polyrotaxanes is important in the context of the development of both sequence‐defined polymers and dynamic functional materials. To date, examples of sequence‐controlled rotaxanes are limited to oligorotaxanes on account of the synthetic challenges they pose. This Review sheds light on the pivotal role that sequence isomerism plays in rotaxanes. Synthetic approaches, including orthogonal templation, active‐metal templation, self‐sorting and snapping, cooperative‐capturing, ring‐through‐ring‐shuttling, and molecular pumping, for the construction of sequence‐controlled rotaxanes are all discussed in this Review. By comparing the advantages and disadvantages of these different approaches, several possible synthetic strategies are proposed in an attempt to foretell the future of sequence‐controlled synthesis of polyrotaxanes.