Coastal phytoplankton blooms expand and intensify in the 21st century.

Phytoplankton blooms in coastal oceans can be beneficial to coastal fisheries production and ecosystem function, but can also cause major environmental problems1,2-yet detailed characterizations of bloom incidence and distribution are not available worldwide. Here we map daily marine coastal algal blooms between 2003 and 2020 using global satellite observations at 1-km spatial resolution. We found that algal blooms occurred in 126 out of the 153 coastal countries examined. Globally, the spatial extent (+13.2%) and frequency (+59.2%) of blooms increased significantly (P < 0.05) over the study period, whereas blooms weakened in tropical and subtropical areas of the Northern Hemisphere. We documented the relationship between the bloom trends and ocean circulation, and identified the stimulatory effects of recent increases in sea surface temperature. Our compilation of daily mapped coastal phytoplankton blooms provides the basis for global assessments of bloom risks and benefits, and for the formulation or evaluation of management or policy actions.

Emergent charge order in pressurized kagome superconductor CsV3Sb5.

The discovery of several electronic orders in kagome superconductors AV3Sb5 (A means K, Rb, Cs) provides a promising platform for exploring unprecedented emergent physics1-9. Under moderate pressure (<2.2 GPa), the triple-Q charge density wave (CDW) order is monotonically suppressed by pressure, while the superconductivity shows a two-dome-like behaviour, suggesting an unusual interplay between superconductivity and CDW order10,11. Given that time-reversal symmetry breaking and electronic nematicity have been revealed inside the triple-Q CDW phase8,9,12,13, understanding this CDW order and its interplay with superconductivity becomes one of the core questions in AV3Sb5 (refs. 3,5,6). Here, we report the evolution of CDW and superconductivity with pressure in CsV3Sb5 by 51V nuclear magnetic resonance measurements. An emergent CDW phase, ascribed to a possible stripe-like CDW order with a unidirectional 4a0 modulation, is observed between Pc1 ≅ 0.58 GPa and Pc2 ≅ 2.0 GPa, which explains the two-dome-like superconducting behaviour under pressure. Furthermore, the nuclear spin-lattice relaxation measurement reveals evidence for pressure-independent charge fluctuations above the CDW transition temperature and unconventional superconducting pairing above Pc2. Our results not only shed new light on the interplay of superconductivity and CDW, but also reveal new electronic correlation effects in kagome superconductors AV3Sb5.

Charge-density-wave-driven electronic nematicity in a kagome superconductor.

Electronic nematicity, in which rotational symmetry is spontaneously broken by electronic degrees of freedom, has been demonstrated as a ubiquitous phenomenon in correlated quantum fluids including high-temperature superconductors and quantum Hall systems1,2. Notably, the electronic nematicity in high-temperature superconductors exhibits an intriguing entanglement with superconductivity, generating complicated superconducting pairing and intertwined electronic orders. Recently, an unusual competition between superconductivity and a charge-density-wave (CDW) order has been found in the AV3Sb5 (A = K, Rb, Cs) family with two-dimensional vanadium kagome nets3-8. Whether these phenomena involve electronic nematicity is still unknown. Here we report evidence for the existence of electronic nematicity in CsV3Sb5, using a combination of elastoresistance measurements, nuclear magnetic resonance (NMR) and scanning tunnelling microscopy/spectroscopy (STM/S). The temperature-dependent elastoresistance coefficient (m11 minus m12) and NMR spectra demonstrate that, besides a C2 structural distortion of the 2a0 × 2a0 supercell owing to out-of-plane modulation, considerable nematic fluctuations emerge immediately below the CDW transition (approximately 94 kelvin) and finally a nematic transition occurs below about 35 kelvin. The STM experiment directly visualizes the C2-structure-pinned long-range nematic order below the nematic transition temperature, suggesting a novel nematicity described by a three-state Potts model. Our findings indicate an intrinsic electronic nematicity in the normal state of CsV3Sb5, which sets a new paradigm for revealing the role of electronic nematicity on pairing mechanism in unconventional superconductors.

A UPR-Induced Soluble ER-Phagy Receptor Acts with VAPs to Confer ER Stress Resistance.

Autophagic degradation of the endoplasmic reticulum (ER-phagy) is triggered by ER stress in diverse organisms. However, molecular mechanisms governing ER stress-induced ER-phagy remain insufficiently understood. Here we report that ER stress-induced ER-phagy in the fission yeast Schizosaccharomyces pombe requires Epr1, a soluble Atg8-interacting ER-phagy receptor. Epr1 localizes to the ER through interacting with integral ER membrane proteins VAPs. Bridging an Atg8-VAP association is the main ER-phagy role of Epr1, as it can be bypassed by an artificial Atg8-VAP tether. VAPs contribute to ER-phagy not only by tethering Atg8 to the ER membrane, but also by maintaining the ER-plasma membrane contact. Epr1 is upregulated during ER stress by the unfolded protein response (UPR) regulator Ire1. Loss of Epr1 reduces survival against ER stress. Conversely, increasing Epr1 expression suppresses the ER-phagy defect and ER stress sensitivity of cells lacking Ire1. Our findings expand and deepen the molecular understanding of ER-phagy.

In situ formation of ZnOx species for efficient propane dehydrogenation.

Propane dehydrogenation (PDH) to propene is an important alternative to oil-based cracking processes, to produce this industrially important platform chemical1,2. The commercial PDH technologies utilizing Cr-containing (refs. 3,4) or Pt-containing (refs. 5-8) catalysts suffer from the toxicity of Cr(VI) compounds or the need to use ecologically harmful chlorine for catalyst regeneration9. Here, we introduce a method for preparation of environmentally compatible supported catalysts based on commercial ZnO. This metal oxide and a support (zeolite or common metal oxide) are used as a physical mixture or in the form of two layers with ZnO as the upstream layer. Supported ZnOx species are in situ formed through a reaction of support OH groups with Zn atoms generated from ZnO upon reductive treatment above 550 °C. Using different complementary characterization methods, we identify the decisive role of defective OH groups for the formation of active ZnOx species. For benchmarking purposes, the developed ZnO-silicalite-1 and an analogue of commercial K-CrOx/Al2O3 were tested in the same setup under industrially relevant conditions at close propane conversion over about 400 h on propane stream. The developed catalyst reveals about three times higher propene productivity at similar propene selectivity.

PTEN Suppresses Glycolysis by Dephosphorylating and Inhibiting Autophosphorylated PGK1.

The PTEN tumor suppressor is frequently mutated or deleted in cancer and regulates glucose metabolism through the PI3K-AKT pathway. However, whether PTEN directly regulates glycolysis in tumor cells is unclear. We demonstrate here that PTEN directly interacts with phosphoglycerate kinase 1 (PGK1). PGK1 functions not only as a glycolytic enzyme but also as a protein kinase intermolecularly autophosphorylating itself at Y324 for activation. The protein phosphatase activity of PTEN dephosphorylates and inhibits autophosphorylated PGK1, thereby inhibiting glycolysis, ATP production, and brain tumor cell proliferation. In addition, knockin expression of a PGK1 Y324F mutant inhibits brain tumor formation. Analyses of human glioblastoma specimens reveals that PGK1 Y324 phosphorylation levels inversely correlate with PTEN expression status and are positively associated with poor prognosis in glioblastoma patients. This work highlights the instrumental role of PGK1 autophosphorylation in its activation and PTEN protein phosphatase activity in governing glycolysis and tumorigenesis.

Subtyping and prognostic model construction based on vesicle-mediated transport-related genes in colorectal cancer.

BACKGROUND: Colorectal cancer (CRC) is impacted by various environmental and genetic variables. Dysregulation of vesicle-mediated transport-related genes (VMTRGs) has been observed in many malignancies, but their effect on prognosis in CRC remains unclear. METHODS: CRC samples were clustered into varying subtypes per differential expression of VMTRGs. R package was utilized to explore differences in survival, immune, and drug sensitivity among different disease subtypes. According to differentially expressed genes (DEGs) between subtypes, regression analysis was employed to build a riskscore model and identify independent prognostic factors. The model was validated through a Gene Expression Omnibus (GEO) dataset. Immune landscape, immunophenoscore (IPS), and Tumor Immune Dysfunction and Exclusion (TIDE) scores for different risk groups were calculated. RESULTS: Two subtypes of CRC were identified based on VMTRGs, which showed significant differences in survival rates, immune cell infiltration abundance, immune functional activation levels, and immune checkpoint expression levels. Cluster2 exhibited higher sensitivity to anti-tumor drugs such as Nilotinib, Cisplatin, and Oxaliplatin compared to Cluster1. DEGs were mainly enriched in biological processes such as epidermis development, epidermal cell differentiation, and receptor-ligand activity, and signaling pathways like pancreatic secretion. The constructed 13-gene riskscore model demonstrated good predictive ability for CRC patients' prognosis. Furthermore, differences in immune landscape, IPS, and TIDE scores were observed among different risk groups. CONCLUSION: This study successfully obtained two CRC subtypes with distinct survival statuses and immune levels based on differential expression of VMTRGs. A 13-gene risk model was constructed. The findings had important implications for prognosis and treatment of CRC.

Vorasidenib in IDH1- or IDH2-Mutant Low-Grade Glioma.

BACKGROUND: Isocitrate dehydrogenase (IDH)-mutant grade 2 gliomas are malignant brain tumors that cause considerable disability and premature death. Vorasidenib, an oral brain-penetrant inhibitor of mutant IDH1 and IDH2 enzymes, showed preliminary activity in IDH-mutant gliomas. METHODS: In a double-blind, phase 3 trial, we randomly assigned patients with residual or recurrent grade 2 IDH-mutant glioma who had undergone no previous treatment other than surgery to receive either oral vorasidenib (40 mg once daily) or matched placebo in 28-day cycles. The primary end point was imaging-based progression-free survival according to blinded assessment by an independent review committee. The key secondary end point was the time to the next anticancer intervention. Crossover to vorasidenib from placebo was permitted on confirmation of imaging-based disease progression. Safety was also assessed. RESULTS: A total of 331 patients were assigned to receive vorasidenib (168 patients) or placebo (163 patients). At a median follow-up of 14.2 months, 226 patients (68.3%) were continuing to receive vorasidenib or placebo. Progression-free survival was significantly improved in the vorasidenib group as compared with the placebo group (median progression-free survival, 27.7 months vs. 11.1 months; hazard ratio for disease progression or death, 0.39; 95% confidence interval [CI], 0.27 to 0.56; P<0.001). The time to the next intervention was significantly improved in the vorasidenib group as compared with the placebo group (hazard ratio, 0.26; 95% CI, 0.15 to 0.43; P<0.001). Adverse events of grade 3 or higher occurred in 22.8% of the patients who received vorasidenib and in 13.5% of those who received placebo. An increased alanine aminotransferase level of grade 3 or higher occurred in 9.6% of the patients who received vorasidenib and in no patients who received placebo. CONCLUSIONS: In patients with grade 2 IDH-mutant glioma, vorasidenib significantly improved progression-free survival and delayed the time to the next intervention. (Funded by Servier; INDIGO ClinicalTrials.gov number, NCT04164901.).

Monocytes Release Pro-Cathepsin D to Drive Blood-to-Brain Transcytosis in Diabetes.

BACKGROUND: Microvascular complications are the major outcome of type 2 diabetes progression, and the underlying mechanism remains to be determined. METHODS: High-throughput RNA sequencing was performed using human monocyte samples from controls and diabetes. The transgenic mice expressing human CTSD (cathepsin D) in the monocytes was constructed using CD68 promoter. In vivo 2-photon imaging, behavioral tests, immunofluorescence, transmission electron microscopy, Western blot analysis, vascular leakage assay, and single-cell RNA sequencing were performed to clarify the phenotype and elucidate the molecular mechanism. RESULTS: Monocytes expressed high-level CTSD in patients with type 2 diabetes. The transgenic mice expressing human CTSD in the monocytes showed increased brain microvascular permeability resembling the diabetic microvascular phenotype, accompanied by cognitive deficit. Mechanistically, the monocytes release nonenzymatic pro-CTSD to upregulate caveolin expression in brain endothelium triggering caveolae-mediated transcytosis, without affecting the paracellular route of brain microvasculature. The circulating pro-CTSD activated the caveolae-mediated transcytosis in brain endothelial cells via its binding with low-density LRP1 (lipoprotein receptor-related protein 1). Importantly, genetic ablation of CTSD in the monocytes exhibited a protective effect against the diabetes-enhanced brain microvascular transcytosis and the diabetes-induced cognitive impairment. CONCLUSIONS: These findings uncover the novel role of circulatory pro-CTSD from monocytes in the pathogenesis of cerebral microvascular lesions in diabetes. The circulatory pro-CTSD is a potential target for the intervention of microvascular complications in diabetes.

Insertion of CO2 in metal ion-doped two-dimensional covalent organic frameworks.

Carbon capture is one of the essential low-carbon technologies required to achieve societal climate goals at the lowest cost. Covalent organic frameworks (COFs) are promising adsorbents for CO2 capture because of their well-defined porosity, large surface area, and high stability. Current COF-based CO2 capture is mainly based on a physisorption mechanism, exhibiting smooth and reversible sorption isotherms. In the present study, we report unusual CO2 sorption isotherms featuring one or more tunable hysteresis steps with metal ion (Fe3+, Cr3+, or In3+)-doped Schiff-base two-dimensional (2D) COFs (Py-1P, Py-TT, and Py-Py) as adsorbents. Synchrotron X-ray diffraction, spectroscopic and computational studies indicate that the sharp adsorption steps in the isotherm originate from the insertion of CO2 between the metal ion and the N atom of the imine bond on the inner pore surface of the COFs as the CO2 pressure reaches threshold values. As a result, the CO2 adsorption capacity of the ion-doped Py-1P COF is increased by 89.5% compared with that of the undoped Py-1P COF. This CO2 sorption mechanism provides an efficient and straightforward approach to enhancing the CO2 capture capacity of COF-based adsorbents, yielding insights into developing chemistry for CO2 capture and conversion.

Recognition of histone acetylation by the GAS41 YEATS domain promotes H2A.Z deposition in non-small cell lung cancer.

Histone acetylation is associated with active transcription in eukaryotic cells. It helps to open up the chromatin by neutralizing the positive charge of histone lysine residues and providing binding platforms for "reader" proteins. The bromodomain (BRD) has long been thought to be the sole protein module that recognizes acetylated histones. Recently, we identified the YEATS domain of AF9 (ALL1 fused gene from chromosome 9) as a novel acetyl-lysine-binding module and showed that the ENL (eleven-nineteen leukemia) YEATS domain is an essential acetyl-histone reader in acute myeloid leukemias. The human genome encodes four YEATS domain proteins, including GAS41, a component of chromatin remodelers responsible for H2A.Z deposition onto chromatin; however, the importance of the GAS41 YEATS domain in human cancer remains largely unknown. Here we report that GAS41 is frequently amplified in human non-small cell lung cancer (NSCLC) and is required for cancer cell proliferation, survival, and transformation. Biochemical and crystal structural studies demonstrate that GAS41 binds to histone H3 acetylated on H3K27 and H3K14, a specificity that is distinct from that of AF9 or ENL. ChIP-seq (chromatin immunoprecipitation [ChIP] followed by high-throughput sequencing) analyses in lung cancer cells reveal that GAS41 colocalizes with H3K27ac and H3K14ac on the promoters of actively transcribed genes. Depletion of GAS41 or disruption of the interaction between its YEATS domain and acetylated histones impairs the association of histone variant H2A.Z with chromatin and consequently suppresses cancer cell growth and survival both in vitro and in vivo. Overall, our study identifies GAS41 as a histone acetylation reader that promotes histone H2A.Z deposition in NSCLC.

Improving comparative analyses of Hi-C data via contrastive self-supervised learning.

Hi-C is a widely applied chromosome conformation capture (3C)-based technique, which has produced a large number of genomic contact maps with high sequencing depths for a wide range of cell types, enabling comprehensive analyses of the relationships between biological functionalities (e.g. gene regulation and expression) and the three-dimensional genome structure. Comparative analyses play significant roles in Hi-C data studies, which are designed to make comparisons between Hi-C contact maps, thus evaluating the consistency of replicate Hi-C experiments (i.e. reproducibility measurement) and detecting statistically differential interacting regions with biological significance (i.e. differential chromatin interaction detection). However, due to the complex and hierarchical nature of Hi-C contact maps, it remains challenging to conduct systematic and reliable comparative analyses of Hi-C data. Here, we proposed sslHiC, a contrastive self-supervised representation learning framework, for precisely modeling the multi-level features of chromosome conformation and automatically producing informative feature embeddings for genomic loci and their interactions to facilitate comparative analyses of Hi-C contact maps. Comprehensive computational experiments on both simulated and real datasets demonstrated that our method consistently outperformed the state-of-the-art baseline methods in providing reliable measurements of reproducibility and detecting differential interactions with biological meanings.

Well-Defined Supported ZnOx Species: Synthesis, Structure, and Catalytic Performance in Nonoxidative Dehydrogenation of C3-C4 Alkanes.

ConspectusZinc oxide (ZnO) is a multipurpose material and finds its applications in various fields such as rubber manufacturing, medicine, food additives, electronics, etc. It has also been intensively studied in photocatalysis due to its wide band gap and environmental compatibility. Recently, heterogeneous catalysts with supported ZnOx species have attracted more and more attention for the dehydrogenation of propane (PDH) and isobutane (iBDH) present in shale/natural gas. The olefins formed in these reactions are key building blocks of the chemical industry. These reactions are also of academic importance for understanding the fundamentals of the selective activation of C-H bonds. Differently structured ZnOx species supported on zeolites, SiO2, and Al2O3 have been reported to be active for nonoxidative dehydrogenation reactions. However, the structure-activity-selectivity relationships for these catalysts remain elusive. The main difficulty stems from the preparation of catalysts containing only one kind of well-defined ZnOx species.In this Account, we describe the studies on PDH and iBDH over differently structured ZnOx species and highlight our approaches to develop catalysts with controllable ZnOx speciation relevant to their performance. Several methods, including (i) the in situ reaction of gas-phase metallic Zn atoms with OH groups on the surface of supports, (ii) one-pot hydrothermal synthesis, and (iii) impregnation/anchoring methods, have been developed/used for the tailored preparation of supported ZnOx species. The first method allows precise control of the molecular structure of ZnOx through the nature of the defective OH groups on the supports. Using this method, a series of ZnOx species ranging from isolated, binuclear to nanosized ZnOx have been successfully generated on different SiO2-based or ZrO2-based supports as demonstrated by complementary ex/in situ characterization techniques. Based on kinetic studies and detailed characterization results, the intrinsic activity (Zn-related turnover frequency) of ZnOx was found to depend on its speciation. It increases with an increasing number of Zn atoms in a ZnmOn cluster from 1 to a few atoms (less than 10) and then decreases strongly for ZnOx nanoparticles. The latter promote the formation of undesired C1-C2 hydrocarbons and coke, resulting in lower propene selectivity in comparison with the catalysts containing only ZnOx species ranging from isolated to subnanometer ZnmOn clusters. In addition, the strategy for improving the thermal stability of ZnOx species and the consequences of mass-transport limitations for DH reactions were also elucidated. The results obtained allowed us to establish the fundamentals for the targeted preparation of well-structured ZnOx species and the relationships between their structures and the DH performance. This knowledge may inspire further studies in the field of C-H bond activation and other reactions, in which ZnOx species act as catalytically active sites or promoters, such as the dehydroaromatization of light alkanes and the hydrogenation of CO2 to methanol.

A probabilistic knowledge graph for target identification.

Early identification of safe and efficacious disease targets is crucial to alleviating the tremendous cost of drug discovery projects. However, existing experimental methods for identifying new targets are generally labor-intensive and failure-prone. On the other hand, computational approaches, especially machine learning-based frameworks, have shown remarkable application potential in drug discovery. In this work, we propose Progeni, a novel machine learning-based framework for target identification. In addition to fully exploiting the known heterogeneous biological networks from various sources, Progeni integrates literature evidence about the relations between biological entities to construct a probabilistic knowledge graph. Graph neural networks are then employed in Progeni to learn the feature embeddings of biological entities to facilitate the identification of biologically relevant target candidates. A comprehensive evaluation of Progeni demonstrated its superior predictive power over the baseline methods on the target identification task. In addition, our extensive tests showed that Progeni exhibited high robustness to the negative effect of exposure bias, a common phenomenon in recommendation systems, and effectively identified new targets that can be strongly supported by the literature. Moreover, our wet lab experiments successfully validated the biological significance of the top target candidates predicted by Progeni for melanoma and colorectal cancer. All these results suggested that Progeni can identify biologically effective targets and thus provide a powerful and useful tool for advancing the drug discovery process.

Walking is like slithering: A unifying, data-driven view of locomotion.

Legged movement is ubiquitous in nature and of increasing interest for robotics. Most legged animals routinely encounter foot slipping, yet detailed modeling of multiple contacts with slipping exceeds current simulation capacity. Here we present a principle that unifies multilegged walking (including that involving slipping) with slithering and Stokesian (low Reynolds number) swimming. We generated data-driven principally kinematic models of locomotion for walking in low-slip animals (Argentine ant, 4.7% slip ratio of slipping to total motion) and for high-slip robotic systems (BigANT hexapod, slip ratio 12 to 22%; Multipod robots ranging from 6 to 12 legs, slip ratio 40 to 100%). We found that principally kinematic models could explain much of the variability in body velocity and turning rate using body shape and could predict walking behaviors outside the training data. Most remarkably, walking was principally kinematic irrespective of leg number, foot slipping, and turning rate. We find that grounded walking, with or without slipping, is governed by principally kinematic equations of motion, functionally similar to frictional swimming and slithering. Geometric mechanics thus leads to a unified model for swimming, slithering, and walking. Such commonality may shed light on the evolutionary origins of animal locomotion control and offer new approaches for robotic locomotion and motion planning.

The development of catalysts and auxiliaries for the synthesis of covalent organic frameworks.

Covalent organic frameworks (COFs) have recently seen significant advancements. Large quantities of structurally & functionally oriented COFs with a wide range of applications, such as gas adsorption, catalysis, separation, and drug delivery, have been explored. Recent achievements in this field are primarily focused on advancing synthetic methodologies, with catalysts playing a crucial role in achieving highly crystalline COF materials, particularly those featuring novel linkages and chemistry. A series of reviews have already been published over the last decade, covering the fundamentals, synthesis, and applications of COFs. However, despite the pivotal role that catalysts and auxiliaries play in forming COF materials and adjusting their properties (e.g., crystallinity, porosity, stability, and morphology), limited attention has been devoted to these essential components. In this Critical Review, we mainly focus on the state-of-the-art progress of catalysts and auxiliaries applied to the synthesis of COFs. The catalysts include four categories: acid catalysts, base catalysts, transition-metal catalysts, and other catalysts. The auxiliaries, such as modulators, oxygen, and surfactants, are discussed as well. This is then followed by the description of several specific applications derived from the utilization of catalysts and auxiliaries. Lastly, a perspective on the major challenges and opportunities associated with catalysts and auxiliaries is provided.

Regulating Benzene Ring Number as Connector in Covalent Organic Framework for Boosting Photosynthesis of H2O2 from Seawater.

Photosynthesis of H2O2 from seawater represents a promising pathway to acquire H2O2, but it is still restricted by the lack of a highly active photocatalyst. In this work, we propose a convenient strategy of regulating the number of benzene rings to boost the catalytic activity of materials. This is demonstrated by ECUT-COF-31 with adding two benzene rings as the connector, which can result in 1.7-fold enhancement in the H2O2 production rate relative to ECUT-COF-30 with just one benzene ring as the connector. The reason for enhancement is mainly due to the release of *OOH from the surface of catalyst and the final formation of H2O2 being easier in ECUT-COF-31 than in ECUT-COF-30. Moreover, ECUT-COF-31 provides a stable photogeneration of H2O2 for 70 h, and a theoretically remarkable H2O2 production of 58.7 mmol per day from seawater using one gram of photocatalyst, while the cost of the used raw material is as low as 0.24 $/g.

Robust Homochiral Polycrystalline Metal-Organic Framework Membranes for High-Performance Enantioselective Separation.

Homochiral MOF membranes offer a promising route to efficient chiral separation, but their fabrication remains challenging. Here, we report for the first time the design and preparation of homochiral polycrystalline MOF-808 membranes for the first time. The membrane exhibits a high integrity and thin membrane thickness. Achieving homochirality through chiral amino acid postsynthetic modification, MOF-808 membranes demonstrate remarkable solvent stability. Notably, they successfully separated racemic naproxen enantiomers, achieving enantiomeric excess (ee) values of up to ∼95.0%. This work paves the way for turning achiral polycrystalline MOF membranes into high-performance chiral membranes for enantioselective separation.

CO2-Based Stable Porous Metal-Organic Frameworks for CO2 Utilization.

The transformation of carbon dioxide (CO2) into functional materials has garnered considerable worldwide interest. Metal-organic frameworks (MOFs), as a distinctive class of materials, have made great contributions to CO2 capture and conversion. However, facile conversion of CO2 to stable porous MOFs for CO2 utilization remains unexplored. Herein, we present a facile methodology of using CO2 to synthesize stable zirconium-based MOFs. Two zirconium-based MOFs CO2-Zr-DEP and CO2-Zr-DEDP with face-centered cubic topology were obtained via a sequential desilylation-carboxylation-coordination reaction. The MOFs exhibit excellent crystallinity, as verified through powder X-ray diffraction and high-resolution transmission electron microscopy analyses. They also have notable porosity with high surface area (SBET up to 3688 m2 g-1) and good CO2 adsorption capacity (up to 12.5 wt %). The resulting MOFs have abundant alkyne functional moieties, confirmed through 13C cross-polarization/magic angle spinning nuclear magnetic resonance and Fourier transform infrared spectra. Leveraging the catalytic prowess of Ag(I) in diverse CO2-involved reactions, we incorporated Ag(I) into zirconium-based MOFs, capitalizing on their interactions with carbon-carbon π-bonds of alkynes, thereby forming a heterogeneous catalyst. This catalyst demonstrates outstanding efficiency in catalyzing the conversion of CO2 and propargylic alcohols into cyclic carbonates, achieving >99% yield at room temperature and atmospheric pressure conditions. Thus, this work provides a dual CO2 utilization strategy, encompassing the synthesis of CO2-based MOFs (20-24 wt % from CO2) and their subsequent application in CO2 capture and conversion processes. This approach significantly enhances overall CO2 utilization.

Highly Efficient and Scalable p-i-n Perovskite Solar Cells Enabled by Poly-metallocene Interfaces.

Inverted p-i-n perovskite solar cells (PSCs) are easy to process but need improved interface characteristics with reduced energy loss to prevent efficiency drops when increasing the active photovoltaic area. Here, we report a series of poly ferrocenyl molecules that can modulate the perovskite surface enabling the construction of small- and large-area PSCs. We found that the perovskite-ferrocenyl interaction forms a hybrid complex with enhanced surface coordination strength and activated electronic states, leading to lower interfacial nonradiative recombination and charge transport resistance losses. The resulting PSCs achieve an enhanced efficiency of up to 26.08% for small-area devices and 24.51% for large-area devices (1.0208 cm2). Moreover, the large-area PSCs maintain >92% of the initial efficiency after 2000 h of continuous operation at the maximum power point under 1-sun illumination and 65 °C.