Revolutionizing the structural design and determination of covalent-organic frameworks: principles, methods, and techniques.

Covalent organic frameworks (COFs) represent an important class of crystalline porous materials with designable structures and functions. The interconnected organic monomers, featuring pre-designed symmetries and connectivities, dictate the structures of COFs, endowing them with high thermal and chemical stability, large surface area, and tunable micropores. Furthermore, by utilizing pre-functionalization or post-synthetic functionalization strategies, COFs can acquire multifunctionalities, leading to their versatile applications in gas separation/storage, catalysis, and optoelectronic devices. Our review provides a comprehensive account of the latest advancements in the principles, methods, and techniques for structural design and determination of COFs. These cutting-edge approaches enable the rational design and precise elucidation of COF structures, addressing fundamental physicochemical challenges associated with host-guest interactions, topological transformations, network interpenetration, and defect-mediated catalysis.

Three-Dimensional Crystalline Organic Framework Stabilized by Molecular Mortise-and-Tenon Jointing.

Three-dimensional (3D) crystalline organic frameworks with complex topologies, high surface area, and low densities afford a variety of application prospects. However, the design and construction of these frameworks have been largely limited to systems containing polyhedron-shaped building blocks or those relying on component interpenetration. Here, we report the synthesis of a 3D crystalline organic framework based on molecular mortise-and-tenon jointing. This new material takes advantage of tetra(4-pyridylphenyl)ethylene and chlorinated bis(benzodioxaborole)benzene as building blocks and is driven by dative B-N bonds. A single-crystal X-ray diffraction analysis of the framework reveals the presence of two-dimensional (2D) layers with helical channels that are formed presumably during the boron-nitrogen coordination process. The protrusion of dichlorobenzene units from the upper and lower surfaces of the 2D layers facilitates the key mortise-and-tenon connections. These connections enable the interlocking of adjacent layers and the stabilization of an overall 3D framework. The resulting framework is endowed with high porosity and attractive mechanical properties, rendering it potentially suitable for the removal of impurities from acetylene.

Self-Interface in Rh Nanosheets-Supported Tetrahedral Rh Nanocrystals for Promoting Electrocatalytic Oxidation of Ethanol.

Direct ethanol fuel cells hold great promise as a power source. However, their commercialization is limited by anode catalysts with insufficient selectivity toward a complete oxidation of ethanol for a high energy density, as well as sluggish catalytic kinetics and low stability. To optimize the catalytic performance, rationally tuning surface structure or interface structure is highly desired. Herein, a facile route is reported to the synthesis of Rh nanosheets-supported tetrahedral Rh nanocrystals (Rh THs/NSs), which possess self-supporting homogeneous interface between Rh tetrahedrons and Rh nanosheets. Due to full leverage of the structural advantages within the given structure and construction of interfaces, the Rh THs/NSs can serve as highly active electro-catalysts with excellent mass activity and selectivity toward ethanol electro-oxidation. The in situ Fourier transform infrared reflection spectroscopy showed the Rh THs/NSs exhibit the highest C1 pathway selectivity of 23.2%, far exceeding that of Rh nanotetrahedra and Rh nanosheets. Density function theory calculations further demonstrated that self-interface between Rh nanosheets and tetrahedra is beneficial for C-C bond cleavage of ethanol. Meanwhile, the self-supporting of 2D nanosheets greatly enhance the stability of tetrahedra, which improves the catalytic stability.

Immune cell receptor-specific nanoparticles as a potent adjuvant for nasal split influenza vaccine delivery.

Mucosal delivery systems have gained much attention as effective way for antigen delivery that induces both systemic and mucosal immunity. However, mucosal vaccination faces the challenges of mucus barrier and effective antigen uptake and presentation. In particular, split, subunit and recombinant protein vaccines that do not have an intact pathogen structure lack the efficiency to stimulate mucosal immunity. In this study, poly (lactic acid-co-glycolic acid-polyethylene glycol) (PLGA-PEG) block copolymers were modified by mannose to form a PLGA-PEG-Man conjugate (mannose modified PLGA-PEG), which were characterized. The novel nanoparticles (NPs) prepared with this material had a particle size of about 150 nm and a zeta potential of -15 mV, and possessed ideal mucus permeability, immune cell targeting, stability and low toxicity. Finally, PLGA-PEG-Man nanoparticles (PLGA-PEG-Man NPs) were successfully applied for intranasal delivery of split influenza vaccine in rat for the first time, which triggered strong systemic and mucosal immune responses. These studies suggest that PLGA-PEG-Man NPs could function as competitive potential nano-adjuvants to address the challenge of inefficient mucosal delivery of non-allopathogenic antigens.

Unraveling the Mechanistic Origin of High N2 Selectivity in Ammonia Selective Catalytic Oxidation on CuO-Based Catalyst.

NH3 emissions from industrial sources and possibly future energy production constitute a threat to human health because of their toxicity and participation in PM2.5 formation. Ammonia selective catalytic oxidation to N2 (NH3-SCO) is a promising route for NH3 emission control, but the mechanistic origin of achieving high N2 selectivity remains elusive. Here we constructed a highly N2-selective CuO/TiO2 catalyst and proposed a CuOx dimer active site based on the observation of a quadratic dependence of NH3-SCO reaction rate on CuOx loading, ac-STEM, and ab initio thermodynamic analysis. Combining this with the identification of a critical N2H4 intermediate by in situ DRIFTS characterization, a comprehensive N2H4-mediated reaction pathway was proposed by DFT calculations. The high N2 selectivity originated from the preference for NH2 coupling to generate N2H4 over NH2 dehydrogenation on the CuOx dimer active site. This work could pave the way for the rational design of efficient NH3-SCO catalysts.

Construction of Benzoxazine-linked One-Dimensional Covalent Organic Frameworks Using the Mannich Reaction.

Covalent polymerization of organic molecules into crystalline one-dimensional (1D) polymers is effective for achieving desired thermal, optical, and electrical properties, yet it remains a persistent synthetic challenge for their inherent tendency to adopt amorphous or semicrystalline phases. Here we report a strategy to synthesize crystalline 1D covalent organic frameworks (COFs) composing quasi-conjugated chains with benzoxazine linkages via the one-pot Mannich reaction. Through [4+2] and [2+2] type Mannich condensation reactions, we fabricated stoichiometric and sub-stoichiometric 1D covalent polymeric chains, respectively, using doubly and singly linked benzoxazine rings. The validity of their crystal structures has been directly visualized through state-of-the-art cryogenic low-dose electron microscopy techniques. Post-synthetic functionalizations of them with a chiral MacMillan catalyst produce crystalline organic photocatalysts that demonstrated excellent catalytic and recyclable performance in light-driven asymmetric alkylation of aldehydes, affording up to 94 % enantiomeric excess.

Non-classical Deactivation Mechanism in a Supported Intermetallic Catalyst for Propane Dehydrogenation.

Platinum-based supported intermetallic alloys (IMAs) demonstrate exceptional performance in catalytic propane dehydrogenation (PDH) primarily because of their remarkable resistance to coke formation. However, these IMAs still encounter a significant hurdle in the form of catalyst deactivation. Understanding the complex deactivation mechanism of supported IMAs, which goes beyond conventional coke deposition, requires meticulous microscopic structural elucidation. In this study, we unravel a nonclassical deactivation mechanism over a PtZn/γ-Al2O3 PDH catalyst, dictated by the PtZn to Pt3Zn nanophase transformation accompanied with dezincification. The physical origin lies in the metal support interaction (MSI) that enables strong chemical bonding between hydroxyl groups on the support and Zn sites on the PtZn phase to selectively remove Zn species followed by the reconstruction towards Pt3Zn phase. Building on these insights, we have devised a solution to circumvent the deactivation by passivating the MSI through surface modification of γ-Al2O3 support. By exchanging protons of hydroxyl groups with potassium ions (K) on the γ-Al2O3 support, such a strategy significantly minimizes the dezincification of PtZn IMA via diminished metal-support bonding, which dramatically reduces the deactivation rate from 0.2044 to 0.0587 h-1.

Coherent Sub-Nanometer Interface between Crystalline and Amorphous Materials Boosts Electrochemical Synthesis of Hydrogen Peroxide.

There are enormous yet largely underexplored exotic phenomena and properties emerging from interfaces constructed by diverse types of components that may differ in composition, shape, or crystal structure. It remains poorly understood the unique properties a coherent interface between crystalline and amorphous materials may evoke, and there lacks a general strategy to fabricate such interfaces. It is demonstrated that by topotactic partial oxidation heterostructures composed of coherently registered crystalline and amorphous materials can be constructed. As a proof-of-concept study, heterostructures consisting of crystalline P3 N5 and amorphous P3 N5 Ox can be synthesized by creating amorphous P3 N5 Ox from crystalline P3 N5 without interrupting the covalent bonding across the coherent interface. The heterostructure is dictated by nanometer-sized short-range-ordered P3 N5 domains enclosed by amorphous P3 N5 Ox matrix, which entails simultaneously fast charge transfer across the interface and bicomponent synergistic effect in catalysis. Such a P3 N5 /P3 N5 Ox heterostructure attains an optimal adsorption energy for *OOH intermediates and exhibits superior electrocatalytic performance toward H2 O2 production by adopting a selectivity of 96.68% at 0.4 VRHE and a production rate of 321.5 mmol h-1 gcatalyst -1 at -0.3 VRHE . The current study provides new insights into the synthetic strategy, chemical structure, and catalytic property of a sub-nanometer coherent interface formed between crystalline and amorphous materials.

Nakagami statistics-based photoacoustic spectroscopy used for label-free assessment of bone tissue.

Quick identification of abnormal molecular metabolism of bone tissues is challenging. Photoacoustic (PA) spectroscopy techniques have great potential in molecular imaging. However, most of them are amplitude-dependent and easily affected by the light deposition, especially for bone tissues with high optical scattering. In this Letter, we propose a Nakagami statistics-based PA spectroscopy (NSPS) method for characterizing molecules in bone tissues. We indicate that the NSPS curve can intelligently identify changes in the content of molecules in bone tissues, with a high disturbance-resisting ability. The NSPS has remarkable potential for use in the early and rapid detection of bone diseases.

Dense NiCo2 O4 Nanoneedles Grown on Carbon Foam Showing Excellent Electrochemical and Microwave Absorption Properties.

Electromagnetic pollution could harm sensitive electronic equipment due to the rising use of electronic devices and communication infrastructure. The supercapacitor's electrochemical performance should be enhanced, and electromagnetic damage should be prevented. This study proposes NiCo2 O4 /CF composites for supercapacitors and microwave absorption. They are made by combining hydrothermal and annealing processes. Dense NiCo2 O4 nanoneedles were uniformly grown on the outer layer of carbon foam (CF) as a growth skeleton, preventing the agglomeration of NiCo2 O4 . The composite had a specific capacitance of 537.5 F/g at 1 A/g. When the current density was set to 1 A/g, the supercapacitor that used NiCo2 O4 /CF as the cathode had a specific capacitance of 70.7 F/g, and when the current density was increased to 10 A/g, the original specific capacitance of 87.2 % could still be maintained after 5000 charge-discharge cycles. At a power density of 3695.5 W/kg, an energy density of 22.1 Wh/kg could be maintained. Furthermore, we performed a microwave absorption test and determined its reflection loss curve for various sample thicknesses. Recombination enhanced the composite material's microwave absorption capability by greatly reducing the dielectric loss and the magnetic loss.

Lymphocyte percentage as a valuable predictor of prognosis in lung cancer.

Lymphocytes and neutrophils are involved in the immune response against cancer. This study aimed to investigate the relationship between lymphocyte percentage/neutrophil percentage and the clinical characteristics of lung cancer patients, and to explore whether they could act as valuable predictors to ameliorate lung cancer prognosis. A total of 1312 patients were eligible to be recruited. Lymphocyte percentage and neutrophil percentage were classified based on their reference ranges. Survival curves were determined using Kaplan-Meier method, and univariate and multivariate cox regression analyses were performed to identify the significant predictors. Decision curve analysis was used to evaluate the clinical benefit. The results of both training and validation cohorts indicated that lymphocyte percentage exhibited high correlation with clinical characteristics and metastasis of lung cancer patients. Both lymphocyte percentage and neutrophil percentage were closely associated with survival status (all p < 0.0001). Low lymphocyte percentage could act as an indicator of poor prognosis; it offered a higher clinical benefit when combined with the clinical characteristic model. Our findings suggested that pretreatment lymphocyte percentage served as a reliable predictor of lung cancer prognosis, and it was also an accurate response indicator in lung adenocarcinoma and advanced lung cancer. Measurement of lymphocyte percentage improved the clinical utility of patient characteristics in predicting mortality of lung cancer patients.

Isoreticular Series of Two-Dimensional Covalent Organic Frameworks with the kgd Topology and Controllable Micropores.

Two-dimensional (2D) covalent organic frameworks (COFs) possess designable pore architectures but limited framework topologies. Until now, 2D COFs adopting the kgd topology with ordered and rhombic pore geometry have rarely been reported. Here, an isoreticular series of 2D COFs with the kgd topology and controllable pore size is synthesized by employing a C6-symmetric aldehyde, i.e., hexa(4-formylphenyl)benzene (HFPB), and C3-symmetric amines i.e., tris(4-aminophenyl)amine (TAPA), tris(4-aminophenyl)trazine (TAPT), and 1,3,5-tris[4-amino(1,1-biphenyl-4-yl)]benzene (TABPB), as building units, referred to as HFPB-TAPA, HFPB-TAPT, and HFPB-TABPB, respectively. The micropore dimension down to 6.7 Å is achieved in HFPB-TAPA, which is among the smallest pore size of reported 2D COFs. Impressively, both the in-plane network and stacking sequence of the 2D COFs can be clearly observed by low-dose electron microscopy. Integrating the unique kgd topology with small rhombic micropores, these 2D COFs are endowed with both short molecular diffusion length and favorable host-guest interaction, exhibiting potential for drug delivery with high loading and good release control of ibuprofen.

Integrating Interactive Noble Metal Single-Atom Catalysts into Transition Metal Oxide Lattices.

Noble metals have broad prospects for catalytic applications yet are restricted to a few packing modes with limited structural flexibility. Here, we achieved geometric structure diversification of noble metals by integrating spatially correlated noble metal single atoms (e.g., Pt, Pd, and Ru) into the lattice of transition metal oxides (TMOs, e.g., Co3O4, Mn5O8, NiO, Fe2O3). The obtained noble metal single atoms exhibited distinct topologies (e.g., crs, fcu-hex-pcu, fcu, and bcu-x) from those of conventional metallic phases. For example, Pt single atoms with a crs topology (Ptcrs-Co3O4) are endowed with synergy of metal-metal and metal-support interactions. A quantitative relationship between various Pt topologies determined by TMO substrates and their electrocatalytic activities was established. We anticipate that this type of interactive single-atom catalysts can bridge the geometric, topological, and electronic structure gaps between the "close-packed" nanoparticles and isolated single atoms as two common categories of heterogeneous catalysts.

Apelin-mediated deamidation of HMGA1 promotes tumorigenesis by enhancing SREBP1 activity and lipid synthesis.

Enhanced fatty acid synthesis provides proliferation and survival advantages for tumor cells. Apelin is an adipokine, which serves as a ligand of G protein-coupled receptors that promote tumor growth in malignant cancers. Here, we confirmed that apelin increased sterol regulatory element-binding protein 1 (SREBP1) activity and induced the expression of glutamine amidotransferase for deamidating high-mobility group A 1 (HMGA1) to promote fatty acid synthesis and proliferation of lung cancer cells. This post-translational modification stabilized the HMGA1 expression and enhanced the formation of the apelin-HMGA1-SREBP1 complex to facilitate SREBP1 activity for lipid metabolism and lung cancer cell growth. We uncovered the pivotal role of apelin-mediated deamidation of HMGA1 in lipid metabolism and tumorigenesis of lung cancer cells.

Quantitative proteomics identified circulating biomarkers in lung adenocarcinoma diagnosis.

BACKGROUND: Lung cancer (LC) is a common malignant tumor with a high incidence and poor prognosis. Early LC could be cured, but the 5-year-survival rate for patients advanced is extremely low. Early screening of tumor biomarkers through plasma could allow more LC to be detected at an early stage, leading to a earlier treatment and a better prognosis. METHODS: This study was based on total proteomic analysis and parallel reaction monitoring validation of peripheral blood from 20 lung adenocarcinoma patients and 20 healthy individuals. Furthermore, differentially expressed proteins closely related to prognosis were analysed using Kaplan-Meier Plotter and receiver operating characteristic curve (ROC) curve analysis. RESULTS: The candidate proteins GAPDH and RAC1 showed the highest connectivity with other differentially expressed proteins between the lung adenocarcinoma group and the healthy group using STRING. Kaplan-Meier Plotter analysis showed that lung adenocarcinoma patients with positive ATCR2, FHL1, RAB27B, and RAP1B expression had observably longer overall survival than patients with negative expression (P < 0.05). The high expression of ARPC2, PFKP, PNP, RAC1 was observably negatively correlated with prognosis (P < 0.05). 17 out of 27 proteins showed a high area under the curve (> 0.80) between the lung adenocarcinoma and healthy plasma groups. Among those proteins, UQCRC1 had an area under the curve of 0.960, and 5 proteins had an area under the curve from 0.90 to 0.95, suggesting that these hub proteins might have discriminatory potential in lung adenocarcinoma, P < 0.05. CONCLUSIONS: These findings provide UQCRC1, GAPDH, RAC1, PFKP have potential as novel biomarkers for the early screening of lung adenocarcinoma.

Single-cell RNA Sequencing Uncovered the Involvement of an Endothelial Subset in Neutrophil Recruitment in Chemically Induced Rat Pulmonary Inflammation.

There is growing support for the notion that chronic inflammation contributes to lung tumorigenesis, but the molecular and cellular basis underlying the protumorigenic effects of inflammation remains to be explored. 3-Methylcholanthrene and diethylnitrosamine were intratracheally instilled into rats to induce multistep lung carcinogenesis, and the presence of pulmonary inflammation was observed in addition to precancerous lesions. By leveraging single-cell RNA sequencing, we sought to unravel the mechanism underlying the inflammatory process at a higher resolution. A total of 14 cell types were identified in chemically treated and control rats. Chemical intervention introduced heterogeneity in cell type composition and gene expression patterns. Nonimmune cells were found to be the most affected, and two subpopulations of endothelial cells with diverse roles were defined. Car4-high endothelial cells were mainly responsible for angiogenesis, whereas Car4-low endothelial cells were involved in neutrophil recruitment, and adhesion between Car4-low endothelial cells and neutrophils was verified in inflamed tissues. Our work unveiled the intricate process of pulmonary inflammation at the single-cell level and characterized a proinflammatory subpopulation of endothelial cells involved in neutrophil recruitment. The conditions provided by chronic inflammatory environment are prerequisites for neoplastic progression. Targeting the specific subsets or processes defined herein holds promise for the early prevention and therapeutic intervention of lung cancer through the manipulation of angiogenesis or the inflammatory response.

Synthesis and Visualization of Entangled 3D Covalent Organic Frameworks with High-Valency Stereoscopic Molecular Nodes for Gas Separation.

The structural diversity of three-dimensional (3D) covalent organic frameworks (COFs) are limited as there are only a few choices of building units with multiple symmetrically distributed connection sites. To date, 4 and 6-connected stereoscopic nodes with Td , D3h , D3d and C3 symmetries have been mostly reported, delivering limited 3D topologies. We propose an efficient approach to expand the 3D COF repertoire by introducing a high-valency quadrangular prism (D4h ) stereoscopic node with a connectivity of eight, based on which two isoreticular 3D imine-linked COFs can be created. Low-dose electron microscopy allows the direct visualization of their 2-fold interpenetrated bcu networks. These 3D COFs are endowed with unique pore architectures and strong molecular binding sites, and exhibit excellent performance in separating C2 H2 /CO2 and C2 H2 /CH4 gas pairs. The introduction of high-valency stereoscopic nodes would lead to an outburst of new topologies for 3D COFs.

Apelin enhances biological functions in lung cancer A549 cells by downregulating exosomal miR-15a-5p.

Apelin acts as a tumor promoter in multiple malignant tumors; however, its regulatory mechanism remains unclear. Previous studies have indicated that exosomes are pivotal to mediating tumor progression and metastasis. This study examined whether apelin enhances proliferation and invasion ability of lung cancer cells via exosomal microRNA (miRNA). Lung cancer A549 cells overexpressing apelin and control vector were generated by lentiviral transfection. Exosomes were isolated from the culture supernatant of each cell group and characterized. A-exo and V-exo were, respectively, cocultured with A549 cells, and assays of proliferation, apoptosis, colony formation and invasion were conducted. Exosomal miRNA sequencing (miRNA-seq) was performed on A-exo and V-exo to select a candidate miRNA. It was found that A549 cells absorbed more A-exo than V-exo, and A-exo could promote proliferation, colony formation, migration and invasion of A549 cells more than V-exo. Exosomal miRNA-seq data revealed that miR-15a-5p was markedly lower in A-exo compared with V-exo. Low expression of miR-15a-5p was also found in lung cancer tissues and cell lines, suggesting that miR-15a-5p may have an anti-tumor role. Overexpression of miR-15a-5p in A549 cells was associated with less cell proliferation, migration, invasion and suppressed cell cycle, and lower amounts of CDCA4 (cell division cycle-associated protein 4) indicated that it may be a potential target for miR-15a-5p. This study elucidated a novel regulatory mechanism that apelin may promote proliferation and invasion of lung cancer cells by inhibiting miR-15a-5p encapsulated in exosomes.

Molecular Scalpel to Chemically Cleave Metal-Organic Frameworks for Induced Phase Transition.

A bottom-up chemical synthesis of metal-organic frameworks (MOFs) permits significant structural diversity because of various combinations of metal centers and different organic linkers. However, fabrication generally complies with the classic hard and soft acids and bases (HSAB) theory. This restricts direct synthesis of desired MOFs with converse Lewis type of metal ions and ligands. Here we present a top-down strategy to break this limitation via the structural cleavage of MOFs to trigger a phase transition using a novel "molecular scalpel". A conventional CuBDC MOF (BDC = 1,4-benzenedicarboxylate) prepared from a hard acid (Cu2+) metal and a hard base ligand was chemically cleaved by l-ascorbic acid acting as chemical scalpel to fabricate a new Cu2BDC structure composed of a soft acid (Cu1+) and a hard base (BDC). Controlled phase transition was achieved by a series of redox steps to regulate the chemical state and coordination number of Cu ions, resulting in a significant change in chemical composition and catalytic activity. Mechanistic insights into structural cleavage and rearrangement are elaborated in detail. We show this novel strategy can be extended to general Cu-based MOFs and supramolecules for nanoscopic casting of unique architectures from existing ones.

Short-Range Ordered Iridium Single Atoms Integrated into Cobalt Oxide Spinel Structure for Highly Efficient Electrocatalytic Water Oxidation.

Noble metals manifest themselves with unique electronic structures and irreplaceable activity toward a wide range of catalytic applications but are unfortunately restricted by limited choice of geometric structures spanning single atoms, clusters, nanoparticles, and bulk crystals. Herein, we propose how to overcome this limitation by integrating noble metal atoms into the lattice of transition metal oxides to create a new type of hybrid structure. This study shows that iridium single atoms can be accommodated into the cationic sites of cobalt spinel oxide with short-range order and an identical spatial correlation as the host lattice. The resultant Ir0.06Co2.94O4 catalyst exhibits much higher electrocatalytic activity than the parent oxide by 2 orders of magnitude toward the challenging oxygen evolution reaction under acidic conditions. Because of the strong interaction between iridium and cobalt oxide support, the Ir0.06Co2.94O4 catalyst shows significantly improved corrosion resistance under acidic conditions and oxidative potentials. This work eliminates the "close-packing" limitation of noble metals and offers promising opportunity to create analogues with desired topologies for various catalytic applications.