Interchain-expanded extra-large-pore zeolites.

Stable aluminosilicate zeolites with extra-large pores that are open through rings of more than 12 tetrahedra could be used to process molecules larger than those currently manageable in zeolite materials. However, until very recently1-3, they proved elusive. In analogy to the interlayer expansion of layered zeolite precursors4,5, we report a strategy that yields thermally and hydrothermally stable silicates by expansion of a one-dimensional silicate chain with an intercalated silylating agent that separates and connects the chains. As a result, zeolites with extra-large pores delimited by 20, 16 and 16 Si tetrahedra along the three crystallographic directions are obtained. The as-made interchain-expanded zeolite contains dangling Si-CH3 groups that, by calcination, connect to each other, resulting in a true, fully connected (except possible defects) three-dimensional zeolite framework with a very low density. Additionally, it features triple four-ring units not seen before in any type of zeolite. The silicate expansion-condensation approach we report may be amenable to further extra-large-pore zeolite formation. Ti can be introduced in this zeolite, leading to a catalyst that is active in liquid-phase alkene oxidations involving bulky molecules, which shows promise in the industrially relevant clean production of propylene oxide using cumene hydroperoxide as an oxidant.

FTO in oral diseases: Functions, mechanisms, and therapeutic potential.

Fat mass and obesity-associated protein (FTO) is the first identified N6-methyladenosine (m6A) demethylase widely distributed in various tissues in adults and children. It plays an essential role in diverse mRNA-associated processes including transcriptional stability, selective splicing, mRNA translocation, and also protein translation. Recently, emerging studies have shown that FTO is involved in the genesis and development of oral diseases. However, the correlation between FTO and oral diseases and its specific regulatory mechanism still needs further study. In this review, we will summarize the discovery, distribution, gene expression, protein structure, biological functions, inhibitors, and quantifying methods of FTO, as well as its regulatory role and mechanism in oral diseases. Notably, FTO genetic variants are strongly associated with periodontal diseases (PDs), temporomandibular joint osteoarthritis (TMJOA), and obstructive sleep apnea (OSA). Besides, the latest studies that describe the relationship between FTO and PDs, head and neck squamous cell carcinoma (HNSCCs), TMJOA, and OSA will be discussed. We elaborate on the regulatory roles of FTO in PDs, HNSCCs, and TMJOA, which are modulated through cell proliferation, cell migration, apoptosis, bone metabolism, and immune response. The review will enrich our understanding of RNA epigenetic modifications in oral diseases and present a solid theoretical foundation for FTO to serve as a novel diagnosis and prognostic biomarker for oral diseases.

Progress and challenges in nitrous oxide decomposition and valorization.

Nitrous oxide (N2O) decomposition is increasingly acknowledged as a viable strategy for mitigating greenhouse gas emissions and addressing ozone depletion, aligning significantly with the UN's sustainable development goals (SDGs) and carbon neutrality objectives. To enhance efficiency in treatment and explore potential valorization, recent developments have introduced novel N2O reduction catalysts and pathways. Despite these advancements, a comprehensive and comparative review is absent. In this review, we undertake a thorough evaluation of N2O treatment technologies from a holistic perspective. First, we summarize and update the recent progress in thermal decomposition, direct catalytic decomposition (deN2O), and selective catalytic reduction of N2O. The scope extends to the catalytic activity of emerging catalysts, including nanostructured materials and single-atom catalysts. Furthermore, we present a detailed account of the mechanisms and applications of room-temperature techniques characterized by low energy consumption and sustainable merits, including photocatalytic and electrocatalytic N2O reduction. This article also underscores the extensive and effective utilization of N2O resources in chemical synthesis scenarios, providing potential avenues for future resource reuse. This review provides an accessible theoretical foundation and a panoramic vision for practical N2O emission controls.

Synthesis of Bridged Five-Membered Ring Systems by Type II [3 + 2] Annulation of Allenylsilane-ene.

The first type II intramolecular [3 + 2] annulation of allenylsilane-ene has been achieved, enabling diastereoselective and efficient construction of synthetically challenging bridged five-membered ring systems such as bicyclo[3.2.1]. This mild and direct process shows a broad substrate scope and is highly stereospecific. Particularly, this work represents the first stereoselective method for the direct synthesis of bicyclo[3.2.1] ring systems from acyclic precursors. Additionally, the first asymmetric total syntheses of (+)- and (-)-strepsesquitriol, and the efficient formation of the synthetically challenging tetracyclic core of pierisjaponol D are achieved by this type II [3 + 2] annulation reaction.

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NOx with NH3.

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet-visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites.

Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols.

We present a novel mechanism for the formation of photocatalytic oxidants in deliquescent NaCl particles, which can greatly promote the multiphase photo-oxidation of SO2 to produce sulfate. The photoexcitation of the [Cl--H3O+-O2] complex leads to the generation of Cl and OH radicals, which is the key reason for enhancing aqueous-phase oxidation and accelerating SO2 oxidation. The mass normalization rate of sulfate production from the multiphase photoreaction of SO2 on NaCl droplets could be estimated to be 0.80 × 10-4 µg·h-1 at 72% RH and 1.33 × 10-4 µg·h-1 at 81% RH, which is equivalent to the known O3 liquid-phase oxidation mechanism. Our findings highlight the significance of multiphase photo-oxidation of SO2 on NaCl particles as a non-negligible source of sulfate in coastal areas. Furthermore, this study underscores the importance of Cl- photochemistry in the atmosphere.

An Alternative Calibration Method for Measuring N2O5 with an Iodide-Chemical Ionization Mass Spectrometer and Influencing Factors.

In this work, we developed an alternative calibration method for measuring N2O5 with an iodide adduct mass spectrometer (I-CIMS). In this calibration method, N2O5 is heated and then quantified based on the decrease in the amount of NO due to its reaction with the pyrolysis product (NO3). This alternative calibration method was compared with the commonly used method utilizing NOx analyzers equipped with a photolytic converter, which gauge NO2 reduction as a result of its reaction with O3 to quantify N2O5. It is notable that the two methodologies demonstrate favorable consistency in terms of calibrating N2O5, with a variance of less than 10 %. The alternative calibration method is a more reliable way to quantify N2O5 with CIMS, considering the instability of the NO2 conversion efficiency of photolytic converters in NOx analyzers and the loss of N2O5 in the sampling line. The effects of O3 and relative humidity (RH) on the sensitivity toward N2O5 were further examined. There was minimal perturbation of N2O5 quantification upon exposure to O3 even at high concentrations. The N2O5 sensitivity exhibited a nonlinear dependence on RH as it initially rose and then fell. Besides I(N2O5)-, the collisional interaction between I(H2O)- and N2O5 also forms I(HNO3)-, which may interfere with the accurate quantification of HNO3. As a consequence of the pronounced dependence on humidity, it is advisable to implement humidity correction procedures when conducting measurements of N2O5.

Hu8F4-CAR T cells with mutated Fc spacer segment improve target specificity and mediate anti-leukemia activity in vivo.

BACKGROUND AIMS: Hu8F4 is a T-cell receptor-like antibody with high affinity for the leukemia-associated antigen PR1/HLA-A2 epitope. Adapted into a chimeric antigen receptor (CAR) format, Hu8F4-CAR is composed of the Hu8F4 single-chain variable fragment, the human IgG1 CH2CH3 extracellular spacer domain, a human CD28 costimulatory domain and the human CD3ζ signaling domain. We have demonstrated high efficacy of Hu8F4-CAR-T cells against PR1/HLA-A2-expressing cell lines and leukemic blasts from patients with acute myeloid leukemia in vitro. Previous studies have shown that modification of the Fc domains of IgG4 CH2CH3 spacer regions can eliminate activation-induced cell death and off-target killing mediated by mouse Fc gamma receptor-expressing cells. METHODS: We generated Hu8F4-CAR(PQ) with mutated Fc receptor binding sites on the CH2 domain of Hu8F4-CAR to prevent unwanted interactions with Fc gamma receptor-expressing cells in vivo. RESULTS: The primary human T cells transduced with Hu8F4-CAR(PQ) can specifically lyse HLA-A2+ PR1-expressing leukemia cell lines in vitro. Furthermore, both adult donor-derived and cord blood-derived Hu8F4-CAR(PQ)-T cells are active and can eliminate U937 leukemia cells in NSG mice. CONCLUSIONS: Herein, we demonstrate that modification of the IgG1-based spacer can eliminate Fc receptor binding-induced adverse effects and Hu8F4-CAR(PQ)-T cells can kill leukemia in vivo.

Inhibition of P21-activated kinases 1 and 4 synergistically suppresses the growth of pancreatic cancer by stimulating anti-tumour immunity.

BACKGROUND: Pancreatic ductal adenocarcinoma (PDA) is one of the most lethal types of cancer, and KRAS oncogene occurs in over 90% of cases. P21-activated kinases (PAK), containing six members (PAK1 to 6), function downstream of KRAS. PAK1 and PAK4 play important roles in carcinogenesis, but their combinational effect remains unknown. In this study, we have determined the effect of dual inhibition of PAK1 and PAK4 in PDA progression using knockout (KO) cancer cell lines. METHODS: Murine wild-type (WT) and PAK1KO pancreatic cancer cell lines were isolated from PAK1+/+ and PAK1-/- KPC (LSL-KrasG12D/+; LSL-Trp53 R172H/+; Pdx-1-Cre) mice. KPC PAK4KO and KPC PAK1&4 KO cell lines were generated from KPC WT and KPC PAK1KO cell lines respectively using the CRISPR-CAS9 gene knockout technique. PAK WT and KO cell lines were used in mouse models of pancreatic tumours. Cells and tumour tissue were also used in flow cytometry and proteomic studies. A human PDA tissue microarray was stained by immunohistochemistry. RESULTS: Double knock out of PAK1 and PAK4 caused complete regression of tumour in a syngeneic mouse model. PAK4KO inhibited tumour growth by stimulating a rapid increase of cytotoxic CD8+ T cell infiltration. PAK1KO synergistically with PAK4KO increased cytotoxic CD8+ T cell infiltration and stimulated a sustained infiltration of CD8+ T cells at a later phase to overcome the immune evasion in the PAK4KO tumour. The human PDA tissue microarray study showed the important role of PAK1 and PAK4 in intra-tumoral T-cell function. CONCLUSION: Our results demonstrated that dual inhibition of PAK1 and PAK4 synergistically suppressed PDA progression by stimulating cytotoxic CD8 + T cell response.

Segregation of endosymbionts in complex symbiotic system of cicadas providing novel insights into microbial symbioses and evolutionary dynamics of symbiotic organs in sap-feeding insects.

The most extraordinary systems of symbiosis in insects are found in the suborder Auchenorrhyncha of Hemiptera, which provide unique perspectives for uncovering complicated insect-microbe symbiosis. We investigated symbionts associated with bacteriomes and fat bodies in six cicada species, and compared transmitted cell number ratio of related symbionts in ovaries among species. We reveal that Sulcia and Hodgkinia or a yeast-like fungal symbiont (YLS) are segregated from other host tissues by the bacteriomes in the nymphal stage, then some of them may migrate to other organs (i.e., fat bodies and ovaries) during host development. Particularly, YLS resides together with Sulcia in the "symbiont ball" of each egg and the bacteriomes of young-instar nymphs, but finally migrates to the fat bodies of adults in the majority of Hodgkinia-free cicadas, whereas it resides in both bacteriome sheath and fat bodies of adults in a few other species. The transmitted Sulcia/YLS or Sulcia/Hodgkinia cell number ratio in ovaries varies significantly among species, which could be related to the distribution and/or lineage splitting of symbiont(s). Rickettsia localizes to the nuclei of bacteriomes and fat bodies in some species, but it was not observed to be transmitted to the ovaries, indicating that this symbiont may be acquired from environments or from father to offspring. The considerable difference in the transovarial transmission process of symbionts suggests that cellular mechanisms underlying the symbiont transmission are complex. Our results may provide novel insights into insect-microbe symbiosis.

Portable and miniature sensors in supply chain for food authentication: a review.

Food fraud, a pervasive issue in the global food industry, poses significant challenges to consumer health, trust, and economic stability, costing an estimated $10-15 billion annually. Therefore, there is a rising demand for developing portable and miniature sensors that facilitate food authentication throughout the supply chain. This review explores the recent advancements and applications of portable and miniature sensors, including portable/miniature near-infrared (NIR) spectroscopy, e-nose and colorimetric sensors based on nanozyme for food authentication within the supply chain. After briefly presenting the architecture and mechanism, this review discusses the application of these portable and miniature sensors in food authentication, addressing the challenges and opportunities in integrating and deploying these sensors to ensure authenticity. This review reveals the enhanced utility of portable/miniature NIR spectroscopy, e-nose, and nanozyme-based colorimetric sensors in ensuring food authenticity and enabling informed decision-making throughout the food supply chain.

Core charge of imidazolium annulated triphenylene derivatives induces discotic columnar mesomorphism.

Thermotropic ionic liquid crystals have remained a relatively little studied group of materials despite their many potential applications as anisotropic ionic liquids and charge (ion and electron/hole) transporting materials. Particularly rare are core charged discotic liquid crystals because their synthesis is usually more involved, and their molecular design is less established. Presented here is a straightforward and versatile synthetic approach to imidazolium annulated triphenylene derivatives. Their neutral imidazole precursors are not liquid crystalline while the imidazolium salts display hexagonal discotic columnar mesophases over a wide range of temperatures and as low as 47 °C. Computational studies at the DFT and PM6 levels of theory confirmed much higher stacking energies for the imidazolium salts compared to the neutral imidazole precursors. They also predicted the anions of columnar stacks of imidazolium salts to be positioned in the bay-positions next to the imidazolium unit and in-plane with the polyaromatic system. The anions were stabilized in the bay position by multiple interactions with partially positively charged H atoms and do not interfere with π-π stacking.

Organocatalyzed Photoelectrochemistry for the Generation of Acyl and Phosphoryl Radicals through Hydrogen Atom-Transfer Process.

An organocatalyzed photoelectrochemical method for the generation of acyl and phosphoryl radicals from formamides, aldehydes, and phosphine oxides has been developed. This protocol utilizes 9,10-phenanthrenequinone (PQ) as both a molecular catalyst and a hydrogen atom-transfer (HAT) reagent, eliminating the requirement for external metal-based reagents, HAT reagents, and oxidants. The generated acyl radicals can be applied to a range of radical-mediated transformation reactions, including C-H carbamoylation of heteroarenes, intermolecular tandem radical cyclization of CF3-substituted N-arylacrylamides, as well as intramolecular cyclization reactions. The use of acyl radicals in these transformations offers an efficient and sustainable approach to accessing structurally diverse carbonyl compounds.

Revealing the Contribution of Interfacial Processes to Atmospheric Oxidizing Capacity in Haze Chemistry.

The atmospheric oxidizing capacity is the most important driving force for the chemical transformation of pollutants in the atmosphere. Traditionally, the atmospheric oxidizing capacity mainly depends on the concentration of O3 and other gaseous oxidants. However, the atmospheric oxidizing capacity based on gas-phase oxidation cannot accurately describe the explosive growth of secondary particulate matter under complex air pollution. From the chemical perspective, the atmospheric oxidizing capacity mainly comes from the activation of O2, which can be achieved in both gas-phase and interfacial processes. In the heterogeneous or multiphase formation pathways of secondary particulate matter, the enhancement of oxidizing capacity ascribed to the O2/H2O-involved interfacial oxidation and hydrolysis processes is an unrecognized source of atmospheric oxidizing capacity. Revealing the enhanced oxidizing capacity due to interfacial processes in high-concentration particulate matter environments and its contribution to the formation of secondary pollution are critical in understanding haze chemistry. The accurate evaluation of atmospheric oxidizing capacity ascribed to interfacial processes is also an important scientific basis for the implementation of PM2.5 and O3 collaborative control in China and around the world.

Effect of Interlayer Anions on NiFe Layered Double Hydroxides for Catalytic Ozone Decomposition.

NiFe layered double hydroxides (NiFe-LDH) exhibited an outstanding performance and promising application potential for removing ozone. However, the effect of interlayer anions on ozone removal remains ambiguous. Here, a series of NiFe-LDH with different interlayer anions (F-, Cl-, Br-, NO3-, CO32-, and SO42-) were prepared to investigate the effect of the interlayer anion on ozone removal for the first time. It was found that the interlayer anions are a key factor affecting the water resistance of the NiFe-LDH catalyst under moist conditions. NiFe-LDH-CO32- exhibited the best water resistance, which was much better than that of NiFe-LDH containing other interlayer anions. The in situ DIRFTS demonstrates that the carbonates in the interlayer of NiFe-LDH-CO32- will undergo coordination changes through the interaction with water molecules under moist conditions, exposing new metal sites. As a result, the newly exposed metal sites could activate water molecules into hydroxyl groups that act as active sites for catalyzing ozone decomposition. This work provides a new insight into the interlayer anions of LDH, which is important for the design and development of LDH catalysts with excellent ozone removal properties.

Modulating the Electronic Structures of Pt on Pt/TiO2 Catalyst for Boosting Toluene Oxidation.

Surface hydroxyl groups commonly exist on the catalyst and present a significant role in the catalytic reaction. Considering the lack of systematical researches on the effect of the surface hydroxyl group on reactant molecule activation, the PtOx/TiO2 and PtOx-y(OH)y/TiO2 catalysts were constructed and studied for a comprehensive understanding of the roles of the surface hydroxyl group in the oxidation of volatiles organic compounds. The PtOx/TiO2 formed by a simple treatment with nitric acid presented greatly enhanced activity for toluene oxidation in which the turnover frequency of toluene oxidation on PtOx/TiO2 was around 14 times as high as that on PtOx-y(OH)y/TiO2. Experimental and theoretical results indicated that adsorption/activation of toluene and reactivity of oxygen atom on the catalyst determined the toluene oxidation on the catalyst. The removal of surface hydroxyl groups on PtOx promoted strong electronic coupling of the Pt 5d orbital in PtOx and C 2p orbital in toluene, facilitating the electron transfers from toluene to PtOx and subsequently the adsorption/activation of toluene. Additionally, the weak Pt-O bond promoted the activation of surface lattice oxygen, accelerating the deep oxidation of activated toluene. This study clarifies the inhibiting effect of surface hydroxyl groups on PtOx in toluene oxidation, providing a further understanding of hydrocarbon oxidation.

Creating Atomically Iridium-Doped PdOx Nanoparticles for Efficient and Durable Methane Abatement.

The urgent environmental concern of methane abatement, attributed to its high global warming potential, necessitates the development of methane oxidation catalysts (MOC) with enhanced low-temperature activity and durability. Herein, an iridium-doped PdOx nanoparticle supported on silicalite-1 zeolite (PdIr/S-1) catalyst was synthesized and applied for methane catalytic combustion. Comprehensive characterizations confirmed the atomically dispersed nature of iridium on the surface of PdOx nanoparticles, creating an Ir4f-O-Pdcus microstructure. The atomically doped Ir transferred more electrons to adjacent oxygen atoms, modifying the electronic structure of PdOx and thus enhancing the redox ability of the PdIr/S-1 catalysts. This electronic modulation facilitated methane adsorption on the Pd site of Ir4f-O-Pdcus, reducing the energy barrier for C-H bond cleavage and thereby increasing the reaction rate for methane oxidation. Consequently, the optimized PdIr0.1/S-1 showed outstanding low-temperature activity for methane combustion (T50 = 276 °C) after aging and maintained long-term stability over 100 h under simulated exhaust conditions. Remarkably, the novel PdIr0.1/S-1 catalyst demonstrated significantly enhanced activity even after undergoing harsh hydrothermal aging at 750 °C for 16 h, significantly outperforming the conventional Pd/Al2O3 catalyst. This work provides valuable insights for designing efficient and durable MOC catalysts, addressing the critical issue of methane abatement.

In-Depth Understanding of the Oxidative Compatibility of Volatile Organic Compounds with Mn2O3 and Pt-Loaded Catalysts.

Designing suitable catalysts for efficiently degrading volatile organic compounds (VOCs) is a great challenge due to the distinct variety and nature of VOCs. Herein, the suitability of different typical VOCs (toluene and acetone) over Pt-based catalysts and Mn2O3 was investigated carefully. The activity of Mn2O3 was inferior to Pt-loaded catalysts in toluene oxidation but showed superior ability for destroying acetone, while Pt loading could boost the catalytic activity of Mn2O3 for both acetone and toluene. This suitability could be determined by the physicochemical properties of the catalysts and the structure of the VOC since toluene destruction activity is highly reliant on Pt0 in the metallic state and linearly correlated with the amount of surface reactive oxygen species (Oads), while the crucial factor that affects acetone oxidation is the mobility of lattice oxygen (Olat). The Pt/Mn2O3 catalyst shows highly active Pt-O-Mn interfacial sites, favoring the generation of Oads and promoting Mn-Olat mobility, leading to its excellent performance. Therefore, the design of abundant active sites is an effective means of developing highly adaptive catalysts for the oxidation of different VOCs.

Efficient Catalytic Elimination of Chlorobenzene Based on the Water Vapor-Promoting Effect within Mn-Based Catalysts: Activity Enhancement and Polychlorinated Byproduct Inhibition.

Achieving no or low polychlorinated byproduct selectivity is essential for the chlorinated volatile organic compounds (CVOCs) degradation, and the positive roles of water vapor may contribute to this goal. Herein, the oxidation behaviors of chlorobenzene over typical Mn-based catalysts (MnO2 and acid-modified MnO2) under dry and humid conditions were fully explored. The results showed that the presence of water vapor significantly facilitates the deep mineralization of chlorobenzene and restrains the formation of Cl2 and dichlorobenzene. This remarkable water vapor-promoting effect was conferred by the MnO2 substrate, which could suitably synergize with the postconstructed acidic sites, leading to good activity, stability, and desirable product distribution of acid-modified MnO2 catalysts under humid conditions. A series of experiments including isotope-traced (D2O and H218O) CB-TPO provided complete insights into the direct involvement of water molecules in chlorobenzene oxidation reaction and attributed the root cause of the water vapor-promoting effect to the proton-rich environment and highly reactive water-source oxygen species rather than to the commonly assumed cleaning effect or hydrogen proton transfer processes (generation of active OOH). This work demonstrates the application potential of Mn-based catalysts in CVOCs elimination under practical application conditions (containing water vapor) and provides the guidance for the development of superior industrial catalysts.

Unexpected Promotion Effect of H2O on the Selective Catalytic Reduction of NOx with NH3 over Cu-SSZ-39 Catalysts.

Water molecules commonly inhibit the selective catalytic reduction (SCR) of NOx with NH3 on most catalysts, and water resistance is a long-standing challenge for SCR technology. Herein, by combining experimental measurements and density functional theory (DFT) calculations, we found that water molecules do not inhibit and even promote the NOx conversion to some extent over the Cu-SSZ-39 zeolites, a promising SCR catalyst. Water acting as a ligand on active Cu sites and as a reactant in the SCR reaction significantly improves the O2 activation performance and reduces the overall energy barrier of the catalytic cycle. This work unveils the mechanism of the unexpected promotion effect of water on the NH3-SCR reaction over Cu-SSZ-39 and provides fundamental insight into the development of zeolite-based SCR catalysts with excellent activity and water resistance.