Synthesis and Catalytic Properties of Metal Clusters Encapsulated within Small-Pore (SOD, GIS, ANA) Zeolites

The synthesis protocols for encapsulation of metal clusters reported here expand the diversity in catalytic chemistries made possible by the ability of microporous solids to select reactants, transition states, and products on the basis of their molecular size. We report a synthesis strategy for the encapsulation of noble metals and their oxides within SOD (Sodalite, 0.28 nm × 0.28 nm), GIS (Gismondine, 0.45 nm × 0.31 nm), and ANA (Analcime, 0.42 nm × 0.16 nm) zeolites. Encapsulation was achieved via direct hydrothermal synthesis for SOD and GIS using metal precursors stabilized by ammonia or organic amine ligands, which prevent their decomposition or precipitation as colloidal hydroxides at the conditions of hydrothermal synthesis (<380 K) and favor interactions between metal precursors and incipient aluminosilicate nuclei during self-assembly of microporous frameworks. The synthesis of ANA requires higher crystallization temperatures (∼415 K) and high pH (>12), thereby causing precipitation of even ligand-stabilized metal precursors as hydroxides. As a result, encapsulation was achieved by the recrystallization of metal clusters containing GIS into ANA, which retained these metal clusters within voids throughout the GIS–ANA transformation

Assembly of Indoline-2-carboxylate-Embodied Dipeptides via Pd-Catalyzed C(sp²)–H Bond Direct Functionalization

Intramolecular dehydrogenative cyclization of 2-methoxyiminoacyl-protected phenylalanine derivatives proceeded at 110 °C under catalysis of Pd­(OAc)₂ in the presence of 1-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate to afford substituted indoline-2-carboxylates that were converted into indoline-2-carboxylate-embodied dipeptides via Raney Ni-catalyzed hydrogenation

Table_1_scRNA-seq characterizing the heterogeneity of fibroblasts in breast cancer reveals a novel subtype SFRP4+ CAF that inhibits migration and predicts prognosis.xlsx

IntroductionCancer-associated fibroblasts (CAFs) are a diverse group of cells that significantly impact the tumor microenvironment and therapeutic responses in breast cancer (BC). Despite their importance, the comprehensive profile of CAFs in BC remains to be fully elucidated.MethodsTo address this gap, we utilized single-cell RNA sequencing (scRNA-seq) to delineate the CAF landscape within 14 BC normal-tumor paired samples. We further corroborated our findings by analyzing several public datasets, thereby validating the newly identified CAF subtype. Additionally, we conducted coculture experiments with BC cells to assess the functional implications of this CAF subtype.ResultsOur scRNA-seq analysis unveiled eight distinct CAF subtypes across five tumor and six adjacent normal tissue samples. Notably, we discovered a novel subtype, designated as SFRP4+ CAFs, which was predominantly observed in normal tissues. The presence of SFRP4+ CAFs was substantiated by two independent scRNA-seq datasets and a spatial transcriptomics dataset. Functionally, SFRP4+ CAFs were found to impede BC cell migration and the epithelial-mesenchymal transition (EMT) process by secreting SFRP4, thereby modulating the WNT signaling pathway. Furthermore, we established that elevated expression levels of SFRP4+ CAF markers correlate with improved survival outcomes in BC patients, yet paradoxically, they predict a diminished response to neoadjuvant chemotherapy in cases of triple-negative breast cancer.ConclusionThis investigation sheds light on the heterogeneity of CAFs in BC and introduces a novel SFRP4+ CAF subtype that hinders BC cell migration. This discovery holds promise as a potential biomarker for refined prognostic assessment and therapeutic intervention in BC.</p

Principal component analysis of soil enzyme activities in the different treatments (CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).

<p>Principal component analysis of soil enzyme activities in the different treatments (CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).</p

Image_1_scRNA-seq characterizing the heterogeneity of fibroblasts in breast cancer reveals a novel subtype SFRP4+ CAF that inhibits migration and predicts prognosis.pdf

IntroductionCancer-associated fibroblasts (CAFs) are a diverse group of cells that significantly impact the tumor microenvironment and therapeutic responses in breast cancer (BC). Despite their importance, the comprehensive profile of CAFs in BC remains to be fully elucidated.MethodsTo address this gap, we utilized single-cell RNA sequencing (scRNA-seq) to delineate the CAF landscape within 14 BC normal-tumor paired samples. We further corroborated our findings by analyzing several public datasets, thereby validating the newly identified CAF subtype. Additionally, we conducted coculture experiments with BC cells to assess the functional implications of this CAF subtype.ResultsOur scRNA-seq analysis unveiled eight distinct CAF subtypes across five tumor and six adjacent normal tissue samples. Notably, we discovered a novel subtype, designated as SFRP4+ CAFs, which was predominantly observed in normal tissues. The presence of SFRP4+ CAFs was substantiated by two independent scRNA-seq datasets and a spatial transcriptomics dataset. Functionally, SFRP4+ CAFs were found to impede BC cell migration and the epithelial-mesenchymal transition (EMT) process by secreting SFRP4, thereby modulating the WNT signaling pathway. Furthermore, we established that elevated expression levels of SFRP4+ CAF markers correlate with improved survival outcomes in BC patients, yet paradoxically, they predict a diminished response to neoadjuvant chemotherapy in cases of triple-negative breast cancer.ConclusionThis investigation sheds light on the heterogeneity of CAFs in BC and introduces a novel SFRP4+ CAF subtype that hinders BC cell migration. This discovery holds promise as a potential biomarker for refined prognostic assessment and therapeutic intervention in BC.</p

Principal component analysis of soil physical-chemical properties under the different treatments(CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).

<p>Principal component analysis of soil physical-chemical properties under the different treatments(CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).</p

Principal component analysis of soil enzyme activities in the different treatments (CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).

<p>Principal component analysis of soil enzyme activities in the different treatments (CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).</p

Response of soil a-galactosidase activity (A), β-galactosidase activity (B), α-glucosidase (C), and β-glucosidase activity (D) to the long-term effects of manure and different levels of N fertilization under greenhouse conditions (CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).

<p>Bars designated with the same letters within each panel are not significantly different. <i>P<0.05</i>. n = 3.</p

Soil organic carbon to total nitrogen ratio (TOC/TN) at the beginning of the experiment (1988; baseline) and after 20 years under the different fertilization treatments (CK unfertilized control; N1 300 kg fertilizer N ha^-1; N2 600 kg fertilizer N ha^-1; M composted manure; MN1 combined application of composted manure and 300 kg N fertilizer ha^-1; MN2 combined application of manure and 600 kg fertilizer N ha^-1).

<p>Standard errors shown as line bars. Bars designated with the same letters are not significantly different. <i>P<0.05</i>. n = 3.</p

Overlooked Role of Coexistent Hydrogen Peroxide in Activated Peracetic Acid by Cu(II) for Enhanced Oxidation of Organic Contaminants

Cu(II)-catalyzed peracetic acid (PAA) processes have shown significant potential to remove contaminants in water treatment. Nevertheless, the role of coexistent H2O2 in the transformation from Cu(II) to Cu(I) remained contentious. Herein, with the Cu(II)/PAA process as an example, the respective roles of PAA and H2O2 on the Cu(II)/Cu(I) cycling were comprehensively investigated over the pH range of 7.0–10.5. Contrary to previous studies, it was surprisingly found that the coexistent deprotonated H2O2 (HO2–), instead of PAA, was crucial for accelerating the transformation from Cu(II) to Cu(I) (kHO2–/Cu(II) = (0.17–1) × 106 M–1 s–1, kPAA/Cu(II) –1 s–1). Subsequently, the formed Cu(I) preferentially reacted with PAA (kPAA/Cu(I) = (5.84 ± 0.17) × 102 M–1 s–1), rather than H2O2 (kH2O2/Cu(I) = (5.00 ± 0.2) × 101 M–1 s–1), generating reactive species to oxidize organic contaminants. With naproxen as the target pollutant, the proposed synergistic role of H2O2 and PAA was found to be highly dependent on the solution pH with weakly alkaline conditions being more conducive to naproxen degradation. Overall, this study systematically investigated the overlooked but crucial role of coexistent H2O2 in the Cu(II)/PAA process, which might provide valuable insights for better understanding the underlying mechanism in Cu-catalyzed PAA processes