High π‑Facial and <i>exo</i>-Selectivity for the Intramolecular Diels–Alder Cycloaddition of Dodeca-3,9,11-trien-5-one Precursors to 2-<i>epi</i>-Symbioimine and Related Compounds

An unconstrained exocyclic stereogenic center and a removable trimethylsilyl group are combined to induce high π-facial selectivity and near-exclusive <i>exo</i>-selectivity in the intramolecular Diels–Alder cycloaddition of dodeca-3,9,11-trien-5-ones. This strategy provides direct access to polysubstituted <i>trans</i>-1-decalones related to the symbioimines in good yield and acceptable diastereoselectivity

Preparation and Characterization of Organic–Inorganic Hybrid Macrocyclic Compounds: Cyclic Ladder-like Polyphenylsilsesquioxanes

Organic–inorganic hybrid macrocyclic compounds, cyclic polyphenylsilsesquioxanes (cyc-PSQs), have been synthesized through hydrolysis and condensation reactions of phenyltrichlorosilane. Structural characterization has revealed that cyc-PSQs consist of a closed-ring double-chain siloxane inorganic backbone bearing organic phenyl groups. The cyc-PSQ molecules have been simulated and structurally optimized using the Forcite tool as implemented in Materials Studio. Structurally optimized cyc-PSQs are highly symmetrical and regular with high stereoregularity, consistent with the dimensions of their experimentally derived structures. Thermogravimetric analysis showed that these macrocyclic compounds have excellent thermal stability. In addition to these perfectly structured compounds, macrocyclic compounds with the same ring ladder structure but bearing an additional Si–OH group, cyc-PSQs-OH, have also been synthesized. A possible mechanism for the formation of the closed-ring molecular structures of cyc-PSQs and cyc-PSQs-OH is proposed

Table_1_Impact of ferroptosis-related risk genes on macrophage M1/M2 polarization and prognosis in glioblastoma.DOCX

ObjectiveTo explore the effect impact of ferroptosis on macrophage polarization and patient prognosis in glioblastoma.MethodsWe screened ferroptosis-related risk from the public datasets of primary and recurrent glioblastoma, combined with reported ferroptosis genes, calculated the risk genes among the ferroptosis-related genes using the LASSO Cox regression model, and investigated the relationship between these ferroptosis-related risk genes in the tumor and the spectrum of infiltrating M1/M2 macrophages. Macrophages were analyzed using the CIBERSORTx deconvolution algorithm. Samples from The Cancer Genome Atlas (TCGA), Chinese Glioma Genome Atlas (CGGA) and a single-cell RNA sequencing dataset (GSE84465) were included. The expression levels of ferroptosis-related risk genes and molecular markers of M1 and M2 macrophages were detected by qPCR and western blot.ResultsA total of fourteen ferroptosis-related risk genes were obtained and the patients’ risk scores were calculated. Compared with patients in the low-risk group, patients in the high-risk group had worse prognosis. The M1/M2 macrophage ratio and risk score were negatively correlated, indicating that the tumor microenvironment of glioblastoma in the high-risk group contained more M2 than M1 macrophages. In the single-cell RNA sequencing dataset, the risk score of ferroptosis-related genes in tumor cells was positively correlated with the proportion of high M2 macrophages. The expression of eight ferroptosis-related risk genes was increased in glioblastoma cell, which promoted the polarization of M1 macrophages to M2.ConclusionWe investigated the fourteen ferroptosis-related risk genes in glioblastoma for the first time, and clarified the impact of ferroptosis-related risk genes on M1/M2 macrophage polarization and patient prognosis.</p

Table_2_Impact of ferroptosis-related risk genes on macrophage M1/M2 polarization and prognosis in glioblastoma.XLSX

ObjectiveTo explore the effect impact of ferroptosis on macrophage polarization and patient prognosis in glioblastoma.MethodsWe screened ferroptosis-related risk from the public datasets of primary and recurrent glioblastoma, combined with reported ferroptosis genes, calculated the risk genes among the ferroptosis-related genes using the LASSO Cox regression model, and investigated the relationship between these ferroptosis-related risk genes in the tumor and the spectrum of infiltrating M1/M2 macrophages. Macrophages were analyzed using the CIBERSORTx deconvolution algorithm. Samples from The Cancer Genome Atlas (TCGA), Chinese Glioma Genome Atlas (CGGA) and a single-cell RNA sequencing dataset (GSE84465) were included. The expression levels of ferroptosis-related risk genes and molecular markers of M1 and M2 macrophages were detected by qPCR and western blot.ResultsA total of fourteen ferroptosis-related risk genes were obtained and the patients’ risk scores were calculated. Compared with patients in the low-risk group, patients in the high-risk group had worse prognosis. The M1/M2 macrophage ratio and risk score were negatively correlated, indicating that the tumor microenvironment of glioblastoma in the high-risk group contained more M2 than M1 macrophages. In the single-cell RNA sequencing dataset, the risk score of ferroptosis-related genes in tumor cells was positively correlated with the proportion of high M2 macrophages. The expression of eight ferroptosis-related risk genes was increased in glioblastoma cell, which promoted the polarization of M1 macrophages to M2.ConclusionWe investigated the fourteen ferroptosis-related risk genes in glioblastoma for the first time, and clarified the impact of ferroptosis-related risk genes on M1/M2 macrophage polarization and patient prognosis.</p

Table_3_Impact of ferroptosis-related risk genes on macrophage M1/M2 polarization and prognosis in glioblastoma.DOCX

ObjectiveTo explore the effect impact of ferroptosis on macrophage polarization and patient prognosis in glioblastoma.MethodsWe screened ferroptosis-related risk from the public datasets of primary and recurrent glioblastoma, combined with reported ferroptosis genes, calculated the risk genes among the ferroptosis-related genes using the LASSO Cox regression model, and investigated the relationship between these ferroptosis-related risk genes in the tumor and the spectrum of infiltrating M1/M2 macrophages. Macrophages were analyzed using the CIBERSORTx deconvolution algorithm. Samples from The Cancer Genome Atlas (TCGA), Chinese Glioma Genome Atlas (CGGA) and a single-cell RNA sequencing dataset (GSE84465) were included. The expression levels of ferroptosis-related risk genes and molecular markers of M1 and M2 macrophages were detected by qPCR and western blot.ResultsA total of fourteen ferroptosis-related risk genes were obtained and the patients’ risk scores were calculated. Compared with patients in the low-risk group, patients in the high-risk group had worse prognosis. The M1/M2 macrophage ratio and risk score were negatively correlated, indicating that the tumor microenvironment of glioblastoma in the high-risk group contained more M2 than M1 macrophages. In the single-cell RNA sequencing dataset, the risk score of ferroptosis-related genes in tumor cells was positively correlated with the proportion of high M2 macrophages. The expression of eight ferroptosis-related risk genes was increased in glioblastoma cell, which promoted the polarization of M1 macrophages to M2.ConclusionWe investigated the fourteen ferroptosis-related risk genes in glioblastoma for the first time, and clarified the impact of ferroptosis-related risk genes on M1/M2 macrophage polarization and patient prognosis.</p

(C₆H₅CH₂NH₃)₂CuBr₄: A Lead-Free, Highly Stable Two-Dimensional Perovskite for Solar Cell Applications

The toxicity and the instability of lead-based perovskites might eventually hamper the commercialization of perovskite solar cells. Here, we present the optoelectronic properties and stability of a two-dimensional layered (C₆H₅CH₂­NH₃)₂CuBr₄ perovskite. This material has a low <i>E</i>_g of 1.81 eV and high absorption coefficient of ∼1 × 10⁵ cm^–1 at the most intensive absorption at 539 nm, implying that it is suitable for light-harvesting in thin film solar cells, especially in tandem solar cells. Furthermore, X-ray diffraction (XRD), ultraviolet–visible (UV–vis) absorption spectra, and thermogravimetric analysis (TGA) confirm the high stability toward humidity, heat, and ultraviolet light. Initial studies produce a mesoscopic solar cell with a power conversion efficiency of 0.2%. Our work may offer some useful inspiration for the further investigation of environment-friendly and stable organic–inorganic perovskite photovoltaic materials