New Theoretical Insights into the Contributions of Poly(methylbenzene) and Alkene Cycles to the Methanol to Propene Process in H‑FAU Zeolite

The contributions of the poly­(methylbenzene) (polyMB) and alkene cycles to the methanol to propene (MTP) process in H-FAU zeolite have been investigated by a two-layer ONIOM (our own <i>n</i>-layered integrated molecular orbital and molecular mechanics) method, which is important to understand the nature of formation of propene in zeolite with large pore sizes. The calculated results demonstrate that the different pathways in the polyMB cycle occur in the following order of reactivity: methyl-transfer pathway > spiro pathway > direct internal H-shift > paring pathway. The polyMB cycle is more competitive than the alkene cycle for the MTP process in H-FAU, which is different from the previous results on H-ZSM-5. Introduction of Li⁺ and Ag⁺ cations into FAU zeolite does not reduce the free energy barriers of the methylation steps involved in polyMB and alkene cycles, indicating that the experimental efforts to improve propene selectivity probably should focus on the physical effect of Li⁺ and Ag⁺ cations. For the step of formation of propene in both cycles, the difference in charge densities suggests a clear electron transfer between the propene fragment and the aromatic ring or propoxy group. Decomposing ONIOM energy barriers into quantum mechanics and molecular mechanics contributions suggests that the stabilizing effect of the zeolite environment on transition states mainly originates from the van der Waals interactions for the spiro and methyl-transfer pathways in the polyMB cycle, but from the electrostatic interactions for the alkene cycle. Generally speaking, the formation step of propene is entropy-increased. The direct internal H-shift and paring pathways are entropy-decreased. The entropy effect in the alkene cycle is larger than that in the polyMB cycle due to the larger entropic barriers

Atmospheric Arsenic Deposition in the Pearl River Delta Region, South China: Influencing Factors and Speciation

This is a comprehensive study on mobilization/speciation and temporal/spatial variation of atmospheric arsenic (As) deposition in the Pearl River Delta (PRD) region. A set of experimental procedures was established for measuring the deposition fluxes of individual As species. The deposition carrying inorganic As^III % was significantly higher than that contained in atmospheric particles. Compared with dry deposition, wet deposition was much more harmful to the regional ecosystem, as it contributed the majority of bulk deposition (>75%) and carried most of the mobilized iAs^III compounds. A stepwise linear regression model was utilized to identify the factors influencing total As deposition (wet: precipitation and PM_2.5, dry: relative humidity, wind speed, and PM₁₀, bulk: precipitation, PM_2.5, and wind speed). By examining the representativeness of the study sites and comparison with the literature data, the statistic models were verified to explain the temporal/spatial variation of total As deposition in the entire PRD region, where significant seasonal variation was only found for wet deposition (wet season > dry season). The annual As load contributed from regional atmospheric deposition increased from 2013 to 2015, when the contributions of individual cities varied annually

Selective Cleavage of Inert Aryl C–N Bonds in <i>N</i>‑Aryl Amides

A highly selective, IBX-promoted reaction has been developed for the oxidative cleavage of inert C­(aryl)–N bonds on secondary amides while leaving the C­(carbonyl)–N bond unchanged. This metal-free reaction proceeds under mild conditions (HFIP/H₂O, 25 °C), providing facile access to various useful primary amides, some of which would be otherwise unattainable using conventional aminolysis and hydrolysis approaches

Image_2_Concurrent sintilimab with sequential chemoradiotherapy for unresectable, stage III non-small cell lung cancer: a retrospective study.tif

BackgroundConcurrent programmed death 1 (PD-1) or programmed death ligand 1 (PD-L1) inhibitors with sequential chemoradiotherapy (SCRT) have been reported in only a limited number of studies involving patients with unresectable stage III non-small-cell lung cancer (NSCLC). A retrospective study was conducted to systematically analyze the efficacy and safety of the emerging therapy among Chinese patients.Materials and methodsWe included patients with unresectable, stage III NSCLC who received concurrent sintilimab with chemotherapy or chemotherapy alone for 3-6 cycles, followed by radical radiotherapy at the First Hospital of Jilin University from Dec 15, 2019, to Jul 15, 2022. The primary end point was the objective response rate (ORR). The secondary end points included progression-free survival (PFS), overall survival (OS), 12-month and 18-month PFS rates, the duration of response (DoR), and safety.ResultsThe retrospective study involved 77 patients, of which 49 receiving concurrent sintilimab with SCRT were assigned to cohort A, and 28 receiving SCRT alone were assigned to cohort B. The ORR was significantly higher in cohort A (79.6%, 95% CI 65.7–89.8) than in cohort B (35.7%, 95% CI 18.6–55.9) (pConclusionConcurrent sintilimab with SCRT resulted in a significantly better ORR and longer PFS than SCRT alone, with manageable safety profiles in Chinese patients with unresectable stage III NSCLC.</p

Presentation_1_Concurrent sintilimab with sequential chemoradiotherapy for unresectable, stage III non-small cell lung cancer: a retrospective study.pdf

BackgroundConcurrent programmed death 1 (PD-1) or programmed death ligand 1 (PD-L1) inhibitors with sequential chemoradiotherapy (SCRT) have been reported in only a limited number of studies involving patients with unresectable stage III non-small-cell lung cancer (NSCLC). A retrospective study was conducted to systematically analyze the efficacy and safety of the emerging therapy among Chinese patients.Materials and methodsWe included patients with unresectable, stage III NSCLC who received concurrent sintilimab with chemotherapy or chemotherapy alone for 3-6 cycles, followed by radical radiotherapy at the First Hospital of Jilin University from Dec 15, 2019, to Jul 15, 2022. The primary end point was the objective response rate (ORR). The secondary end points included progression-free survival (PFS), overall survival (OS), 12-month and 18-month PFS rates, the duration of response (DoR), and safety.ResultsThe retrospective study involved 77 patients, of which 49 receiving concurrent sintilimab with SCRT were assigned to cohort A, and 28 receiving SCRT alone were assigned to cohort B. The ORR was significantly higher in cohort A (79.6%, 95% CI 65.7–89.8) than in cohort B (35.7%, 95% CI 18.6–55.9) (pConclusionConcurrent sintilimab with SCRT resulted in a significantly better ORR and longer PFS than SCRT alone, with manageable safety profiles in Chinese patients with unresectable stage III NSCLC.</p

Image_1_Concurrent sintilimab with sequential chemoradiotherapy for unresectable, stage III non-small cell lung cancer: a retrospective study.tif

BackgroundConcurrent programmed death 1 (PD-1) or programmed death ligand 1 (PD-L1) inhibitors with sequential chemoradiotherapy (SCRT) have been reported in only a limited number of studies involving patients with unresectable stage III non-small-cell lung cancer (NSCLC). A retrospective study was conducted to systematically analyze the efficacy and safety of the emerging therapy among Chinese patients.Materials and methodsWe included patients with unresectable, stage III NSCLC who received concurrent sintilimab with chemotherapy or chemotherapy alone for 3-6 cycles, followed by radical radiotherapy at the First Hospital of Jilin University from Dec 15, 2019, to Jul 15, 2022. The primary end point was the objective response rate (ORR). The secondary end points included progression-free survival (PFS), overall survival (OS), 12-month and 18-month PFS rates, the duration of response (DoR), and safety.ResultsThe retrospective study involved 77 patients, of which 49 receiving concurrent sintilimab with SCRT were assigned to cohort A, and 28 receiving SCRT alone were assigned to cohort B. The ORR was significantly higher in cohort A (79.6%, 95% CI 65.7–89.8) than in cohort B (35.7%, 95% CI 18.6–55.9) (pConclusionConcurrent sintilimab with SCRT resulted in a significantly better ORR and longer PFS than SCRT alone, with manageable safety profiles in Chinese patients with unresectable stage III NSCLC.</p

Dimeric Abietane Diterpenoids and Sesquiterpenoid Lactones from <i>Teucrium viscidum</i>

A new abietane diterpenoid, teuvisone (<b>2</b>), a pair of new dimeric abietane diterpenoid stereoisomers, biteuvisones A (<b>3</b>) and B (<b>4</b>), and three new sesquiterpenoid lactones, teuvislactones A–C (<b>6</b>, <b>7</b>, and <b>10</b>), were isolated from the whole plants of <i>Teucrium viscidum</i>, along with four known terpenoids (<b>1</b>, <b>5</b>, <b>8</b>, and <b>9</b>). The structures of the new compounds were elucidated by spectroscopic analysis, and the absolute configurations of <b>5</b>–<b>10</b> were determined by electronic circular dichroism analysis. The isolated compounds were evaluated for their cytotoxic effects against five human cancer cell lines and for their α-glucosidase inhibitory effects

Cytotoxic Fusicoccane-Type Diterpenoids from <i>Streptomyces violascens</i> Isolated from <i>Ailuropoda melanoleuca</i> Feces

Six new fusicoccane-type diterpenoids (<b>2</b>–<b>7</b>) were isolated from the fermentation broth of <i>Streptomyces violascens</i>, which was isolated from <i>Ailuropoda melanoleuca</i> (giant panda) feces. The structures of these new compounds were elucidated by a detailed spectroscopic data and X-ray crystallographic analysis. Compounds <b>5</b>–<b>7</b> demonstrated cytotoxicity against five human cancer cell lines, with IC₅₀ values ranging from 3.5 ± 0.7 to 14.1 ± 0.8 μM. Cell adhesion, migration, and invasion assays showed that <b>6</b> inhibited the migration and invasion of human hepatocellular carcinoma SMMC7721 cells in a dose-dependent manner. Through further investigation, it was revealed that <b>6</b> inhibited the enzymatic activity of matrix metalloproteinase-2 (MMP-2) and matrix metalloproteinase-9 (MMP-9), in addition to down-regulating the expressions of MMP-2 and MMP-9 at both the protein and mRNA levels to influence the migration and invasion of cancer cells

Violapyrones A–G, α‑Pyrone Derivatives from <i>Streptomyces violascens</i> Isolated from <i>Hylobates hoolock</i> Feces

Seven new 3,4,6-trisubstituted α-pyrone derivatives, violapyrones A–G (<b>1</b>–<b>7</b>), were isolated from <i>Streptomyces violascens</i> obtained from <i>Hylobates hoolock</i> feces. Their structures were elucidated on the basis of detailed spectroscopic analysis. The antimicrobial activities of <b>1</b>–<b>7</b> were evaluated against Gram-positive and Gram-negative bacteria and against fungi. Compounds <b>1</b>–<b>3</b> showed moderate antibacterial activities against <i>Bacillus subtilis</i> and <i>Staphylococcus aureus</i> with MIC values of 4–32 μg/mL

Cytotoxic Fusicoccane-Type Diterpenoids from <i>Streptomyces violascens</i> Isolated from <i>Ailuropoda melanoleuca</i> Feces

Six new fusicoccane-type diterpenoids (<b>2</b>–<b>7</b>) were isolated from the fermentation broth of <i>Streptomyces violascens</i>, which was isolated from <i>Ailuropoda melanoleuca</i> (giant panda) feces. The structures of these new compounds were elucidated by a detailed spectroscopic data and X-ray crystallographic analysis. Compounds <b>5</b>–<b>7</b> demonstrated cytotoxicity against five human cancer cell lines, with IC₅₀ values ranging from 3.5 ± 0.7 to 14.1 ± 0.8 μM. Cell adhesion, migration, and invasion assays showed that <b>6</b> inhibited the migration and invasion of human hepatocellular carcinoma SMMC7721 cells in a dose-dependent manner. Through further investigation, it was revealed that <b>6</b> inhibited the enzymatic activity of matrix metalloproteinase-2 (MMP-2) and matrix metalloproteinase-9 (MMP-9), in addition to down-regulating the expressions of MMP-2 and MMP-9 at both the protein and mRNA levels to influence the migration and invasion of cancer cells