Dichloropalladium complexes ligated by 4,5-bis(arylimino)pyrenylidenes: Synthesis, characterization, and catalytic behavior towards Heck-reaction

A series of 4,5-bis(arylimino)pyrenylidenylpalladium(II) chloride complexes (C1–C4) were synthesized and characterized by FT-IR and NMR spectroscopy, elemental analysis as well as by single crystal X-ray diffraction for the representative complexes C1 and C3, which revealed a square planar geometry at the palladium center. All palladium complexes exhibited high activity for the Heck cross-coupling reaction, which were effective when conducted in various solvents. Furthermore, the in-situ mixture of palladium dichloride and the ligand (L1) provided an effective catalytic system for the Heck-reaction

Synthesis, characterization and ethylene polymerization behaviour of binuclear nickel halides bearing 4,5,9,10-tetra(arylimino)pyrenylidenes

Pyrene-4,5,9,10-tetraone was prepared via the oxidation of pyrene, and reacted with various anilines to afford a series of 4,5,9,10-tetra(arylimino)pyrenylidene derivatives (L1–L4). The tetraimino-pyrene compounds L1 and L2 were reacted with two equivalents of (DME)NiBr₂ in CH₂Cl₂ to afford the corresponding dinickel bromide complexes (Ni1 and Ni2). The organic compounds were fully characterized, whilst the bi-metallic complexes were characterized by FT-IR spectra and elemental analysis. The molecular structures of representative organic and nickel compounds were confirmed by single-crystal X-ray diffraction studies. These nickel complexes exhibited high activities towards ethylene polymerization in the presence of either MAO or Me₂AlCl, maintaining a high activity over a prolonged period (longer than previously reported dinickel complex pre-catalysts). The polyethylene obtained was characterized by GPC, DSC and FT-IR spectroscopy and was found to possess branched features

Aerosol Characterization of Northern China and Yangtze River Delta Based on Multi-Satellite Data: Spatiotemporal Variations and Policy Implications

Horizontal and vertical distributions of aerosol properties in the Taklimakan Desert (TD), North central region of China (NCR),North China Plain(NCP), and Yangtze River Delta (YRD) were investigated by statistical analysis using Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) L3 data from 2007 to 2020, to identify the similarities and differences in atmospheric aerosols in different regions, and evaluate the impact of pollution control policies developed in China in 2013 on aerosol properties in the study area. The aerosol optical depth (AOD) distribution had substantial seasonal and spatial distribution characteristics. AOD had high annual averages in TD (0.38), NCP (0.49), and YRD (0.52). However, these rates showed a decline post-implementation of the long-term pollution control policies; AOD values declined by 5%, 13.8%, 15.5%, and 23.7% in TD, NCR, NCP, and YRD respectively when comparing 2014–2018 to 2007–2013, and by 7.8%, 11.5%, 16%, and 10.4% when comparing 2019–2020 to 2014–2018. The aerosol extinction coefficient showed a clear regional pattern and a tendency to decrease gradually as height increased. Dust and polluted dust were responsible for the changes in AOD and extinction coefficients between TD and NCR and NCP and YRD, respectively. In TD, with change of longitude, dust aerosol first increased and then decreased gradually, peaking in the middle. Similarly in NCP, polluted dust aerosol first increased and then decreased, with a maximum value in the middle. The elevated smoke aerosols of NCP and YRD were significantly higher than those observed in TD and NCR. The high aerosol extinction coefficient values (>0.1 km−1) were mainly distributed below 4 km, and the relatively weak aerosol extinction coefficients (>0.001 km−1) were mainly distributed between 5–8 km, indicating that the high-altitude long-range transport of TD and NCR dust aerosols affects NCP and YRD

Methylene-bridged bimetallic α-diimino nickel(ii) complexes: Synthesis and high efficiency in ethylene polymerization

A series of 1,2-bis(arylimino)acenaphthylidenes (L1-L5) and their corresponding 4,4′-methylenebis(1-(2,6-diisopropylphenylimino)-2- (arylimino)acenaphthylene) derivatives (L6-L10) were synthesized and used to form mono-nuclear nickel bromides LnNiBr2 (n = 1-5, Ni1-Ni5) and bi-nuclear nickel halides LnNi2X4 (n = 6-10: X = Br, Ni2-1-Ni2-5; n = 4, X = Cl, Ni2-6). All the organic compounds were fully characterized by FT-IR spectra, NMR measurements and elemental analysis. The nickel complexes were characterized by FT-IR spectra and elemental analysis and the molecular structures of the representative complexes Ni1, Ni2-1 and Ni2-3 were confirmed by single-crystal X-ray diffraction. Upon activation with either Et2AlCl or MAO, all the nickel complex pre-catalysts exhibited high activity toward ethylene polymerization over the temperature range from ambient to 50 °C. In general, the bi-nuclear complexes showed a positive synergetic effect with higher activity than their mono nuclear analogs. The resultant polyethylene possessed higher molecular weight and a high degree of branching. © 2013 The Royal Society of Chemistry

Aerosol Characterization of Northern China and Yangtze River Delta Based on Multi-Satellite Data: Spatiotemporal Variations and Policy Implications

Horizontal and vertical distributions of aerosol properties in the Taklimakan Desert (TD), North central region of China (NCR),North China Plain(NCP), and Yangtze River Delta (YRD) were investigated by statistical analysis using Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) L3 data from 2007 to 2020, to identify the similarities and differences in atmospheric aerosols in different regions, and evaluate the impact of pollution control policies developed in China in 2013 on aerosol properties in the study area. The aerosol optical depth (AOD) distribution had substantial seasonal and spatial distribution characteristics. AOD had high annual averages in TD (0.38), NCP (0.49), and YRD (0.52). However, these rates showed a decline post-implementation of the long-term pollution control policies; AOD values declined by 5%, 13.8%, 15.5%, and 23.7% in TD, NCR, NCP, and YRD respectively when comparing 2014–2018 to 2007–2013, and by 7.8%, 11.5%, 16%, and 10.4% when comparing 2019–2020 to 2014–2018. The aerosol extinction coefficient showed a clear regional pattern and a tendency to decrease gradually as height increased. Dust and polluted dust were responsible for the changes in AOD and extinction coefficients between TD and NCR and NCP and YRD, respectively. In TD, with change of longitude, dust aerosol first increased and then decreased gradually, peaking in the middle. Similarly in NCP, polluted dust aerosol first increased and then decreased, with a maximum value in the middle. The elevated smoke aerosols of NCP and YRD were significantly higher than those observed in TD and NCR. The high aerosol extinction coefficient values (>0.1 km−1) were mainly distributed below 4 km, and the relatively weak aerosol extinction coefficients (>0.001 km−1) were mainly distributed between 5–8 km, indicating that the high-altitude long-range transport of TD and NCR dust aerosols affects NCP and YRD

Nickel(II) complexes bearing 4,5-bis(arylimino)pyrenylidenes: Synthesis, characterization, and ethylene polymerization behaviour

A series of nickel(II) dihalides complexes bearing 4,5-bis(arylimino) pyrenylidenes, NiX2(2,6-R1-4-R2C 6H2N)2C16H8, was synthesized and characterized by FT-IR spectroscopy, elemental analysis, and single crystal X-ray diffraction for the organic compounds (L2 and L3) and the nickel complexes (C1 and C2). The molecular structures of C1 (R1 = Me, R2 = H, X = Br) and C2 (R1 = R2 = Me, X = Br) revealed a distorted tetrahedral geometry around the nickel centre. Upon treatment with the co-catalysts MAO, EASC and MMAO, all the nickel pre-catalysts exhibited high activities (of up to 4.42 × 106 g(PE) mol(Ni)-1 h-1) for ethylene polymerization, and produced polyethylene products with a high degree of branching (up to 130 branched per 1000 carbons) and narrow molecular weight distribution. The influence of the reaction parameters and the nature of the ligands on the catalytic behavior of the title nickel complexes have been investigated. © 2013 The Royal Society of Chemistry

Image4_Single-Cell RNA Sequencing Reveals the Role of Phosphorylation-Related Genes in Hepatocellular Carcinoma Stem Cells.tif

Abnormal activation of protein kinases and phosphatases is implicated in various tumorigenesis, including hepatocellular carcinoma (HCC). Advanced HCC patients are treated with systemic therapy, including tyrosine kinase inhibitors, which extend overall survival. Investigation of the underlying mechanism of protein kinase signaling will help to improve the efficacy of HCC therapy. Combining single-cell RNA sequencing data and TCGA RNA-seq data, we profiled the protein kinases, phosphatases, and other phosphorylation-related genes (PRGs) of HCC patients in this study. We found nine protein kinases and PRGs with high expression levels that were mainly detected in HCC cancer stem cells, including POLR2G, PPP2R1A, POLR2L, PRC1, ITBG1BP1, MARCKSL1, EZH2, DTYMK, and AURKA. Survival analysis with the TCGA dataset showed that these genes were associated with poor prognosis of HCC patients. Further correlation analysis showed that these genes were involved in cell cycle-related pathways that may contribute to the development of HCC. Among them, AURKA and EZH2 were identified as two hub genes by Ingenuity Pathway Analysis. Treatment with an AURKA inhibitor (alisertib) and an EZH2 inhibitor (gambogenic) inhibited HCC cell proliferation, migration, and invasion. We also found that both AURKA and EZH2 were highly expressed in TP53-mutant HCC samples. Our comprehensive analysis of PRGs contributes to illustrating the mechanisms underlying HCC progression and identifying potential therapeutic targets for future clinical trials.</p

Table6_Single-Cell RNA Sequencing Reveals the Role of Phosphorylation-Related Genes in Hepatocellular Carcinoma Stem Cells.xlsx

Abnormal activation of protein kinases and phosphatases is implicated in various tumorigenesis, including hepatocellular carcinoma (HCC). Advanced HCC patients are treated with systemic therapy, including tyrosine kinase inhibitors, which extend overall survival. Investigation of the underlying mechanism of protein kinase signaling will help to improve the efficacy of HCC therapy. Combining single-cell RNA sequencing data and TCGA RNA-seq data, we profiled the protein kinases, phosphatases, and other phosphorylation-related genes (PRGs) of HCC patients in this study. We found nine protein kinases and PRGs with high expression levels that were mainly detected in HCC cancer stem cells, including POLR2G, PPP2R1A, POLR2L, PRC1, ITBG1BP1, MARCKSL1, EZH2, DTYMK, and AURKA. Survival analysis with the TCGA dataset showed that these genes were associated with poor prognosis of HCC patients. Further correlation analysis showed that these genes were involved in cell cycle-related pathways that may contribute to the development of HCC. Among them, AURKA and EZH2 were identified as two hub genes by Ingenuity Pathway Analysis. Treatment with an AURKA inhibitor (alisertib) and an EZH2 inhibitor (gambogenic) inhibited HCC cell proliferation, migration, and invasion. We also found that both AURKA and EZH2 were highly expressed in TP53-mutant HCC samples. Our comprehensive analysis of PRGs contributes to illustrating the mechanisms underlying HCC progression and identifying potential therapeutic targets for future clinical trials.</p

Methylene-bridged bimetallic α-diimino nickel(ii) complexes: synthesis and high efficiency in ethylene polymerization

A series of 1,2-bis(arylimino)acenaphthylidenes (L1-L5) and their corresponding 4,4′-methylenebis(1-(2,6-diisopropylphenylimino)-2- (arylimino)acenaphthylene) derivatives (L6-L10) were synthesized and used to form mono-nuclear nickel bromides LnNiBr2 (n = 1-5, Ni1-Ni5) and bi-nuclear nickel halides LnNi2X4 (n = 6-10: X = Br, Ni2-1-Ni2-5; n = 4, X = Cl, Ni2-6). All the organic compounds were fully characterized by FT-IR spectra, NMR measurements and elemental analysis. The nickel complexes were characterized by FT-IR spectra and elemental analysis and the molecular structures of the representative complexes Ni1, Ni2-1 and Ni2-3 were confirmed by single-crystal X-ray diffraction. Upon activation with either Et2AlCl or MAO, all the nickel complex pre-catalysts exhibited high activity toward ethylene polymerization over the temperature range from ambient to 50 °C. In general, the bi-nuclear complexes showed a positive synergetic effect with higher activity than their mono nuclear analogs. The resultant polyethylene possessed higher molecular weight and a high degree of branching. © 2013 The Royal Society of Chemistry