C–P Bond-Forming Reactions via C–O/P–H Cross-Coupling Catalyzed by Nickel

The first Ni-catalyzed C–O/P–H cross-coupling producing organophosphorus compounds is disclosed. This method features wide generality in regard to both C–O and P–H compounds: for C–O compounds, the readily available alcohol derivatives of aryl, alkenyl, benzyl, and allyl are applicable, and for P–H compounds, both >P^V(O)H compounds (secondary phosphine oxide, H-phosphinate, and H-phosphonate) and hydrogen phosphines (>P^IIIH) can be used as the substrates. Thus, a variety of valuable C­(sp²)–P and C­(sp³)–P compounds can be readily obtained in good to excellent yields by this new strategy

Nickel-Catalyzed Phosphorylation of Phenol Derivatives via C–O/P–H Cross-Coupling

An efficient nickel-catalyzed phosphorylation of phenol derivatives with P­(O)–H compounds via C–O/P–H cross-coupling is described. Under the reaction conditions, various phenyl pivalates coupled readily with hydrogen phosphoryl compounds to afford the corresponding coupling products aryl phosphonates and aryl phosphine oxides in good to high yields

ZnGa_2–<i>x</i>In_<i>x</i>S₄ (0 ≤ <i>x</i> ≤ 0.4) and Zn_{1–2<i>y</i>}(CuGa)_<i>y</i>Ga_1.7In_0.3S₄ (0.1 ≤ <i>y</i> ≤ 0.2): Optimize Visible Light Photocatalytic H₂ Evolution by Fine Modulation of Band Structures

Band structure engineering is an efficient technique to develop desired semiconductor photocatalysts, which was usually carried out through isovalent or aliovalent ionic substitutions. Starting from a UV-activated catalyst ZnGa₂S₄, we successfully exploited good visible light photocatalysts for H₂ evolution by In³⁺-to-Ga³⁺ and (Cu⁺/Ga³⁺)-to-Zn²⁺ substitutions. First, the bandgap of ZnGa_2–<i>x</i>­In_<i>x</i>S₄ (0 ≤ <i>x</i> ≤ 0.4) decreased from 3.36 to 3.04 eV by lowering the conduction band position. Second, Zn_{1–2<i>y</i>}(CuGa)_<i>y</i>­Ga_1.7In_0.3S₄ (<i>y</i> = 0.1, 0.15, 0.2) provided a further and significant red-shift of the photon absorption to ∼500 nm by raising the valence band maximum and barely losing the overpotential to water reduction. Zn_0.7Cu_0.15­Ga_1.85In_0.3S₄ possessed the highest H₂ evolution rate under pure visible light irradiation using S^2– and SO₃^2– as sacrificial reagents (386 μmol/h/g for the noble-metal-free sample and 629 μmol/h/g for the one loaded with 0.5 wt % Ru), while the binary hosts ZnGa₂S₄ and ZnIn₂S₄ (synthesized using the same procedure) show 0 and 27.9 μmol/h/g, respectively. The optimal apparent quantum yield reached to 7.9% at 500 nm by tuning the composition to Zn_0.6Cu_0.2­Ga_1.9In_0.3S₄ (loaded with 0.5 wt % Ru)

Pharmacokinetics and Biodistribution of Aurantiamide and Aurantiamide Acetate in Rats after Oral Administration of Portulaca oleracea L. Extracts

Aurantiamide and aurantiamide acetate are the main active constituents of purslane (Portulaca oleracea L.), an edible plant with various biological activities. In this study, we developed a validated UHPLC-MS/MS method to quantitate the concentrations of aurantiamide and aurantiamide acetate in the plasma and various organ tissues of rat as the basis to study their pharmacological profile and distribution in vivo. Aurantiamide and aurantiamide acetate were rapidly absorbed following oral administration, both achieving a <i>C</i>_max at around 0.2 h. The extent of their metabolisms also varied among different organ tissues, resulting in about 90% reduction in concentrations 4 h after their administration, thus leaving no long-term accumulation in the tissues. This is the first study to examine the pharmacokinetic and biodistribution of aurantiamide and aurantiamide acetate in rat, and our work may serve as the first step toward the investigation of the underlying mechanisms associated with the biological activity of purslane

Pharmacokinetics and Biodistribution of Aurantiamide and Aurantiamide Acetate in Rats after Oral Administration of Portulaca oleracea L. Extracts

Aurantiamide and aurantiamide acetate are the main active constituents of purslane (Portulaca oleracea L.), an edible plant with various biological activities. In this study, we developed a validated UHPLC-MS/MS method to quantitate the concentrations of aurantiamide and aurantiamide acetate in the plasma and various organ tissues of rat as the basis to study their pharmacological profile and distribution in vivo. Aurantiamide and aurantiamide acetate were rapidly absorbed following oral administration, both achieving a <i>C</i>_max at around 0.2 h. The extent of their metabolisms also varied among different organ tissues, resulting in about 90% reduction in concentrations 4 h after their administration, thus leaving no long-term accumulation in the tissues. This is the first study to examine the pharmacokinetic and biodistribution of aurantiamide and aurantiamide acetate in rat, and our work may serve as the first step toward the investigation of the underlying mechanisms associated with the biological activity of purslane

Mechanistic Studies on the Palladium-Catalyzed Cross Dehydrogenative Coupling of P(O)–H Compounds with Terminal Alkynes: Stereochemistry and Reactive Intermediates

The mechanism of the palladium-catalyzed cross dehydrogenative coupling of P­(O)–H compounds with terminal alkynes was studied. Successive ligand-exchange reactions of Pd­(OAc)₂ with a hydrogen phosphoryl compound and a terminal alkyne take place readily to replace the two acetates on palladium, producing the corresponding (phosphoryl) (alkynyl)palladium complexes, which upon heating decomposed to the corresponding alkynylphosphorus compound. It is also confirmed that in the stoichiometric reactions of the complexes, the configuration at phosphorus is retained. On the basis of these stoichiometric reactions, an efficient synthesis of <i>P</i>-chiral alkynylphosphoryl compounds via palladium-catalyzed stereoselective cross dehydrogenative coupling of <i>P</i>-chiral P­(O)–H compounds with terminal alkynes was developed. The key palladium complexes and the stereochemistry of the chiral phosphorus compounds are all unambiguously determined by single-crystal X-ray analysis

DataSheet_4_Material basis and molecular mechanisms of Chaihuang Qingyi Huoxue Granule in the treatment of acute pancreatitis based on network pharmacology and molecular docking-based strategy.zip

ObjectivesThis study aimed to analyze active compounds and signaling pathways of CH applying network pharmacology methods, and to additionally verify the molecular mechanism of CH in treating AP.Materials and methodsNetwork pharmacology and molecular docking were firstly used to identify the active components of CH and its potential targets in the treatment of AP. The pancreaticobiliary duct was retrogradely injected with sodium taurocholate (3.5%) to create an acute pancreatitis (AP) model in rats. Histological examination, enzyme-linked immunosorbent assay, Western blot and TUNEL staining were used to determine the pathway and mechanism of action of CH in AP.ResultsNetwork pharmacological analysis identified 168 active compounds and 276 target proteins. In addition, there were 2060 targets associated with AP, and CH had 177 targets in common with AP. These shared targets, including STAT3, IL6, MYC, CDKN1A, AKT1, MAPK1, MAPK3, MAPK14, HSP90AA1, HIF1A, ESR1, TP53, FOS, and RELA, were recognized as core targets. Furthermore, we filtered out 5252 entries from the Gene Ontology(GO) and 186 signaling pathways from the Kyoto Encyclopedia of Genes and Genomes(KEGG). Enrichment and network analyses of protein-protein interactions predicted that CH significantly affected the PI3K/AKT signaling pathway, which played a critical role in programmed cell death. The core components and key targets showed strong binding activity based on molecular docking results. Subsequently, experimental validation demonstrated that CH inhibited the phosphorylation of PI3K and AKT in pancreatic tissues, promoted the apoptosis of pancreatic acinar cells, and further alleviated inflammation and histopathological damage to the pancreas in AP rats.ConclusionApoptosis of pancreatic acinar cells can be enhanced and the inflammatory response can be reduced through the modulation of the PI3K/AKT signaling pathway, resulting in the amelioration of pancreatic disease.</p

Ga₄B₂O₉: An Efficient Borate Photocatalyst for Overall Water Splitting without Cocatalyst

Borates are well-known candidates for optical materials, but their potentials in photocatalysis are rarely studied. Ga³⁺-containing oxides or sulfides are good candidates for photocatalysis applications because the unoccupied 4s orbitals of Ga usually contribute to the bottom of the conducting band. It is therefore anticipated that Ga₄B₂O₉ might be a promising photocatalyst because of its high Ga/B ratio and three-dimensional network. Various synthetic methods, including hydrothermal (HY), sol–gel (SG), and high-temperature solid-state reaction (HTSSR), were employed to prepare crystalline Ga₄B₂O₉. The so-obtained HY-Ga₄B₂O₉ are micrometer single crystals but do not show any UV-light activity unless modified by Pt loading. The problem is the fast recombination of photoexcitons. Interestingly, the samples obtained by SG and HTSSR methods both possess a fine micromorphology composed of well-crystalline nanometer strips. Therefore, the excited e^– and h⁺ can move to the surface easily. Both samples exhibit excellent intrinsic UV-light activities for pure water splitting without the assistance of any cocatalyst (47 and 118 μmol/h/g for H₂ evolution and 22 and 58 μmol/h/g for O₂ evolution, respectively), while there is no detectable activity for P25 (nanoparticles of TiO₂ with a specific surface area of 69 m²/g) under the same conditions

DataSheet_7_Material basis and molecular mechanisms of Chaihuang Qingyi Huoxue Granule in the treatment of acute pancreatitis based on network pharmacology and molecular docking-based strategy.zip

ObjectivesThis study aimed to analyze active compounds and signaling pathways of CH applying network pharmacology methods, and to additionally verify the molecular mechanism of CH in treating AP.Materials and methodsNetwork pharmacology and molecular docking were firstly used to identify the active components of CH and its potential targets in the treatment of AP. The pancreaticobiliary duct was retrogradely injected with sodium taurocholate (3.5%) to create an acute pancreatitis (AP) model in rats. Histological examination, enzyme-linked immunosorbent assay, Western blot and TUNEL staining were used to determine the pathway and mechanism of action of CH in AP.ResultsNetwork pharmacological analysis identified 168 active compounds and 276 target proteins. In addition, there were 2060 targets associated with AP, and CH had 177 targets in common with AP. These shared targets, including STAT3, IL6, MYC, CDKN1A, AKT1, MAPK1, MAPK3, MAPK14, HSP90AA1, HIF1A, ESR1, TP53, FOS, and RELA, were recognized as core targets. Furthermore, we filtered out 5252 entries from the Gene Ontology(GO) and 186 signaling pathways from the Kyoto Encyclopedia of Genes and Genomes(KEGG). Enrichment and network analyses of protein-protein interactions predicted that CH significantly affected the PI3K/AKT signaling pathway, which played a critical role in programmed cell death. The core components and key targets showed strong binding activity based on molecular docking results. Subsequently, experimental validation demonstrated that CH inhibited the phosphorylation of PI3K and AKT in pancreatic tissues, promoted the apoptosis of pancreatic acinar cells, and further alleviated inflammation and histopathological damage to the pancreas in AP rats.ConclusionApoptosis of pancreatic acinar cells can be enhanced and the inflammatory response can be reduced through the modulation of the PI3K/AKT signaling pathway, resulting in the amelioration of pancreatic disease.</p

DataSheet_10_Material basis and molecular mechanisms of Chaihuang Qingyi Huoxue Granule in the treatment of acute pancreatitis based on network pharmacology and molecular docking-based strategy.zip

ObjectivesThis study aimed to analyze active compounds and signaling pathways of CH applying network pharmacology methods, and to additionally verify the molecular mechanism of CH in treating AP.Materials and methodsNetwork pharmacology and molecular docking were firstly used to identify the active components of CH and its potential targets in the treatment of AP. The pancreaticobiliary duct was retrogradely injected with sodium taurocholate (3.5%) to create an acute pancreatitis (AP) model in rats. Histological examination, enzyme-linked immunosorbent assay, Western blot and TUNEL staining were used to determine the pathway and mechanism of action of CH in AP.ResultsNetwork pharmacological analysis identified 168 active compounds and 276 target proteins. In addition, there were 2060 targets associated with AP, and CH had 177 targets in common with AP. These shared targets, including STAT3, IL6, MYC, CDKN1A, AKT1, MAPK1, MAPK3, MAPK14, HSP90AA1, HIF1A, ESR1, TP53, FOS, and RELA, were recognized as core targets. Furthermore, we filtered out 5252 entries from the Gene Ontology(GO) and 186 signaling pathways from the Kyoto Encyclopedia of Genes and Genomes(KEGG). Enrichment and network analyses of protein-protein interactions predicted that CH significantly affected the PI3K/AKT signaling pathway, which played a critical role in programmed cell death. The core components and key targets showed strong binding activity based on molecular docking results. Subsequently, experimental validation demonstrated that CH inhibited the phosphorylation of PI3K and AKT in pancreatic tissues, promoted the apoptosis of pancreatic acinar cells, and further alleviated inflammation and histopathological damage to the pancreas in AP rats.ConclusionApoptosis of pancreatic acinar cells can be enhanced and the inflammatory response can be reduced through the modulation of the PI3K/AKT signaling pathway, resulting in the amelioration of pancreatic disease.</p