Highly efficient and selective photocatalytic oxidation of sulfide by a chromophore-catalyst dyad of ruthenium-based complexes.

Electronic coupling across a bridging ligand between a chromophore and a catalyst center has an important influence on biological and synthetic photocatalytic processes. Structural and associated electronic modifications of ligands may improve the efficiency of photocatalytic transformations of organic substrates. Two ruthenium-based supramolecular assemblies based on a chromophore-catalyst dyad containing a Ru-aqua complex and its chloro form as the catalytic components were synthesized and structurally characterized, and their spectroscopic and electrochemical properties were investigated. Under visible light irradiation and in the presence of [Co(NH3)5Cl]Cl2 as a sacrificial electron acceptor, both complexes exhibited good photocatalytic activity toward oxidation of sulfide into the corresponding sulfoxide with high efficiency and >99% product selectivity in neutral aqueous solution. The Ru-aqua complex assembly was more efficient than the chloro complex. Isotopic labeling experiments using (18)O-labeled water demonstrated the oxygen atom transfer from the water to the organic substrate, likely through the formation of an active intermediate, Ru(IV)═O.

Photochemical, electrochemical, and photoelectrochemical water oxidation catalyzed by water-soluble mononuclear ruthenium complexes.

Two mononuclear ruthenium complexes [Ru(H2tcbp)(isoq)2] (1) and [Ru(H2tcbp)(pic)2] (2) (H4tcbp=4,4',6,6'-tetracarboxy-2,2'-bipyridine, isoq=isoquinoline, pic=4-picoline) are synthesized and fully characterized. Two spare carboxyl groups on the 4,4'-positions are introduced to enhance the solubility of 1 and 2 in water and to simultaneously allow them to tether to the electrode surface by an ester linkage. The photochemical, electrochemical, and photoelectrochemical water oxidation performance of 1 in neutral aqueous solution is investigated. Under electrochemical conditions, water oxidation is conducted on the deposited indium-tin-oxide anode, and a turnover number higher than 15,000 per water oxidation catalyst (WOC) 1 is obtained during 10 h of electrolysis under 1.42 V vs. NHE, corresponding to a turnover frequency of 0.41 s(-1). The low overpotential (0.17 V) of electrochemical water oxidation for 1 in the homogeneous solution enables water oxidation under visible light by using [Ru(bpy)3](2+) (P1) (bpy=2,2'-bipyridine) or [Ru(bpy)2(4,4'-(COOEt)2-bpy)](2+) (P2) as a photosensitizer. In a three-component system containing 1 or 2 as a light-driven WOC, P1 or P2 as a photosensitizer, and Na2S2O8 or [CoCl(NH3)5]Cl2 as a sacrificial electron acceptor, a high turnover frequency of 0.81 s(-1) and a turnover number of up to 600 for 1 under different catalytic conditions are achieved. In a photoelectrochemical system, the WOC 1 and photosensitizer are immobilized together on the photoanode. The electrons efficiently transfer from the WOC to the photogenerated oxidizing photosensitizer, and a high photocurrent density of 85 µA cm(-2) is obtained by applying 0.3 V bias vs. NHE.

The DeltaN p63 Promotes EMT and Metastasis in Bladder Cancer by the PTEN/AKT Signalling Pathway.

Bladder cancer is a common tumour of the urinary system, and more than 90% is urothelial carcinoma. Therefore, it is important for discovering the key target genes and molecules of bladder tumour cell metastasis and invasion. Our research initially explored the regulation of deltaN p63 on the progression and metastasis of bladder cancer and found that deltaN p63 can influence the occurrence of EMT through PTEN and ultimately regulate the growth and metastasis of bladder cancer. In summary, this study identified a new EMT regulator, deltaN p63, further revealed the mechanism of the invasion and metastasis of bladder cancer cells, and provided a theoretical basis for finding new target molecules and drugs to treat bladder cancer. In conclusion, this study will further reveal the mechanism of tumour cell invasion and metastasis and provide a theoretical basis for cancer treatment to find new target molecules and drugs.