Ancillary Ligand Effects on Heteroleptic IrIII Dye in Dye-Sensitized Photocatalytic CO2 Reduction: Photoaccumulation of Charges on Arylated Bipyridine Ligand and Its Control on Catalytic Performance

Herein, we report the synthesis, and photochemical and -physical properties, as well as the catalytic performance, of a series of heteroleptic Ir^III photosensitizers (IrPSs), [Ir(C^N)₂(N^N^Aryl)]⁺, possessing ancillary ligands that are varied with aryl-substituents on bipyridyl unit [C^N=(2-pyridyl)benzo[b]thiophen-3-yl (btp); N^N^Aryl=4,4′-Y₂-bpy (Y=−Ph or −PhSi(Ph)₃]. We found that the π-extension of bipyridyl ligand by aryl-substitution put bipyridyl ligand in use as an electron relay unit that performed charge accumulation before delivering to the catalytic center, greatly improving the overall CO₂-to-CO conversion activities. In a typical run, the aryl-substituted IrPS ( ^{t Bu} IrP-Ph^Si )-sensitized homogeneous systems (IrPS+Re^I catalyst) gave a turnover number of 1340 (Φ_CO=24.2 %) at the early stage of photolysis (<5 h). This study demonstrates that the π-character modulation on the ancillary bipyridyl ligand is critical for forthcoming catalytic performance.     

Electrochemical determination of ionization constants of tetrabutylammonium salt in acetonitrile and ο-nitrophenyloctylether

Cyclic voltammetry of ferrocene at glassy carbon electrode in acetonitrile (ACN), ο-nitrophenyloctylether (NPOE) and ACN-NPOE mixture with 0.2 M tetrabutylammonium tetrafluoroborate (TBABF₄) were investigated. Both cathodic and anodic peak current were diffusion-controlled at any NPOE fraction. However, the peak current was decreased with the increasing NPOE fraction. In addition, the peak potential difference increased not only with an increase in the NPOE fraction but also in the scan rate, while the values of half-wave potential did not vary largely with the fraction or the scan rate. This indicated that the variation of peak current and peak potential should be due to the variation of the solution resistance. In order to demonstrate this assumption, the conductance of TBABF₄ in ACN, NPOE, and ACN-NPOE mixture were determined by AC impedance. All of the solution conductances were inversely linear to the viscosity of the solvent, which was increased with the fraction of NPOE. The calculated ionization constant of TBABF₄ in ACN was 2.8 times of that in NPOE. TBABF₄ in ACN can work as a supporting electrolyte, whereas they work partly in NPOE.     

The improved photosensitivity of photosensitive polyimides containing o-nitrobenzyl ether groups induced by the addition of photoacid generator

In this article, photosensitive polyimides (PSPIs) with photosensitive groups, o-nitrobenzyl ether groups (Nb), were successfully synthesized based on 2,2′-dihydroxy benzophenone-3,3′,4,4′-tetracarboxylic dianhydride and on diamine containing ethylene glycol chains (ODA). Also, a series of polyimide (PI), ODA-1-PI, ODA-3-PI, and ODA-5-PI with a number of ethylene glycol chains of 1, 3, and 5 were prepared to investigate the relationship between structure and solubility. Interestingly, ODA-5-PI, which possesses a large number of ethylene glycols, exhibited the most excellent solubility. Therefore, due to the good solubility of ODA-5-PI in organic solvents and alkaline solutions, a PSPI, poly(1,4-phenyleneoxy-3,6,9,12,15-pentaoxaoctane-1,4-phenylene-2,2′-di[2-nitrobenzyloxy]benzophenone-3,3′,4,4′-tetracarboxdiimide), named ODA-5-PSPI, was synthesized by linking Nb, which is a photosensitive group. Aiming at producing positive tone patterns, the synthesized ODA-5-PSPI was exposed to UV irradiation and then to a post-exposure bake. Afterward, it was developed using a 2.38 wt% tetramethylammonium hydroxide solution. Furthermore, a photoacid generator (PAG) was additionally incorporated for a micropatterning process. Notably, in the presence of the PAG, the photocleavage of ODA-5-PSPI occurred not only by the intramolecular rearrangement of Nb but also by its hydrolysis reaction. As a result, due to the synergistic effect of photocleavage, the micropatterning of ODA-5-PSPI with PAG could be clearly obtained with less energy (2.0 J/cm²) compared with that without PAG (3.6 J/cm²). Therefore, through the addition of PAG, the photosensitivity was improved by 45%.     

A novel preventive mechanism of gentamicin‐induced nephrotoxicity by atorvastatin

Atorvastatin (ATO) inhibits the synthesis of nonsteroidal isoprenoid compounds and possesses a pleiotropic effect. However, the detailed mechanism of ATO in preventing gentamicin (GM)‐induced renal injury remains obscure. Although underlying multifaceted mechanisms involving GM‐induced nephrotoxicity were well known, further work on elucidating the essential mechanism was needed. Using a fluorogenic derivatization–liquid chromatography tandem mass spectrometry proteomic method (FD‐LC–MS/MS method), we investigated the effects and mechanisms of ATO treatment on GM‐induced nephrotoxicity in rats. Consequently, 49 differentially expressed proteins were identified. The most significant mechanisms of nephrotoxicity caused by GM were mitochondrial dysfunction, fatty acid metabolism and oxidative stress. Their upstream regulator was found to be PPARα. The proteins involved in GM nephrotoxicity were sodium–hydrogen exchanger regulatory factor (SLC9A3R1), cathepsin V (CTSV), macrophage migration inhibitory factor (MIF) and RhoGDP dissociation inhibitor alpha (ARHGDIA). After ATO intervention, we observed a reversed enrichment pattern of their expression, especially in CTSV and SLC9A3R1 (P‐value<0.05). We predicted that ATO may improve abnormal phospholipid metabolism and phospholipidosis caused by GM and also alleviate cell volume homeostasis and reverse the interference of GM with the transporter. Furthermore, proteomic results also provided clues as to GM‐induced nephrotoxicity biomarkers such as CTSV and transthyretin.     

Molecular Cloning and Heterologous Expression in Pichia pastoris of X-Prolyl-dipeptidyl Aminopeptidase from Basidiomycete Ustilago maydis

Dipeptidyl aminopeptidases are enzymes involved in the posttranslational control of bioactive peptides. Here we identified the gene dapUm in Ustilago maydis by homology with other fungal dipeptidyl aminopeptidases. Analysis of the dapUm-deduced amino acid sequence indicated that it encodes for membrane-type serine protease with a characteristic prolyl oligopeptidase catalytic motif triad: Ser, Asp, His. In order to overexpress the DapUm, the gene encoding for it was cloned and transformed into Pichia. Using this system, we observed a ～125-kDa recombinant protein with an optimal enzymatic activity at pH 6.0 and at 40 °C for the Ala-Pro-p-nitroanilide substrate and an experimental pH of 6.9. U. maydis DapUm was specifically inhibited by phenylmethylsulfonyl fluoride and Pefabloc, confirming the presence of a serine residue in the active site. To our knowledge, this study is the first report on the cloning and expression of a DPP IV dipeptidyl aminopeptidase from a basidiomycete organism. Moreover, the use of recombinant DapUm will allow us to further study and characterize this enzyme, in addition to testing chemical compounds for pharmaceutical purposes.     

Quantum chemistry study on the formation of OH radical for NO oxidation by heterogeneous Fenton reaction

The denitrification of low-temperature flue gas is a difficult problem facing the industry. OH radicals can effectually oxidize NO in flue gas, which can achieve denitrification of low-temperature flue gas. Heterogeneous Fenton reaction is an important method for the formation of OH radicals. A four-step reaction mechanism of the formation of OH radicals by heterogeneous Fenton reaction is proposed and investigated in this paper. Theoretical results show that activation energy of the formation of OH radicals catalyzed by ZSM5-Si/Fe is much lower than that without catalyst. After doping Al/Ce/Ti, the activation energy is further reduced significantly. The activity is related to the active center atom of the catalyst. By comparing, ZSM5-Ce/Al–Fe has better catalytic performance because of its more fluffy structure. This study would provide an important theoretical reference for the design of the catalysts in heterogeneous Fenton reaction and their industrial applications.