A Mechanistic Dichotomy in Two-Electron Reduction of Dioxygen Catalyzed by N,N’-Dimethylated Porphyrin Isomers

Selective two-electron reduction of dioxygen (O₂) to hydrogen peroxide (H₂O₂) has been achieved by two saddle-distorted N,N’-dimethylated porphyrin isomers, an N21,N’22-dimethylated porphyrin ( anti -Me₂P ) and an N21,N’23-dimethylated porphyrin ( syn -Me₂P ) as catalysts and ferrocene derivatives as electron donors in the presence of protic acids in acetonitrile. The higher catalytic performance in an oxygen reduction reaction (ORR) was achieved by anti -Me₂P with higher turnover number (TON=250 for 30 min) than that by syn -Me₂P (TON=218 for 60 min). The reactive intermediates in the catalytic ORR were confirmed to be the corresponding isophlorins ( anti -Me₂Iph or syn -Me₂Iph ) by spectroscopic measurements. The rate-determining step in the catalytic ORRs was concluded to be proton-coupled electron-transfer reduction of O₂ with isophlorins based on kinetic analysis. The ORR rate by anti -Me₂Iph was accelerated by external protons, judging from the dependence of the observed initial rates on acid concentrations. In contrast, no acceleration of the ORR rate with syn -Me₂Iph by external protons was observed. The different mechanisms in the O₂ reduction by the two isomers should be derived from that of the arrangement of hydrogen bonding of a O₂ with inner NH protons of the isophlorins.     

Gas-Sensing Activity of Amorphous Copper Oxide Porous Nanosheets

In this paper, the gas-sensing properties of copper oxide porous nanosheets in amorphous and highly crystalline states were comparatively investigated on the premise of almost the same specific surface area, morphology and size. Unexpectedly, the results show that amorphous copper oxide porous nanosheets have much better gas sensing properties than highly crystalline copper oxide to a serious of volatile organic compounds, and the lowest detection limit (LOD) of the amorphous copper oxide porous nanosheets to methanal is even up to 10 ppb. By contrast, the LOD of the highly crystalline copper oxide porous nanosheets to methanal is 95 ppb. Experiments prove that the oxygen vacancies contained in the amorphous copper oxide porous nanosheets play a key role in improving gas sensitivity, which greatly improve the chemical activity of the materials, especially for the adsorption of molecules containing oxygen-groups such as methanal and oxygen.     

Operando Isotopic Exchange in Solid Oxide Fuel Cells: Oxygen-Transport Dependency on Applied Potential

The oxygen isotopic exchange technique is a powerful tool to investigate the oxygen transport kinetics in an oxide solid. In a solid oxide fuel cell, isotopic surface exchange and diffusion coefficients are classically determined by using the Isotopic Exchange Depth Profiling method followed by ex situ SIMS characterizations. Despite its relevance, the utilization of in situ or operando techniques to measure the isotopic exchange under an electrical bias remains marginal. We developed here a set-up which enables operando monitoring of oxygen exchange in SOFC type cells under polarization. The system has been used for studying the oxygen mobility dependency upon polarization on a symmetrical Pt/YSZ/Pt cell (YSZ: yttria-stabilized zirconia). Homomolecular and heterolytic exchange reactions were undertaken to investigate the oxygen activation step and discriminate the limiting step among the sequence of elementary steps which constitute the oxygen transport process in the SOFC system. Oxygen ions incorporation into the dense ionic conductor was identified to be the rate determining step, and its first order rate constant dependency on applied potential was established.     

Imine‐linked porous organic polymers showing mesoporous microspheres architectures with tunable surface roughness

Different kinds of porous organic polymers (POPs) bearing 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BDP) fluorophores have been developed to generate singlet oxygen upon light illumination. Herein, four imine‐linked POPs were prepared by copolymerization of amine and aldehyde with different ratios of di‐aldehyde A1 and A2. The POPs were investigated by a combination of techniques such as solid ¹³C NMR, FTIR, and nitrogen absorption–desorption isotherms and electronic microscopy. The results demonstrated that these POPs were prone to form hierarchical porous architectures. Scanning electron microscopy and transmission electron microscopy images revealed that the spherical morphologies showed different roughness, that is, BDP‐POPs with more BDP aldehyde A2 presented rougher surface. Finally, these POPs were used to generate singlet oxygen (¹O₂) monitored by 1,3‐diphenylisobenzofuran and bioimaging in HeLa cells. Our results indicated that the ability to generate ¹O₂ is dependent on the amount of BDP. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 319–327     

Functional and bioactive properties of Larimichthys polyactis protein hydrolysates as influenced by plasma functionalized water-ultrasound hybrid treatments and enzyme types

The effects of plasma functionalized water (PFW) and its combination with ultrasound (UPFW) on the functional and bioactive properties of small yellow croaker protein hydrolysates (SYPHs) produced from three enzymes were investigated. Fluorescence and UV–Vis spectroscopy indicated that SYPHs tended to unfold with increasing intensity and shift in wavelengths to more flexible conformations under PFW and UPFW treatments. Particle size distribution and microstructure analysis revealed that treatments could disrupt aggregation of protein molecules to increase the roughness, specific surface area, and decrease the particle size of peptides during hydrolysis. The partially denatured structure of SYPHs induced by treatments increased the susceptibility of the fish proteins to exogenous enzymes, thereby accelerating the hydrolytic process to yield peptides with improved solubility, decreased emulsifying and foaming properties, and improved enzyme-specific antioxidant properties. The results revealed that the functionality of SYPHs was influenced by the treatment method and the enzyme type employed.     

SiOx precipitate composition in Si,revisited: Discussion closed?

The composition SiO_x of oxide precipitates in Si has been discussed for the past thirty years with experimentally estimated x ‐values ranging between 1 and 2. It is shown that this spread of x ‐values can be explained by calculating the average composition taking into account temperature and anneal time dependent size and shape of the precipitates and the limitations and probing volumes of the various characterization techniques. Hereby it is assumed that the oxygen‐rich (SiO₂?) core of the precipitates is surrounded by a 2 nm thin SiO layer as revealed by recent electron energy loss spectroscopy analyses. For plate‐like precipitates thinner than and for octahedral precipitates smaller than 6 nm, x ≈ 1. For larger precipitates, the central part of the precipitate consists of SiO_x with x close to 2 and the precipitate has an average x between 1 and 1.3 for plate‐like and up to 1.9 for octahedral precipitates. The predicted x ‐values for different precipitate sizes and morphologies, are compared with published experimental data. SiO_x precipitate nucleation and initial growth should be simulated assuming x = 1 and Fourier transform infrared spectra of precipitates assuming a mixture of SiO₂ and amorphous Si. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Tunable Oxygen Activation for Catalytic Organic Oxidation: Schottky Junction versus Plasmonic Effects

The charge state of the Pd surface is a critical parameter in terms of the ability of Pd nanocrystals to activate O₂ to generate a species that behaves like singlet O₂ both chemically and physically. Motivated by this finding, we designed a metal–semiconductor hybrid system in which Pd nanocrystals enclosed by {100} facets are deposited on TiO₂ supports. Driven by the Schottky junction, the TiO₂ supports can provide electrons for metal catalysts under illumination by appropriate light. Further examination by ultrafast spectroscopy revealed that the plasmonics of Pd may force a large number of electrons to undergo reverse migration from Pd to the conduction band of TiO₂ under strong illumination, thus lowering the electron density of the Pd surface as a side effect. We were therefore able to rationally tailor the charge state of the metal surface and thus modulate the function of Pd nanocrystals in O₂ activation and organic oxidation reactions by simply altering the intensity of light shed on Pd–TiO₂ hybrid structures.     

Study on the electroreduction process of oxygen to superoxide ion by using acetylene black powder microelectrode

In this paper, the powder microelectrode technique was employed in studying the voltametric response of the O₂/₂⁻ couple, which demonstrated a nearly reversible redox process at an acetylene black powder microelectrode in N,N-dimethylformamide (DMF). A well-developed steady state current plateau for the electrochemical reduction of oxygen was obtained in this system. The electron transfer number (n) and heterogeneous electron transfer rate constant k _s were measured by steady-state voltametric response, and the results were 1.08, 3.4 × 10⁻³ cm s⁻¹, respectively. Additionally, the scavenging activity of O₂⁻ with biological antioxidant (ascorbic acid) was evaluated by cyclic voltammetry; IC₅₀ came to 5 × 10⁻⁴ mol/l. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 8, pp. 1040–1044. The text was submitted by the authors in English.