Formation of protonic defects in perovskite-type oxides with redox-active acceptors: case study on Fe-doped SrTiO(3)

The thermodynamics of water incorporation into Fe-doped SrTiO(3) was investigated by thermogravimetric measurements. Changes in valence states of redox-active dopant ions (Fe(3+)/Fe(4+)) with water vapor pressure were taken into account in the defect chemical analysis. The proton solubility was significantly enhanced by the presence of the redox centers. The hydration enthalpies and entropies were -60 kJ mol(-1) and -122 J mol(-1) K(-1). The defect chemical model was applied to describe the water vapor dependence of the electrical conductivity in mixed ionic and electronic conducting Fe-doped SrTiO(3) single crystals.     

Preparation of crosslinked polystyrene-supported ethylenediamine via a S-containing spacer and adsorption properties towards metal ions

Two novel chelating resins were prepared by anchoring ethylenediamine to crosslinked polystyrene via a spacer containing sulfide. Their structures were characterized by Fourier transform-infrared spectra (FTIR) and scanning electron microscopy (SEM). Porous structure parameters of the resins were measured by ASAP 2020 using BET and BJH methods. Their adsorption capacities for several heavy metal ions especially Hg²⁺ were investigated. The results showed that for the two resins, the more N contents did not mean the better adsorption capacity and the saturated adsorption capacity of poly(2-ethylenediamidomercaptomethylstyrene) (PSM-EDA) for Hg²⁺ could reach to 3.0 mmol/g at room temperature. Isothermal adsorptions of the resins for Hg²⁺ could be described by Langmuir formula. The adsorption mechanism of the resins for Hg²⁺, Cu²⁺ and Ag⁺ was confirmed by X-ray photoelectron spectroscopy (XPS) and FTIR.     

Reactions of N-silylphosphoranimines with alcohols: synthesis and structure of cyclotriphosphazenes with nongeminal methyl and phenyl substituents

The reactions of Me(3)SiN=P(OR")RR'(R" = Ph, CH(2)CF(3); R, R' = Me, Ph) with alcohols were investigated. With nonequivalent amounts of CF(3)CH(2)OH, the reactions produced high yields of the cyclic phosphazene (Me(2)PN)(3) and both the cis and trans isomers of nongeminally substituted [(Ph)(Me)PN](3). The isomers of this new cyclic phosphazene were separated by column chromatography and characterized by NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Crystals of the cis isomer 6a have a monoclinic crystal system, while the trans isomer 6b has a triclinic crystal system with two different molecules in an asymmetric unit. The bond lengths and bond angles are very similar to those of the simpler cyclic trimers (Me(2)PN)(3) and (Ph(2)PN)(3.) A likely pathway for the formation of these compounds is discussed.     

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of phospholipase A2 and fibrinolytic enzyme, two enzymes obtained from Chinese Agkistrodon blomhoffii Ussurensis venom

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to analyze two enzymes, phospholipase A2 and fibrinolytic enzyme isolated from Chinese Agkistrodon blomhoffii Ussurensis venom. Using sinapinic acid as the matrix, positive ion mass spectra of the enzymes were obtained. In addition to the dominant protein [M + H]+ ions, multimeric and multiply charged ions were also observed in the mass spectra. The higher the concentration of the enzymes, the more multiply charged polymer and multimeric ions were detected. Our results indicate that MALDI-TOFMS can provide a rapid and accurate method for molecular weight determination of snake venom enzymes. Mass accuracies of 0.1 and 0.3% were achieved by analysis of highly dialyzed phospholipase A2 and fibrinolytic enzyme, and these results are much better than those obtained using sodium dodecyl sulfate-polyacrylamide gel electrophoresis. MALDI-TOFMS thus provides a reliable method to determine the purity and molecular weight of these enzymes, which are of potential use as therapeutants.     

芳香二磺酸的配位化学研究化合物[Ni(cyclam)(1,5nds)]·1/3H_2O(1)和[Co(cyclam)(H_2O)_2](1,5nds)·2H_2O(2)的合成与结构(英文)

合成了两个二价的过渡金属磺酸化合物,并通过X-射线衍射单晶结构分析进行结构表征。化合物犤Ni(cyclam)(1,5nds)犦·1/3H2O(1)以P2(1)/c空间群结晶,晶胞参数为a=8.583(5),b=10.533(6),c=12.946(7)?,β=92.433(9)°。犤Ni(cyclam)犦2+与两个磺酸基团形成弱配位,从而构筑了一维的配聚物。犤Ni(cyclam)犦2+与磺酸基团之间的作用还通过O2S-O…H-N型氢键进一步被加强。化合物犤Co(cyclam)(H2O)2犦(1,5nds)·2H2O(2)以P1珔空间群结晶,晶胞参数为a=8.738(5),b=9.324(5),c=10.118(5)?,α=81.382(8),β=64.868(8),γ=62.999(8)°。在该化合物中,磺酸基团没有与Co2+形成配位键,而是以平衡离子的形式存在并与配离子形成氢键,构筑了有序的三维结构。     

Electrochemical studies of the oxidation mechanism of polyamide on glassy carbon electrode

Polyamides containing N-methyl pyrroles and N-methyl imidazoles are a type of small molecule that can bind and recognize the bases of DNA with high affinity and specificity. Five polyamides were studied at glassy carbon electrode in acetate buffer by cyclic and differential pulse voltammetry to clarify their redox pathways. The polyamide electrochemical responses are compared by peak currents and peak potentials. The slopes of the three anodic E_p vs. pH plots of a typical polyamide are linear and show 0.059, 0.057, 0.056 V per pH in acid media, respectively, which correspond to a mechanism involving the equal number of electrons and protons. A possible mechanism for the redox pathway of various polyamides is proposed: the oxidation product of imidazole ring is acylamide and the results of in situ UV–Vis spectroscopy at Pt web electrode support the proposed mechanism. electrospray ionization mass spectroscopy (ESI-MS) indicates that one or two oxygen atoms are added into polyamide molecule after electrochemical oxidation.     

The luminescence efficiency of YAG: Ce phosphors

The luminescence intensity of Yttrium aluminium garnet activated by the Ce³⁺ (YAGCe³⁺) under cathode-ray excitation depends on the preparation method and content of some dopants. Samples containing Fe, Pt, Ir or some colour centre, respectively, show relatively low luminescence. The maximum luminescence intensity was obtained with the Czochralski method grown single crystals in 98% Ar+2% H₂ atmosphere which were sensitized by oxygen annealing followed by treatment at 1500 °C in molybdenum container using a wet hydrogen atmosphere.     

Preparation of nanometer FeCuP alloy and its application in decomposition of PH3

A new ternary Fe-based alloy catalyst FeCuP applied to decompose PH_3 was prepared with low-cost material by chemical reduction deposition method.The properties of it were characterized by XRD,ICP and SEM.Its catalytic activity on the decomposition of PH_3 and the decomposition conditions were studied.FeCuP alloy exhibits high thermal stabilities and high catalytic activity.Using it as catalyst,the decomposition temperature of phosphine decreases from over 800℃to 400-500℃.The decomposition rate of phosphine achieved 100%.     

Factors affecting the catalytic epoxidation of olefins by iron porphyrin complexes and H2O2 in protic solvents

The catalytic epoxidation of cyclohexene by iron(III) porphyrin complexes and H2O2 has been investigated in alcohol solvents to understand factors affecting the catalyst activity in protic solvents. The yields of cyclohexene oxide and the Fe(III/II) reduction potentials of iron porphyrin complexes were significantly affected by the protic solvents, and there was a close correlation between the product yields and the reduction potentials of the iron porphyrin catalysts. The role of alcohol solvents was proposed to control the electronic nature of iron porphyrin complexes that determines the catalyst activity in the epoxidation of olefins by H2O2. We have also demonstrated that an electron-deficient iron porphyrin complex can catalyze the epoxidation of olefins by H2O2 under conditions of limiting substrate with high conversion efficiency in a solvent mixture of CH3OH and CH2Cl2.     

One-pot oxidation of sulfides to sulfones by reusable heterogeneous ruthenium catalyst in the presence of molecular oxygen

A reusable solid catalyst, MnFe_1.8Cu_0.15Ru_0.05O₄, has been developed as an effective catalyst for the aerobic oxidation of sulfides and sulfoxides to sulfones. The ruthenium modified spinel catalyst is the first example reported for such reaction under mild condition with molecular oxygen as the only oxidant. The oxidation reaction proceeded via an electrophilic attack of the oxygen atom of the catalyst on the electron-rich sulfur atom of the substrate.