Studies on the Phenol Oxidation with H2O2 Catalyzed by Metallomicelle Made from Crowned Schiff Base Mn(III) Complexes

Metallomicelles made from two Schiff base manganese(III) complexes (MnL¹ and MnL²) and surfactants (CTAB and Brij35) were used as mimetic peroxidase in the catalytic oxidation of phenol by H₂O₂. The catalytic activity of the complexes (MnL¹ and MnL²) were investigated. The mechanism and a kinetic mathematic model of the phenol catalytic oxidation were also studied. The results show the optimum acidity of the enzyme-like system in the paper is ca. pH 7.0, the optimum temperature which is ca. 35°C and the optimum molar ratio of H₂O₂ to the complex is ca. 30 in the complexes-H₂O₂-buffered solution; the Schiff base manganese(III) complexes and their metallomicelles as peroxidase mimics exhibit good catalytic activity and similar catalytic character to natural enzyme.     

新一代白光LED照明用一种适于近紫外光激发的单一白光荧光粉

首次报道单一Sr2MgSiO5：Eu^2 材料的白光发射性质。发射光谱由两个谱带组成,分别位于470,570nm处,并具有不同的荧光寿命,归结为处于不同格位上的二价铕离子的发射,它们混合成白光。这两个发射带所对应的激发光谱均分布在250～450nm的紫外区,利用该荧光粉和具有400nm近紫外光发射的InGaN管芯制成了白光LED。正向驱动电流为20mA时,色温为5664K;发光色坐标为x=0．33,y=0．34;显色指数为85％;光强达8100cd／m^2。实验表明,器件的色坐标和显色指数等参数随正向驱动电流的变化起伏量小于5％,优于目前商用的蓝光管芯泵浦白光LED,报道的单一白光荧光粉在新一代白光LED照明领域具有广阔的应用前景。     

高压下稀土离子的电子态

给出了稀土离子电子态在高静水压下的某些特性,包括高压下的发光光 谱及能级特性,晶体场强度的压力效应,4f电子库仑排斥及自旋轨道耦合等作用随压力 的变化等。     

Dioxygen affinities and catalytic epoxidation performance of mono-Schiff base transition-metal complexes with aza-crown or morpholino pendants

Mono-Schiff base Co^II complexes, CoL ₂ ¹ –CoL ₂ ⁶ with aza-crown or morpholino pendants were synthesized. The O₂ uptake of these complexes in MeOCH₂CH₂OMe solution was determined at different temperatures, and the equilibrium constants (KO₂) and thermodynamic parameters (ΔH ⁰, ΔS ⁰) for oxygenation were calculated. The corresponding Mn^III complexes, MnL ₂ ¹ Cl–MnL ₂ ⁶ Cl, were employed to catalyze epoxidation of styrene at ambient temperature and pressures. Crown ether effects on the modulation of O₂-binding capability and the catalytic oxidation of styrene are discussed. The results indicate that the dioxygen affinities of the Co^II complexes are much more enhanced by aza-crown pendants than that by morpholino pendants, and the O₂-binding capabilities of CoL ₂ ¹ –CoL ₂ ³ with aza-crown pendants can also be enhanced by adding alkali metal (Li⁺, Na⁺ and K⁺) cations; similarly, the catalytic activities of the Mn^III complexes with aza-crown pendants, MnL ₂ ¹ Cl–MnL ₂ ³ Cl, are higher than those of the Mn^III complexes with morpholino pendants, MnL ₂ ⁴ Cl–MnL ₂ ⁶ Cl.     

A Kinetic Study of Phenolic Oxidation by H2O2 Using the Schiff Base Complexes As Mimetic Peroxidases

The Schiff base complexes containing a transition metal ion, Co^II and Cu^II, were used as mimetic peroxidase in the catalytic oxidation of phenol by H₂O₂. The characteristic spectra of the Schiff base complexes in H₂O₂-buffered solution were recorded and analyzed, respectively. The mechanism and the kinetic mathematic model of the phenol catalytic oxidation were studied. The results showed that the Schiff base complexes containing the transition metal ion, Co^II and Cu^II, as peroxidase mimics exhibited good catalytic activity and the character of the peroxidase in the catalytic oxidation of phenol by H₂O₂ under different conditions.     

Study of the Intramolecular Reaction of an Activated Phosphate Ester in the Micelle System Containing Macrocyclic Complex

The intramolecular nucleophilic substitution of an activated phosphate diester, bis(p-nitrophenyl) phosphate (BNPP) as the nucleic acids substitute, was investigated. A macro-cyclic ligand and the corresponding Cu (II) and Ni (II) complexes were synthesized and characterized. The metallomicelles made up of macrocyclic divalent metal complex and micelle, as mimic hydrolytic metalloenzyme, was used in BNPP catalytic hydrolysis. The metallomicelles displayed higher catalytic activity although they do not attain the catalytic efficiency of enzymes. The analysis of specific absorption spectra showed that the course of the BNPP catalytic reaction was different from that of the BNPP spontaneous hydrolysis, and was an intramolecular nucleophilic substitution reaction. Based on the analytic result of the specific absorption spectrum, an intramolecular nucleophilic substitution mechanism of BNPP catalytic hydrolysis was proposed and a correlative kinetic mathematical model was established, and the corresponding thermodynamic and kinetic constant was calculated. The result of this study proved validity of the mechanism and mathematical model proposed in the article.     

荧光体CaSO_4∶Eu的近紫外发光性质

CaSO4∶Eu是一种人们早已较为熟知的发光材料,由于其优异的热释发光特性而被广泛应用于辐射剂量学方面。近年来由于崭新的光致发光液晶显示模式的出现,人们又对其近紫外发射特性产生了极大兴趣。考察了CaSO4∶Eu的发光特性和材料的各种制备方法,以及制备条件对发光性能的影响,特别是对其近紫外发射性能的影响。实验表明,对于还原彻底、结晶良好的样品,激活剂Eu几乎全部以二价铕离子的形式存在,是一种很好的近紫外发射材料。该材料能被低压汞蒸气放电辐射有效激发,其发射带的峰值在386 nm附近,随Eu的掺杂浓度不同而略有差异,半峰全宽约为16 nm,基本满足了近紫外发射的要求,可应用于光致发光液晶显示器件的背照明光源中。     

二维板声发射源定位实验的一种简易实现方法

对声发射技术中的二维平面定位问题提出一种新的简易实验方案.采用新三角时差算法实现二维板的声源定位和GPS模拟,同时利用简易实验方法,仅用两个超声波传感器完成实验,简化实验器材,降低实验成本,适合普及,计算过程简单,同时也利于物理问题深入地理解.     

Studies on the Kinetics and Mechanism of Hydrolysis of p-nitrophenyl Picolinate (PNPP) by Unsymmetrical bis-Schiff Base Complexes with Aza-crown Ether or Morpholino Pendants

Two novel unsymmetrical bis-Schiff base manganese(III) and cobalt(II) complexes with benzo-10-aza-crown ether pendants (MnL¹Cl, CoL¹), and their analogoues with morpholino pendants (MnL²Cl, CoL²), have been synthesized and employed as models to mimic hydrolase in p-nitrophenyl picolinate (PNPP). The kinetics and the mechanism of PNPP hydrolysis catalyzed by these complexes were investigated. A kinetic mathematical model of PNPP cleavage catalyzed by these complexes was proposed. The effects of the complexes structure and reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results showed that the rate for the catalytic PNPP hydrolysis increased following the increase in pH of the buffer solution; four complexes exhibited high activity in the catalytic PNPP hydrolysis. Compared with the crown-free analogoues MnL²Cl and CoL², the crowned Schiff base complexes (MnL¹Cl, CoL¹) exhibit a higher catalytic activity; the pseudo-first-order-rate (k_obs) for the PNPP hydrolysis catalyzed by the complex MnL¹Cl containing benzo-10-aza-crown ether is 1.04 × 10³ that of spontaneous hydrolysis of PNPP at pH = 7.00, [S] = 2.0×10⁻⁴ mol dm⁻³.     

荧光体CaSO4：Eu的近紫外发光性质

CaSO₄:Eu是一种人们早已较为熟知的发光材料,由于其优异的热释发光特性而被广泛应用于辐射剂量学方面。近年来由于崭新的光致发光液晶显示模式的出现,人们又对其近紫外发射特性产生了极大兴趣。考察了CaSO₄:Eu的发光特性和材料的各种制备方法,以及制备条件对发光性能的影响,特别是对其近紫外发射性能的影响。实验表明,对于还原彻底、结晶良好的样品,激活剂Eu几乎全部以二价铕离子的形式存在,是一种很好的近紫外发射材料。该材料能被低压汞蒸气放电辐射有效激发,其发射带的峰值在386nm附近,随Eu的掺杂浓度不同而略有差异,半峰全宽约为16nm,基本满足了近紫外发射的要求,可应用于光致发光液晶显示器件的背照明光源中。