Mechanistic Insights into the Reversible Formation of Iodosylarene–Iron Porphyrin Complexes in the Reactions of Oxoiron(IV) Porphyrin π‐Cation Radicals and Iodoarenes: Equilibrium,Epoxidizing Intermediate,and Oxygen Exchange

We have shown previously that iodosylbenzene–iron(III ) porphyrin intermediates ( 2 ) are generated in the reactions of oxoiron(IV ) porphyrin π‐cation radicals ( 1 ) and iodobenzene (PhI), that 1 and 2 are at equilibrium in the presence of PhI, and that the epoxidation of olefins by 2 affords high yields of epoxide products. In the present work, we report detailed mechanistic studies on the nature of the equilibrium between 1 and 2 in the presence of iodoarenes (ArI), the determination of reactive species responsible for olefin epoxidation when two intermediates (i.e., 1 and 2 ) are present in a reaction solution, and the fast oxygen exchange between 1 and H₂¹⁸O in the presence of ArI. In the first part, we have provided strong evidence that 1 and 2 are indeed at equilibrium and that the equilibrium is controlled by factors such as the electronic nature of iron porphyrins, the electron richness of ArI, and the concentration of ArI. Secondly, we have demonstrated that 1 is the sole active oxidant in olefin epoxidation when 1 and 2 are present concurrently in a reaction solution. Finally, we have shown that the presence of ArI in a reaction solution containing 1 and H₂¹⁸O facilitates the oxygen exchange between the oxo group of 1 and H₂¹⁸O and that the oxygen exchange is markedly influenced by factors such as ArI incubation time, the amounts of ArI and H₂¹⁸O used, and the electronic nature of ArI. The latter results are rationalized by the formation of an undetectable amount of 2 from the reaction of 1 and ArI through equilibrium that leads to a fast oxygen exchange between 2 and H₂¹⁸O.     

Magnetic and electrical transport properties of delta-doped amorphous Ge:Mn magnetic semiconductors

We report on the growth and characterization of delta-doped amorphous Ge:Mn diluted magnetic semiconductor thin films on GaAs (0 0 1) substrates. The fabricated samples exhibit different magnetic behaviors, depending on the Mn doping concentration. The Curie temperature was found to be dependent on both the Mn doping concentration and spacing between the doping layers. A sharp drop in magnetization and rise in resistivity are observed at low temperature in samples with high Mn doping concentrations, which is also accompanied by a negative thermal remanent magnetization (TRM) in the higher temperature range. The temperature at which the magnetization starts to drop and the negative TRM appears show a correlation with the Mn doping concentration. The experimental results are discussed based on the formation of ferromagnetic regions at high temperature and antiferromagnetic coupling between these regions at low temperature.     

Photochemical Reactions of Protein Tryptophanyls in the Eye Lenses of Rats in the Presence of Chloroform

The modifying action of chloroform on photochemical reactions induced in the eye lenses of rats by UVB radiation is revealed. In anesthetic concentrations, halogenmethane increases the quantum yield of photodisintegration of protein tryptophanyls with formation of a new photochemical product that absorbs radiation in the UVA range and possesses the photosensitizing activity.     

甚高频等离子体增强化学气相沉积法沉积μc-Si∶H薄膜中氧污染的初步研究

对不同的本底真空条件下,采用甚高频等离子体增强化学气相沉积技术沉积的氢化微晶硅（μc_Si∶H）薄膜中的氧污染问题进行了比较研究.对不同氧污染条件下制备的薄膜样品的x射线光电子能谱与傅里叶变换红外吸收光谱测量结果表明：μc_Si∶H薄膜中,氧以Si—O，O—O和O—H三种不同的键合模式存在,不同的键合模式源自不同的物理机理.μc_Si∶H薄膜的Raman光谱、电导率与激活能的测量结果进一步显示：沉积过程中氧污染程度的不同,对μc_Si∶H薄膜的结构特性与电学特性产生显著影响；而不同氧污染对μc_Si∶H薄膜电学特性的影响不同于氢化非晶硅（a_Si:H）薄膜. 关键词： 氢化微晶硅薄膜 甚高频等离子体增强化学气相沉积 氧污染     

神经网络在大型复杂武器装备质量综合评价排序中的应用

从大型复杂武器装备系统的具体特点出发,运用基于神经网络的评价方法,构建了大型复杂武器装备质量综合评价模型。实证分析的结果表明该方法得出的结果与实际情况相符。     

THE NBELC AND NWELC CLASSES OF LIFE DISTRIBUTIONS

ＴＨＥＮＢＥＬＣＡＮＤＮＷＥＬＣＣＬＡＳＳＥＳＯＦＬＩＦＥＤＩＳＴＲＩＢＵＴＩＯＮＳ￥ＣＡＯＪＩＮＨＵＡ；ＷＡＮＧＹＵＥＤＯＮＧ（ＩｎｓｔｉｔｕｔｅｏｆＡｐｐｌｉｅｄＭａｔｈｅｍａｔｉｃｓ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅ，Ｂｅｉｊｉｎ...     

Strong,large distance impurity dipole interaction in KNbO3 single crystals

It is found that the unrelaxed impurity dipoles can arrange themselves linearly in the structure joining each other end-to-end in pseudocubic [110] direction at the tetragonal to the orthorhombic phase transition. It is shown that this alignment precedes the domain formation at the phase transition, which implies quick movements of the dipoles in the structure, and a strong dipolar interaction. The experiments with the application of dc fields to the crystals showed that the dipolar interaction becomes stronger with the field. The dipoles can see each other across the existing domain walls implying the large distance nature of the interaction. The observation of impurity clusters arranged in pseudocubic [110] direction confirmed the large distance nature of the interaction. It is concluded that this strong, large distance interaction is very interesting in as much as such an interaction of dipoles forms the basis of ferroelectricity.     

Charge order and spin order in Nd_(0.5)Sr_(0.5)Mn_(1-x)(Ga_x, Ti_x)O_3 system

Magnetic properties of Nd_(0.5)Sr_(0.5)Mn_(1-x)(Ga_x, Ti_x)O_3 system (0.04≤x≤0.4) were inves- tigated through magnetization and electron spin resonance (ESR) measurements. It was observed that a small amount of Ti substitution for Mn will destroy the charge-ordering (CO) phase completely and induce the cluster-spin-glass phase in the system, which displays a procedure of collapse of CO and of an enhancement of spin ordering (SO) phase. In contrast, the Ga substitution for Mn induces a melt- ing of CO phase in the system. It was observed that with substitution the CO phase is suppressed gradually and the remanent CO phase is retained all the while, and withal, there is a co-existence of AFM CO phase and FM SO at low temperature. In addition, an abrupt rise of magnetization was observed in M-T curves. We attributed this abnormal phenomenon to a transition from canted AFM SO to FM SO in CO region.     

Phase Separation Driven by a Fluctuating Two-Dimensional Self-Affine Potential Field

We study phase separation in a system of hard-core particles driven by a fluctuating two-dimensional self-affine potential landscape which evolves through Kardar–Parisi–Zhang (KPZ) dynamics. We find that particles tend to cluster together on a length scale which grows in time. The final phase-separated steady state is characterized by an unusual cusp singularity in the scaled correlation function and a broad distribution for the order parameter. Unlike the one-dimensional case studied earlier, the cluster-size distribution is asymmetric between particles and holes, reflecting the broken reflection symmetry of the KPZ dynamics, and has a contribution from an infinite cluster in addition to a power law part. A study of the surface in terms of coarse-grained depth variables helps understand many of these features.     

Electrocatalytic activity of sol-gel-prepared RuO2/Ti anode in chlorine and oxygen evolution reactions

Electrocatalytic properties of RuO₂/Ti anode with different coating masses, which are prepared by the alkoxide sol-gel procedure, are investigated in chlorine and oxygen evolution reactions by polarization measurements and electrochemical impedance spectroscopy in H₂SO₄ and NaCl electrolytes. According to polarization measurements, the activity of anodes at overpotentials below 100 mV is independent of coating mass. However, impedance measurements above 100 mV reveal changes in the activity of anodes in chlorine evolution reaction for different coating masses. The diffusion limitations related to the evolved chlorine are registered in low-frequency domain at 1.10 V (SCE), diminishing with the increase in potential to the 1.15 V (SCE). The observed impedance behavior is discussed with respect to the activity model for activated titanium anodes in chlorine evolution reaction involving formation of gas channels within porous coating structure. Gas channels enhance the mass transfer rate similarly to the forced convection, which also increases the activity of anode. This is more pronounced for the anode of greater coating mass due to its more compact surface structure. The more compact structure appears to be beneficial for gas channels formation. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1173–1179. The text was submitted by the authors in English.