The Chemistry of DPPH· Free Radical and Congeners

Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH^·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.     

Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

Catalytic properties and electronic structure of copper ions in Cu-ZSM-5

The effect of ion exchange conditions, such as Si/Al ratio, precursor copper salt, pH and concentration of the solution, on the catalytic activity in SCR of NO by propane and on the electronic state of copper ions in Cu-ZSM-5 has been studied. The NO conversion in NO SCR by C₃H₈ has been found to reach a maximum value at Cu/Al ratio about 0.37–0.4 and remain constant at higher Cu/Al.

ESR and UV–vis DR spectroscopy have been used to elucidate stabilization conditions of copper ions in Cu-ZSM-5 zeolites as isolated Cu²⁺ ions, chain copper oxide structures and square-plain oxide clusters. The ability of copper ions for reduction and reoxidation in the chain structures may be responsible for the catalytic activity of Cu-ZSM-5. These transformations of copper ions are accompanied by the observation of intervalence transitions Cu²⁺–Cu⁺ and CTLM of the chain structures in the UV–vis spectra.     

Synthesis, Characterization and Crystal Structure of Quaternary Complex of Gadolinium （Ⅲ）

Ａｎｕｍｂｅｒｏｆｌａｎｔｈａｎｉｄｅｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｃｏｎ ｔａｉｎｉｎｇｈｅｔｅｒｏｃｙｃｌｉｃａｍｉｎｅｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄｓｉｎｃｅ1960 [1] .Ｉｎｒｅｃｅｎｔｙｅａｒｓｍｕｃｈａｔｔｅｎｔｉｏｎｈａｓｂｅｅｎｐａｉｄｔｏｑｕａｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓｏｆｌａｎｔｈａｎｉｄｅｓｂｅｃａｕｓｅｏｆｉｎ ｔｅｒｅｓｔｉｎｇｓｔｒｕｃｔｕｒｅ ,ｃｏｏｒｄｉｎａｔｉｏｎｍｏｄｅ ,ｃｏｍｐｅｔｉｔｉｏｎｒｅ ａｃｔｉｏｎａｎｄｐｒｏｐｅｒｔｙ[2～ 9] .ＥＳＲｃａｎｅ…     

用电子自旋共振研究导热油的热稳定性

用电子自旋共振对国内几种典型合成油，基础油及加有添加剂的基础油，分别在不同温度下测定生成自由基的相对浓度，以及一定温度下放置一段时间自由基衰减情况，来考察导热油的热稳定性。     

In-situ ESR spectroelectrochemical studies of overoxidation behaviour of poly(3,4-butylenedioxythiophene)

The behaviour of poly(3,4-butylenedioxythiophene) (PBuDOT), a relative of poly(3,4-ethylenedioxythipohnene) PEDOT within the poly(3,4-alkylenedioxythiophene) family, has been investigated at potentials above its electrochemical stability threshold using in situ ESR spectroelectrochemistry. The aim was to investigate the effect of electrochemical overoxidation on the charge carrying species, namely polarons, normally generated and annihilated during reversible redox doping and dedoping reactions, by determining the potential dependencies of spectroscopic parameters of the ESR spectra of the polymer over a selected potential range. Specific features of the trends of these dependencies allowed also for an evaluation of presence of the second type of charge carrying species—diamagnetic bipolarons and the effects of their interactions with polarons at different potentials. Around 1.5 V, where the boundary of electrochemical stability of the polymer lies, sharp drop of the concentration of paramagnetic centres has been observed together with a transitory narrowing of the ESR line. These changes were found to be irreversible as evidenced by the course of subsequent reduction half-cycle, which differed from the one for a not overoxidised polymer, observed in previous studies. Aided by the results of electrochemical studies it was concluded that the overoxidation process leads to a degradation of the polymer most probably due decrease of the conjugation length of the main chain π-bond through cross-linking or addition reactions. While the electrochemical results pointed to a non-complete degradation of the polymer, the specific parameters of the ESR line in the reduction half-cycle indicate that the remaining spins are confined to isolated segments of a partially degraded polymer where their behaviour resembles oligomer-like radicals.     

计算机控制的SEESR实验系统的研制

SEESR(Simultaneous Electrochemical ESR)是研究电极过程中的自由基中间体行为的理想和方便的手段。在以前研制的ESR仪数据系统的基础上,我们应用IBM-PC/XT微机与JES-FE1XG型(JEOL产)ESR谱仪及HDV-7型恒电位仪研制了一套由计算机控制的SEESR实验装置。该系统可以完成包括循环伏安法、电流阶跃、电位阶跃及电位反转等多种电化学方法的SEESR实验。系统还具有包括数据平滑、曲线拟合等功能的多种数据处理软件,使用方便。我们应用模型化合物对该系统进行了实际测量,所得结果与文献报道一致。     

Surface designing of polypropylene by critical monitoring of the grafting conditions

The grafting of acrylic acid onto electron beam‐irradiated polypropylene was carried out using preirradiation method. The stability of peroxy radicals was investigated by electron spin resonance. It was found that the decay of peroxy radicals is much faster at 70°C than at 40°C and ambient temperature. The grafting has been observed to be strongly dependent on the monomer dilution in the reaction medium. The grafting was ascertained by attenuated total reflectance (ATR). The distribution of grafts across the samples was monitored by infrared microscopy. It was found that the graft management is considerably influenced by composition of the grafting medium. The grafting involving pure monomer leads to the surface enrichment with the polyacrylic acid chains. The samples grafted in pure monomer led to much lower contact angles as compared to the diluted monomer solution. The swelling of the grafted samples also showed a trend that was governed by the graft management. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 546–553, 2006     

Study of miscibility enhancement in poly(styrene‐co‐4‐vinylphenol)/poly(ethylene oxide) blends by the spin labelling method

The electron spin resonance (ESR) spectra of end‐group spin labelled poly(ethylene oxide) (SLPEO) using 2,2,6,6‐tetramethyl‐piperdine‐1‐oxyl nitroxide and its blends with poly(styrene‐co‐4‐vinylphenol) (STVPhs) of different hydroxyl contents were recorded over a wide temperature range. For a blend of SLPEO and pure polystyrene (PS), the ESR spectrum was composed of a single motion component, indicating that PS was immiscible with PEO. For blends composed of SLPEO and different‐hydroxyl‐content STVPhs, two spectral components with different motion rates were observed over a certain temperature range. The difference between the motion rates should be attributed to micro‐heterogeneity in the blends, with the faster rate corresponding to a nitroxide radical motion trapped in the PEO‐rich domain and the slower rate corresponding to a nitroxide radical motion trapped in the STVPh‐rich domain. Variations in the values of a number of the ESR parameters (T_a, T_d and T_50G) and the apparent activation energy (E_a) with hydroxyl content in the blends indicated that the miscibility of the blends increased with increasing hydrogen‐bonding density due to specific interactions between the hydroxyl groups in STVPh and the ether oxygens in PEO. Copyright © 2004 Society of Chemical Industry