喷嘴-平板直流电晕放电中的OH(A2S+→X2P, 0-0)光谱研究

 为更深入地认识电晕放电低温等离子体中自由基的生成机理，以发射光谱测量为基础并结合背景气体淬灭率影响，研究了常压下喷嘴-平板电晕自由基簇射过程中放电参数、背景气体、电极气成分等因素对OH(A²S⁺→X²p, 0-0)发光的影响。结果表明：在放电参数影响中，放电电压及放电电流都会影响OH生成量，OH发光随功率增加而大大增强；在加湿氮气直流电晕放电中有明显的OH(A²S⁺→X²p, 0-0)光谱存在，但加湿空气条件下OH生成较少；载气增湿后OH生成量明显增多，而Ar和O­2的存在分别增强和减弱了OH(A²S⁺→X²p, 0-0)发光，可能的原因是这两种物质影响了放电和OH(A²S⁺)的淬灭。     

微波液相放电等离子体发射光谱研究

液相放电能够产生各种活性物质,其中羟基自由基(OH),氢自由基(H)被认为是引发液相化学反应的主要活性物种,但由于其活性强寿命短的特点,测量比较困难,由于缺少标准样品,定量测量更为困难。用光学方法测量自由基是一种直接测量方法,其特点是瞬时在线测量,能立即获得数据,进行时间和空间分布测量。为了研究微波水中放电产生的自由基特性,利用发射光谱诊断技术对微波水中放电产生的活性物质进行了在线检测,考察了微波功率、反应器内部压强对OH自由基相对光谱强度的影响,并观测了等离子体中OH自由基强度的空间分布;同时,估算了微波液相等离子体中的电子激发温度。实验结果表明,微波水中放电可以产生大量的OH,H,O自由基,其中OH自由基的相对光谱强度最强,并随微波功率的增加呈现明显上升的趋势,随反应器内部压强的增大而迅速减弱;以OH为主的自由基主要产生于电极尖端附近。微波液相等离子体的电子激发温度约为0.33×104 K。     

空气电晕放电中的OH自由基发射光谱

测量了大气压下向空气中喷射不饱和水蒸气的电晕放电产生的OH自由基的发射光谱。通过对光谱线强度变化的分析,研究了电场强度、放电方式、水蒸气比例等因素对OH自由基产生过程的影响,及OH自由基浓度在放电反应空间的分布特点。     

时间分辨电子自旋共振及其应用

简要介绍了作者研制的高时间分产电子自旋共振（ＴＲＥＳＲ）波谱仪的结构与特点。报道了均相与微复相体系中光解自由基的自旋相关自由基极化;在对苯醌的乙二醇／水／硫酸溶液中,观察到苯醌自由基与溶液中质子发生交换效应。综述了ＴＲＥＳＲ在光诱导极化与光诱导电子转移研究方面的应用。     

Spin-labeled gel for the production of radical-free dynamic nuclear polarization enhanced molecules for NMR spectroscopy and imaging

Dynamic nuclear polarization (DNP) has recently received much attention as a viable approach to enhance the sensitivity of nuclear magnetic resonance (NMR) spectroscopy and the contrast of magnetic resonance imaging (MRI), where the significantly higher electron spin polarization of stable radicals is transferred to nuclear spins. In order to apply DNP-enhanced NMR and MRI signal to biological and in vivo systems, it is crucial to obtain highly polarized solution samples at ambient temperatures. As stable radicals are employed as the source for the DNP polarization transfer, it is also crucial that the highly polarized sample lacks residual radical concentration because the polarized molecules will be introduced to a biological system that will be sensitive to the presence of radicals. We developed an agarose-based porous media that is covalently spin-labeled with stable radicals. The loading of solvent accessible radical is sufficiently high and their mobility approximates that in solution, which ensures high efficiency for Overhauser mechanism induced DNP without physically releasing any measurable radical into the solution. Under ambient conditions at 0.35 T magnetic field, we measure the DNP enhancement efficiency of (1)H signal of stagnant and continuously flowing water utilizing immobilized stable nitroxide radicals that contain two or three ESR hyperfine splitting lines and compare them to the performance of freely dissolved radicals.     

Effective ultrasound electrochemical degradation of methylene blue wastewater using a nanocoated electrode

A novel sonoelectrochemical catalytic oxidation-driven process using a nanocoated electrode to treat methylene blue (MB) wastewater was developed. The nano-scale (nanocoated) electrode generated more hydroxyl radicals than non-nano-scale (non-nanocoated) electrodes did. However, hydroxyl radicals were easily adsorbed by the nanomaterial and thus were not able to enter the solution. Supersonic waves were found to enhance the mass-transfer effect on the nanocoated electrode surface, resulting in rapid diffusion of the generated hydroxyl radicals into the solution. In solution, the hydroxyl radicals then reacted with organic pollutants in the presence of ultrasonic waves. The effect of the nanocoated electrode on the MB wastewater treatment process was enhanced by ultrasound when compared to the non-nanocoated electrode used under the same conditions. The synergy of the nanocoated electrode and ultrasonic waves towards MB degradation was then studied. The optimum operating conditions resulted in a 92% removal efficiency for TOC and consisted of a current of 600 mA, an ultrasound frequency of 45 kHz, and a supersonic power of 250 W. The mechanism of ultrasound enhancement of the nanocoated electrode activity with respect to MB treatment is discussed. The reaction intermediates of the sonoelectrochemical catalytic oxidation process were monitored, and degradation pathways were proposed. The sonoelectrochemical catalytic oxidation-driven process using nanocoated electrodes was found to be a very efficient method for the treatment of non-biodegradable wastewater.     

线板式脉冲电晕放电反应器OH自由基二维分布的光谱学研究

脉冲电晕放电过程中OH自由基等活性基团的空间分布特性对燃煤烟气污染物的氧化脱除具有重要作用。为了探索脉冲电晕放电污染物控制技术的机理,采用激光诱导荧光法检测线板式反应器内部脉冲电晕放电过程中OH自由基的空间二维分布特性,主要研究了不同相对湿度和含氧量对OH自由基空间二维分布特性的影响。实验表明,脉冲电晕放电过程中OH自由基主要存在于线电极下方的区域中,并以线电极为中心面向板电极呈现扇形分布,并且其扇形分布区域的纵向长度和横向宽度的最大值均小于1 cm;相对湿度的增大有利于OH自由基的生成,促进OH自由基空间二维分布区域面积的扩大,当相对湿度为65%时OH自由基的空间二维分布区域面积达到最大值;当含氧量为2%时最有利于OH自由基的生成,并且OH自由基的空间二维分布区域面积达到最大值,当含氧量超过15%时对OH自由基的生成及其空间二维分布主要起抑制作用。同时,相对湿度和含氧量的增加均提高了激发态OH自由基中猝灭部分所占的比重,从而降低了OH自由基的荧光产率,其中含氧量对OH自由基荧光产率和OH自由基空间二维分布的影响作用大于相对湿度。     

Analysis of EPR-time profiles of transient radicals with unresolved spectra

A method for analysing EPR-time profiles of transient radicals in solution with unresolved hyperfine structure is proposed. It is based on considering the magnetic field integral of the magnetization, i.e., the total EPR signal intensity, instead of single components of overlapping EPR transitions. For a radical system involving chemical kinetics, chemically induced electron polarization (CIDEP), and spin relaxation, an analytical solution is found for the evolution of the integral magnetization in the Laplace domain. The solution in the time domain is given for the case of negligible saturation, i.e., omega2(1)T1T2 < 1. The formulae presented are suitable to avoid equivocal multi-parameter fits when analysing the results of time-resolved continuous-wave EPR experiments for the observables, which characterize the chemical kinetics, CIDEP, and electron spin relaxation of radical systems.     

Electrochemical generation of free radicals in an EPR loop-gap resonator

An electrochemical cell for in situ generation of free radicals in a loop-gap resonator at X band is described. The cell is assembled from commercially available components and requires no glass blowing. The design is flexible and accommodates a variety of electrodes and electrode geometries. Remarkably small amounts of material are required. The filling factor is favorable for short-lived radicals. Performance of the cell is demonstrated by generation of the dianion radical of p-nitrobenzoic acid.     

脉冲放电等离子体/活性炭联合体系中OH自由基的发射光谱研究

基于OH自由基的强氧化性(2.8 V)及脉冲放电等离子体(pulsed discharge plasma, PDP)与活性炭(activated carbon, AC)联合体系的协同作用,依托于光谱检测技术简单、准确性高、灵敏度高等优点,利用发射光谱技术测量了以O2作为载气的PDP/AC联合体系中产生的OH自由基的相对发射光谱,用以表征体系中OH自由基相对生成量的变化。通过考察PDP水处理体系中不同AC添加量、脉冲峰值电压、电极间距对OH自由基相对发射光谱强度的影响,分析了影响OH自由基生成量的因素;通过比较,分析去离子水和酸性橙II(acid orange, AO7)溶液中OH自由基发射光谱强度的变化规律,表征了OH自由基生成量的变化,以说明PDP/AC的协同作用机理及OH自由基对有机物的氧化作用。研究结果表明,增加AC的添加量可以增强其在PDP体系中的催化效果,导致PDP/AC联合体系中OH自由基的相对发射光谱强度的增加;随着脉冲峰值电压的升高,注入PDP体系中的能量增加,从而增加了体系中OH自由基的产量;电极间距增加导致PDP体系能量效率降低,降低了OH自由基的产生量;无论是以去离子水还是以AO7溶液为溶液相,PDP/AC联合体系中OH自由基的产量均高于其在单独PDP体系中的生成量,且在PDP/AC联合体系和单独的PDP作用体系中,去离子水中OH自由基的相对发射光谱强度均高于其在AO7溶液中的强度值,这证明了AC对PDP体系中OH自由基生成的协同作用和有机物对OH自由基的消耗。     

Estimation of hydroxyl free radicals produced by ultrasound in Fricke solution used as a chemical dosimeter

Hydroxyl free radicals produced in Fricke solution exposed to 80 kV X-rays or 23 kHz ultrasound (intensity 3 W cm⁻²) or 20 kHz ultrasound (intensity 18.9 W cm⁻²) or 3.5 MHz clinical ultrasound (intensity 1.47 W cm⁻²), as estimated from the Fricke dosimetric data, exhibited a linear dose-response relationship. The dosimeter was found to be effective in the concentration range 1.0–8.0 mM of FeSO₄ solution. The hydroxyl radicals produced in Fricke solution were inhibited by the OH radical scavengers dimethyl sulfoxide (200 mM), -histidine (10 mM) and sodium benzoate (10 mM) in a manner proportional to the rate constants of their reaction with the OH radicals. The power threshold for OH radical formation, which is presumably the threshold for cavity formation, was estimated for 23 kHz ultrasound by this dosimeter as 1.28 W cm⁻² for a 4 cm³ sample volume.     

Deprotonation of Transient Guanosyl Cation Radical Catalyzed by Buffer in Aqueous Solution: TR-CIDNP Study

The reaction of deprotonation of the guanosyl cation radical formed in the photoinduced reaction of guanosine monophospate (GMP) with triplet 2,2??-dipyridyl-d₈ is studied in aqueous solution by time-resolved chemically induced dynamic nuclear polarization (TR-CIDNP). In the course of the cyclic photoreaction, spin-polarized products are generated. Their polarization patterns that reflect the properties at the radical stage are analyzed using high-resolution nuclear magnetic resonance. The identification of transient radicals contributing to the polarization kinetics is based on its sensitivity to the degenerate electron exchange reaction of transient radicals with the parent diamagnetic molecules. Degenerate electron exchange is allowed only for the cation radical and manifests itself in the fast decay of the CIDNP signal in time with the rate of decay proportional to the concentration of parent GMP molecules. Because the formation of the neutral transient radical stops the exchange, the deprotonation changes the CIDNP kinetics from a decaying to a growing one. The rate constant of deprotonation, k _d, was obtained from modeling of CIDNP kinetics data with taking into consideration the difference of the CIDNP enhancement factors for neutral and cation guanosyl radicals. The value obtained at pH^* 5 for k _d?=?1?×?10⁶?s^?1 is consistent with the proton dissociation constant of the radical (pK _a?=?3.9). The linear dependence of the deprotonation rate on the buffer concentration is revealed for phosphate, formate, and acetate. Deprotonation is catalyzed by the buffer to a degree that depends on the difference in pK _a value of the buffer and the guanosyl cation radical in full accordance with Eigen??s model.     

辐射引发和热引发聚丙烯腈纤维的自由基研究

利用电子自旋共振波谱(ESR)研究了聚丙烯腈(PAN)纤维在真空以及空气气氛下经γ射线辐射引发和热引发产生的自由基. 结果显示,室温下辐射诱导产生的自由基为烷基自由基和聚亚胺自由基,辐射产生的自由基随温度升高而衰减,150 ℃时完全消失. 热引发的自由基则依赖于温度和氧气, 当PAN纤维在空气中加热至190 ℃时,开始产生多烯自由基,而且自由基浓度随温度升高而迅速增加;在真空条件下,PAN纤维经加热只产生极少量自由基. 据此推断,热引发自由基是通过热氧化反应产生的,这类自由基位于共轭结构上,其共轭长度也随温度的升高而增加.     

Electron spin relaxation by spin-rotation interaction in benzoyl and other acyl type radicals

In various studies of the spin dynamics in radical pairs, benzoyl-type radicals have been one of the two paramagnetic pair species. Their electron spin relaxation has been assumed to be slow enough to be neglected in the data analysis. This assumption is checked by measuring the electron spin relaxation in a sequence of three acyl radicals (benzoyl, 2,4,6-trimethylbenzoyl and hexahydrobenzoyl) by time-resolved electron paramagnetic resonance spectroscopy. In contrast to the assumed slow relaxation, rather short spin-lattice relaxation times (100–400 ns) are found for benzoyl and 2,4,6-trimethylbenzoyl radicals from the decay of the integral initial electron polarization to thermal equilibrium at different temperatures and viscosities. The relaxation is induced by a spin-rotation coupling arising from two different types of radical movements: overall rotation of the whole radical and hindered internal rotation of the CO group. The predominant second contribution depends on the barrier of the internal rotation. The obtained results are well explained in the frame of Bull’s theory when using a modified rotational correlation time τ _J . The size of the spin-rotation coupling due to the internal CO group rotation in benzoyl radicals is estimated to be |C _α|=1510 MHz.     

Time resolved CIDNP study of electron transfer reactions in proteins and model compounds

Intramolecular electron transfer (IET) from tyrosine to tryptophan cation radicals is investigated using time resolved chemically induced dynamic nuclear polarization (CIDNP) spectroscopy in combination with laser flash photolysis. In both the tryptophan-tyrosine dipeptide and the denatured state of hen lysozyme in aqueous solution, the transformation TrpH⁺ → TyrO by IET leads to an increase in the tyrosine radical concentration, growth in the tyrosine CIDNP signal, fast decay of the tryptophan CIDNP, and inversion of the phase of the CIDNP of the photosensitizing dye, 2,2′-dipyridyl. IET effects are not observed for mixtures of the amino acid or for the native state of lysozyme. The steady state CIDNP effects seen for denatured lysozyme thus depend not only on the accessibility of the amino acid residues on the surface of the protein but also on the reactivity of the radical intermediates.     

Determination of the kinetic parameters of radical pairs with heavy atom substitutions in micellar solution by optical detected × and Ku band ESR

A study is reported of the dynamics of radical pairs formed by the photochemical reaction of benzophenone and its heavy atom substitutions, dichlorobenzophenone and bromobenzophe-none, in a sodium dodecylsulphate micellar solution. Changes were observed in the time profiles of the transient absorptions and in the yields of the escaping radicals induced by the irradiation of an × (9.15 GHz) or Ku band (17.44 GHz) microwave short pulse. From these experiments, the hydrogen abstraction reaction rates, the recombination rates of the singlet radical pairs, the relaxation rates, the escape rates, the decay rates of the radical pairs without the external magnetic field, and the intersystem recombination rates due to the spin-orbit coupling were determined.     

Hypocrellin A与二苄胺和N-甲基苄胺的光化学反应

为了探讨HypocrellinA (HA)与胺基衍生物反应的自由基形成机制 ,我们采用ESR谱分别研究了HA与二苄胺 (DBA)和N 甲基苄胺 (NMBA)的光化学反应 .在含胺类物质和溶解氧的溶剂系统下 ,可见光照射HA激发成HA ,然后将溶解氧转变成1O2 ,1O2 诱导DBA或NMBA的氯仿溶液都能产生半醌自由基和氮氧自由基 .氮氧自由基的信号强度随光照时间的增加而减弱 ,而半醌自由基的信号强度随光照时间的增加而增强 ,氮氧自由基的含量与光照产生的半醌自由基成反比 .在除氧条件下 ,光照含HA和DBA的氯仿溶液体系时 ,半醌自由基是主要的自由基 .结果表明 ,在有氧的氯仿溶液中 ,HA诱导胺类物质生成HA半醌自由基     

EPR Technology Spectroscopic Investigation of Generation of Reactive Oxygen Species Free Radicals in Laccase-Activated Jute Fiber

Lignins in jute fibers can be activated by laccase to generate reactive oxygen species (ROS) free radicals for subsequent use in radical graft polymerization. The effect of incubation conditions on the generation of ROS free radicals when jute powders were incubated with laccase was investigated through spin-trapping technique to detect the spin adduct of N-tert-butyl-α-phenylnitrone and ROS free radical using electron paramagnetic resonance spectroscopy. Results revealed that the highest concentrations of ROS free radicals were generated when jute was incubated with laccase (0.54 U/mL) and copper ions (10 mM) in solution at pH 3.5 and a temperature of 60 °C for 1 h.     

Evidence concerning the formation of a heterogeneous solid solution in the plastic phase of cyclohexane doped with a nitroxide free radical from magnetic resonance studies

Existing published E.P.R., nuclear spin lattice relaxation, dynamic nuclear polarization and electron-electron double-resonance data on the plastic phase of cyclohexane doped with a nitroxide free radical are re-examined and analysed in a consistent way. It is shown that (i) the local concentration of free radicals is higher than foreseen, assuming a uniform distribution and (ii) the molecular motions near the radical are slower than in the pure system. These results suggest that this system should be pictured as a heterogeneous solid solution where the local properties around the radicals are significantly different from those far from the radicals.     

Structural modifications in metal complexes of a plant metallothionein caused by reductive radical stress: a Raman study

The effect of radical stress in the biological environment is a very active field of research connecting various disciplines of life science. Thus, a comprehensive vision of all possible reactive species is necessary for contributing to the solution of puzzling questions on free radicals. In this contest, damages to Zn(II) and Cd(II) complexes of a plant metallothionein (Quercus suber—QsMT), because of reductive radical stress, were investigated by Raman spectroscopy. QsMT is a low‐molecular‐weight cysteine‐rich protein obtained by in vivo synthesis to have a physiologically representative model. Gamma‐irradiation was used to simulate the endogenous formation of reductive species. By changing the appropriate conditions of irradiation, a selection of the reacting radical species (hydrogen atom and hydrated electron) was carried out. Specific damages occur at sensitive amino acid sites, selectively, rather than indiscriminately. In particular, Cys resulted to be among the most sensitive residues toward radical attack, suggesting that the thiolate clusters of both metal and QsMTs act as efficient interceptors of reducing species. Under reductive stress, Zn–QsMT undergoes a significant thiolate group oxidation and the participation of ligands other than the cysteine‐derived thiolate bonds (i.e. His) in zinc coordination becomes necessary for the protein stabilization. Regarding Met residues, they resulted to be more sensitive to the reductive radical attack when the protein binds Cd(II) ions, indicating that the protein structure can play a significant role in blocking the ready access of free radicals to the sulfur‐containing residues, so strongly affecting the radiosensitivity of the protein. In conclusion, the results obtained from γ‐irradiation experiments indicate that reductive stress causes changes in the primary QsMT structure and in the secondary and tertiary structures, and the radical‐induced effects are dependent on the metal bound. Copyright © 2009 John Wiley & Sons, Ltd.