用DETC铁络合物捕捉生物组织NO自由基的ESR波谱解析

一氧化氮自由基具有重要的生物功能.但目前使用的自旋捕捉剂都不能有效捕捉细胞和组织体系产生的一氧化氮自由基.实验表明DETC(mononitrosyl dithiocarbamate)铁络合物可以有效捕捉生物体系产生的一氧化氮自由基,但用DETC在细胞和组织体系检测一氧化氮自由基需要在低温检测.生物组织在低温的ESR波谱和DETC铁络合物捕捉的一氧化氮自由基的ESR波谱互相重叠,使谱线解析有一定困难.本文分析了用DETC铁络合物检测细胞和组织体系产生一氧化氮自由基在低温可能出现的ESR信号的g值和超精细分裂常数.提出了克服使用DETC铁络合物检测生物体系一氧化氮自由基困难的方法.     

多自由基体系溶液ESR谱的数据分析

将ER-200D ESR波谱仪ASPECT 3000计算机采集的ESR图谱传输到IBM PC/XT计算机上,通过自行设计的ESR图谱模拟程序ESRSIMU,同屏显示比较,方便、灵活地对多自由基体系溶液ESR一级近似谱进行了模拟,获取了各个自由基的ESR波谱参数和体系中各类自由基的相对浓度等信息.对单个自由基ESR谱的模拟,ESRSIMU的运行速度比BRUKER EPR 3002快近100倍.     

双流化床煤气化试验研究

建立了一套3米高的双流化床煤气化试验装置,煤在鼓泡流化床中热解气化,生成的半焦送入循环流化床中燃烧,两床间采用气动控制阀连接.分别采用神华烟煤、龙口褐煤和大同烟煤进行了试验.煤中的碳转化成煤气和烟气的总转化率达到90%以上;冷煤气效率随着窄气/煤比的提高而增加;采用神华煤时焦油产率可达到1.5%;采用龙口褐煤时气化效果较好,在气化炉空气/煤比为0.3 kg/kg时,冷煤气热值为10.7 MJ/Nm3,冷煤气效率为48%.经过分析计算,龙口褐煤产生煤气中的可燃成分主要来自热解.     

茶多酚及其单体结构自由基的ESR研究

通过ESR检测方法研究了邻苯三酚、茶多酚及其四种单体的自氧化醌类自由基的ESR波谱信号,系统阐明了这几种物质的内在结构联系.     

谱-空间2D ESR成像

在Bruker ER 200D ESR 谱仪上安装一套自制的谱-空间2D ESR成像系统,这套系统由一对梯度场线圈、电源、微机及图像重建程序组成. 用滤波反投影图像重建方法,实现了两种自由基样品的谱-空间2D ESR成像,由2D 图像得到样品中自由基的自旋密度空间分布及相应的波谱参数. 讨论了成像参数与图像精度的关系.     

二苯甲酮与烃的光化夺氢反应中产生的活泼自由基的ESR研究

本文用具立体阻碍的自旋捕捉剂2,4,6-三-特丁基亚硝基苯(TBN)与ESR相结合的方法,研究了十种烷烃及四种芳烃与二苯甲酮光化夺氢反应中产生的活泼自由基。结果表明,R₃R₂R₁Ċ和TBN形成烷氧苯胺自由基加合物。R-ĊH-R'与TBN形成烷氧苯胺自由基加合物和氮氧自由基加合物。TBN可用于区分有、无空间位阻的烷烃,芳烃自由基。自旋加合物的ESR波谱可表明自由基中未偶电子所在碳原子附近的有效质子数目。     

聚四氟乙烯的辐射效应及其ESR研究

该文回顾了从上世纪50年代中期至近年来人们在聚四氟乙烯（PTFE）辐射效应方面的研究工作,初步总结了辐射PTFE产生的自由基及其相应的过氧化自由基的电子自旋共振（ESR）波谱学应用研究,总结并讨论了实验温度、辐射剂量、PTFE粉末形式、结晶度和交联等因素对辐射PTFE自由基ESR信号的影响. 同时还简要介绍了辐射PTFE后的自由基反应以及辐射交联的进展情况.     

烷烃蒸汽微波放电分解反应活泼自由基的ESR研究

本文用前文^[5]报道的气相有机化合物微波放电装置、自旋捕捉剂苯亚甲基叔丁基氮氧化物PhCH=NC↑^O(CH₃)₃(PBR)与ESR相结合,系统研究了十种烷烃蒸汽微波放电分解产生的活泼自由基。从ESR谱的超精细结构及其随PBN与放电腔距离的变化,不仅证实了上述体系放电分解既有H·生成,又有碳中心自由基R·产生,而且还找到了PBN与R·H·生成加合物比值变化的规律。由PBN与放电腔距离的不同,得出的碳中心自由基R·加合物的ESR波谱参数,证明了PBN捕捉不同的自由基R·。     

煤粉高温空气燃烧与氮氧化物生成特性

借助循环流化床在高过剩空气系数下燃烧提供高温低氧空气的工艺,在直径为220 mm高为3000 mm的实验台上研究褐煤、烟煤和无烟煤在高温低氧空气下的燃烧特性和氮氧化物生成特性.实验结果表明,褐煤、烟煤和无烟煤在高温低氧空气下燃烧稳定性好,温度波动小;高温低氧的气氛降低了褐煤、烟煤、尤其是无烟煤燃烧的氮氧化物排放;褐煤、烟煤和无烟煤燃烧的氮氧化物排放值分别为440 mg/m3,390 mg/m3和332 mg/m3.     

二苯酮与胺光化夺氢反应的时间分辨ESR研究

报道用时间分辨ESR方法研究了二苯酮与典型胺类化合物体系紫外光照产生的瞬态自由基及化学诱导动态电子自旋极化效应,得出的反应机理可与稳态ESR结果相互补充.     

卷烟烟气中活性自由基的自旋捕获ESR研究

卷烟烟气中的瞬态自由基对人体健康是相当有害的，而检测活性自由基最常用的方法是自旋捕获方法. 本研究中使用高效新型捕捉剂DEPMPO能够直接在水相中捕捉到烷基自由基与羟基自由基，并未发现烷氧自由基加合物. 考虑到DEPMPO对活性自由基的捕捉能力和加合物ESR谱图解析特征性都优于PBN与DMPO，且在有机溶剂中溶解较多的氧分子. 因此认为以往文献中所捕获的烷氧自由基来源于烷基自由基氧化后的次级自由基产物.     

关于氧化锌/双吡啶高氯酸盐非均相光诱导电子转移过程的研究

用ESR方法对9种不同双吡啶高氯酸盐与氧化锌组成的非均相体系的光诱导电子转移过程进行了系统的研究。ZnO-PQ⁺⁺-胶束-苯的分散系,经350nm~420nm的紫外光照后,PQ⁺⁺被还原成PQ⁺。具有大共轭结构的PQ⁺的ESR信号较强。胶束的存在也可使ESR信号增强。当体系充氧时,PQ⁺信号消失,并有超氧阴离子基O₂^·和羟基·OH被检出。     

ESR study of fullerene black

Fullerene black before and after annealing at 850°C has been studied by electron spin resonance (ESR). For initial fullerene black, the ESR line exhibits wide wings and its shape is caused by magnetic dipole-dipole interactions between radicals localized randomly on the carbon surface. Dioxygen decreases reversibly the amplitude of the ESR line without changes in its shape, width (0.19 mT) andg-factor (2.0022). This is explained by the assumption that dioxygen molecules adsorbed on the surface broaden strongly ESR lines only of neighboring radicals. For annealed fullerene black, the ESR line is Lorentzian, dioxygen reversibly broadens the line, and theg-factor decreases with the broadening of the line by dioxygen. This is explained by radical-radical and radical-dioxygen spin exchange interactions via conjugated bonds formed in the course of annealing. Flattening of curved carbon surfaces after annealing explains in a uniform way changes in parameters of ESR lines and in reactivity and catalytic activity of fullerene black.     

An Electron Spin Resonance Study of Gamma-Irradiated 5,6-Dihydropyrimidines

Electron spin resonance (ESR) spectra are observed from gamma-irradiated, poly-crystalline samples of 5,6-dihydrouracil, 5,6-dihydro-5-methyluracil, and 5,6-dihydro-6-methyluracll. The spectra indicate that the radiation-induced free radicals are formed by the loss of hydrogen atoms from the parent compounds. The crystal structure of the dihydropyrimidines is apparently such that there is a proton near the unpaired electron which can simultaneously flip with the flip of the unpaired electron resulting in the formation of satellite lines relative to the main spectral lines. Annealing the irradiated samples at 100°C produces a decrease in the radical content of all compounds except in dihydro-5-methyluracll where the radical content increases. These differences are discussed in terms of the close proximity of the radicals formed during irradiation of dihydro-5-methyluracil. The     

Spin Pumping from a Quantum Dot in the Presence of Decoherence

We study the pumped spin current of an interacting quantum dot tunnel coupled to a single lead in the presence of electron spin resonance （ESR） field. The spin decoherence in the dot is included by the Bffttiker approach. Using the nonequilibrium Green＇s function technique, we show that ESR-induced spin flip can generate finite spin current with no charge transport. Both the Coulomb interaction and spin decoherence decrease the amplitude of spin current. The dependence of pumped spin current on the intensity and frequency of ESR field, and the spin decoherence is discussed.     

pH自旋探针分子的ESR波谱性质和量子化学研究─pH自旋探针应用研究之二

系统研究了咪唑类氮氧自由基作为pH自旋探针的ESR波谱特性．用量子化学方法AM1研究了pH自旋探针分子的几何结构、电子结构及电子自旋密度分布．aN理论值与实验结果基本一致．得到了pka值与电子密度关系曲线．指出了它们在生命科学中的应用前景．     

Evidence for free radicals produced in aqueous solutions by diagnostic ultrasound

Recent theoretical calculations have shown that small gas nuclei in water exposed to microsecond ultrasonic pulses above an intensity threshold may grow into transient cavities that collapse violently, leading to the formation of .OH radicals and .H atoms. We have detected these free radicals in aqueous solutions exposed to microsecond pulsed ultrasound using spin trapping and electron spin resonance (ESR). The public health implications of our results are discussed.     

Identification of free radicals in irradiated MA-AMPS copolymer

Methacrylamide-2-acrylamido-2-methylpropanesulphonic acid (MA-AMPS) (80:20) is subjected to n -irradiation and the generated free radicals are identified by the electron spin resonance (ESR) technique. The ESR spectrum "obser"ved for MA-AMPS (80:20) has shown a complex line shape, indicating the presence of more than one free radical. Computer simulations are employed to unravel the radicals responsible for the ESR spectrum. Radical "identification has been done with the magnetic parameters employed during computer simulation. The observed ESR spectrum of the copolymer is simulated to be a superposition of component quartet, quintet and singlet spectra. The component spectra are assigned to ～CH 2 - . (CONH 2 )-CH 2 ～ or ～CH 2 - . H-CH 2 ～, . H 3 radicals, "respectively. The possibility of formation of such radicals in the sample material has been discussed.     

An electron spin resonance study of radical decay in γ-ray irradiated pepper by thermal treatments

Applied Magnetic Resonance - We examined by electron spin resonance (ESR) spectroscopy the thermal decay of radicals as induced by γ-irradiation on pepper. Upon irradiation, the satellite...