利用EPR研究三氧化钼中氧还活性位点形成的温度依赖性（英文）

本文利用热处理还原法,利用三氧化钼诱导形成具有氧化还原活性的中间产物及其温度相关特性.电子顺磁共振波谱(EPR)实验结果表明,热处理后在Mo~Ⅵ离子被还原成Mo~Ⅴ离子并形成了超氧阴离子自由基O_2~-.这两种活性中心的最佳热还原温度约300～350℃.自350℃逐渐升温,两种EPR信号强度迅速下降,下降～50%所对应的温度是400～450℃;当温度升至600℃或更高时,EPR信号降至0.结果表明,较高温处理或持续长时间处理都使热还原更容易发生,积累了越来越多的电子,在基底中形成类似于反铁磁耦合的电子离域.随着离域程度增大,EPR信号强度开始下降并直至消失.     

基于电子顺磁共振的锶铁氧体磁特性研究

为了研究配料、温度、氧环境和掺杂等条件对锶铁氧体的磁性能的影响问题, 利用溶胶-凝胶法制备了锶铁氧体粉末, 建立了一种基于电子顺磁共振技术研究锶铁氧体粉末的磁特性的方法. 用电子顺磁共振波谱仪对烧结后的产物进行测试发现: 400 ℃预烧下, 锶铁摩尔比为1:9时, 中间产物顺磁相α-Fe₂O₃含量最多, 高于400 ℃时其含量减少, 亚铁磁相增加, 并确定最佳煅烧温度介于800-900 ℃. 这是由于外磁场和其他磁场综合作用产生亚铁磁相, 进而产生较强的磁矩相互作用所致. 结合工业实际应用, 发现缺氧退火环境下, 顺磁相α-Fe₂O₃含量较大, 不利于亚铁磁相生成; X-射线衍射(XRD)表征结果表明: 除了少量杂相, 其余均为顺磁相和亚铁磁相; 电子顺磁共振谱和XRD 谱检测结果综合表明, 锶铁摩尔比为1:9时, 最终产物的顺磁相含量最少, 亚铁磁相含量最多, 磁性最强; 毫特斯拉计的剩磁检测结果也证实了上述结果. 掺杂实验发现镧离子占锶镧总摩尔数的20% 至30% 时, 能够有效降低顺磁相的产生, 增强最终产物的亚铁磁性.     

BiSrCaCu2OY高Tc超导体在240K附近的位移相变

用电子顺磁共振(EPR)技术研究了 BiSrCaCu_20_y 高 T_c 超导体的电子顺磁行为,实验上发现样品在0.27T 附近的 EPR 信号的谱形、平均朗德因子可值、线宽以及积分信号强度在240K 附近均显示出反常的行为.不同温度下样品的 X 光衍射分析表明在80—300K 温区里没有观察到明显的结构相变,比较 Fe~(3+)离子注入的 SrTiO_3样品的 EPR 研究结果,我们认为240K 附近观察到的顺磁反常是由于样品在240K 附近发生一位移相变所引起的.     

浸渍法制备Al2O3∶Ni2+及其EPR研究

使用浸渍法制备了Al2O3∶Ni2+晶体,并对不同温度400℃～1000℃焙烧的7种样品进行了分析,采用日本岛津电子公司生产的JES-FA200电子顺磁共振谱仪测试了样品的电子顺磁共振谱,分析了EPR信号对应的离子归属,对今后使用电子顺磁共振研究Al2O3∶Ni2+提供了借鉴参考依据.     

钛酸锶单晶(SrTiO_3)的电子顺磁共振

近年来,Muller,Unoki[1-4] 等人用火焰法生长的SrTiO3晶体作为样品,利用它含有微量的Fe3 顺磁杂质的特点,可以观察到Fe3 的顺磁谱线,并通过测量Fe3 的电子顺磁共振谱随温度的变化,对SrTiO3晶体的相变过程进行了详细的研究,第一次指出了SrTiO3单晶在110K处的相变是刚性氧八面体绕立方轴旋转了一个角度.Muller等人还从电子顺磁共振谱的谱形在相变过程中的变化,研究了SrTiO3的临界动力学,并估算了SrTiO3中的中心峰的宽度[5].我们采用助熔提拉法生长的SrTiO3单晶作为样品,在室温和液氮温度下进行了电子顺磁共振谱的测量.结果没有发现…     

Nd0.7Sr0.3MnO3顺磁-铁磁转变的电子自旋共振谱

用电子自旋共振(ESR)在100～300K温区对Nd0.7Sr0.3MnO3的顺磁-铁磁相变进行了细致的观测.所得ESR信号显示,在居里温度附近温区,顺磁相中存在着铁磁团簇,铁磁相中也存在顺磁成分.巨磁电阻峰值出现在ESR谱形状变化急剧的温区.ESR线宽在顺磁态随温度升高而线性增大,在居里温度附近呈现了极小值.     

EPR and DFT Study of the Polycyclic Aromatic Radical Cations from Friedel-Crafts Alkylation Reactions

利用电子顺磁共振和电子核双共振技术在间二甲苯与氯代烷烃和对二甲苯与氯代烷烃进行付-克烷基化反应体系中分别检测到二个多核芳烃正离子自由基信号．研究结果表明,所观察到顺磁共振信号分别来自于2,6-二甲基蒽正离子和1,4,5,8-四甲基蒽自由基的贡献．提出了这二个自由基的生成是在付-克烷基化反应中生成的氯代芳基在AlCl3存在下发生Scholl缩合反应生成多核芳烃,后者发生单电子氧化转变为相应的多核芳烃正离子自由基。利用密度泛函理论计算了这两个自由基的超精细偶合常数,与实验值符合相当满意,从理论上支持了对实验超精细谱线的归属．     

浸渍法制备Al2O3：Ni2+及其EPR研究

使用浸渍法制备了Al2O3：Ni2+晶体,并对不同温度400°C-1000°C焙烧的7种样品进行了分析,采用日本岛津电子公司生产的JES-FA200电子顺磁共振谱仪测试了样品的电子顺磁共振谱,分析了EPR信号对应的离子归属,对今后使用电子顺磁共振研究Al2O3：Ni2+提供了借鉴参考依据.     

掺杂金刚石薄膜的缺陷研究

利用多普勒增宽谱和电子顺磁共振研究了掺硼和掺硫金刚石薄膜的缺陷状态.多普勒增宽谱的结果表明，不同杂质元素掺杂的金刚石薄膜，其中使正电子湮没的缺陷种类是相同的；正电子与不同杂质元素硼、硫之间的相互作用不明显；少量硼可使金刚石膜中的空位浓度减少.EPR结果表明，各掺杂样品的顺磁信号主要来自于金刚石的碳悬键. 关键词： 金刚石 掺杂 多普勒增宽谱 电子顺磁共振     

基于电子顺磁共振的ZnTPP激发态及其TEMPO各向异性的研究

为了研究卟啉类敏化剂的光致激发态能量转移和电子转移问题,本文基于紫外可见光谱仪和电子顺磁共振波谱仪,构建了以锌卟啉为研究对象的"锌卟啉-稳态自由基-二甲苯"实验体系.锌卟啉的紫外可见光谱显示,在可见光谱的B带和Q带出现明显的特征峰,是锌卟啉分子中电子由基态能级跃迁至激发态能级产生的.低温条件下受紫外可见光辐照的实验体系的电子顺磁共振波谱,检测到了稳态自由基四甲基哌啶氧化物的增强吸收电子顺磁共振波谱.根据分子激发态相关理论、光化学物理反应理论和化学诱导电子自旋极化理论对实验结果进行了分析,结果表明,四甲基哌啶氧化物稳态自由基电子顺磁共振波谱的增强吸收对应于锌卟啉光致激发态的能量转移和电子转移;四甲基哌啶氧化物在低温(143 K)下的电子顺磁共振波谱表现出的各向异性特征现象来源于氮氧自由基电子与氮核的各向异性超精细相互作用.     

Paramagnetic centres in exinite, vitrinite and inertinite

Exinite, vitrinite and inertinite from durain, vitrain and clarain of Polish medium-rank coal with 85.6% C were investigated by X-band (9.3 GHz) electron paramagnetic resonance spectroscopy. Multicomponent structure of the EPR spectra of these macérais was analysed. The number of component lines, their lineshapes and parameters: linewidths andg factors, were determined. Total concentrations and concentrations of paramagnetic centres responsible for the component lines were measured. The broad Gaussian, broad Lorentzian and narrow Lorentzian lines were observed in the experimental spectra of exinite and vitrinite. The EPR spectra of inertinite are superposition of two narrow Lorentzian lines with different linewidths. The evolution of paramagnetic centres during heating of the macerais at 300–650°C was studied. Paramagnetic centres with broad Lorentzian lines are the most active ones in the thermal decomposition. The EPR results indicate reactions between individual macerais during thermal decomposition of coal. Thermally excited multiplet states were found in exinite and vitrinite.     

Thermally excited multiplet states in macerals separated from bituminous coal

Electron paramagnetic resonance searches of thermally excited multiplet states in macerals, exinite, vitrinite, and inertinite of Polish medium-rank coal (85.6 wt% C), were performed. Numerical analysis of lineshape indicates a multicomponent structure of the EPR spectra of macerals heated at 300 degrees and 650 degrees C. EPR spectra of exinite and vitrinite are a superposition of broad Gauss, broad Lorentz (Lorentz 1), and narrow Lorentz (Lorentz 3) lines. Two narrow Lorentz (Lorentz 2 and Lorentz 3) lines were observed in the resonance absorption curves of inertinite. The influence of the measuring temperature (100-300 K) on the EPR lines of the macerals was also studied. The experimentally obtained temperature dependence of the EPR line intensities were fitted by the theoretical functions characteristic for paramagnetic centers with ground doublet state (S = 12) and paramagnetic centers with thermally excited triplet (S = 1) and quadruplet (S = 32) states. Thermally excited multiplet states were found in exinite and vitrinite. Both paramagnetic centers with doublet ground state (S = 12) and paramagnetic centers with thermally excited states, probably quadruplet states (S = 32), exist in the group of paramagnetic centers of exinite and vitrinite with the broad Lorentz 1 lines. Intensities (I) of the broad Gauss and the narrow Lorentz 3 lines of exinite and vitrinite changes with temperature according to the Curie law (I = C/T). The existence of thermally excited multiplet states was not stated for inertinite. The two groups of paramagnetic centers of inertinite with Lorentz 2 and Lorentz 3 lines obey the Curie law. Copyright 2000 Academic Press.     

Thermal induced EPR signals in tooth enamel

Electron paramagnetic resonance (EPR) spectroscopy was used to detect the effects of temperature on powdered human tooth enamel, not irradiated in the laboratory. Samples were heated at temperature between 350 and 450, at 600 and at 1000°C, for different heating times, between 6 min and 39 h. Changes in the EPR spectra were detected, with the formation of new signals. Possible correlation between the changes in EPR spectra and modifications in the enamel and in the mineral phase of bone detected with other techniques is discussed. The implications for dosimetric applications of signals induced by overheating due to mechanical friction during sample preparation are underlined.     

Influence of microwave power on EPR spectra of coal macerals

The paper contains a numerical analysis of the electron paramagnetic resonance (EPR) spectra of coal macerals (exinite, vitrinite, inertinite) obtained from Polish medium-rank coal (85.6 wt% C). We determine the lineshapes and the parameters of the component lines, i.e., the intensities and linewidths. As a result, we find that the EPR spectra of the studied macerals are superpositions of broad Gaussian, broad Lorentzian 1 and narrow Lorentzian 3 lines for vitrinite and exinite and two narrow Lorentzian 2 and Lorentzian 3 lines for inertinite. The influence of microwave power on the component lines of the EPR spectrum is studied. A comparison of the results obtained at 223 and 293 K shows that the EPR lines at both temperatures saturate at the same microwave power. It also indicates similar changes of the linewidths with changes of microwave power at both temperatures, a slight increase with increasing microwave power.     

Special aspects of the temperature dependence of EPR absorption of chemically carbonized polyvinylidene fluoride derivatives

The temperature dependences of electron paramagnetic resonance (EPR) absorption of two samples of chemically carbonized derivatives of polyvinylidene fluoride (PVDF) synthesized under different conditions have been measured in the range of 100–300 K. It has been found that the temperature dependence of the integrated intensity of the EPR signal of both samples is nonmonotonic and does not obey the classical Curie dependence characteristic of free radicals. An analytical expression that is consistent with experimental data and suggests the presence of an activation component of paramagnetism in the test samples has been obtained. The presence of a term independent of temperature in this equation also indicates the paramagnetic contribution of free electrons. The magnitude of the activation energy of the singlet–triplet transitions has been evaluated: δ = 0.067 eV. The HYSCORE spectra of chemically carbonized PVDF derivatives have been obtained for the first time.     

Multifrequency (X-band to W-band) CW EPR of the organic free radical in petroleum asphaltene

Petroleum of Arabian and Colombian origin was studied by electron paramagnetic resonance (EPR) spectroscopy at X- (9 GHz), Q- (34 GHz) and W-bands (94 GHz). The experiments were performed at room temperature (about 300 K) and at 77 K (W-band only). The asymmetry in the lines corresponding to free radicals was observed more intensely in the W-band spectra. The values of the line width ΔH in the spectra increased linearly with the microwave frequency utilized in the EPR experiments. A mathematical simulation of the free radical signal for the EPR spectra in three bands with a set of parameters corresponding to a single species was attempted, but this was not exactly coincident with the experimental signals, suggesting that the hyperfine interaction of the unpaired electron with its neighborhood corresponds to more than one species of radical in the molecular structure of the petroleum asphaltene.     

Electron paramagnetic resonance study of gamma-irradiated potassium hydroquinone monosulfonate single crystal

Gamma-irradiated potassium hydroquinone monosulfonate (PHM) single crystals were investigated between 125 and 300?K using the electron paramagnetic resonance (EPR) technique. Between 125 and 300?K no changes in the spectra have taken place. The spectra were found to be temperature independent. The investigation of EPR spectra of irradiated single crystals of PHM showed the presence of two PHM anion radicals. The g values of the radiation damage centers observed in the PHM single crystal and the hyperfine structure constants of the free electron with nearby protons were obtained.     

EPR study of radiation damage in gamma-irradiated 3-nitroacetophenone single crystal

This paper presents the results of the electron paramagnetic resonance (EPR) study of the anion radical formed from 3-nitroacetophenone (C₈H₇NO₃) (3NAP) single crystal, by gamma irradiation. The EPR spectra of gamma-irradiated single crystals of 3NAP have been recorded at 10-degree intervals for different orientations of crystals in a magnetic field, at room temperature. The EPR analysis of gamma-irradiated crystals of 3NAP has shown that the radiation damage center produced by gamma irradiation is the carbon-centered 3NAP anion radical. One-electron reduction of 3NAP results in general bond loosening. The single crystals have been investigated between 120 and 450?K. The spectra have been found to be temperature-dependent. The EPR parameters of the 3NAP anion radical have been evaluated.     

EPR Studies of DOPA–Melanin Complexes with Fe(III)

Paramagnetic centers in 3,4-dihydroxyphenylalanine–melanin and its complexes with Fe(III) were examined by electron paramagnetic resonance (EPR) spectroscopy. Paramagnetic centers of melanin play an important role in detoxification of environment and they reveal high activity in binding of metal ions. Two different signals were observed in EPR spectra: lines of o-semiquinone free radicals and lines of paramagnetic Fe(III). Amplitudes of EPR lines of both free radicals and iron ions decrease with increasing Fe(III) content in melanin–metal ion complexes. Free radical concentrations in the melanin samples, g-factors, amplitudes and line widths of EPR spectra were determined. It was stated that fast spin–lattice relaxation processes exist in both free radical system and paramagnetic iron ions in melanin complexes.     

EPR study of gamma-irradiated 2-Bromo-4′-methoxyacetophenone single crystals

The gamma-irradiated single crystals of 2-Bromo-4′-methoxyaceto-phenone (2B4MA) were investigated using electron paramagnetic resonance (EPR) technique. Density-functional theory calculations were employed to investigate and identify the radicals that have been assumed to be formed upon irradiation of 2B4MA single crystals. The EPR spectra of 2B4MA were recorded at different orientations in the magnetic field at room temperature. Taking into account the chemical structure and experimental spectra of irradiated single crystal of 2B4MA, it was assumed that at least two different radicals were produced in the sample. Following this assumption, six possible radicals were modeled and EPR parameters were calculated by using the DFT, B3LYP/6-311+G(d), for the modeled radicals individually. The calculated hyperfine coupling constants and g-tensors were used as initial values for simulation studies. The three crystallographic axes on the simulated spectra were well matched with experimental spectra for the two modeled radicals. Thus, we identified the R1 type radical and R4 type radical as paramagnetic species produced in gamma-irradiated 2B4MA.