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1.
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.  相似文献   

2.
白令君 《波谱学杂志》1986,3(2):131-138
将R.Neiman和D.Kivclson[1]关于具有D4h对称性、S=(1/2)的过渡金属化合物冷冻溶液ESR谱线型的研究工作进行了扩展,解出二级近似下的吸收峰强度公式,并设计了利用PC-1500袖珍计算机进行微分谱图模拟的程序。  相似文献   

3.
本工作采用直接测量大豆、菠菜完整叶片ESR谱的方法,证实了我们制备的离体叶绿素A二聚物确系(Chla·H2O)2在紫外光和He-Ne激光诱导下,其自由基信号和大豆完整叶片的信号Ⅰ具有同一起沅,从而可以用它来模拟研究大豆叶片中反应中心的结构和功能。指出了自由基理论分析完整大豆叶片ESR谱的适用性。  相似文献   

4.
糖与氨基酸反应涉及一种新的自由基的生成。这种自由基EPR谱特征的超精细结构是由一组两个等性的氮核、三组等性的质子所贡献。谱的超精细特征和谱线分裂的数目主要取决于氨基酸的结构。从13C NMR谱和反应过程的分析,我们提出如下设想:这种新自由基产物应该是1,2-4,5四取代的哌嗪双自由基。用实验中测得的波谱参数在ASPECT-2000型计算机上进行了EPR谱的模拟,模拟的理论谱与实验谱很好地重合,进一步支持了上述的设想。本文还提出了反应中自由基形成的可能机理。  相似文献   

5.
冯克  欧阳巍 《波谱学杂志》1994,11(3):295-299
考察了磺化乙丙三元胶锰盐离聚体在二甲苯/正己醇混合溶剂中的ESR谱,结果表明醇对金属离子的溶剂化作用破坏了溶液中Mn2+的聚集,出现超精细分裂的ESR谱线,溶剂化程度与醇含量、醇分子体积、温度和Mn2+浓度有关,这些结果与离聚体溶液粘性行为得到的结论相一致。  相似文献   

6.
在数学相关分析的基础上,建立了获得连续波电子自旋共振(continuous-wave electronspin resonance, CW-ESR)的二维相关谱的方法. 对光照产生的2-甲基-2-亚硝基-丙烷(2-methyl-2-nitrosopropane, MNP)的自捕捉自由基的一系列CW-ESR谱进行相关分析处理,首次得到了同步和异步的二维电子自旋共振(2D ESR)相关谱. 这种利用数学相关分析方法所得到的2D ESR相关谱将为扩大CW ESR的应用领域及获取更多的有用信息开拓新的途径.  相似文献   

7.
采用TM110谐振腔和φ2mm样品管,在17℃室温条件下成功地记录了MMA本体聚合反应过程中增长自由基的ESR谱。当把DMA加入到MMA和BPO中后,立即抽取0.17ml混合液到φ2mm样品管并记谱。以后每隔2分钟记谱一次,波谱从13(5+8)条线逐渐变成9(5+4)条线。我们用阻碍振荡模型和构象重叠模型作了模拟。从全部谱图看,前者似更合理些。ESR实验表明:在聚合过程前期,自由基浓度基本保持不变,但从聚合中期的某一时刻开始,浓度剧增,它正好同步地与本体聚合反应的自加速效应相对应,而且其变化规律和单体转化率相平行。最后,我们用微波功率饱和方法观测到9线谱的协同自旋跳跃所产生的卫线,证明了主导的电子自旋晶格弛豫机理来自电子一核自旋间的偶极偶合角调制。  相似文献   

8.
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  相似文献   

9.
本文研究了不同处理条件(处理功率、处理时间和处理压力)下等离子体气体(Ar、N2、O2和空气等)对高密度聚乙烯表面处理产生的自由基的ESR谱。我们观察到等离子体处理产生的自由基是相当稳定的,它的ESR信号强度随处理功率和处理时间增加而增加。但处理压力对它影响不大。我们证明了紫外线对高密度聚乙烯表面产生自由基作用随处理条件而变化。并初步解释了谱的超精细相互作用。  相似文献   

10.
詹瑞云 《波谱学杂志》1995,12(6):613-620
用ESK研究多相氧载体CoO-MgO表面上氧的吸附作用,发现在77-150K温度范围内表面Co2+离子和O2的结合是可逆的,吸附产生Co3+-O2-自由基加合物有超精细结构的ESR谱;当温度增加,吸附态O2-自由基发生转移并稳定在Mg2+离子上形成Mg2+-O2-自由基,文中着重讨论Co3+-O2-自由基的电子结构和成键本质,认为自由基是通过自旋成对的方式形成的,由于σ-л键作用引起的自旋极化以及由于电子离域作用而引起的偶极作用与ESR制的超精细结构线产生有关。  相似文献   

11.
自由基存在于人体和卷烟烟气中,会引起人体病理反应和氧化损伤,种类和形态多样,如: O-·2,HO·,R·,RO·,ROO·. 电子顺磁共振法(EPR)是检测和定量分析自由基的重要方法之一. 银杏叶提取物(EGB)是由黄酮、内酯、原花青素类成分组成的植物药,具有较好清除自由基和抗氧化能力. 本文以槲皮素、芦丁、原花青素等化合物为对照,运用EPR法结合自旋捕集技术研究EGB和EGB卷烟对DPPH,HO·,O2-·、烟气气相自由基、烟气粒相自由基的抑制水平. 结果表明,EGB能够有效抑制化学/生物系统和卷烟烟气产生的自由基. 尽管抑制自由基整体水平比黄酮单体和原花青素弱,但EGB提取方法简单容易得到,可作为天然抗氧化剂和自由基清除剂用于食品和烟草等行业. EPR法灵敏度高,稳定性好,是用于自由基研究的可靠方法. 捕集剂D EPMPO捕集O2-·更加高效,PBN捕集烟气气相自由基比DMPO更有优势. 该研究讨论了EGB清除自由基的机理,丰富的酚羟基结构是其抗氧化作用的主要原因.  相似文献   

12.

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.  相似文献   

13.
Electron paramagnetic resonance (EPR) spin trapping is one of the choice techniques for identifying free radicals and is often used in the study of biological systems. However, its sensitivity can result in a typical complicated EPR spectrum. The accurate simulation of these systems is essential for correct identification of the radical species, whenever more than one species contributes to the spectrum. Programs implementing the linear combination of single simulations allow the interpretation of EPR spectra without modifying experimental conditions. In this study, this approach was used to investigate the influence of the ferrous ion and the role of oxygen, as well on the formation of transient radical species, in the whole mechanism of hyaluronan degradation. Degradation was carried out under different environmental conditions (air, O2, Ar, N2, N2 + CO2) and EPR spin trapping studies were performed. The advantages of the simulation of multiple species EPR spectra were applied to the obtained results and some aspects of hyaluronan degradation mechanism were elucidated. The depolymerization reaction pathway has been defined according to two possible subsequent steps: the first is consistent with formation of an amidyl radical that induces a series of strand scissions, which stabilize at two different levels of molecular weight. The second step occurs when the molecular weight is lower than before and two different adducts are generated.  相似文献   

14.
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16.
The rate equations describing spin polarization in a system of three spins are derived and solved for the case of a free radical dissolved in a solvent containing two nuclear spins. Triple irradiation experiments indicate that a nuclear spin A can be effectively coupled to an electron spin C via a second nuclear spin B and measurements of both the steady state and transient Overhauser effects are in accord with the theoretical predictions for a three-spin system. The ‘three spin effect’ is found to operate only in dilute solutions of free radicals in which case the probabilities for transitions between different nuclear or electronic energy levels can be determined. It was found to be effective for fluorine nuclei—in the presence of both protons and a free radical and for carbon [13] nuclei in the presence of either protons or fluorine nuclei and a free radical. Detailed measurements have been performed for CHFCl2, para-difluorobenzene, and meta-fluorotoluene containing the tritertiary butyl phenoxyl radical.  相似文献   

17.
Electron paramagnetic resonance (EPR) spectra of two consecutive radical pairs (RPs) diffusing inside micelles are numerically calculated. Calculations are carried out for various values of the micelle radius, exchange integral, and mutual diffusion coefficient. In the simple case when the hyperfine interaction with magnetic nuclei can be neglected, it is demonstrated that the spin dynamics in the primary radical pair (RP1) manifests itself in the EPR spectrum of the secondary radical pair (RP2) in a characteristic way: the oddness of the EPR spectrum with respect to its center is violated, and the EPR line intensities and widths for the two partners in the RP2 differ. These features of the RP2 EPR spectrum shape are interpreted as follows: the spin dynamics in the RP1 produces a longitudinal spin polarization and a transverse spin polarization (i.e., spin coherence). Both polarizations are transferred from RP1 to RP2. This spin polarization transfer causes the above features of the RP2 EPR spectrum shape. It is shown that the RP2 EPR spectrum in a sequence of RPs cannot be simulated as a spectrum of a single RP. The features of the RP2 EPR spectrum shape may be, in principle, exploited to reveal the existence of the short-lived RP1.  相似文献   

18.
An algorithm is developed that extends the well known nitroxide slow-motional continuous wave electron paramagnetic resonance (EPR) simulation technique developed originally by Meirovitch et al. [E. Meirovitch, D. Inger, E. Inger, G. Moro, J.H. Freed, J. Chem. Phys. 77 (1982) 3915-3938], and implemented by Schneider and Freed [D.J. Schneider, J.H. Freed, Calculating slow motional magnetic resonance spectra: a user's guide, in: Biological Magnetic Resonance, vol. 6, Plenum Publishing Corporation, 1989]. This paper deals with the more general case of coupling of one electron spin to two nuclear spins. A complete listing of the matrix elements of the Liouville superoperator for this extension has been included. This advance has been successfully tested by reproducing the observed spectral lineshapes of a solution of the novel radical Mes(*)(CH(3))P-PMes(*) [Mes(*)=2,4,6 (tBu)(3)C(2)H(2)] in tetrahydrofuran (THF), in which the radical is undergoing slow tumbling, with the coupling of one electron spin to two physically and magnetically inequivalent phosphorus ((31)P) nuclei.  相似文献   

19.
The sign of the exchange interactionJ in a series of radical triplet pairs (RTPs), formed by a nitroxide free radical and a triplet excited fullerene, has been determined from the spin polarization of time-resolved electron paramagnetic resonance spectra. Radical and fullerene are linked together by covalent bonds in different geometries. It is shown that the sign ofJ depends on the overlap between the orbital of nitroxide unpaired electron and the LUMO of fullerene, which is singly occupied in the excited triplet state. When the overlap does not vanish, a negative contribution toJ arises from the admixing of a charge transfer structure in the wave function of the excited doublet state D* of the RTP, which does not take place in the excited quartet state Q*. The mixing of D* and Q* states lowers the energy of the former spin state and gives antiferromagnetic coupling.  相似文献   

20.
Electron spin resonance investigations on an electron-beam irradiated solid state nuclear track detector, based on cellulose nitrate (KODAK LR-311), are reported. The nature of free radicals induced in polymers by irradiation is discussed. The dependence of resonance spectral parameters on irradiation times, as well as on storage time and temperature, is studied. The experimental results are related to the stability of latent tracks and it is concluded that the free radicals induced by irradiation are located within the latent tracks. We have shown that both latent track and free radical thermal fading obey an Arrheniuslike dependence, with the same activation energy.  相似文献   

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