Involvement of triplet state in the photodissociation of hydrogen peroxide: experimental evidence from time-resolved EPR study

The dissociation of photoexcited hydrogen peroxide to generate a pair of hydroxyl radicals is generally believed to take place in a repulsive electronic singlet state. The results presented here, based on time-resolved EPR experiments on the spin polarisation pattern of the acetone ketyl radical (CH₃)₂C^?OH, generated on photodissociation of H₂O₂ in 2-propanol with a 248?nm laser light, strongly indicate significant involvement of a repulsive triplet state of excited hydrogen peroxide.     

Spin concentration in a possible ESR dosimeter: An electron spin echo study on X-irradiated ammonium tartrate

Several single crystals and powder samples of ammonium tartrate, recently proposed as a possible ESR dosimeter, have been X-irradiated with different doses. The total radical concentration has been determined by quantitative cw ESR, by comparison with a standard. The samples have been studied by electron spin echo spectroscopy. The two-pulse echo decay has been obtained and simulated by a single exponential function for different values of the microwave power of the pulses and for different pulse lengths. The dependence of the phase memory time TM on the microwave power has been exploited to get information on the contribution of the instantaneous diffusion to spin dephasing. At room temperature in the range of radical concentrations of 10(18)-10(19) spins/cm3 the instantaneous diffusion is the dominant spin dephasing mechanism. The linear dependence of the instantaneous diffusion on the total concentration of the radicals is in agreement with the theory. From the latter result we conclude that the average radical-radical distance corresponds to a random distribution of the radicals in the matrix. A simple method of measuring the radical concentration by the ESE decays in powder samples of irradiated ammonium tartrate is described.     

Multiplet-to-net CIDEP conversion by MW-pulses with adiabatically ramped amplitude

ABSTRACT

A method is proposed to manipulate electron spin order of spin-correlated radical pairs. As radical pairs are often born in a well-defined spin state, e.g. in the singlet state, they acquire Chemically Induced Dynamic Electron Polarisation (CIDEP). In the case of singlet-state preparation CIDEP is of the multiplet (or anti-phase) type resulting in reduction of EPR (electron paramagnetic resonance) signals due to overlap of absorptive and emissive lines in the spectrum. Here we propose to convert the singlet spin order into net magnetisation of the radical pair by applying a microwave field, with its amplitude slowly (adiabatically) reduced to zero. We demonstrate that by properly choosing the microwave frequency one can completely convert the singlet order into net polarisation of the radical pair with significant enhancement of the signal as compared to multiplet CIDEP. Calculations show that the technique is operative for both weakly coupled and strongly coupled spin pairs. Potential applications of the method are discussed.     

Saturation recovery electron spin–lattice relaxation studies on benzene anion radical and its derivatives: application of Kivelson–Orbach mechanism of electron spin relaxation

The role of low-lying excited states on the spin–lattice relaxation times (T₁) of organic radicals has been investigated. To test the applicability of Kivelson's electric field fluctuation model (D. Kivelson, J. Chem. Phys. 45, 1324 (1966)), based on the Orbach mechanism of spin relaxation, the T₁s of the anion radicals of benzene, benzene-1-d, toluene, ethyl benzene, isopropyl benzene, t-butyl benzene, p-xylene, 1,2,4-trimethyl benzene and 1,3,5-trimethyl benzene in liquid solutions, with potassium cation as the counter ion, have been measured by the pulse saturation recovery technique. The energy gap between the ground and the first excited electronic states changed with the substitutions to different extent. The spin–lattice relaxation rates showed correlation with this energy gap. Anion radicals of benzene and benzene-1-d showed the shortest T₁ among the radicals studied here. A small but measurable energy splitting due to the deuterium substitution in benzene-1-d radical was obtained from the temperature dependence of T₁. Spin–lattice relaxation times of benzene anion measured here decreased monotonically in the range of ?60 to ?125 °C, in contrast to some reported claims of very unusual temperature dependence, based on the continuous wave microwave power saturation studies. Our results also showed that the ion pairing between benzene anion and potassium cation did not significantly influence the spin–lattice relaxation times.     

Detection of ketyl radicals using 31P NMR spin trapping

Our recent work has allowed the development of ³¹P NMR spin trapping techniques for the detection and, at times, absolute quantification of many oxygen‐ and carbon‐centered free radical species. These methods are based on the ability of the nitrone phosphorus compound, 5‐diisopropoxy‐phosphoryl‐5‐methyl‐1‐pyrroline‐N‐oxide (DIPPMPO), to react with free radical species and form stable radical adducts, which are suitably detected and accurately quantified using ³¹P NMR. Our continuing efforts have now been focused on the application of this powerful system for the trapping of ketyl radicals, which are very difficult intermediates to be detected and quantified with traditional techniques (i.e., EPR). Ketyl radicals were initially produced using photochemical reactions of acetophenone, whose excited triplet state is able to abstract hydrogen from an H donor. As such, the ³¹P NMR signals for the radical adducts of the DIPPMPO spin trap with the ketyl radicals were assigned. Furthermore, in an effort to confirm the structure of these adducts, their mass spectra and fragmentation patterns were carefully examined under Gas Chromatography–Mass Spectrometry (GC–MS) conditions. Subsequently, the DIPPMPO spin trapping system was applied to the oxidation of 1‐(3,4‐dimethoxyphenyl)ethanol in the presence of horseradish peroxidase (HRP), hydrogen peroxide, and 1‐hydroxybenzotriazole (HBT) as the electron carrier (mediator). Our work confirmed that the mechanism consists of a hydrogen abstraction reaction from the α position, involving the ketyl radical: during the oxidation, the hydroxyl, hydroperoxyl, and ketyl radical intermediates were all detected. These efforts demonstrate the efficacy of our methodology that provides for the first time a facile means for the detection of the otherwise elusive ketyl radical species, with important implications in biology, chemistry, and biochemistry. Copyright © 2009 John Wiley & Sons, Ltd.     

Pulsed EPR study on large dynamic electron polarisation created in the quenching of photo-excited xanthene dyes by nitroxide radicals in aqueous solutions

Dynamic electron polarisation (DEP) produced by the quenching of dye molecules in the triplet excited states by nitroxide radicals was investigated in aqueous solutions by pulsed electron paramagnetic resonance and transient absorption spectroscopy. An analysis of the measured quenching rate constants suggests that quenching is promoted by either exchange or charge-transfer mechanisms for a triplet dye and a doublet radical pair. An unusually large DEP on the radical was found generated in the nitroxide and Eosin Y or Rose Bengal systems in aqueous solutions. Quantitative analysis indicates that the DEP values in aqueous solutions range from ?40 to ?150 in the unit of thermal spin polarisation, which is in contrast to previously reported small DEP values of less than ?10 for organic triplet molecules in benzene solutions [22–27,29,31,32]. From the theoretical analysis of DEP, an origin of this large DEP was attributed to the notably slow diffusion motion of Eosin Y and Rose Bengal in water.     

光诱导呫吨酮电子转移和氢转移反应的激光闪光光解研究

用时间分辨激光闪光光解的方法研究了在乙腈溶剂中呫吨酮的激发三重态的性质，并得到了呫吨酮激发三重态和胺类、醇类以及酚类反应的瞬态吸收光谱和猝灭速率常数(kq)．除了苯胺和3-硝基苯胺被认为是能量转移外，呫吨酮和其余胺类的反应随着自由能变的减校lgkq逐渐增大，由此认为发生了电子转移反应．而对于二甲基-对甲苯胺、3,5,N,N-四甲基苯胺、N,N-二甲基苯胺、三乙胺来说，通过瞬态吸收光谱的变化可以知道既有电子转移反应又有氢转移反应发生．呫吨酮和醇类只发生氢转移反应，其猝灭速率常数和醇的?-C?H的键能有关．由     

Theoretical study of the intensity of chemically induce dynamic electron polarization of radical-triplet pairs

Considering the interaction between encited triplet molecule and cloublet radical,based on the second-order perturbation theroy and the motion equation of density matrix,the polarzation intersity of RTPM were theoretically calculated with the overpopulated doublet spin states and quartet spin states of radical0triplet paris as initial conditions the radical result from the zero-field-splitting(zfs)and the multiplet A/E and E/A polarization result from hyperfine (hf) interactions of the triplet molcule,The hyperfine ralated A A/E or E E/A CIDEP on the radical were the overpopulation of the net abscrptive or emissive polarization and multiple A/E or E/A polarization.     

Radiation damage in polyacrylonitrile

Radiation damage in polyacrylonitrile (PAN) has been studied in the temperature range 273 to 420 K using thermoluminescence, electron spin resonance and optical absorption techniques. ATL glow peak has been observed with maximum at 362 K. The species responsible for theTL glow peak has been identified to be due to the free radical -CH₂-CH(CN)-ĊH-CH(CN)-CH₂-by correlation with the data obtained by the temperature variation ofESR and optical absorption spectra of thex-irradiated, pre- and post-x-irradiated and thermally-treated samples. A mechanism of formation of network structures accelerated by the free radicals formed on irradiation has been investigated to explain the optical absorption spectra. TheTL glow peak is analysed by various methods and corresponds to an activation energy of 1 eV, following second order kinetics.     

Time-resolved EPR study of the photoreduction of phthalic anhydride and chlorinated phthalic anhydrides in 2-propanol

The photoreduction of phthalic anhydride (PA), 3,6-dichlorophthalic anhydride (3,6-DCPA), 4,5-dichlorophthalic anhydride (4,5-DCPA) and tetrachlorophthalic anhydride (TCPA) in 2-propanol has been studied with time-resolved electron paramagnetic resonance. The chemically induced dynamic electron polarization spectra show that the reaction takes place through the excited triplet states. From PA, cyclohexadienyl-type hydrogen adduct and ketyl radicals were observed, whereas 3,6-DCPA produced the 3,6-DCPA anion and hydrogen adduct radicals. With 4,5-DCPA only the anion radical appeared, whilst the TCPA system showed no apparent anion and adduct radical formation. These data show that the hydrogen adduct formation occurs at the 4 position in the benzene ring, but that 4,5-DCPA and TCPA do not undergo this reaction. The anion radicals of PAs are formed in subsequent deprotonation reactions of the ketyl radicals. We propose that the hydrogen adduct radical formation in PA and 3,6-DCPA takes place through direct hydrogen abstraction by the excited triplet molecules, in competition with similar abstraction by the carbonyl group to form the ketyls.     

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.     

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     

InGaN薄膜中电子自旋偏振弛豫的时间分辨吸收光谱研究

采用飞秒时间分辨圆偏振光抽运-探测光谱对In_01Ga_09N薄膜的电子自旋注入和弛豫进行了研究.获得初始自旋偏振度约为02,此结果支持在圆偏振光激发下,重、轻空穴带的跃迁强度比为3∶1,而不支持1∶1或1∶094的观点同时获得自旋偏振弛豫时间为490±70ps,定性分析了自旋弛豫机理,认为BAP机理是电子自旋弛豫的主要机理. 关键词： 电子自旋 InGaN 自旋极化 自旋弛豫     

Stochastic Liouville equation studies of FT-EPR spectra of singlet-triplet mixing photo-chemically generated radical pair system

A stochastic Liouville equation (SLE) was numerically solved to obtain pulsed Fourier-transform (FT) EPR spectra on a radical pair system created in a photo-induced chemical reaction. Numerical calculations were applied to the photo-chemical reaction of deuterated acetone and 2-propanol at low temperatures. In this reaction system, the antiphase structures of the EPR signals, so called spin-correlated radical pair (SCRP) signals of two identical isopropyl ketyl radicals and spin-polarized free isopropyl ketyl radicals were observed by FT-EPR and continuous wave time-resolved (CW TR) EPR techniques. In the present work, FT-EPR spectra of the antiphase structure signals of the radical pair themselves as well as spin-polarized free radical signals were simulated. Additionally, rising behavior of free radical signals polarized by the radical pair mechanism (RPM) was also clarified. Furthermore two-dimensional (2D) FT-EPR nutation spectra were simulated in the both cases with and without the radical pairs by the use of SLE. In these simulations, strong DC components in the nutation frequency dimension, were well reproduced as was obtained in experiments. It was shown that relaxation during the microwave pulse was essential for the appearance of the DC components.     

Silyloxyamines as sources of silyl radicals: ESR spin‐trapping,laser flash photolysis investigation,and photopolymerization ability

Two silyloxyamines derived from 8‐(pentamethyldisilyloxy)‐julolidine and diethyl 3‐(pentamethyldisilyloxy)‐aniline are proposed as new sources of silyl radicals. The decomposition mechanism, excited state processes and the radical generation are explored by steady state photolysis, laser flash photolysis (LFP), electron spin resonance (ESR), and MO calculations. The Si? Si bond cleavage is clearly demonstrated. The formation of a radical cation on the amine moiety is also observed. Moreover, these compounds work as efficient Type I and Type II photoinitiators (PI) of free radical photopolymerization (FRP). Copyright © 2010 John Wiley & Sons, Ltd.     

乙二醇均相溶液中苊醌三重激发态淬灭反应的TR-ESR研究

利用时间分辨电子自旋共振（TR-ESR）方法,研究了乙二醇（EG）均相溶液中稳定自由基TEMPO和生物抗氧化剂维生素C（VC）对苊醌（ACQ）激发三重态3ACQ*的淬灭反应。光解ACQ/EG体系,观察到苊醌中性自由基ACQH•和乙二醇烷基自由基的发射/吸收+发射（E/A+E）的CIDEP信号,ACQH•和CH2(OH)C•HOH由3ACQ*从EG上夺氢生成。光解ACQ/TEMPO/EG体系,3ACQ*与TEMPO相互作用将极化转移给TEMPO。光解ACQ/VC/EG体系,3ACQ*除了从EG上夺氢外,还从VC上夺氢生成VC负离子基As•-。较强的As•-的CIDEP信号表明VC对3ACQ*有明显的淬灭作用。     

异丙醇在锐钛矿TiO2(101)表面的光化学

通过程序升温脱附谱的方法探究了266 nm激光照射下异丙醇在锐钛矿TiO₂（101）表面的光化学,并提出了详细的解离机理.在光照作用下,异丙醇发生分步解离：首先,O-H键断裂生成异丙氧基;然后,仲碳的C-H键在光照的作用下进一步发生解离,从而生成丙酮,两步生成的氢原子均转移到相邻的桥氧上.在升温过程中,这部分氢原子会与分子态的异丙醇发生置换反应,从而以低温水和高温异丙基的形式从表面脱附出来.     

Alkylperoxyl spin adducts of pyrroline‐N‐oxide spin traps: Experimental and theoretical CASSCF study of the unimolecular decomposition in organic solvent,potential applications in water

Spin trapping coupled with electron paramagnetic resonance spectroscopy is the most direct method for detection of very low concentrations of free radicals, and it has been intensively used to detect superoxide or alkylperoxyl radicals in biological systems, using cyclic nitrones as spin traps. The half‐life time of the ensuing spin adducts depends dramatically on the spin trap structure; however, their mechanism of decay has never been definitely established. We investigated at the MRMP2/CASSCF (MultiReference second‐order Møller‐Plesset perturbation theory/Complete Active Set Self Consistent Field) level of theory the mechanism of decay of methylperoxyl and tert‐butylperoxyl spin adducts formed with various cyclic nitrones. We showed that no transition state can be located for the O─O homolytic cleavage, which yields an intermediate biradical with the following sequence ^?O─N─C─O^?. Then, homolytic cleavage of the N─C bond yields a nitrosoaldehyde, through an early transition state with a very low activation energy. For each nitrone used as spin trap, electrospray ionization mass spectrometry analysis of the spin trapping mixture allowed to detect the presence of the expected nitrosoaldehyde. We generated tert‐butylperoxyl spin adducts in toluene, and we found a good correlation between their half‐life time and the bond dissociation energy of their peroxidic O─O bond. The theoretical method was then extended to hydroperoxyl spin adducts in water and provided promising results.     

Proton Exchange Effects in Laser Photolystic P-Benzosemiquinone Spin Polarized Radicals

The TRESR spectra of benzosemiquinone radical and the ethylene glycoi ketyl radical formed from laser photolysis of P-benzoquinone in ethylene glycoi or ethylene glycol/water systems are presented. The photon exchange between p-benzosemiquinone radicals PBQH⁺ and their protonated forms PBQH⁺ is studied by adding H₂SO₄ to the solution. The experimental results show that different hyperfine lines for PBQH⁺ have different time-dependence which depend upon the fraction of the overall number of nuclear spin states, and that the lines with smaller fraction are decay fast.