乙二醇均相及其TX-100胶束溶液中光敏分子菲醌的激光光解研究

用时间分辨电子自旋共振（TR-ESR）和瞬态吸收光谱技术,研究了菲醌在乙二醇均相及其TX-100含水胶束溶液中的光化学反应机理。化学诱导动态电子极化（CIDEP）谱和瞬态吸收光谱都表明,在乙二醇均相溶液中,菲醌光激发三重态3PAQ* 夺取氢原子形成中性自由基PAQH.,三重态机理是CIDEP形成的主要机理。在TX-100含水胶束溶液中,光解主要得到菲醌负离子基PAQ-．,PAQ-．由PAQH.解离形成,解离过程中伴随着极化转移。     

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)CHOH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上夺氧外,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.     

285 nm激光光解对苯醌-乙二醇体系的CIDEP波谱解析

在285 nm紫外激光辐照下,用时间分辨电子自旋共振(TRESR)波谱仪研究了对苯醌/乙二醇(PBQ/EG)体系,得到了发射的苯半醌中性自由基PBQH.和乙二醇碳自由基R.(OH)2的CIDEP谱.在化学诱导动态电子极化(CIDEP)基本原理的基础上,建立合理的计算模型,编写相应的程序,对PBQH.和R.(OH)2的CIDEP形成机理进行了定量的解析.通过对不同延时下该体系各种自由基及不同机理成分的对比,明显看出由RPM形成的PBQH.比由TM形成的PBQH.衰减快.这种分析方法可以推广应用于其它体系的CIDEP实验谱的解析.     

时间分辨电子顺磁共振技术

该文简要分析了时间分辨技术的发展历史以及实现方法,总结归纳出时间分辨技术的核心本质--特定时间延迟下的波谱序列信息采集. 具体分析了时间分辨电子顺磁共振技术（TR-EPR）的实现方法,对国内TR-EPR仪器的发展情况做了简单总结,并结合CIDEP研究简要介绍了TR-EPR仪器的应用情况,并对如何进一步提高时间分辨电子顺磁共振技术的时间分辨率做了讨论.     

杜醌自由基光化学路径的CIDEP研究

用自制的高时间分辨电子自旋共振波谱仪,测量得到了酸性、碱性和胶束环境下的光解杜醌/乙二醇(DQ/EG)溶液瞬态自由基的化学诱导动态电子自旋极化(CIDEP)谱.在光解均相DQ/EG溶液时,观察到了以增强发射的的中性杜半醌自由基(DQH.)的CIDEP信号;在碱性环境下(pH=9)和TX-100胶束环境下光解DQ/EG体系时得到杜醌负离子自由基(DQ-.)的CIDEP信号;在酸性环境下(pH=2.5)光解DQ/EG体系时,出现的又是中性杜半醌自由基(DQH.)的CIDEP信号.实验结果显示,DQH.由3DQ*与EG之间的氢原子转移反应生成,DQ.-由DQH.的去质子化反应生成,反应中伴随着极化转移.     

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。     

激光光解苯甲醛自由基的时间-分辨ESR研究

利用高时间分辨ESR波谱仪,对苯甲醛为光敏分子的各体系进行了CIDEP(化学诱导动态电子极化)研究,揭示了苯甲醛体系的CIDEP信号的产生过程,并进一步确认了其产生过程中的极化特征.     

光解苯半醌自由基的CIDEP谱

用高时间分辨ESR谱仪实验给出了光解对苯醌产生的苯半醌自由基的CIDEP发射谱.用三重态机理,同时考虑了自由基对机理的影响,从理论上分析了极化强度,计算出了增强因子V(Ⅰ)=-0.66,V(R)=0.2,一级反应速率k_1,A=0.05/μs,二级反应速率β=0.02/μs,横向和纵向弛豫时间T₁≈T₂=2.3μs.     

吩噻嗪-1,4萘醌-乙二醇体系光化学过程的时间分辨ESR研究

用时间分辨ESR方法研究了吩噻嗪(PTH)-1,4-萘醌(NQ)-乙二醇(RH)体系中的光化学过程.只观察到萘醌的中性半醌自由基NQH^*的全发射极化的CIDEP(化学诱导动态极化)信号,并未观察到极化的萘醌负离子NQ·^-*的CIDEP信号,表明RH与三重态NQ间的质子转移反应远比PTH与NQ间的电子转移反应为快.NQH·^*的CIDEP信号随pH值的变化表明体系中同时有极化自由基NQH·^*与NQH·₂^+*存在,并且其间有质子交换.     

丙酮/1,2-丙二醇体系的化学诱导动态电子自旋极化研究

285 nm紫外激光照射下,用时间分辨电子自旋共振(TRESR)波谱仪研究了光解丙酮/1,2-丙二醇(ACETONE/PG)体系,得到了丙酮羰自由基(CH3)2.COH和1,2-丙二醇羰自由基CH3.COHCHOH的发射/吸收(E/A)型极化信号,这是一个自由基对(RPM)极化过程。在酸性环境中,溶剂分子的CIDEP谱明显减弱,(CH3)2.COH的CIDEP谱无明显变化,由此可判断光解ACETONE/PG体系是一个夺氢反应;在碱性环境中,(CH3)2.COH反应生成负离子基(CH3)2.CO-.     

吩噻嗪-1,4萘醌-乙二醇体系光化学过程的时间分辨ESR研究

用时间分辨ＥＳＲ方法研究了吩噻嗪（ＰＴＨ）－１，４－萘醌（ＮＱ）－乙二醇（ＲＨ）体系中的光化学过程．只观察到萘醌的中性半醌自由基ＮＱＨ．＊的全发射极化的ＣＩＤＥＰ（化学诱导动态极化）信号，并未观察到极化的萘醌负离子ＮＱ－·＊的ＣＩＤＥＰ信号，表明ＲＨ与三重态ＮＱ间的质子转移反应远比ＰＴＨ与ＮＱ间的电子转移反应为快．ＮＱＨ．＊的ＣＩＤＥＰ信号随ｐＨ值的变化表明体系中同时有极化自由基ＮＱＨ．＊与ＮＱＨ．＋＊２存在，并且其间有质子交换．     

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.     

Dynamic electron polarization created by the radical-triplet pair mechanism: Application to the studies on excited state deactivation processes by free radicals

The radical-triplet pair mechanism for chemically induced dynamic electron polarization (CIDEP) created in the quenching of excited state molecules by free radicals is explained on the basis of recent time-resolved electron spin resonance spectroscopic results and theoretical studies. The CIDEP of 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) and galvinoxyl radicals exhibit various CIDEP patterns of net and mutliplet types and CIDEP phases of absorption and emission. The CIDEP patterns are described by the quartet-doublet state mixings within the radical-triplet encounter pairs. The mixings by the spin-dipolar and the hyperfine interactions are responsible for the net and the multiplet patterns, respectively. The factors controlling the CIDEP phases are the spin multiplicity of the excited state quenched by radicals and the sign of the intermolecular exchange interaction of the radical-triplet encounter pairs. In particular, the intermolecular charge transfer effect on the exchange interaction is discussed much in detail from the viewpoints of CIDEP magnitudes and phases. A CIDEP creation in the O₂(¹Δ_g)-TEMPO system is also introduced and is described by the radical-triplet pair mechanisms. Applications of this CIDEP used as a probe of O₂(¹Δ_g) in condensed phase are mentioned.     

Photo-Induced Electron Transfer in P3DDT, P3OT, M3EH-PPV Conjugated Polymers Blended with Maleic Anhydride in THF Solution Under UV Flash Photolysis Studied by Means of CW TR ESR

Free-radical signals of positive polarons in conjugated polymer chains and maleic anhydride (MA) anion radicals were registered in poly(3-octylthiophene) P3OT:MA and (poly[2,5-dimethoxy-1,4-phenylene-1,2-ethenylene-2-methoxy-5-(2-ethylhexyloxy)?C(1,4-phenylene-1,2-ethenylene)]) M3EH-PPV:MA blends in tetrahydrofuran (THF) solutions under ultraviolet flash photolysis (308?nm) by continuous-wave time-resolved electron spin resonance. Their emissive chemically induced dynamic electron polarization (CIDEP) originated mainly from excited triplet states (triplet mechanism of CIDEP) and partly by from the radical pair mechanism due to the singlet?Ctriplet mixing states. The observed M3EH-PPV polaron spectrum (g ₀?=?2.0029) supports the supposition that the previously registered CIDEP spectra in P3DDT:MA blends (g ₀?=?2.0021) can be attributed to the polaron signals instead of the possible solvate electron signal one.     

国内CIDEP研究进展

化学诱导动态电子极化（CIDEP）是检测瞬态顺磁粒子并表征其特征的强有力的手段,对于研究光化学和光物理瞬态过程的微观机理和规律有重要意义. 本文较为详细地总结了4种常见的CIDEP机理,讨论了各种极化谱及相应的极化条件;简要介绍了国内研究小组在CIDEP理论以及在均相溶液和微复相体系中光化学过程的CIDEP研究成果.      

CIDEP Created by the Quenching of Photo-Excited Tryptophan at Protein Surface: A Challenge to CIDEP Probing of Protein Structural Changes

Quenching of the triplet excited state of molecular tryptophan by nitroxide radical in 1,4-dioxane and water solutions was investigated by means of time-resolved electron paramagnetic resonance (EPR) and Fourier-transform (FT)-EPR. The chemically induced dynamic electron polarization (CIDEP) signals with net emissive phase were recorded at these quenching events and were analyzed through radical-triplet pair mechanism. The CIDEP time profiles were well reproduced by Bloch and kinetic equations, assuming radical-triplet pair mechanism with the appropriate quenching rate constants. From a comparison of the simulation and the experiment, CIDEP enhancement factor in 1,4-dioxane was determined to be −30 × P _eq, where P _eq is the spin polarization of nitroxide at thermal equilibrium. Net emissive CIDEP was also observed by FT-EPR measurements on the nitroxide quenching of the triplet excited state of tryptophan residue in α-lactalbumin. Magnitude of CIDEP created in α-lactalbumin/nitroxide system depends on the pH condition of α-lactalbumin solution, which is related to protein folding dynamics. We argue the CIDEP mechanism at the α-lactalbumin surface and propose a possibility of a novel CIDEP method to probe a protein surface and structural changes.     

吩噻嗪-对苯醌体系光化学过程的时间分辨ESR研究

报道了用时间分辨电子自旋共振波谱仪对吩噻嗪与对苯醌的乙二醇溶液体系的紫外光照过程进行实时检测,从测得的电子自旋共振极化港可知,电子转移和质子转移在光照过程中同时存在并且相互竞争.