二硫化碳氢化性自由基对生物靶分子损伤机理研究

利用脉冲辐解技术研究了二硫化碳（CS2）被氧化生成的阳离子自由基，以时间分辨瞬态吸收光谱方法获取CS2阳离子自由基的特征吸收谱。同时，研究了CS2阳离子自由基损伤生物靶分子的机理，测定了相关的反应动力学常数。结果发现，CS2阳离子自由基能与DNA、dGMP、酪氨酸和色氨酸反应产生新的产物，在CS2对生物靶分子的氧化损伤中可能起着重要的作用。     

二硫化碳氧化性自由基对生物靶分子损伤机理研究

利用脉冲辐解技术研究了二硫化碳（CS2）被氧化生成的阳离子自由基，以时间分辨瞬态吸收光谱方法获取CS2阳离子自由基的特征吸收谱，同时，研究了CS2阳离子自由基损伤生物靶分子的机理，测定了相关的反应动力学常数。结果发现，CS2阳离子自由基能与DNA、dGMP、酪氨酸和色氨酸反应产生亲的产物，在CS2对生物靶分子的氧化损伤中可能起着重要的作用。     

ADE光诱导原初过程的时间分辨研究：I.合成及溶液中的光物理

利用纳秒级激光光解和脉冲辐解技术对放线菌素D(AMD)的模型化合物2—氨基—4，6—二甲基—3—吩恶嗪酮—1，9—二甲酸甲酯(ADE)的光物理性质进行了系统研究，确认了ADE光解时产生的瞬态物种，并测得了其激发三重态的自淬灭速率常数、摩尔消光系数和量子产额等重要光物理参数。这些结果将为详细了解ADE以及放线菌素D的光动力作用过程提供理论依据。     

SO4^·－自由基与酪氨酸反应机理的表征

采用激光光解和脉冲辐解两种技术研究了水及水-乙腈混合溶液中SO4·-自由基氧化酪氨酸(TyrOH)的反应机理.通过两种方法所得结果的相互验证及空白对照和pH对照实验,阐明了SO4·-自由基氧化TyrOH的反应机理,并借助于·OH与TyrOH的加成反应确证了SO4·-自由基与TyrOH通过直接电子转移发生氧化反应的机理.研究表明SO4·-自由基与TyrOH之间的反应不受乙腈加入的影响.     

苯胺的脉冲辐解和激光光解研究

用脉冲辐解与激光光解时间分辨技术,从瞬态方面研究了苯胺Photo-Fenton降解的可行性。研究表明,水溶液中苯胺可为308nm的激光光电离,光电离的瞬态产物为阳离子自由基及脱质子后的中性自由基;并测得阳离子自由基脱质子转变为中性自由基的pKa值为7．5,以二苯甲酮为参比,测得苯胺光分解的量子产额极高（0．08）。应用脉冲辐解时间分辨技术研究了苯胺被羟基自由基降解的反应机理,结果表明,36％的羟基自由基直拉进攻－NH2形成苯胺,54％的羟基自由基与苯胺邻位加成,10％的羟基自由基与苯胺对位加成。     

异喹啉的脉冲辐解和激光光解研究

用脉冲辐解和激光光解相结合,研究了异喹啉这种难降解杂环化合物在紫外光作用下的变化和与HO·的反应.结果表明,在波长为266nm的激光作用下,异喹啉不仅发生光激发,而且发生单光子电离,其量子产额为1.58×10-4.异喹啉光电离产生的阳离子自由基可以脱去质子,其pKa为5.50.异喹啉可以与HO·发生反应,其反应速率常数为3.4×109 mol-1·dm3·s-1.本工作的研究将为photo-Fenton法降解异喹啉提供理论上的依据.     

硫辛酸清除自由基的反应动力学研究

利用脉冲辐解和激光光解瞬态吸收光谱装置,研究了硫辛酸清除活性氧自由基（ROS）的反应机理,获得涉及反应的瞬态吸收光谱和反应速率常数,测得硫辛酸清除OH,eaq,CO3^-,SO4^-,Br2^-的反应速率常数分别为7．4×10^9、1．3×10^10、9．8×10^8、2．3×10^9、2．0×10^9L·mol^-1·s^-1,并对可能的反应机理进行了探讨。结果表明,硫辛酸能有效地清除活性氧自由基,是个高效的抗氧化剂。     

SO4·-自由基与酪氨酸反应机理的表征

采用激光光解和脉冲辐解两种技术研究了水及水-乙腈混合溶液中SO4·-自由基氧化酪氨酸(TyrOH)的反应机理.通过两种方法所得结果的相互验证及空白对照和pH对照实验,阐明了SO4·-自由基氧化TyrOH的反应机理,并借助于·OH与TyrOH的加成反应确证了SO4·-自由基与TyrOH通过直接电子转移发生氧化反应的机理.研究表明SO4·-自由基与TyrOH之间的反应不受乙腈加入的影响.     

脉冲辐解研究 DNA 羟基加成自由基快速修复过程

脉冲辐解研究ＤＮＡ羟基加成自由基快速修复过程⒇姜岳姚思德林念芸（中国科学院辐射化学开放研究实验室中国科学院上海原子核研究所上海２０１８００）氧自由基由于具有极其活泼的化学活性和致癌、致心血管疾病、感染及促进衰老等作用而引起人们的广泛关注。而羟自由基氧...     

鬼臼毒素及其衍生物的化学活性研究

动用脉冲辐解和激光光解技术，对鬼臼毒素及其衍生物的光学活性和化学活性进行了详细的研究。结果表明：它们不仅在激光作用扯具有很强的光敏性，而且还有多个活性基团分别与水合电子，氢原子，羟基自由基作用生成不同的瞬态粒子，且推断了相应的反应机理。为医学工作者进一步了解和利用反臼毒素，化学工作者合成更高抗肿瘤活性和低毒性物质提供参考。     

喹啉及其衍生物的脉冲辐解和激光光解研究

Quinoline and some of its derivatives were reported to be carcinogenic, toxic and mutagenic. The widespread use of quinoline and its derivatives entails that these compounds are distributed in the environment, polluting soil and water together with many other environmental chemicals.     

海藻酸钠的电离辐射降解研究

采用γ射线辐照、激光光解和脉冲辐解技术，就海藻酸钠水溶液分子量与辐照剂量的关系，SO4^*-氧化切断海藻酸钠C1-O-C4键的机理开展研究。探索了海藻酸钠辐射降解规律，推导其在γ射线照射下的降解，主要由水辐解产物羟基自由基进攻其C1-O-C4键，导致链断裂引起的。     

珍贵三环核苷衍生物的理论计算与实验研究

N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleosides is probably a new member of Y-nucleosides found in tRNA [1]. The structure of dYt has tricyclic ring with rigid conformation and high electron delocalization. Both the absorption and emission bands of dYt are well separated from normal bases, so it could probably be used as an effective natural fluorescent probe to study RNA structure and sequence[2].Fig.1 The secondary structure of yeast tRNAPbe anticodon loop and molecular structures ofguanosine and N-4-desmethylwyosine An ab initio study was performed to evaluate stability of three isomers of this compound. Ionization potential (IP) of dYt was calculated. It was found that the value was lower than that of guanosine and guanine. This shows that dYt loses electron more easily than guanine.In addition, the result has been verified by experimental studies performed by nanosecond laser photolysis.The reactions of dYt and a series of transient species such as reduction radicals eaq-, H· and oxidation radicals ·OH,SO4·-, CO3·- and N3· have been carried out by nanosecond pulse radiolysis. Rate constants of these reactions have been determined and related mechanisms were discussed.     

超临界水的辐化反应研究

It is known that water exists in supercritical state above 374C and 22.1MPa, where gas phase and liquid phase are merged into a single phase. In the supercritical state, the density is controllable by changing the pressure. The properties such as the ionic product, solubilities of salts, gas and organic compounds, and dielectric constant of supercritical water are very different from those of water at room temperature.Recently much attention has been paid to supercritical water because many possible applications such as synthesis of functional materials, waste oxidation, and biomass conversion have been proposed by using above peculiar properties of the supercritical water. Thus, much intensive work is in progress all over the world. In addition, a new concept of nuclear reactor using the supercritical water as a coolant has been proposed, which has been chosen by DOE, USA as one of the forth generation nuclear reactors.Therefore, radiation chemistry study of the supercritical water seems inevitably important, yet little work has been done so far. We started radiation chemistry study of supercritieal water by pulse radiolysis and γ radiolysis five years ago. We have observed hydrated electrons as a first target. We also measured inorganic radicals, metal ions, organic radicals in high temperature and supercritical water by a pulse radiolysis technique. It was found that absorption spectra of the transient species are dependent on temperature. Some transients show red-shift, and some bands are blue-shifted, with increasing temperatures. A G-value evaluation of water decomposition products was also done by using methyl viologen as a scavenger and it was revealed that the values are significantly dependent not only on temperature but also on density in supercritical water. An extended study on the behavior of solvated eleclions in different alcohols at high temperatures and super critical state is also in progress.     

激光光解研究焦脱镁叶绿酸-a作为光活化农药的可能性

利用激光光解时间分辨吸收方法，对蚕砂叶绿素中提取的焦脱镁叶绿酸-a的光化学性质进行了初步的研究。发现，该化合物在实验检测的波长范围内都有较强的吸收，且能产生较高量子产额的三重激发态。进而讨论它作为光活化农药的可能性。     

Pulse radiolysis study on aqueous solution of nicotine

Nicotine has been studied for the first time by pulse radiolysis techniques. It has been found that hydrated electrons, hydrogen radicals and hydroxyl radicals can react with nicotine to produce anion radicals and neutral radicals, respectively, and the related rate constants have been determined.     

吲哚荷尔蒙自由基脉冲辐解光谱及其酸基平衡和还原电位性质研究

The Absorption spectral, acid-base equilibrium potential properties and formation and decay kinetics of four kinds of radicals from natural existing indole hormones were studied by pulse radiolysis.One of the most important properties for these four indolyl hormones, melatonin, 5-methoxygramine (MTA),5-methoxy-N, N-dimethylthytrytamine (DMM TA) and 5-methoxy-N, N-diethylthytrytamine (DEMT A), which are involved in biochemical processes and play crucial roles in many neuropathy and cancer related diseases, is their facile one electron oxidation with formation of radical cations or their conjugated base, the indolyl radicals.Formation kinetics and properties of the radicals were investigated by pulse radiolysis using the Linac accelerator with fast time-resolving optical system in UTNL.In the present study, these radicals were generated through oxidation of the corresponding hormone with azide radical in radiation induced process. Their spectroscopic properties were investigated and it was found that the transient spectra in all these cases exhibit similar absorption and pH dependence: in acidic solution, the radicals are characterized with three absorption maxima around 320-350, 440-460, 520-550nm. The spectra of MTA at various pH were shown as an example. From the absorption changes as a function of pH, two pK values were determined to be around 5 and 9 for the indolyl radicals except for melatonin, in which, only one pK was distinguished to be 4.4. Formation kinetics of the radicals was measured by following the growth of their absorption peaks and it was found that these indolyl derivatives transfer an electron to N3, with different rate constants, i.e.1.2×1010, 4.5×109, 4.9×109, 1.6×109 dm3 mol-1 s-1 for melatonin, MTA, DMMTA, and DEMTA, respectively.Reduction potentials of the radicals vs their molecules were also determined and they are dependent on the pH of medium. At pH 7, the reduction potentials were estimated to be 1.10, 1.18, 1.18, 1.20eV for melatonin, MTA,DMMTA and DEMTA, respectively. Because of its relatively high contents in human brain cells, melatonin is the main antioxidant among hormones against the oxidizing species in brain cells.