一类2(1H)-喹喔啉衍生物的电子轰击质谱分析

以邻苯二胺为原料合成表征了一类喹喔啉衍生物；1-烷基-3-甲基-2（1H）-喹喔啉-2-酮（1-alkyl-3-methly-2(1H)-quinoxalin-2-one，简称AMQ，其中alky=H、CH3、Et、n-C3H5、n-C5H11、n-C16H33)。用电子轰击电离质谱（EI-MS）和核磁共振谱图（^1H-NMR)鉴定了AMQ，研究了不同取代基对这类化合物EI-MS谱图的影响，分析得到一些裂解规律。结果表明：所有样品谱图中均有芳香化合物的特征CnHn^ 系列峰m/z78，65，52，39和（或）m/z77、76、64、63、51、50、38、37。对于末取代的样品及低级烷烃取代的样品，谱图中的基峰为分子离子峰，对于取代基中碳数大于等于3的样品。谱图中的基峰不是分子离子峰，分子离子峰强度随着碳数的增加而降低。这些样品一般容易发生骨架重排，丢失一分子CO，生成1-烷基-2-甲基苯并哒唑正离子。此外，还讨论了谱图中其它的一些碎片离子峰。这对于研究和指导喹喔啉衍生物 的合成，探讨它们在药效及结构特征与生理活性的关系等方面具有重要的应用价值和理论意义。     

喹喔啉-三唑衍生物的设计与合成及其抗肿瘤活性

喹喔啉和1,2,3-三唑都是具有广泛生物活性的杂环结构母体。本文基于药物设计的拼合原理,以简单易得的邻苯二胺、苯乙炔及有机叠氮为原料,通过三组分"两步一锅法"将喹喔啉和1,2,3-三唑活性亚结构进行拼接,合成了一系列共14个新型喹喔啉-三唑衍生物(3a~3n)。该法操作简单,无需分离中间体,两步总产率52.6%~78.4%。合成的目标化合物结构经~1H NMR、~(13)C NMR和HRMS确证。初步体外抗肿瘤活性测试表明,合成的目标化合物具有一定的抗肿瘤活性。     

含喹喔啉杨梅素衍生物的合成及生物活性

利用活性拼接原理, 将喹喔啉引入到杨梅素结构中, 合成了一系列含喹喔啉基团的杨梅素新型衍生物. 采用浊度法测试了目标化合物的体外抑菌活性, 结果表明, 目标化合物对柑橘溃疡病菌(X. Citri)和水稻白叶枯病菌(X. Oryzae)均表现出较好的抑制活性. 目标化合物对柑橘溃疡病菌的抑制活性(EC₅₀)均优于对照药叶枯唑和噻菌铜(EC₅₀分别为54.85和61.13 μg/mL), 其中化合物4o抑制活性(EC₅₀=11.17 μg/mL)最优; 目标化合物对水稻白叶枯病菌的抑制活性EC₅₀均优于对照药叶枯唑和噻菌铜(EC₅₀分别为148.20和175.47 μg/mL), 其中化合物4f抑制活性(EC₅₀=34.49 μg/mL)最优. 采用半叶枯斑法测试了目标化合物的抗烟草花叶病毒(TMV)活性, 结果表明, 所有目标化合物在浓度为500 mg/L时均有一定的抑制作用.     

3-甲基-2(1H)-喹喔啉系列衍生物的电子轰击质谱

用电子轰击质谱（EI－MS）研究了1－烷基－3－甲基－2（1H）－喹喔啉－2－酮（烷基为H，CH3，Et,n-C5H11),1-烷基－3－甲基－6－硝基－2（1H）－喹喔啉－2－酮（烷基为CH3，Et)和1－甲基－3－甲基－6－胺基－2（1H）－喹喔啉－2－酮，结合其结构特征总结出一些裂解规律。讨论了不同取代基对这类化合物熔点的影响，结果表明：在同类喹喔啉化合物中，随着烷基链的增长，样品熔点通常会有所降低，而硝基及胺基的引入会使其熔点升高。     

可见光诱导下喹喔啉酮与吡咯衍生物的氧化偶联（英文）

发展了一种区域选择性的喹喔啉酮3-位氧化偶联富电子吡咯衍生物的方法.以Mes-Acr-Me⁺ClO₄^-(3 mol%)为光敏剂,空气氧为氧化剂,高收率得到喹喔酮与吡咯衍生物的氧化偶联产物.该方法底物的官能团适用范围广,反应高效绿色,可快速构建基于喹喔啉酮-吡咯衍生物的药物分子库.相同测试条件下的Stern-Volmer荧光淬灭实验表明缺电子芳烃1-甲基喹喔啉酮对光敏剂的淬灭速率常数K_q=1.2×10⁹ L·mol^-1·s^-1,而富电子芳烃1-甲基吡咯/1-甲基吲哚的淬灭常数约为1.06～1.07×10¹⁰ L·mol^-1·s^-1,后者的荧光淬灭速率几乎是前者的10倍.     

SBA-15/NiCl2催化超声合成喹喔啉衍生物

以苯偶姻和邻苯二胺为原料,SBA/NiCl2为催化剂,在超声条件下合成了喹喔啉衍生物,其结构经1H NMR和IR确证。考察催化剂类型、原料摩尔比和催化剂的用量对产率的影响。在最佳条件(苯偶姻和邻苯二胺物质的量比为1.0/1.0,催化剂用量为苯偶姻的10 mmol%,于70℃超声反应5 min)下,产率可达94.7%。     

一类2(1H)-喹喔啉化合物的裂解机理

用电子轰击质谱（EI-MS）研究了一类喹喔啉化合物；1-烷基-3-甲基-2（1H）-喹喔啉-2-酮（1-alkyl-3-methyl-2(1H)-quinoxalin-2-one，简称AMQ，其中alky1=H,CH3，C2H5，n-C3H7，n-C5H11；结果表明随着烷基链的增长，样品熔点通常会有所降低，结合在电子轰击下所产生的裂解碎片离子，并根据其结构特征为乙基化样品为代表，推导了该类化合物在电子轰击作用下可能发生的裂解机理。     

铜催化一锅法合成吡咯[1,2-a]喹喔啉衍生物

建立了一种简单实用、经济高效的以邻碘苯胺、吡咯甲醛为起始原料,廉价的CuI为催化剂,价廉、易获得的2,2-联吡啶为配体,110℃条件下一锅法合成吡咯[1,2-a]喹喔啉类衍生物的催化体系,得到中等到优良产率.本方法具有催化剂廉价易得、操作简便、合成效率高的优点.     

喹喔啉—2,3—二甲酰胺与3d过渡金属配合物的合成及性质研究

首次合成了喹喔啉－２，３－二甲酰胺（Ｑｘｄａ）与３ｄ过渡金属的三种固体配合物：Ｍ（Ｑｘｄａ）２ｃｌ２（Ｍ＝Ｃｏ（Ｉ），Ｎｉ（Ｉ），Ｃｕ（Ⅱ）。通过元素分析，摩尔电导，红外光谱，电子光谱，磁化率，热分析等手段对配合物的组成和性质进行了研究。     

樟脑基喹喔啉类化合物的合成及其生物活性

将D-(+)-樟脑用二氧化锡氧化制得樟脑醌,再与系列取代邻苯二胺化合物缩合,合成得到19个樟脑基喹喔啉类化合物(3a～3s),并用UV-Vis、 ¹H NMR、 ¹³C NMR、 FT-IR和HR-MS(ESI)进行结构表征。初步的抑菌和除草活性测试表明：在用药量为50 μg·mL^-1时,目标化合物对花生褐斑病菌、小麦赤霉病菌、黄瓜枯萎病菌、苹果轮纹病菌、番茄早疫病菌、玉米小斑病菌、西瓜炭疽病菌以及水稻纹枯病菌等8种植物病原菌具有一定的抑制活性,其中化合物樟脑基5,8-二溴喹喔啉3r(R¹=R⁴=Br,R²=R³=H)对苹果轮纹病菌的抑制率达78.6%,优于阳性对照百菌清。在用药量为100 μg·mL^-1时,化合物樟脑基6-氟喹喔啉3f(R³=F, R¹=R²=R⁴=H)和樟脑基7-氟喹喔啉3g(R²=F, R¹=R³=R⁴=H)对油菜胚根生长的抑制率分别为75.8%和68.5%,均优于阳性对照丙炔氟草胺。      

Studies on the Photodynamic Mechanism of Tetrapyrrole Compounds by Laser Flash Photolysis

Photodynamic therapy (PDT) is a promising new treatment technique which can potentially destroy unwanted and malignant tissues, such as those of cancer. The photodynamic mechanisms of three tetrapyrrole compounds: Mg‐purpurin‐18, tetra(meso‐chlorophenyl)porphyrin (m‐TCPP) and 2,7,12,18‐tetramethyl‐3,8‐di[(1‐isobutoxyl)‐ ethyl]‐13,17‐bis[3‐di(2‐chloroethyl)aminopropyl]porphyrin (TDBP) in acetonitrile were investigated by 355 nm laser flash photolysis. It was found that after laser flash photolysis (LFP), the excited states of TDBP and Mg‐purpurin‐18 could react with O₂ and ¹O₂ was produced, which proved that TDBP and Mg‐purpurin‐18 took effects through type II mechanism in PDT. This suggested that TDBP and Mg‐purpurin‐18 should be suitable for target tissues containing enough O₂. Mg‐purpurin‐18 has two extra absorptions at 550 and 700 nm, which means it has broad choices of laser wavelength in PDT. It was also found that m‐TCPP could be photoionized when excited with 355 nm laser under N₂‐saturated condition. It could also react with O₂ to produce reactive oxygen species such as superoxide and the peroxide anions, but not ¹O₂. These were known as the Type I mechanism. So m‐TCPP could be used even at low oxygen concentration or more polar environments with good behavior in PDT. From the above studies on the three different tetrapyrrole compounds it could be concluded that the structure of porphin ring takes a main role in PDT. And there was important impact on the photodynamic mechanism for the functional group directly connecting with porphin ring, while little influence for the functional group indirectly connecting with porphin ring. These will be of great value in the discovery of new PDT drugs.     

没食子酸的激光光解研究

The transient species of gallic acid(GA)have been studied by 266 nm nanosecond laser flash photolysis inaqueous solution and acetonitrile.The intermediate with absorption at 320 nm was identified as excited triplet state(~3GA~*),the decay rates of which were obtained in aqueous solution and acetonitrile respectively.Energy transferfrom ~3GA~* to β-carotene was observed and the energy transfer rate constant k_(ent)was determined to be 2.2×10~9mol~(-1)·L·s~(-1).GA underwent photoionization during photolysis and the quantum yield of photoionization was de-termined to be 0.12 at room temperature with KI as a reference.     

纳秒激光闪光光解装置功能扩展──有机非线性材料二阶非线性系数测定

纳秒级激光闪光光解装置可用于有机光化学、光物理过程，瞬态发光和吸收的动力学过程的研究，在不改变原装置整体布局和结构的基础上，建立了有机非线性光学材料的二阶非线性系数测定方法，并为国家８６３专家委员会承担过仲裁测定。     

Determination of Astaxanthin and Canthaxanthin Triplet Properties in Different Polarities of the Solvent by Laser Flash Photolysis

Triplet‐triplet extinction coefficients for astaxanthin ( I ) and canthaxanthin ( II ) in different deaerated polarity solutions of MeCN and benzene were evaluated by laser flash photolysis at 298 K in the spectral region from 350 to 650 nm by energy transfer method, employing 2‐acetonaphthone as sensitizer. The triplet‐triplet extinction coefficients in MeCN and benzene were different in terms of the carotenoid present. The maximum triplet‐triplet extinction coefficient was 0.1–1.7×10⁵ L·mol⁻¹·cm⁻¹ in different solvents. The rate constants of triplet decay were I : 1.25×10¹⁰ L·mol⁻¹·s⁻¹, II : 1.12×10¹⁰ L·mol⁻¹·s⁻¹ in MeCN; and I : 1.75×10¹⁰ L·mol⁻¹·cm⁻¹, II : 3.27×10¹⁰ L·mol⁻¹·s⁻¹ in benzene. The bimolecular rate constants of energy transfer from triplet excited 2‐acetonaphthone to carotenoids were determined from the linear regression of the decay rate constant of 2‐acetonaphthone triplet at varying carotenoid concentrations. The triplet lifetimes of ³AST* and ³CAN* in different solvents were also determined. The results indicated that triplet energy transfer was nearly diffusion‐controlled.     

C60-地塞米松的激光激发

利用激光光解装置检测了C60-地塞米松(C60-DE)的苯溶液在355 nm激光照射下产生的激发三重态, 3C60-DE*出现四个吸收峰, 分别位于700、440、350 和310 nm. 在330 nm处观察到了它的漂白吸收最大值, 这与其基态吸收最大值相对应. 3C60-DE*能够将能量转移给O2分子而淬灭. 与3C60*相比, 3C60-DE*的三重态鄄三重态(T-T)淬灭速率常数减小(3C60*为(5.03±1.31)×109 L·mol-1·s-1, 3C60-DE*为(3.53±0.87)×109 L·mol-1·s-1), 而寿命增加了(3C60*为(12.0±2.6) μs, 3C60-DE*为(18.0±3.3) μs), 这可能是C60分子上连接了地塞米松分子后减小了C60球之间碰撞的几率所致.     

纳秒激光闪光光解装置功能扩展──有机非线性材料二阶非线性系数测定

纳秒级激光闪光光解装置可用于有机光化学，光物理过程，瞬态发光和吸收的动力学过程的研究。在不改变原装置整体布局和结构的基础上，建立了有机非线性光学材料的二阶非线性系数测定方法，并为国家８６３专家委员会承担过仲裁测定。     

环-Phe-His二肽水溶液的激光光解

报导了利用纳秒级激光光解瞬态吸收光谱技术研究环苯丙氨酰组氨酰水溶液光解和光敏化作用过程。发现了该环肽在２４８ｎｍ激光的激励下产生光电离和光解离,光电离和光解离过程发生在苯丙氨酸残基上,生成具有３２０ｎｍ和４１０ｎｍ特征吸收的自由基,光解离发生具有３２０ｎｍ特征吸收的苄基自由基。而具有亲电子性的丙酮能在该环肽的苯丙氨酸残基的苯环上抽取电子,形成３２０ｎｍ和４１０ｎｍ的特征吸收峰,求出了自由基的有关动     

芘四磺酸钠水溶液激光闪光光解机理

采用激光闪光光解-瞬态吸收光谱技术研究了355nm激光作用下芘四磺酸钠(PyTS)水溶液的光化学反应机理及其产生水合电子的动力学行为.研究首次发现PyTS水溶液激发单线态(PyTS1*)在260nm、激发三线态(PyTS3*)在300nm及阴离子自由基(PyTS-?)在330nm处的特征吸收峰;分析了生成的水合电子(e-aq)的主要反应途径包括自猝灭反应及与PyTS的反应,得到水合电子与PyTS反应的准一级速率常数为2.7′105s-1;并计算得到在此实验条件下,PyTS水溶液经双光子吸收产生的水合电子量子产率为3.2′10-2.     

CS2与亚硝酸水溶液复相体系的激光闪光光解

利用激光光解-瞬态吸收技术研究了氮气饱和条件下CS2与亚硝酸水溶液复相体系的355nm光解机理.瞬态吸收光谱分析结果表明:CS2与·OH自由基快反应生成CS2OH,产生的CS2OH继续与HONO反应生成CS2OH-HONO加合物,其吸收峰分别为285,305,475,490和980nm,反应CS2OH+HONOCS2OH-HONO的二级速率常数为(2.79±0.05)×108L/(mol·s);230nm处的吸收峰归属为CS2NO+,其一级衰减速率常数为1.28×105s-1.     

pH Dependence of Photochemical Kinetics of Thioxanthen-9-one from Nanosecond Time-Resolved Laser Flash Photolysis

pH dependent fluorescence emission of a thioxanthone-based probe has been reported recently. The potential determinant factors of pH dependence may provide important clues to design novel thioxanthone-based probes in the future. pH dependence of photochemical kinetics of thioxanthone itself was investigated in this work using nanosecond time-resolved laser flash photolysis. The nanosecond time-resolved transient absorption spectra and kinetics of TX in aqueous acetonitrile were recorded, as well as for a model reaction system including TX with diphenylamine (DPA) as a co-initiator. Besides the well-known absorption peak of \begin{document}$ ^3 $\end{document}TX\begin{document}$ ^* $\end{document}, other peaks at 417, 518, 673 and 780 nm, have been reliably attributed to major intermediates in the overall reaction between TX and DPA with photolysis, which has been confirmed to occur along a multistep process. In the strong acidic solution (pH\begin{document}$ \approx $\end{document}3.0), TX and protonated TX ions (TXH\begin{document}$ ^+ $\end{document}) coexist due to protonated equilibrium. Consequently, high proton concentration promotes the predominant decay pathway after photolysis from electron transfer to proton affinity. Subsequently, the different primary products, \begin{document}$ ^3 $\end{document}TXH\begin{document}$ ^{+*} $\end{document} or TX\begin{document}$ ^{\bullet-} $\end{document}, proceed different secondary reaction channels. In addition, within the wide pH range from weak acid (pH = 5.0) to alkaline solution (pH = 13.0), the overall reaction mechanism and rates do not show visible changes.