黄酮醇类及其衍生物黄硫酮醇光诱导一氧化碳释放分子的研制

发布时间：2018-05-20 23:31

  本文选题：一氧化碳(CO) + 黄酮醇　； 参考：《西北大学》2017年硕士论文

【摘要】：研究发现少量一氧化碳(CO)的产生有益于疾病的康复,开发CO治疗试剂引起了人们的强烈兴趣。为有效避免传统上利用金属羰基化合物作为光诱导CO释放分子(photoinduced CO releasing molecules简称photoCORMs)时无法避免的内在局限性(需要的诱导光的波长较短,365 nm;光诱导CO释放反应可逆等)。本论文使用黄酮醇、4-甲氧基黄酮醇、4-甲氧基黄硫酮醇化合物作为CO释放单元,通过其与过渡金属及辅助螯合配体的结构调整,使形成的配合物经过可见光诱导CO释放,开发出photoCORMs的新体系。具体如下:1.本论文设计、合成和表征了 3个光诱导CO释放单元黄酮醇(FLH)、4-甲氧基黄酮醇(4-MeOFLH)、4-甲氧基黄硫酮醇(4-MeOFLTH)和5个辅助螯合配体三(2-吡啶甲基)胺(TPA)及其衍生物,采用重结晶、柱层析等方法对产物进行分离提纯,通过核磁手段对产物进行了表征。2.以二((6-甲基-2-吡啶)甲基)-(2-吡啶甲基)胺(6-Me2TPA)为辅助螯合配体、4-甲氧基黄酮醇(4-MeOFLH)为CO释放单元,设计、合成和表征了 一系列(5个)photoCORMs[(6-Me2TPA)M(4-MeOFLH)]C104(M = Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ),Zn(Ⅱ)),并对配合物的结构、光谱和CO释放量进行了比较研究,测试发现金属锌(Ⅱ)的配合物能够以适当的速度释放出等摩尔量的CO。3.以金属锌(Ⅱ)离子和取代基不同的辅助螯合配体(5个)与CO释放单元黄酮醇(FLH)、4-甲氧基黄酮醇(4-MeOFLH)、4-甲氧基黄硫酮醇(4-MeOFLTH)设计、合成和表征了一系列(13个)新的photoCORMs,并对配合物的结构、光谱、CO释放量及产物鉴定进行了系统的研究。4.通过对每个配合物溶剂选择、照射波长、产物鉴定、02依赖评价每一个配合物的光诱导一氧化碳释放反应性能,提出了可能的反应机理。5.通过UV-vis检测的方法对合成的每一个配合物进行了稳定性的测试。
[Abstract]:It is found that the production of a small amount of carbon monoxide (CO) is beneficial to the recovery of the disease, and the development of CO therapy reagent has aroused strong interest. In order to avoid the inherent limitation (the wavelength of induced light is shorter than 365nm) and the reversibility of photo-induced CO release reaction (photo-induced CO releasing molecules), metal carbonyl compounds are used as photo-induced CO releasing molecule (photo-induced CO releasing molecules) can not be avoided (the wavelength of induced light is shorter than 365nm; the photo-induced CO release reaction is reversible, etc.) In this paper, the compounds of flavonol 4-methoxy flavonol and 4-methoxy yellow mercaptan were used as CO releasing units, and the resulting complexes were induced to release CO by visible light by adjusting their structure with transition metals and auxiliary chelate ligands. A new system of photoCORMs has been developed. The details are as follows: 1. In this paper, we designed, synthesized and characterized three photo-induced CO-releasing unit flavonol, FLHHZO4-MEOFLHHYL-FLTH) and five auxiliary chelating ligands, tri-2-pyridylmethyl) amine) and their derivatives, and recrystallized them by recrystallization. The products were separated and purified by column chromatography and characterized by NMR. Using 6-Me2TPA-6-Me2TPA as the auxiliary chelating ligand, 4-MeOFLH) was designed as CO releasing unit. A series of (5) photoCorms [6-Me2TPAM- (4-MeOFLH)] C104M = Mn( 鈪，

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