黃酮醇類及其衍生物黃硫酮醇光誘導(dǎo)一氧化碳釋放分子的研制
發(fā)布時(shí)間:2018-05-20 23:31
本文選題:一氧化碳(CO) + 黃酮醇; 參考:《西北大學(xué)》2017年碩士論文
【摘要】:研究發(fā)現(xiàn)少量一氧化碳(CO)的產(chǎn)生有益于疾病的康復(fù),開發(fā)CO治療試劑引起了人們的強(qiáng)烈興趣。為有效避免傳統(tǒng)上利用金屬羰基化合物作為光誘導(dǎo)CO釋放分子(photoinduced CO releasing molecules簡稱photoCORMs)時(shí)無法避免的內(nèi)在局限性(需要的誘導(dǎo)光的波長較短,365 nm;光誘導(dǎo)CO釋放反應(yīng)可逆等)。本論文使用黃酮醇、4-甲氧基黃酮醇、4-甲氧基黃硫酮醇化合物作為CO釋放單元,通過其與過渡金屬及輔助螯合配體的結(jié)構(gòu)調(diào)整,使形成的配合物經(jīng)過可見光誘導(dǎo)CO釋放,開發(fā)出photoCORMs的新體系。具體如下:1.本論文設(shè)計(jì)、合成和表征了 3個(gè)光誘導(dǎo)CO釋放單元黃酮醇(FLH)、4-甲氧基黃酮醇(4-MeOFLH)、4-甲氧基黃硫酮醇(4-MeOFLTH)和5個(gè)輔助螯合配體三(2-吡啶甲基)胺(TPA)及其衍生物,采用重結(jié)晶、柱層析等方法對(duì)產(chǎn)物進(jìn)行分離提純,通過核磁手段對(duì)產(chǎn)物進(jìn)行了表征。2.以二((6-甲基-2-吡啶)甲基)-(2-吡啶甲基)胺(6-Me2TPA)為輔助螯合配體、4-甲氧基黃酮醇(4-MeOFLH)為CO釋放單元,設(shè)計(jì)、合成和表征了 一系列(5個(gè))photoCORMs[(6-Me2TPA)M(4-MeOFLH)]C104(M = Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ),Zn(Ⅱ)),并對(duì)配合物的結(jié)構(gòu)、光譜和CO釋放量進(jìn)行了比較研究,測試發(fā)現(xiàn)金屬鋅(Ⅱ)的配合物能夠以適當(dāng)?shù)乃俣柔尫懦龅饶柫康腃O。3.以金屬鋅(Ⅱ)離子和取代基不同的輔助螯合配體(5個(gè))與CO釋放單元黃酮醇(FLH)、4-甲氧基黃酮醇(4-MeOFLH)、4-甲氧基黃硫酮醇(4-MeOFLTH)設(shè)計(jì)、合成和表征了一系列(13個(gè))新的photoCORMs,并對(duì)配合物的結(jié)構(gòu)、光譜、CO釋放量及產(chǎn)物鑒定進(jìn)行了系統(tǒng)的研究。4.通過對(duì)每個(gè)配合物溶劑選擇、照射波長、產(chǎn)物鑒定、02依賴評(píng)價(jià)每一個(gè)配合物的光誘導(dǎo)一氧化碳釋放反應(yīng)性能,提出了可能的反應(yīng)機(jī)理。5.通過UV-vis檢測的方法對(duì)合成的每一個(gè)配合物進(jìn)行了穩(wěn)定性的測試。
[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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