【作者】 李岩峰；

【导师】 刘在群；

【作者基本信息】 吉林大学 ， 有机化学， 2012， 博士

【摘要】 生物抗氧化剂是物理有机化学的研究课题之一，本论文的工作主要是在化学体系和化学模拟生物体系内，研究了不同位置羟基取代的二茂铁Schiff碱、异黄酮以及三苯吡唑类化合物的抗氧化活性，并将化学动力学公式应用于化学体系以及化学模拟生物学体系的测试中。主要研究内容为：1设计合成了三种二茂铁Schiff碱类化合物，并用五种方法对其抗氧化能力进行了研究。结果表明，二茂铁基团的引入增强了Schiff碱类化合物的抗氧化能力；当羟基处于苯环对位时，分子的还原能力较强，而当羟基处于苯环邻位时，分子清除二苯代苦味肼基自由基(DPPH)以及羟基自由基的能力较强，而当羟基位于苯环间位时，化合物抗氧化性较弱。2设计合成了三种异黄酮类化合物，并用十种方法对其抗氧化能力进行了研究，结果表明，羟基处于间位时，还原2,2’-连氮-双-(3-乙基苯并噻唑啉-6-磺酸)二铵盐(ABTS~+)和羟基自由基的能力较强，而当羟基处于邻位时，淬灭DPPH、Galvinoxyl自由基的能力较强，羟基处于对位的化合物则还原亚硝基阴离子和单线态氧的能力较强。3设计合成了四种三苯吡唑类化合物，并用六种方法对其抗氧化能力进行了研究。结果表明，三苯吡唑类化合物在有羟基或无羟基的情况下，均可淬灭自由基。含有羟基的三苯吡唑类化合物在抑制2,2’-偶氮二异丁基脒二盐酸盐(AAPH)引发的DNA氧化损伤实验中，均表现出了很好的抗氧化性，并且在胶束体系内抑制AAPH引发的DNA氧化损伤中，也表现出了一定的活性。更多还原

【Abstract】 Study on synthesis and antioxidant activity of bio-antioxidants was one of thecentral issues in organic chemistry in recent years. In this work, we selectedferrocenyl Schiff base, homoisoflavonoids and triphenyl pyrazoles as the center withdifferent position of hydroxyl substituent attached, synthesized10kinds ofcompounds, and researched their antioxidant activities.The antioxidants evaluation methods are usually defined as two types which arechemical systems and chemical mimic biological systems. The former contains DPPHmethod、ABTS method and galvinoxyl method. Chemical-system method couldrapidly quantitative determine the antioxidant activity, but because of the difference ofthe internal environments between chemical system and chemical mimic biologicalsystem, the results from this method usually do not match those of chemical simulatedbiological system. The latter contains AAPH-、Cu2+/GSH-and OH-induced DNAoxidation. This method overcomes the inadequacies of the chemical system method,still no objective quantitative criteria to evaluate the antioxidant activity.In this thesis, we combined two methods. The new method evaluates theantioxidant activities comprehensively and systematically. Chemical kinetic equationis introduced to both of the two methods, which provided quantitative criteria toevaluate antioxidant activity. The following is the main work: 1. Studies on synthesis and antioxidant activities of ferrocenyl Schiff baseWe synthesized o-(1-Ferrocenylethylideneamino)phenol (OFP), m-(1-Ferrocen-ylethylideneamino)phenol (MFP) and p-(1-Ferrocenylethylideneamino)phenol (PFP),and determined antioxidant activities by using scavenging ABTS+and DPPH freeradicals methods and protect DNA against AAPH-、Cu2+/GSH-and OH-inducedoxidation methods.The ability of OFP to scavenge DPPH free radical is the highest, shows weekantioxidant activity in·OH-induced DNA oxidation and plays a pro-oxidant role inCu2+/GSH-induced DNA oxidation. The antioxidant abilities of MFP are not too highfor all the methods. PFP shows a high capability to scavenge ABTS+free radical,plays a pro-oxidant role in both·OH-, Cu2+/GSH-induced DNA oxidation. But PFPshows the highest activity in AAPH-induced DNA oxidation. And for this method, theantioxidant activities of OFP, MFP and PFP are higher than those of non-ferrocenylSchiff base, indicating that the ferrocenyl group could improve the antioxidantactivities.2. Studies on synthesis and antioxidant activities of homoisoflavonoidsWe synthesized3-(2′-hydroxybenzylidene)-7-methoxychroman-4-one (o-HBM-C),3-(3′-hydroxybenzylidene)-7-methoxychroman-4-one (m-HBMC) and3-(4′-hydr-oxybenzylidene)-7-methoxychroman-4-one (p-HBMC), determined antioxidantactivities by using scavenging ABTS+, DPPH and galvinoxyl free radicals methods,reducing peroxynitrite method, quenching singlet oxygen method, β-carotenebleaching test, protect methyl linoleate against AAPH-induced oxidation and protectDNA against AAPH-、Cu2+/GSH-and OH-induced oxidation methods.The ability of m-HBMC to scavenge ABTS+is the highest, and shows thestrongest ability in·OH-induced DNA oxidation. o-HBMC shows the highestantioxidant activities in scavenging DPPH and galvinoxyl free radical, β-carotenebleaching test, protect methyl linoleate and DNA against AAPH-induced oxidationassay. But it plays a pro-oxidant role in Cu2+/GSH-,·OH-induced DNA oxidation. And the capability of p-HBMC is higher than the other two on reducing peroxynitritemethod, quenching singlet oxygen method and protecting DNA againstCu2+/GSH-induced oxidation methods aspect.3. Studies on synthesis and antioxidant activities of triphenyl pyrazolesWe synthesized1,3,5-triphenyl-1H-pyrazole (TPP),4-(1,5-diphenyl-1H-pyrazol-3-yl)phenol (APP),4-(1,3-diphenyl-1H-pyrazol-5-yl)phenol (BPP),4-(3,5-diphenyl-1H-pyrazol-1-yl)phenol (CPP), and determined antioxidant activities by usingscavenging ABTS+and DPPH free radicals methods, protect DNA against Cu2+/GSH-and OH-induced oxidation methods, protect DNA against AAPH-induced DNAoxidation in homogenous and micelle system.TPP is only sensitive to DPPH and ABTS+free radical, APP shows a highcapability to scavenge DPPH, but weak ability in other methods. The ability of BPP isquite high in any of the methods including protect DNA against AAPH-inducedoxidation in micelle system. And play a pro-oxidant role in protecting DNA against OH-induced oxidation methods. CPP has the same ability to APP.更多还原