Abstract
Abstract In this thesis, we designed novel photo-degradable polymers and developed a new method for their synthesis. These new materials contain a silyl group, which can control the photodegradability. Furthermore, the derivatives of nordihydroguaiaretic acid (NDGA) were synthesized and results from experiments and computations indicate that tetraglycinylated NDGA 4 HCl (G4N) could function as a new class of anti-HIV agents. In Part 1 of this thesis, a series of silicon-containing poly(butadienes) was synthesized in two steps, which involve nitration of poly(butadienes) by use of sodium nitrite and ceric ammonium nitrate (CAN) followed by the silicon-promoted Nef reaction. The results of photo-degradation efficency indicate that introduction of a b-(triorgano)silyl ketonic unit ((-CH(CH2SiR3)C(=O)-) into poly(butadienes) allowed dramatic improvement on their photo-degradability. In Part 2, new N-phenyl aromatic polyureas containing bis[(N,N'-diphenyluredio)methyl]silane units (-[HNC(=O)NPhCH2SiMe2CH2NPhC(=O) NH]-) in the skeleton were designed as a new type of photo-degradable polymers. The mechanistic studies indicate that both of the Si-CH2N bonds in the bis[(N,N'-diphenylureido)methyl]silane unit were cleaved through sequential single electron transfer, silyl group migration, and solvolysis. In Part 3, the treatment of NDGA with N,N-dimethylglycine in the presence of dicyclohexylcarbodiimide and a catalytic amount of dimethylaminopyridine in CH2Cl2. The resultant tetraglycinylated NDGA was allowed to react with HCl(g) in situ to give the corresponding tetraglycinylated NDGA 4 HCl (G4N). G4N has a suitable geometry and binding sites for interacting with GC Box DNA through the major groove as revealed by the computational analysis. Use of the fluorescence and the UV techniques in combination provided the apparent binding constants (Kapp). Our results indicate that G4N can effectively bind DNA. Under pH 5.0 buffer solution, G4N showed greater binding ability.