【摘要】：樹(shù)枝狀大分子是擁有高度支化結(jié)構(gòu)、單分散性、多價(jià)性、球狀的一類(lèi)高分子化合物,其獨(dú)一無(wú)二的分子構(gòu)型使其具有諸如分子尺寸、形狀和結(jié)構(gòu)的可控性,易于功能化修飾,生物相容性和自組裝性能等特性,因而被廣泛的應(yīng)用于生物醫(yī)學(xué)、催化和光電材料等領(lǐng)域。卟啉類(lèi)衍生物具有獨(dú)特物化性質(zhì)及優(yōu)異的光電性質(zhì)使其具有很的強(qiáng)熒光特性及產(chǎn)生單線(xiàn)態(tài)氧的能力,因而被視為可用于光動(dòng)力治療(PDT)的理想光敏劑材料。因此,本論文擬通過(guò)簡(jiǎn)便的點(diǎn)擊化學(xué)(Click)法制備一系列不同代數(shù)的卟啉為核的聚酰胺-胺樹(shù)枝狀大分子,然后利用功能化修飾分別獲得具有pH敏感性,靶向性及溫敏性,催化還原性的多功能型高分子材料。本論文的內(nèi)容具體如下:1、合成了不同代數(shù)的卟啉為核的含硅聚酰胺-胺樹(shù)枝狀大分子(PP-Si-PAMAM-Dm,m=1,2,3)。首先采用發(fā)散的方法合成了不同代數(shù)的端炔基的樹(shù)突狀含硅聚酰胺-胺Si-PAMAM-Dm(m=1,2,3),然后與疊氮基四苯基卟啉核通過(guò)點(diǎn)擊化學(xué)法制備了卟啉為核的含硅聚酰胺-胺樹(shù)枝狀大分子PP-Si-PAMAM-Dm,通過(guò)對(duì)聚合物的熒光特性,產(chǎn)生單線(xiàn)態(tài)氧能力和pH敏感性的研究,發(fā)現(xiàn)所制備的PP-Si-PAMAM-Dm具有較高的熒光量子產(chǎn)率和較強(qiáng)的產(chǎn)生單線(xiàn)態(tài)氧的能力,此外還發(fā)現(xiàn)PP-Si-PAMAM-Dm的熒光特性對(duì)pH的變化有一定的響應(yīng)性。因此,本實(shí)驗(yàn)制備的PP-Si-PAMAM-Dm有望成為一種可用于PDT的具有治療和成像診斷雙功能的新型光敏劑。2、合成了糖基化殼的卟啉為核的含硅聚酰胺-胺樹(shù)枝狀大分子(PP-Si-PAMAM-Dm-Lac,m=1,2,3)。首先根據(jù)前面的研究基礎(chǔ),利用乳糖酸對(duì)扇形的樹(shù)突狀聚酰胺-胺進(jìn)行了外圍端基的糖基功能化,利用端胺基引發(fā)乳糖酸的開(kāi)環(huán)聚合制備得到Si-PAMAM-Dm-Lac(m=1,2,3),然后與疊氮基卟啉核通過(guò)點(diǎn)擊化學(xué)法制備了糖基化殼的卟啉核的含硅聚酰胺-胺樹(shù)枝狀大分子PP-Si-PAMAM-Dm-Lac。通過(guò)一系列的性能研究表明,PP-Si-PAMAM-Dm-Lac具有較強(qiáng)的產(chǎn)生單線(xiàn)態(tài)氧能力,對(duì)凝集素有很強(qiáng)的識(shí)別能力,且具有一定的溫度響應(yīng)性。因此,本實(shí)驗(yàn)制備的材料有望成為具有特異靶向性的生物醫(yī)學(xué)材料,有望用于兼化療和光療一體的雙重療法來(lái)治療惡性疾病。3、制備了卟啉為核的聚酰胺-胺樹(shù)枝狀大分子封裝的膠體銀納米復(fù)合物(PP-PAMAM-G_3/Ag)。首先利用點(diǎn)擊化學(xué)法高效的制備了第三代PP-PAMAM-G_3,然后采用原位還原的方法通過(guò)PP-PAMAM-G_3的水溶液與硝酸銀水溶液進(jìn)行暗反應(yīng)后獲得具有均一分散性、尺寸分布均勻的球形PP-PAMAM-G_3/Ag納米粒子。對(duì)其催化效果的測(cè)試表明,本實(shí)驗(yàn)制備的PP-PAMAM-G_3/Ag可以高效的把污染物4-硝基苯酚還原成無(wú)污染的4-氨基苯酚。因此,本實(shí)驗(yàn)所制備的PP-PAMAM-G_3/Ag有望在催化降解污染物、抗菌等領(lǐng)域發(fā)揮重要作用。
[Abstract]:Dendritic macromolecules are a kind of polymer compounds with highly branched structure, monodisperse, multivalent and spherical. Their unique molecular configuration makes them controllable, such as molecular size, shape and structure, and is easy to functionalize. Biocompatibility and self-assembly properties have been widely used in biomedicine, catalysis and optoelectronic materials. Because of their unique physicochemical properties and excellent photoelectric properties, porphyrin derivatives have strong fluorescence properties and the ability to produce singlet oxygen, so they are regarded as an ideal photosensitizer material for photodynamic therapy of (PDT). Therefore, a series of polyamide-amine dendrimer with different algebra as nucleus were prepared by simple click chemical (Click) method, and then functional modification was used to obtain pH sensitivity, targeting and temperature sensitivity, respectively. Catalytic reductive multifunctional polymer materials. The main contents of this thesis are as follows: 1. The dendrimer containing silicon polyamide amine (PP-Si-PAMAM-Dm,m=1,2,3) with different algebra was synthesized. Firstly, dendritic polyamide-amine Si-PAMAM-Dm (m 鈮，

本文編號(hào)：2473381