卟啉为核的聚酰胺—胺树枝状大分子的合成及其功能化研究
发布时间：2019-05-10 05:36
【摘要】：树枝状大分子是拥有高度支化结构、单分散性、多价性、球状的一类高分子化合物,其独一无二的分子构型使其具有诸如分子尺寸、形状和结构的可控性,易于功能化修饰,生物相容性和自组装性能等特性,因而被广泛的应用于生物医学、催化和光电材料等领域。卟啉类衍生物具有独特物化性质及优异的光电性质使其具有很的强荧光特性及产生单线态氧的能力,因而被视为可用于光动力治疗(PDT)的理想光敏剂材料。因此,本论文拟通过简便的点击化学(Click)法制备一系列不同代数的卟啉为核的聚酰胺-胺树枝状大分子,然后利用功能化修饰分别获得具有pH敏感性,靶向性及温敏性,催化还原性的多功能型高分子材料。本论文的内容具体如下:1、合成了不同代数的卟啉为核的含硅聚酰胺-胺树枝状大分子(PP-Si-PAMAM-Dm,m=1,2,3)。首先采用发散的方法合成了不同代数的端炔基的树突状含硅聚酰胺-胺Si-PAMAM-Dm(m=1,2,3),然后与叠氮基四苯基卟啉核通过点击化学法制备了卟啉为核的含硅聚酰胺-胺树枝状大分子PP-Si-PAMAM-Dm,通过对聚合物的荧光特性,产生单线态氧能力和pH敏感性的研究,发现所制备的PP-Si-PAMAM-Dm具有较高的荧光量子产率和较强的产生单线态氧的能力,此外还发现PP-Si-PAMAM-Dm的荧光特性对pH的变化有一定的响应性。因此,本实验制备的PP-Si-PAMAM-Dm有望成为一种可用于PDT的具有治疗和成像诊断双功能的新型光敏剂。2、合成了糖基化壳的卟啉为核的含硅聚酰胺-胺树枝状大分子(PP-Si-PAMAM-Dm-Lac,m=1,2,3)。首先根据前面的研究基础,利用乳糖酸对扇形的树突状聚酰胺-胺进行了外围端基的糖基功能化,利用端胺基引发乳糖酸的开环聚合制备得到Si-PAMAM-Dm-Lac(m=1,2,3),然后与叠氮基卟啉核通过点击化学法制备了糖基化壳的卟啉核的含硅聚酰胺-胺树枝状大分子PP-Si-PAMAM-Dm-Lac。通过一系列的性能研究表明,PP-Si-PAMAM-Dm-Lac具有较强的产生单线态氧能力,对凝集素有很强的识别能力,且具有一定的温度响应性。因此,本实验制备的材料有望成为具有特异靶向性的生物医学材料,有望用于兼化疗和光疗一体的双重疗法来治疗恶性疾病。3、制备了卟啉为核的聚酰胺-胺树枝状大分子封装的胶体银纳米复合物(PP-PAMAM-G_3/Ag)。首先利用点击化学法高效的制备了第三代PP-PAMAM-G_3,然后采用原位还原的方法通过PP-PAMAM-G_3的水溶液与硝酸银水溶液进行暗反应后获得具有均一分散性、尺寸分布均匀的球形PP-PAMAM-G_3/Ag纳米粒子。对其催化效果的测试表明,本实验制备的PP-PAMAM-G_3/Ag可以高效的把污染物4-硝基苯酚还原成无污染的4-氨基苯酚。因此,本实验所制备的PP-PAMAM-G_3/Ag有望在催化降解污染物、抗菌等领域发挥重要作用。
[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，
本文编号：2473381
[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，
本文编号：2473381
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