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Complex Macromolecular Architectures for Potential Biological Applications.

机译:用于潜在生物应用的复杂高分子体系结构。

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摘要

This thesis describes original research aimed at the development of highly efficient synthetic methods towards complex polymer architectures. An explanation of different polymer architectures, their synthesis and applications, in particular as biomaterials, is provided. Dendronized polymers and block copolymers are identified as two classes of polymer architectures that are important for a variety of applications but whose fabrications still pose a challenge.;In the macromonomer route for the synthesis of dendronized polymers, the preferred route due to complete and uniform dendron functionalization, high degrees of polymerization are difficult to achieve due to steric crowding. This limitation was overcome by incorporating linkers between the polymerizable group (norbornene) and the poly(amide)-based dendrons. By increasing the length of the linker, the rate of polymerization increased.;The synthesis of block copolymers using non-living polymerization methods often requires the copolymerization of monomers by different polymerization mechanisms. This methodology is hampered by non-quantitative conversions of the precursor polymer into the required macroinitiator. This limitation was overcome by using a bifunctional initiator. Poly(norbornene)-block -poly(lactic acid)s were synthesized using a ruthenium initiator for the ring-opening metathesis polymerization (ROMP) and a hydroxy group to initiate the ring-opening polymerization (ROP) of L-lactide. This method opens up new routes for the creation of functional block copolymers that are created by a combination of ROMP and ROP.;Finally, potential strategies towards the synthesis of complex polymer architectures for biomaterials using the methodologies developed in this thesis are described. Firstly, the synthesis of orthogonally functionalizable dendronized polymers for targeted drug-delivery is proposed. Second, studies to establish the relationship between architectures and properties for biological applications for dendronized polymers are described. Lastly, the methodology to synthesize poly(norbornene)-block-poly(peptide)s using a bifunctional initiator is proposed.
机译:本论文描述了旨在针对复杂聚合物结构开发高效合成方法的原始研究。提供了不同聚合物结构,其合成和应用(特别是作为生物材料)的解释。树枝状的聚合物和嵌段共聚物被认为是两类聚合物结构,它们对各种应用都很重要,但是其制造仍然构成挑战。在合成树枝状聚合物的大分子途径中,由于树枝状分子的完全和均匀是优选的途径由于空间拥挤,难以实现官能化,高聚合度。通过在可聚合基团(降冰片烯)和聚(酰胺)基树突之间引入连接基可以克服这一限制。通过增加连接基团的长度,提高了聚合速率。使用非活性聚合方法合成嵌段共聚物通常需要通过不同的聚合机理进行单体的共聚。前体聚合物向所需的大分子引发剂的非定量转化阻碍了该方法。通过使用双功能引发剂可以克服此限制。使用钌引发剂进行开环复分解聚合(ROMP)和羟基引发L-丙交酯的开环聚合(ROP),合成聚(降冰片烯)嵌段-聚乳酸。该方法为通过ROMP和ROP的组合而产生的功能性嵌段共聚物的开发开辟了新的途径。最后,描述了使用本论文开发的方法合成生物材料的复杂聚合物结构的潜在策略。首先,提出了用于目标药物递送的正交可官能化的树枝状聚合物的合成。其次,描述了建立树突状聚合物生物应用的结构和性质之间关系的研究。最后,提出了使用双功能引发剂合成聚降冰片烯-嵌段-聚肽的方法。

著录项

  • 作者

    Jung, Hwayoon.;

  • 作者单位

    New York University.;

  • 授予单位 New York University.;
  • 学科 Chemistry Polymer.;Engineering Materials Science.
  • 学位 Ph.D.
  • 年度 2013
  • 页码 174 p.
  • 总页数 174
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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