Utilising chiral mono- and bis-oxazolines for the synthesis of a new class of stereodefined peptidomimetic polymers

聚（恶唑啉）（PAOx）对于许多工业应用是有希望的，其展示了强度和稳定性的组合，同时也比基于PEG的系统对免疫系统的拮抗性更小。PAOx具有多肽样结构，赋予通过酰胺侧链容易地调节疏水性的能力。PAOx已用于生物医学应用，例如靶向药物递送、药物配制、组织工程和作为组织粘合剂。除了生物医学应用之外，它们的可调特性还提供了用作表面改性剂、表面活性剂和相容剂以及涂料的机会。已经开发了利用活性阳离子开环聚合（CROP）的稳健方法以获得具有一定程度的结构控制的PAOx。尽管最近有扩大PAOx库的动力，但迄今为止的研究集中在简单的非手性2-取代的恶唑啉单体上。这些聚合物在主链中不含手性信息，并且只能通过叔酰胺键具有附加的官能度。本计画将探讨手性恶唑啉单体的聚合反应，以提供新一代具有特定立构规整度的高度官能化拟肽聚合物。在聚合物主链中引入额外的官能度，沿着精确的立体控制，提供了引导聚合物所采用的二级结构的机会。更广泛地说，产生具有受控立构规整度的PAOx的能力将使聚合物微观结构和宏观结构之间的关系能够针对这类新兴的工业重要聚合物进行研究。

Poly(oxazoline)s (PAOx) are promising for many industrial applications, demonstrating a combination of strength and stability whilst also being less antagonistic to the immune system than PEG based systems. PAOx have a polypeptide-like structure, conferring the ability to easily tune the hydrophobicity through the amide side chain. PAOx have been employed in biomedical applications such as targeted drug delivery, drug formulation, tissue engineering and as tissue adhesives. Beyond biomedical applications, their tunable properties present opportunities for use as surface modifiers, surfactants and compatibilisers, and in coatings. Robust methodologies utilizing living cationic ring-opening polymerization (CROP) have been developed to access PAOx with a degree of structural control. Despite the recent drive to expand the library of PAOx, studies so far have focused on simple non-chiral 2-substituted oxazoline monomers. These polymers contain no chiral information in the backbone and can only have appended functionality through the tertiary amide bond. This project will probe the polymerization of chiral oxazoline monomers to provide access to a new generation of highly functionalized peptidomimetic polymers with defined tacticity. The incorporation of additional functionality into the polymer backbone, along with precise stereocontrol, presents the opportunity to direct the secondary structure adopted by the polymer. More broadly, the ability to generate PAOx with controlled tacticity will enable the relationship between polymer microstructure and macrostructure to be investigated for this emerging class of industrially important polymers.