Oxygen-Mediated Initiation of Thiol-ene Adhesives and Sealants

描述(申请人提供)：已经出现了几种组织粘合剂和密封剂的材料和方法；然而，仍然需要大量的研究关注，以充分实现材料的潜力，这些材料可以液体形式应用于伤口部位并在原位固化，从而减轻对缝合或绷带的需求。虽然自由基介导的聚合反应是一种很有吸引力的制备生物材料的方法，但由于其在室温下无需溶剂即可快速固化，大多数自由基介导的聚合反应容易受到氧气的抑制。在拟议的工作中，氧引发而不是抑制聚合，因此引起反作用。我们提出了新的氧介导的硫醇-烯聚合体系，以解决目前医疗过程中原位聚合方法的缺点。这种引发硫醇-烯聚合的方法类似于氰基丙烯酸酯聚合，在氰基丙烯酸酯聚合中，液体单体在包装中保持稳定，但一旦应用到伤口部位，就会迅速愈合。然而，与氰基丙烯酸酯不同，硫醇-烯材料的化学和机械性能很容易变化。首先，将开发氧介导的自由基产生方法来引发硫醇-烯聚合。随后，硫醇-烯树脂将利用这些氧介导的引发方案用于生物医学粘合剂和密封剂，并将以商业材料为基准进行配方和基准测试。最后，将对聚合进行建模，以指导和优化有关应用限制的配方开发，例如聚合引起的厚度和温升。 与公共卫生相关：该项目寻求开发硫醇-烯生物医用粘合剂和密封剂，这些粘合剂和密封剂在暴露在氧气中时会聚合。硫醇-烯体系表现出优异的机械性能、生物相容性和在常温下快速固化的能力，有望极大地提高现有材料的实用性和有效性。

DESCRIPTION (provided by applicant): Several materials and approaches for tissue adhesives and sealants have emerged; however, substantial research attention is still required to fully realize the potential of materials that can be applied to a wound site in liquid form and solidify in situ, alleviating the need for sutures or bandages. Although radical-mediated polymerizations are an attractive means for fabricating materials for use in biological applications, owing to their ability to rapidly cure without solvent at room temperature, the majority of radical-mediated polymerizations are susceptible to oxygen inhibition. In the proposed work, oxygen initiates rather than inhibits the polymerization, therefore eliciting the counter effect. We propose novel, oxygen-mediated thiol-ene polymerization systems to address the shortcomings of current approaches to in situ polymerization for medical procedures. This approach for the initiation of thiol-ene polymerization is analogous to cyanoacrylate polymerization, where liquid monomer remains stable while in its packaging but, upon application to a wound site, cures rapidly. However, unlike cyanoacrylates, the chemical and mechanical properties of thiol-ene materials are readily varied. Initially, approaches for oxygen-mediated radical generation will be developed to initiate thiol-ene polymerization. Subsequently, thiol-ene resins, utilizing these oxygen-mediated initiation schemes for biomedical adhesives and sealants, will be formulated and benchmarked against commercial materials. Finally, modeling of the polymerization will be performed to guide and optimize formulation development with respect to application constraints such as thickness and temperature rise due to polymerization. PUBLIC HEALTH RELEVANCE: This project seeks to develop thiol-ene biomedical adhesives and sealants which polymerize upon exposure to oxygen. Utilizing thiol-ene systems, which demonstrate superior mechanical properties, biocompatibility, and ability to rapidly cure at ambient conditions, is expected to greatly improve upon both the utility and efficacy of existing materials.