A kinetic scission model for molecular weight evolution in bioresorbable polymers
A kinetic scission model for molecular weight evolution in bioresorbable polymers
复制标题
生物可吸收聚合物分子量演变的动力学断裂模型
DOI：
10.1002/pen.26131
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
W. Ronan
中科院分区：
文献类型：
--
作者：
Aoife Hill;W. Ronan
用于临床应用的生物可吸收装置的进一步开发（其中它们可以降低长期风险）受到生物可吸收聚合物表现出的复杂降解机制以及这在设计合适的装置中引起的困难的阻碍。此外，实验性降解研究通常需要数年才能完成，并且测试样品设计的微小变化可能会显著改变降解行为。受现有降解模型的启发，我们提出了一个动力学断裂模型来预测生物可吸收聚合物的分子量分布如何随降解时间而变化。在这里，一个完善的动力学模型已被开发，以捕捉通过链断裂产生的羧酸末端的自催化作用，和我们的框架占分子量的减少，通过裂解的单体从链末端和从在中间的聚合物链的断裂。这些发展允许在降解过程中的分子量分布的更完整的代表性。杨氏模量是根据先前所谓的“熵弹簧”模型通过近似分子量分布的熵变化来估计的。得到的结果进行定量比较，并与现有的实验数据进行校准PLGA薄膜。最后，探讨了初始羧酸末端对降解行为的影响。
Further development of bioresorbable devices for use in clinical applications, where they can reduce long term risks, has been hindered by the complex degradation mechanisms that bioresorbable polymers exhibit and the difficulty this causes in designing suitable devices. Furthermore, experimental degradation studies often take years to complete, and small changes to the design of the test sample may significantly alter the degradation behavior. Motivated by existing degradation models, we present a kinetic scission model to predict how the molecular weight distribution evolves as a function of degradation time for bioresorbable polymers. Here, a refined kinetic model has been developed to capture the autocatalytic effect of carboxylic acid ends created via chain scissions, and our framework accounts for reduction in molecular weight via the cleavage of monomers from chain ends and from scissions in the middle of the polymer chain. These developments allow for a more complete representation of the molecular weight distribution during degradation. Young's modulus is estimated by approximating the changes in entropy for the molecular weight distributions following previous so‐called “entropy spring” models. The results obtained are quantitatively compared to and calibrated with existing experimental data for PLGA films. Finally, the effect of the initial carboxylic acid end on the degradation behavior is explored.
影响因子：
3.8
作者：
Batycky, RP;Hanes, J;Edwards, DA
通讯作者：
Edwards, DA