State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
R&D Center, Lifetech Scientific (Shenzhen) Co., Ltd., Shenzhen 518057, China.
ACS Appl Mater Interfaces. 2022 Jun 1;14(21):24197-24212. doi: 10.1021/acsami.2c05184. Epub 2022 May 17.
Enabling a biodegradable polymer radiopaque under X-ray is much desired for many medical devices. Physical blending of a present biodegradable polymer and a commercialized medical contrast agent is convenient yet lacks comprehensive fundamental research. Herein, we prepared a biodegradable polymer-based radiopaque raw material by blending poly(l-lactic acid) (PLLA or simply PLA) and iohexol (IHX), where PLA constituted the continuous phase and IHX particles served as the dispersed phase. The strong X-ray adsorption of IHX enabled the composite radiopaque; the hydrolysis of the polyester and the water solubility of the contrast agent enabled the composite biodegradable in an aqueous medium. The idea was confirmed by in vitro characterizations of the resultant composite, in vivo subcutaneous implantation in rats up to 6 months, and the clear visualization of a part of a biodegradable occluder in a Bama piglet under X-ray. We also found that the crystallization of PLA was significantly enhanced in the presence of the solid particles, which should be taken into consideration in the design of an appropriate biomaterial composite because crystallization degree influences the biodegradation rate and mechanical property of a material to a large extent. We further tried to introduce a small amount of poly(vinylpyrrolidone) into the blend of PLA and IHX. Compared to the bicomponent composite, the tricomponent one exhibited decreased modulus and increased elongation at break and tensile strength. This paves more ways for researchers to select appropriate raw materials according to the regenerated tissue and the application site.
在 X 射线下使可生物降解聚合物具有放射线不透性是许多医疗设备所期望的。将现有可生物降解聚合物与商业化的医用造影剂物理共混是方便的,但缺乏全面的基础研究。在此,我们通过将聚(L-乳酸)(PLLA 或 PLA)和碘海醇(IHX)共混来制备基于可生物降解聚合物的放射线不透性原料,其中 PLA 构成连续相,而 IHX 颗粒作为分散相。IHX 的强 X 射线吸收使复合材料具有放射线不透性;聚酯的水解和造影剂的水溶性使复合材料在水介质中可生物降解。这一想法通过对所得复合材料的体外特性、大鼠皮下植入长达 6 个月以及在 X 射线下巴马仔猪可生物降解封堵器的一部分的清晰可视化得到了证实。我们还发现,在存在固体颗粒的情况下,PLA 的结晶度显著增强,这在设计合适的生物材料复合材料时应予以考虑,因为结晶度在很大程度上影响材料的生物降解速率和机械性能。我们进一步尝试在 PLA 和 IHX 的共混物中引入少量的聚乙烯吡咯烷酮。与双组分复合材料相比,三组分复合材料的模量降低,断裂伸长率和拉伸强度增加。这为研究人员根据再生组织和应用部位选择合适的原料提供了更多途径。