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通过改变邻醌光引发剂对聚乙二醇二甲基丙烯酸酯生物医学材料的孔结构进行调控

Pore Structure Tuning of Poly-EGDMA Biomedical Material by Varying the O-Quinone Photoinitiator.

作者信息

Yudin Vladimir V, Shurygina Margarita P, Egorikhina Marfa N, Aleynik Diana Ya, Linkova Daria D, Charykova Irina N, Kovylin Roman S, Chesnokov Sergey A

机构信息

G. A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences, 49 Tropinina, 603950 Nizhny Novgorod, Russia.

Federal State Budgetary Educational Institution of Higher Education, Privolzhsky Research Medical University of the Ministry of Health of the Russian Federation, 10/1 Ploshchad Minina i Pozharskogo, 603005 Nizhny Novgorod, Russia.

出版信息

Polymers (Basel). 2023 Jun 2;15(11):2558. doi: 10.3390/polym15112558.

Abstract

Porous polymer monoliths with thicknesses of 2 and 4 mm were obtained via polymerization of ethylene glycol dimethacrylate (EGDMA) under the influence visible-light irradiation in the presence of a 70 wt% 1-butanol porogenic agent and o-quinone photoinitiators. The o-quinones used were: 3,5-di-tret-butyl-benzoquinone-1,2 (35Q), 3,6-di-tret-butyl-benzoquinone-1,2 (36Q), camphorquinone (CQ), and 9,10-phenanthrenequinone (PQ). Porous monoliths were also synthesized from the same mixture but using 2,2'-azo-bis(iso-butyronitrile) (AIBN) at 100 °C instead o-quinones. According to the results of scanning electron microscopy, all the resulting samples were conglomerates of spherical, polymeric particles with pores between them. Use of mercury porometry showed that the interconnected pore systems of all the polymers were open. The average pore size, , in such polymers strongly depended on both the nature of the initiator and the method of initiation of polymerization. For polymers obtained in the presence of AIBN, the value was as low as 0.8 μm. For polymers obtained via photoinitiation in the presence of 36Q, 35Q, CQ, and PQ, the values were significantly greater, i.e., 9.9, 6.4, 3.6, and 3.7 μm, respectively. The compressive strength and Young's modulus of the porous monoliths increased symbatically in the series PQ < CQ < 36Q < 35Q < AIBN with decreasing proportions of large pores (over 12 μm) in their polymer structures. The photopolymerization rate of the EGDMA and 1-butanol, 30:70 wt% mixture was maximal for PQ and minimal for 35Q. All polymers tested were non-cytotoxic. Based on the data from MTT testing, it can be noted that the polymers obtained via photoinitiation were characterized by their positive effect on the proliferative activity of human dermal fibroblasts. This makes them promising osteoplastic materials for clinical trials.

摘要

通过在70 wt% 1-丁醇致孔剂和邻醌光引发剂存在下,在可见光照射的影响下使乙二醇二甲基丙烯酸酯(EGDMA)聚合,获得了厚度为2毫米和4毫米的多孔聚合物整体材料。使用的邻醌有:3,5-二叔丁基苯醌-1,2(35Q)、3,6-二叔丁基苯醌-1,2(36Q)、樟脑醌(CQ)和9,10-菲醌(PQ)。多孔整体材料也由相同混合物合成,但在100℃下使用2,2'-偶氮二异丁腈(AIBN)代替邻醌。根据扫描电子显微镜的结果,所有所得样品都是球形聚合物颗粒的聚集体,它们之间有孔隙。压汞法表明,所有聚合物的相互连通的孔隙系统都是开放的。此类聚合物中的平均孔径 强烈依赖于引发剂的性质和聚合引发方法。对于在AIBN存在下获得的聚合物, 值低至0.8μm。对于在36Q、35Q、CQ和PQ存在下通过光引发获得的聚合物, 值明显更大,分别为9.9、6.4、3.6和3.7μm。多孔整体材料的抗压强度和杨氏模量在PQ < CQ < 36Q < 35Q < AIBN系列中随着其聚合物结构中大于12μm的大孔比例降低而同步增加。EGDMA和1-丁醇(30:70 wt%)混合物的光聚合速率对于PQ最大,对于35Q最小。所有测试的聚合物均无细胞毒性。基于MTT测试的数据,可以注意到通过光引发获得的聚合物对人皮肤成纤维细胞的增殖活性具有积极作用。这使它们成为有前景的用于临床试验的骨替代材料。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5de2/10255199/2a776c95b6af/polymers-15-02558-sch001.jpg

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