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添加蒙脱石和庆大霉素对静电纺聚己内酯纤维性能的影响。

Effects of Montmorillonite and Gentamicin Addition on the Properties of Electrospun Polycaprolactone Fibers.

作者信息

Stodolak-Zych Ewa, Kurpanik Roksana, Dzierzkowska Ewa, Gajek Marcin, Zych Łukasz, Gryń Karol, Rapacz-Kmita Alicja

机构信息

Department of Biomaterials and Composites, AGH University of Science and Technology, 30-059 Krakow, Poland.

Department of Ceramics and Refractories, AGH University of Science and Technology, 30-059 Krakow, Poland.

出版信息

Materials (Basel). 2021 Nov 16;14(22):6905. doi: 10.3390/ma14226905.

Abstract

Electrospinning was used to obtain multifunctional fibrous composite materials with a matrix of poly-ɛ-caprolactone (PCL) and 2 wt.% addition of a nanofiller: montmorillonite (MMT), montmorillonite intercalated with gentamicin sulphate (MMTG) or gentamicin sulphate (G). In the first stage, the aluminosilicate gallery was modified by introducing gentamicin sulfate into it, and the effectiveness of the intercalation process was confirmed on the basis of changes in the clay particle size from 0.5 µm (for MMT) to 0.8 µm (for MMTG), an increase in the interplanar distance from 12.3 Å (for MMT) to 13.9 Å (for MMTG) and altered clay grain morphology. In the second part of the experiment, the electrospinning process was carried out in which the polymer nonwovens with and without the modifier were prepared directly from dichloromethane (DCM) and N,N-dimethylformamide (DMF). The nanocomposite fibrous membranes containing montmorillonite were prepared from the same polymer solution but after homogenization with the modifier (13 wt.%). The degree of dispersion of the modifier was evaluated by average microarray analysis from observed area (EDS), which was also used to determine the intercalation of montmorillonite with gentamicin sulfate. An increase in the size of the fibers was found for the materials with the presence of the modifier, with the largest diameters measured for PCL_MMT (625 nm), and the smaller ones for PCL_MMTG (578 nm) and PCL_G (512 nm). The dispersion of MMT and MMTG in the PCL fibers was also confirmed by indirect studies such as change in mechanical properties of the nonwovens membrane, where the neat PCL nonwoven was used as a reference material. The addition of the modifier reduced the contact angle of PCL nonwovens (from 120° for PCL to 96° for PCL_G and 98° for PCL_MMTG). An approximately 10% increase in tensile strength of the nonwoven fabric with the addition of MMT compared to the neat PCL nonwoven fabric was also observed. The results of microbiological tests showed antibacterial activity of all obtained materials; however, the inhibition zones were the highest for the materials containing gentamicin sulphate, and the release time of the active substance was significantly extended for the materials with the addition of montmorillonite containing the antibiotic. The results clearly show that the electrospinning technique can be effectively used to obtain nanobiocomposite fibers with the addition of nonintercalated and intercalated montmorillonite with improved strength and increased stiffness compared to materials made only of the polymer fibers, provided that a high filler dispersion in the spinning solution is obtained.

摘要

采用静电纺丝法制备了以聚-ε-己内酯(PCL)为基质、添加2 wt.%纳米填料的多功能纤维复合材料,纳米填料包括蒙脱石(MMT)、硫酸庆大霉素插层蒙脱石(MMTG)或硫酸庆大霉素(G)。在第一阶段,通过将硫酸庆大霉素引入硅铝酸盐层间对其进行改性,并根据粘土粒径从0.5 µm(MMT)变为0.8 µm(MMTG)、层间距从12.3 Å(MMT)增加到13.9 Å(MMTG)以及粘土颗粒形态的改变,证实了插层过程的有效性。在实验的第二部分,进行了静电纺丝过程,直接从二氯甲烷(DCM)和N,N-二甲基甲酰胺(DMF)制备了含和不含改性剂的聚合物非织造布。含蒙脱石的纳米复合纤维膜由相同的聚合物溶液制备,但在与改性剂(13 wt.%)均质化后制备。通过观察区域的平均微阵列分析(EDS)评估改性剂的分散程度,该方法也用于确定蒙脱石与硫酸庆大霉素的插层情况。发现含有改性剂的材料纤维尺寸增加,PCL_MMT的直径最大(625 nm),PCL_MMTG(578 nm)和PCL_G(512 nm)的直径较小。MMT和MMTG在PCL纤维中的分散也通过间接研究得到证实,如非织造布膜力学性能的变化,其中纯PCL非织造布用作参考材料。改性剂的添加降低了PCL非织造布的接触角(从PCL的120°降至PCL_G的96°和PCL_MMTG的98°)。与纯PCL非织造布相比,添加MMT的非织造布的拉伸强度也提高了约10%。微生物测试结果表明,所有获得的材料均具有抗菌活性;然而,含硫酸庆大霉素的材料抑菌圈最大,添加含抗生素蒙脱石的材料活性物质释放时间显著延长。结果清楚地表明,静电纺丝技术可有效地用于制备添加了未插层和插层蒙脱石的纳米生物复合纤维,与仅由聚合物纤维制成的材料相比,其强度提高且刚度增加,前提是在纺丝溶液中获得高填料分散性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f93f/8618055/911b61a2e4c0/materials-14-06905-g001.jpg

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