Ivanova Anna A, Syromotina Dina S, Shkarina Svetlana N, Shkarin Roman, Cecilia Angelica, Weinhardt Venera, Baumbach Tilo, Saveleva Mariia S, Gorin Dmitry A, Douglas Timothy E L, Parakhonskiy Bogdan V, Skirtach Andre G, Cools Pieter, De Geyter Nathalie, Morent Rino, Oehr C, Surmeneva Maria A, Surmenev Roman A
Physical Materials Science and Composite Materials Centre, Research School of Chemistry & Applied Biomedical Sciences, National Research Tomsk Polytechnic University 634050 Tomsk Russia
Laboratory for Applications of Synchrotron Radiation, Karlsruhe Institute of Technology Eggenstein-Leopoldshafen Germany.
RSC Adv. 2018 Nov 22;8(68):39106-39114. doi: 10.1039/c8ra07386d. eCollection 2018 Nov 16.
This article reports on a study of the mineralisation behaviour of CaCO deposited on electrospun poly(ε-caprolactone) (PCL) scaffolds preliminarily treated with low-temperature plasma. This work was aimed at developing an approach that improves the wettability and permeability of PCL scaffolds in order to obtain a superior composite coated with highly porous CaCO, which is a prerequisite for biomedical scaffolds used for drug delivery. Since PCL is a synthetic polymer that lacks functional groups, plasma processing of PCL scaffolds in O, NH, and Ar atmospheres enables introduction of highly reactive chemical groups, which influence the interaction between organic and inorganic phases and govern the nucleation, crystal growth, particle morphology, and phase composition of the CaCO coating. Our studies showed that the plasma treatment induced the formation of O- and N-containing polar functional groups on the scaffold surface, which caused an increase in the PCL surface hydrophilicity. Mineralisation of the PCL scaffolds was performed by inducing precipitation of CaCO particles on the surface of polymer fibres from a mixture of CaCl- and NaCO-saturated solutions. The presence of highly porous vaterite and nonporous calcite crystal phases in the obtained coating was established. Our findings confirmed that preferential growth of the vaterite phase occurred in the O-plasma-treated PCL scaffold and that the coating formed on this scaffold was smoother and more homogenous than those formed on the untreated PCL scaffold and the Ar- and NH-plasma-treated PCL scaffolds. A more detailed three-dimensional assessment of the penetration depth of CaCO into the PCL scaffold was performed by high-resolution micro-computed tomography. The assessment revealed that O-plasma treatment of the PCL scaffold caused CaCO to nucleate and precipitate much deeper inside the porous structure. From our findings, we conclude that O-plasma treatment is preferable for PCL scaffold surface modification from the viewpoint of use of the PCL/CaCO composite as a drug delivery platform for tissue engineering.
本文报道了一项关于碳酸钙在经低温等离子体预处理的电纺聚（ε-己内酯）（PCL）支架上矿化行为的研究。这项工作旨在开发一种方法，以改善PCL支架的润湿性和渗透性，从而获得一种涂覆有高度多孔碳酸钙的优质复合材料，这是用于药物递送的生物医学支架的一个先决条件。由于PCL是一种缺乏官能团的合成聚合物，在氧气、氨气和氩气气氛中对PCL支架进行等离子体处理能够引入高反应性化学基团，这些基团会影响有机相和无机相之间的相互作用，并控制碳酸钙涂层的成核、晶体生长、颗粒形态和相组成。我们的研究表明，等离子体处理在支架表面诱导形成了含O和N的极性官能团，这导致PCL表面亲水性增加。PCL支架的矿化是通过从氯化钙和碳酸钠饱和溶液的混合物中诱导碳酸钙颗粒在聚合物纤维表面沉淀来进行的。在所获得的涂层中确定了存在高度多孔的球霰石和无孔的方解石晶相。我们的研究结果证实，在经氧气等离子体处理的PCL支架中优先生长球霰石相，并且在该支架上形成的涂层比在未处理的PCL支架以及经氩气和氨气等离子体处理的PCL支架上形成的涂层更光滑、更均匀。通过高分辨率微计算机断层扫描对碳酸钙渗入PCL支架的穿透深度进行了更详细的三维评估。评估结果显示，对PCL支架进行氧气等离子体处理会使碳酸钙在多孔结构内部更深的位置成核和沉淀。从我们的研究结果来看，从将PCL/碳酸钙复合材料用作组织工程药物递送平台的角度出发，氧气等离子体处理对于PCL支架表面改性是更可取的。
