Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Av. Limeira, 901, Piracicaba, São Paulo 13414-903, Brazil.
Laboratory of Technological Plasmas, Institute of Science and Technology, São Paulo State University (UNESP), Av. Três de Março, 511, Sorocaba, São Paulo 18087-180, Brazil.
ACS Biomater Sci Eng. 2023 Sep 11;9(9):5389-5404. doi: 10.1021/acsbiomaterials.3c00491. Epub 2023 Aug 10.
Along with poor implant-bone integration, peri-implant diseases are the major causes of implant failure. Although such diseases are primarily triggered by biofilm accumulation, a complex inflammatory process in response to corrosive-related metallic ions/debris has also been recognized as a risk factor. In this regard, by boosting the titanium (Ti) surface with silane-based positive charges, cationic coatings have gained increasing attention due to their ability to kill pathogens and may be favorable for corrosion resistance. Nevertheless, the development of a cationic coating that combines such properties in addition to having a favorable topography for implant osseointegration is lacking. Because introducing hydroxyl (-OH) groups to Ti is essential to increase chemical bonds with silane, Ti pretreatment is of utmost importance to achieve such polarization. In this study, plasma electrolytic oxidation (PEO) was investigated as a new route to pretreat Ti with OH groups while providing favorable properties for implant application compared with traditional hydrothermal treatment (HT). To produce bactericidal and corrosion-resistant cationic coatings, after pretreatment with PEO or HT (Step 1), surface silanization was subsequently performed via immersion-based functionalization with 3-aminopropyltriethoxysilane (APTES) (Step 2). In the end, five groups were assessed: untreated Ti (Ti), HT, PEO, HT+APTES, and PEO+APTES. PEO created a porous surface with increased roughness and better mechanical and tribological properties compared with HT and Ti. The introduction of -OH groups by HT and PEO was confirmed by Fourier transform infrared spectroscopy and the increase in wettability producing superhydrophilic surfaces. After silanization, the surfaces were polarized to hydrophobic ones, and an increase in the amine functional group was observed by X-ray photoelectron spectroscopy, demonstrating a considerable amount of positive ions. Such protonation may explain the enhanced corrosion resistance and dead bacteria ( and ) found for PEO+APTES. All groups presented noncytotoxic properties with similar blood plasma protein adsorption capacity vs the Ti control. Our findings provide new insights into developing next-generation cationic coatings by suggesting that a tailorable porous and oxide coating produced by PEO has promise in designing enhanced cationic surfaces targeting biomedical and dental implant applications.
除了不良的种植体-骨整合,种植体周围疾病是种植体失败的主要原因。尽管这些疾病主要是由生物膜积聚引发的,但人们也认识到,与腐蚀性相关的金属离子/碎片有关的复杂炎症过程也是一个危险因素。在这方面,通过在基于硅烷的正电荷上增强钛(Ti)表面,阳离子涂层因其能够杀死病原体而受到越来越多的关注,并且可能有利于耐腐蚀性。然而,缺乏一种阳离子涂层,它除了具有有利于种植体骨整合的有利形貌外,还具有这些特性。因为引入羟基(-OH)基团对于增加与硅烷的化学结合至关重要,所以 Ti 的预处理对于实现这种极化至关重要。在这项研究中,等离子体电解氧化(PEO)被研究为一种新的途径,用于在提供有利于种植体应用的性能的同时,用 OH 基团预处理 Ti,与传统的水热处理(HT)相比。为了生产杀菌和耐腐蚀的阳离子涂层,在经过 PEO 或 HT(步骤 1)预处理后,通过浸入式功能化用 3-氨丙基三乙氧基硅烷(APTES)(步骤 2)进行表面硅烷化。最后,评估了五个组:未经处理的 Ti(Ti)、HT、PEO、HT+APTES 和 PEO+APTES。与 HT 和 Ti 相比,PEO 产生了具有增加的粗糙度和更好的机械和摩擦学性能的多孔表面。通过傅里叶变换红外光谱证实了 HT 和 PEO 引入 -OH 基团,并且增加了润湿性产生超亲水表面。硅烷化后,表面被极化到疏水性,并且通过 X 射线光电子能谱观察到胺官能团的增加,表明存在相当数量的正离子。这种质子化可能解释了 PEO+APTES 增强的耐腐蚀性和死亡细菌(和)。与 Ti 对照相比,所有组均表现出非细胞毒性特性和相似的血浆蛋白吸附能力。我们的发现为开发下一代阳离子涂层提供了新的见解,表明通过 PEO 生产的可定制多孔和氧化物涂层在设计针对生物医学和牙科植入物应用的增强阳离子表面方面具有很大的前景。