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用三嗪基甲基丙烯酸酯单体修饰的二氧化钛纳米管以改善胶粘剂的物理化学和生物学性能。

Titanium dioxide nanotubes with triazine-methacrylate monomer to improve physicochemical and biological properties of adhesives.

机构信息

Dental Materials Department, School of Dentistry, Federal University of Rio Grande do Sul. Ramiro Barcelos Street, 2492, Rio Branco, 90035-003, Porto Alegre, RS, Brazil.

Laboratory of Molecular Catalysis, Institute of Chemistry, Federal University of Rio Grande do Sul. Bento Gonçalves Avenue, 9500, Agronomia, 91501-970, Porto Alegre, RS, Brazil.

出版信息

Dent Mater. 2021 Feb;37(2):223-235. doi: 10.1016/j.dental.2020.11.004. Epub 2020 Nov 24.

Abstract

OBJECTIVE

Formulate experimental adhesives containing titanium dioxide nanotubes (nt-TiO) or titanium dioxide nanotubes with a triazine-methacrylate monomer (nt-TiO:TAT) and evaluate the effect of these fillers on the physical, chemical, and biological properties of the adhesives.

METHODS

First, nt-TiO were synthesized via a hydrothermal method. The nt-TiO were mixed with a triazine-methacrylate monomer (TAT) to formulate nt-TiO:TAT, which were characterized by transmission electron microscopy (TEM). The nt-TiO, TAT, and nt-TiO:TAT were evaluated via Fourier Transform Infrared, Ultraviolet-visible, and micro-Raman spectroscopies. An experimental adhesive resin was formulated with bisphenol A glycerolate dimethacrylates, 2-hydroxyethyl methacrylate, and photoinitiator/co-initiator system. nt-TiO or nt-TiO:TAT were incorporated at 2.5 wt.% and 5 wt.% in the adhesive. The base resin without nt-TiO or nt-TiO:TAT was used as a control group. The adhesives were evaluated for antibacterial activity, cytotoxicity, polymerization kinetics, degree of conversion (DC), Knoop hardness, softening in solvent (ΔKHN%), ultimate tensile strength (UTS), 24 h- and 1 year- microtensile bond strength (μ-TBS).

RESULTS

TEM confirmed the nanotubular morphology of TiO. FTIR, UV-vis, and micro-Raman analyses showed the characteristic peaks of each material, indicating the impregnation of TAT in the nt-TiO. Adhesives with nt-TiO:TAT showed antimicrobial activity against biofilm formation compared to control (p < 0.05), without differences in the viability of planktonic bacteria (p > 0.05). All groups showed high percentages of pulp cell viability. The polymerization kinetics varied among groups, but all presented DC above 50%. The addition of 5 wt.% of nt-TiO and both groups containing nt-TiO:TAT showed higher values ​​of Knoop hardness compared to the control (p < 0.05). The groups with nt-TiO:TAT presented lower ΔKHN% (p < 0.05) and higher UTS (p < 0.05) than the control group. After one year, the group with 5 wt.% of nt-TiO, as well as both groups containing nt-TiO:TAT, showed higher μ-TBS than the control (p < 0.05).

SIGNIFICANCE

The mixing of a triazine-methacrylate monomer with the nt-TiO generated a filler that improved the physicochemical properties of the adhesive resins and provided antibacterial activity, which could assist in preventing carious lesions around tooth-resin interfaces. The set of physical, chemical, and biological properties of the formulated polymer, together with the greater stability of the bond strength over time, make nt-TiO:TAT a promising filler for dental adhesive resins.

摘要

目的

制备含有二氧化钛纳米管(nt-TiO)或含有三嗪-甲基丙烯酸酯单体的二氧化钛纳米管(nt-TiO:TAT)的实验性胶粘剂,并评估这些填料对胶粘剂的物理、化学和生物性能的影响。

方法

首先,通过水热法合成 nt-TiO。将 nt-TiO 与三嗪-甲基丙烯酸酯单体(TAT)混合以制备 nt-TiO:TAT,并通过透射电子显微镜(TEM)进行表征。通过傅里叶变换红外光谱、紫外-可见光谱和微拉曼光谱对 nt-TiO、TAT 和 nt-TiO:TAT 进行了评价。用双酚 A 甘油二甲基丙烯酸酯、2-羟乙基甲基丙烯酸酯和光引发剂/共引发剂体系配制实验性胶粘剂树脂。将 2.5wt.%和 5wt.%的 nt-TiO 或 nt-TiO:TAT 掺入胶粘剂中。不含 nt-TiO 或 nt-TiO:TAT 的基础树脂用作对照组。评估了抗菌活性、细胞毒性、聚合动力学、转化率(DC)、努普硬度、溶剂软化(ΔKHN%)、极限拉伸强度(UTS)、24 小时和 1 年微拉伸结合强度(μ-TBS)。

结果

TEM 证实了 TiO 的纳米管形态。FTIR、UV-vis 和微拉曼分析显示了每种材料的特征峰,表明 TAT 浸渍在 nt-TiO 中。与对照组相比,含有 nt-TiO:TAT 的胶粘剂对生物膜形成具有抗菌活性(p < 0.05),但对浮游细菌的活力没有差异(p > 0.05)。所有组的牙髓细胞存活率均较高。聚合动力学在各组之间有所不同,但所有组的 DC 均高于 50%。与对照组相比,添加 5wt.%nt-TiO 和含有 nt-TiO:TAT 的两组的努普硬度值更高(p < 0.05)。含有 nt-TiO:TAT 的组的 ΔKHN%(p < 0.05)较低,UTS 较高(p < 0.05)。1 年后,添加 5wt.%nt-TiO 和含有 nt-TiO:TAT 的两组的 μ-TBS 均高于对照组(p < 0.05)。

意义

将三嗪-甲基丙烯酸酯单体与 nt-TiO 混合生成了一种填料,改善了胶粘剂树脂的物理化学性能,并提供了抗菌活性,有助于防止牙-树脂界面周围的龋齿病变。所制备的聚合物的一系列物理、化学和生物学特性,以及随着时间的推移结合强度的稳定性增加,使 nt-TiO:TAT 成为一种有前途的牙科胶粘剂树脂填料。

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