School of Dentistry, University of Missouri - Kansas City, Kansas City, MO, 64108, USA.
Department of Chemistry, University of Missouri - Kansas City, MO, 64110, USA.
Dent Mater. 2021 Jul;37(7):1193-1201. doi: 10.1016/j.dental.2021.04.010. Epub 2021 May 6.
The aim of the study was to investigate the effects of a novel polymerizable collagen cross-linker methacrylate-functionalized proanthocyanidins (MAPA) on the polymerization, microhardness and leaching of a HEMA-based experimental dental adhesive system.
Three MAPAs were synthesized using different methacrylate (MA) to proanthocyanidins (PA) feeding ratios of 1:2, 1:1, and 2:1 to obtain MAPA-1, MAPA-2, and MAPA-3, respectively. The resulting three MAPAs and PA were added to an experimental adhesive formulated with HEMA and a tri-component photoinitiator system (0.5 wt% CQ/EDMAB/DPIHP) at 1%, 5% and 10% MAPA or PA concentrations (wt%). The adhesive polymerization kinetics was measured continuously in real-time for 10 min using a Fourier-transform infrared spectroscopy (FTIR) with an attenuated total reflectance (ATR) accessory. Degree of conversion (DC) and Vickers microhardness (MH) of cured adhesives were measured at 72 h post-cure. The leaching of cured adhesives in DI water was monitored using UV-vis spectrophotometer. Statistical analysis was performed using one-way and two-way ANOVA, Tukey's (p < 0.05).
The adhesive formulations with 1%, 5% and 10% MAPAs-1, -2, -3 all generated higher rate of polymerization and 10-min DC than the formulations with PA at the same concentrations. At 72 h post-cure, the adhesive formulation with 5% MAPA-2 exhibited significantly higher DC (99.40%) and more than doubled MH (18.93) values than the formulation with 5% PA (DC = 89.47%, MH = 8.41) and the control (DC = 95.46%, MH = 9.33). Moreover, the cured adhesive with 5% MAPA-2 demonstrated significantly reduced PA leaching in comparison with cured adhesive with 5% PA.
Synthesized MAPA is a novel class of polymerizable collagen cross-linker that not only stabilizes dentin collagen via its PA component, but also improves polymerization, mechanical properties and stability of HEMA-based adhesives via its MA component. By inheriting the benefit while overcoming the drawback of PA, MAPA offers a revolutionary solution for improved bond-strength and longevity of dental restorations.
本研究旨在探讨新型可聚合胶原交联剂甲基丙烯酰化原花青素（MAPA）对 HEMA 基实验性牙科胶粘剂体系聚合、显微硬度和浸出的影响。
采用不同的甲基丙烯酸（MA）与原花青素（PA）进料比（1:2、1:1 和 2:1）合成 3 种 MAPA，分别得到 MAPA-1、MAPA-2 和 MAPA-3。将这三种 MAPA 和 PA 添加到由 HEMA 和三组分光引发剂系统（0.5wt%CQ/EDMAB/DPIHP）组成的实验性胶粘剂中，MAPA 或 PA 的浓度为 1%、5%和 10%（wt%）。采用傅里叶变换红外光谱（FTIR）与衰减全反射（ATR）附件连续实时测量 10 分钟的胶粘剂聚合动力学。在固化后 72 小时测量固化胶粘剂的转化率（DC）和维氏显微硬度（MH）。采用紫外-可见分光光度计监测固化胶粘剂在 DI 水中的浸出情况。采用单因素方差分析和双因素方差分析、Tukey 检验（p<0.05）进行统计分析。
在相同浓度下，含 1%、5%和 10%MAPA-1、-2、-3 的胶粘剂配方的聚合速率和 10 分钟 DC 均高于含 PA 的配方。在固化后 72 小时，含 5%MAPA-2 的胶粘剂配方的 DC（99.40%）和 MH（18.93）值显著高于含 5%PA 的配方（DC=89.47%，MH=8.41%）和对照（DC=95.46%，MH=9.33%）。此外，与含 5%PA 的固化胶粘剂相比，含 5%MAPA-2 的固化胶粘剂中 PA 的浸出明显减少。
合成的 MAPA 是一种新型可聚合胶原交联剂，不仅通过其 PA 成分稳定牙本质胶原，还通过其 MA 成分提高 HEMA 基胶粘剂的聚合、力学性能和稳定性。通过继承 PA 的优点同时克服其缺点，MAPA 为提高牙科修复体的粘结强度和耐久性提供了一种革命性的解决方案。
