Preparation and evaluation of novel bio-based Bis-GMA-free dental composites with low estrogenic activity

• Published in: Dental materials Vol. 38; no. 2; pp. 281 - 293
• Main Authors: Sun, Yinan, Zhou, Zeying, Jiang, Hao, Duan, Yuting, Li, Jialin, Liu, Xiaoqiu, Hong, Lihua, Zhao, Chengji
• Format: Journal Article
• Language: English
• Published: England Elsevier Inc 01.02.2022; Elsevier BV
• Subjects: Acrylates; Benzhydryl Compounds; Bio-based; Biological materials; Bisphenol A; Bisphenol A glycidyl methacrylate; Bisphenol A-Glycidyl Methacrylate - chemistry; BPA free; Breast cancer; Cell proliferation; Composite materials; Composite Resins - chemistry; Conversion; Creosol; Cytocompatibility; Cytotoxicity; Dental cement; Dental composite; Dental materials; Dental restorative materials; Epichlorohydrin; Estrogenic activity; Evaluation; Flexural strength; Humans; Infrared spectroscopy; Materials Testing; Mechanical properties; Methacrylates - chemistry; Mixtures; Monomers; NMR; Nuclear magnetic resonance; Phenols; Polyethylene Glycols - chemistry; Polymethacrylic Acids - chemistry; Raw materials; Resins; Risk assessment; Shrinkage; Silicon Dioxide; Spectroscopy, Fourier Transform Infrared; Synthesis; Toxicity; Triethylene glycol dimethacrylate; Water depth; Water immersion; Xenoestrogens; Bis-DMA; MCF-7; FM; Bis-GMA; NaOH; Bis-EMA; MTT; FS; DMEM; OD; FBS; SL; CCK-8; EA; WS; VHN; CD; BCF-EP; BCF; DMAEMA; TEGDMA; BPA free; TBAB; ECH; BCF-GMA; PPh3; CQ; CS; BPA; BCF-EA; Cytocompatibility; Creosol; TMS; RGR; VS; Bio-based; Estrogenic activity; DC; ATR; Dental composite
• ISSN: 0109-5641; 1879-0097
• DOI: 10.1016/j.dental.2021.12.010

Although bisphenol Aglycidyl methacrylate (Bis-GMA) are widely used in the dental composite, its raw materials include the petroleum-based product bisphenol A (BPA) with high estrogenic activity (EA). In this study, two new BPA-free dimethacrylate monomers from bio-based material creosol were synthesized and evaluated. The renewable bisphenol monomer 5, 5'-methylenedicreosol (BCF) was prepared from bio-based material creosol. By the human breast cancer cells (MCF-7 cells) proliferation assay, a risk assessment of BCF was performed to determine if BCF possessed reduced EA in comparison to BPA. Then, the novel monomers 5, 5'-methylenedicreosol diglycidyl ether diacrylate (BCF-EA) and 5, 5'-methylenedicreosol diglycidyl ether dimethacrylate (BCF-GMA) were synthesized from BCF with epichlorohydrin and (meth)acrylate. All products were investigated by 1H NMR and FT-IR spectra. The control resin was a mixture based on Bis-GMA and tri(ethyleneglycol) dimethacrylate (TEGDMA) with a weight ratio of 5:5 (5B5T). Similarly, experimental resin matrix was a mixture based on BCF-EA/TEGDMA (5E5T) and BCF-GMA/TEGDMA (5G5T). And their corresponding composites were then prepared with corresponding resin matrices and hybrid SiO2 (5E5TC, 5G5TC and 5B5TC). The properties of these composites were investigated according to the standard or referenced methods. Each sample was evaluated for double bond conversion (DC), shrinkage stress (SS) and volumetric polymerization shrinkage (VS). Water sorption (WS), water solubility (SL), mechanical properties and cytotoxicity were also measured. 1H NMR and FT-IR spectra confirmed the chemical structure of each monomer. EA test revealed that bio-based bisphenol monomer BCF as the precursor of BCF-EA and BCF-GMA showed lower EA than BPA. Cured resin matrix: Both 5E5T and 5G5T had nearly the same DC (p < 0.05), which was higher than 5B5T (p < 0.05); 5E5T and 5G5T had lower VS, SL and cytotoxicity than 5B5T (p < 0.05); mechanical properties of 5E5T and 5G5T were all better than those of 5B5T (p < 0.05). Cured composite: There was no significant difference in conversion (p < 0.05); 5E5TC and 5G5TC had significantly lower VS (p < 0.05); WS of 5E5TC and 5G5TC were similar (p < 0.05), but higher compared to 5B5TC (p < 0.05); 5E5TC and 5G5TC had the deeper depth of cure (p > 0.05); before water immersion, there was no significant difference in flexural strength between 5E5TC and 5G5TC (p > 0.05), and higher than 5B5TC (p < 0.05); 5E5TC and 5G5TC showed less cytotoxicity than 5B5TC (p < 0.05). The new BPA-free di(meth)acrylates are promising photocurable dental monomers owning to bio-based raw material, high degree of conversion coupled with low curing shrinkage and good mechanical properties. Therefore, BCF-EA and BCF-GMA has a potential to be used as the substitution for Bis-GMA to prepare Bis-GMA-free dental composite.