Multiparameter evaluation of acrylamide HEMA alternative monomers in 2step adhesives ABSTRACT Objectives: As frequently added to adhesives, the mono-functional monomer 2-hydroxyethyl methacrylate (HEMA) acts as co-solvent and improves surface wetting. Nevertheless, HEMA promotes watersorption and hydrolysis at adhesive interfaces, affecting bond durability to dentin. This study investigated if two acrylamide co-monomer alternatives could replace HEMA in experimental adhesive-resin formulations as part of 3/2-step universal adhesives applied, respectively, in etch-andrinse (E&R) and self-etch (SE) bonding modes.Methods: Upon priming dentin with the 10-MDP-based Clearfil SE Bond 2' primer ('CSE2p'; Kuraray Noritake), three experimental adhesive resins, consisting of 50wt% Bis-GMA, 15wt% TEGDMA, and either 35wt% diethyl acrylamide ('DEAA'), hydroxyethyl acrylamide ('HEAA') or HEMA ('HEMA+'), were applied. The control HEMA-free adhesive resin contained 60wt% Bis-GMA and 40wt% TEGDMA ('HEMA-'). All adhesives were evaluated for 'immediate' and 'aged' micro-tensile bond strength (μTBS) to dentin upon, respectively, 1-week (1w) and 6-month (6m) water storage, TEM adhesive-dentin interfacial interaction, 24-hour and 6m three-point bending, contact-angle wetting, viscosity and watersorption.Results: Linear mixed-effects model statistics revealed significantly better bonding performance of the adhesives applied in E&R than SE mode, except for DEAA_1w, with the highest μTBSs recorded for DEAA and HEMA-applied in SE mode. In E&R mode, aging did not significantly reduce DEAA's μTBS.Best wetting on primed dentin was recorded for HEMA+, significantly better than DEAA, further HEAA and HEMA-, these directly related to their viscosity. HEAA absorbed significantly more water than all other adhesive-resin formulations. HEMA->DEAA>HEAA>HEMA+ was the significant order for 6m bending strength.
Conclusions:The acrylamide co-monomer DEAA could replace HEMA, while HEAA not.Universal adhesives provide acidic aqueous single-solution blends of hydrophilic and hydrophobic components to achieve time-stable bonding to dentin (and enamel) following both main bonding modes [5, 6]. The mono-functional monomer 2-hydroxyethyl methacrylate (HEMA) is frequently added to many of today's commercial adhesives as an essential component. Thanks to its inherent hydrophilic nature, HEMA acts as co-solvent for other hydrophobic monomers that mix less good in water, hereby preventing phase separation between monomer ingredients and water [7]. In addition, HEMA promotes surface wetting and intra-substrate infiltration thanks to its small molecular size [8].Nevertheless, HEMA exhibits a noticeably low degree of polymerization conversion (DC) [9]. It holds water, present as basic ingredient in dental adhesives up to 40% [5,10], inside the adhesive, by which water is more difficult to remove by gentle air-blowing upon the adhesive's application. If water remains within the adhesive, it impairs polymerization. All these factors enhance the adhesive's solubility and...