Eugenyl-2-Hydroxypropyl Methacrylate-Incorporated Experimental Dental Composite: Degree of Polymerization and In Vitro Cytotoxicity Evaluation

The aim of this study was to evaluate the properties of new dental formulations containing eugenyl-2-hydroxypropyl methacrylate (EgGMA) monomer, as restorative dental material, in terms of their degree of photopolymerization and cytotoxicity. The target model composites (TBEg0, TBEg2.5, and TBEg5) were prepared by mixing 35% organic matrix (TEGDMA/BisGMA (50/50 wt%) of which 0, 2.5, and 5 wt%, respectively, were replaced with EgGMA monomer) with 65% filler (silanized hydroxyapatite (HA)/zinc oxide (ZnO2), 4:3 by weight). The vinylic double-bond conversion (DC) after light-curing was studied using Fourier transform infrared technique whereas cell viability was in vitro tested using primary human gingival fibroblasts cells over 7 days by means of AlamarBlue colorimetric assay. The obtained data were statistically analyzed using ANOVA and Tukey post-hoc tests. The results revealed no significant difference in DC between TBEg2.5 (66.49%) and control (TBEg0; 68.74%), whereas both differ significantly with TBEg5, likely due to the inhibitory effect of eugenol moiety at high concentration. The cell viability test indicated that all the composites are biocompatible. No significant difference was counted between TBEg2.5 and TBEg5, however, both differed significantly from the control (TBEg0). Thus, even though its apparent negative effect on polymerization, EgGMA is potentially safer than bisphenol-derived monomers. Such potential properties may encourage further investigations on term of EgGMA amount optimization, compatibility with other dental resins, and antimicrobial activity.

Dextran-Coated Latex Nanoparticles via Photo-RAFT Mediated Polymerization Induced Self-Assembly

Polysaccharide coated nanoparticles represent a promising class of environmentally friendly latex to replace those stabilized by small toxic molecular surfactants. We report here an in situ formulation of free-surfactant core/shell nanoparticles latex consisting of dextran-based diblock amphiphilic copolymers. The synthesis of copolymers and the immediate latex formulation were performed directly in water using a photo-initiated reversible addition fragmentation chain transfer-mediated polymerization induced self-assembly strategy. A hydrophilic macromolecular chain transfer-bearing photosensitive thiocarbonylthio group (eDexCTA) was first prepared by a modification of the reducing chain end of dextran in two steps: (i) reductive amination by ethylenediamine in the presence of sodium cyanoborohydride, (ii) then introduction of CTA by amidation reaction. Latex nanoparticles were then formulated in situ by chain-extending eDexCTA using 2-hydroxypropyl methacrylate (HPMA) under 365 nm irradiation, leading to amphiphilic dextran-b-poly(2-hydroxypropyl methacrylate) diblock copolymers (DHX). Solid concentration (SC) and the average degree of polymerization - Xnˉ- of PHPMA block (X) were varied to investigate their impact on the size and the morphology of latex nanoparticles termed here SCDHX. Light scattering and transmission electron microscopy analysis revealed that SCDHX form exclusively spherical nano-objects. However, the size of nano-objects, ranging from 20 nm to 240 nm, increases according to PHPMA block length.

New Monomer Based on Eugenol Methacrylate, Synthesis, Polymerization and Copolymerization with Methyl Methacrylate–Characterization and Thermal Properties

Poly(eugenyl-2-hydroxypropyl methacrylate) (PEUGMA), poly(methyl methacrylate) (PMMA) and poly(eugenyl-2-hydroxypropyl methacrylate-co-methyl methacrylate) (PEUGMA-co-MMA) were synthesized by a free radical polymerization route in the presence of azobisisobutyronitrile. EUGMA was synthesized by etherification of the eugenol phenolic hydroxyl group with glycidyl methacrylate. Polymers and copolymers were characterized using size exclusion chromatography, Fourier transform infrared, and nuclear magnetic resonance. The effects of the encumbering substituent on the thermal behavior of the polymers and copolymers were studied by differential scanning calorimetry, thermogravimetry (TG) and direct analysis, using real-time, time-of-flight mass spectroscopy (DART-ToF-MS) methods. The results obtained revealed that for PEUGMA, the average molecular weight was 1.08 × 105, and increased slowly with the decrease in the EUGMA content in the copolymer. The order of the distribution of dyads comonomer units in the copolymer chains estimated by the Igarashi method based on the reactivity ratio does reveal a random distribution with a tendency toward alternation. The glass transition temperature of PEUGMA (46 °C) increased with the MMA content in the copolymer, and those of the copolymer fit well with the Johnston’s linearized expression. The TG analysis of pure PEUGMA revealed a significantly high thermal stability compared to that of PMMA. During its degradation, the preliminary decomposition was at 340 °C, and decreased as the MMA units increased in the copolymer. The DART-ToF-MS analysis revealed that the isothermal decomposition of PEUGMA led to a regeneration of raw materials such as EUGMA, GMA and EUG, in which the maximum amount was achieved at 450 °C.

Synthesis of poly(stearyl methacrylate)-poly(2-hydroxypropyl methacrylate) diblock copolymer nanoparticles via RAFT dispersion polymerization of 2-hydroxypropyl methacrylate in mineral oil

RAFT dispersion polymerization of 2-hydroxypropyl methacrylate produces diblock copolymer spheres, worms or vesicles in mineral oil; the Pickering emulsifier performance of the spheres is examined.

Aqueous solution behavior of stimulus-responsive poly(methacrylic acid)-poly(2-hydroxypropyl methacrylate) diblock copolymer nanoparticles

RAFT aqueous dispersion polymerization is used to prepare poly(methacrylic acid)-poly(2-hydroxypropyl methacrylate) diblock copolymer nanoparticles, which exhibit stimulus-responsive behaviour on adjusting the solution temperature and/or solution pH.