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. 2020 Jun 17;10(1):9811.
doi: 10.1038/s41598-020-66819-8.

Advanced characterization of surface-modified nanoparticles and nanofilled antibacterial dental adhesive resins

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Advanced characterization of surface-modified nanoparticles and nanofilled antibacterial dental adhesive resins

Fernando Luis Esteban Florez et al. Sci Rep. .

Abstract

Nanotechnology can improve the performance of dental polymers. The objective of this study was to modify the surfaces of nanoparticles with silanes and proteins, characterize nanoparticles' agglomeration levels and interfaces between nanoparticles and the polymeric matrix. Undoped (n-TiO2), nitrogen-doped (N_TiO2) and nitrogen-fluorine co-doped titanium dioxide nanoparticles (NF_TiO2) were synthesized and subjected to surface modification procedures in preparation for Small-Angle X-Ray Scattering (SAXS) and Small-Angle Neutron Scattering (SANS) characterizations. Experimental adhesives were manually synthesized by incorporating 20% (v/v) of n-TiO2, N_TiO2 or NF_TiO2 (as-synthesized or surface-modified) into OptiBond Solo Plus (OPTB). Specimens (n = 15/group; d = 6.0 mm, t = 0.5 mm) of OPTB and experimental adhesives were characterized using Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS), 2-D ToF-SIMS chemical imaging and SANS. SAXS results indicated that surface-modified nanoparticles displayed higher scattering intensities in a particle-size dependent manner. ToF-SIMS results demonstrated that nanoparticles' incorporation did not adversely impact the parental polymer. 2-D ToF-SIMS chemical imaging demonstrated the distribution of Ti+ and confirmed nitrogen-doping levels. SANS results confirmed nanoparticles' functionalization and revealed the interfaces between nanoparticles and the polymer matrix. Metaloxide nanoparticles were successfully fabricated, incorporated and covalently functionalized in a commercial dental adhesive resin, thereby supporting the utilization of nanotechnology in dentistry.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Figure 1
Figure 1
Helium-Ion Microscopy. Images (25 μm field of view) of unaltered (A) and experimental dental adhesive resins containing 20% (v/v) of (B) n-TiO2, (C) N_TiO2 and (D) NF_TiO2.
Figure 2
Figure 2
Results from the small-angle X-ray spectroscopy of surface-modified nanoparticles suspended on D2O. (A) shows the effect of surface modification (either NaOH, NaOH+APTES or NaOH+APTES + Alb) and (B) the effect of ionic solutions (either NaCl [0.1 M] or HCl [0.1 M]) on nanoparticles’ agglomeration levels.
Figure 3
Figure 3
ToF-SIMS of unaltered (OPTB) and experimental dental adhesive resins containing 20% of either n-TiO2, N_TiO2 or NF_TiO2 (A) as-synthesized or (B) surface-modified by NaOH + APTES + Alb. From top to bottom in (A) and (B) OPTB, OPTB + n-TiO2, OPTB + N_TiO2 and OPTB + NF_TiO2.
Figure 4
Figure 4
ToF-SIMS chemical imaging for Ti+ immobilized in (A) OPTB, (B) OPTB + n-TiO2, (C) OPTB + N_TiO2 and (D) N_F_TiO2. Mass spectrum analysis for TiN+ is shown in (E).
Figure 5
Figure 5
Results from the small-angle neutron scattering of (A) N_TiO2 (as-synthesized or surface-modified) suspended in D2O or D2O containing 0.1 M HCl, (B) unaltered and experimental dental adhesive resins containing either as-synthesized or surface-modified n-TiO2, N_TiO2 and NF_TiO2 and (C) Representative Guinier-Porod fitting unaltered OPTB.

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