Abstract

A radical new methodology for the exogenous mineralization of hard tissues is demonstrated in the context of laser-biomaterials interaction. The proposed approach is based on the use of femtosecond pulsed lasers (fs) and Fe3+-doped calcium phosphate minerals (specifically in this work fluorapatite powder containing Fe2O3 nanoparticles (NP)). A layer of the synthetic powder is applied to the surface of eroded bovine enamel and is irradiated with a fs laser (1040 nm wavelength, 1 GHz repetition rate, 150 fs pulse duration and 0.4 W average power). The Fe2O3 NPs absorb the light and may act as thermal antennae, dissipating energy to the vicinal mineral phase. Such a photothermal process triggers the sintering and densification of the surrounding calcium phosphate crystals thereby forming a new, dense layer of typically ∼20 μm in thickness, which is bonded to the underlying surface of the natural enamel. The dispersed iron oxide NPs, ensure the localization of temperature excursion, minimizing collateral thermal damage to the surrounding natural tissue during laser irradiation. Simulated brushing trials (pH cycle and mechanical force) on the synthetic layer show that the sintered material is more acid resistant than the natural mineral of enamel. Furthermore, nano-indentation confirms that the hardness and Young’s modulus of the new layers are significantly more closely matched to enamel than current restorative materials used in clinical dentistry. Although the results presented herein are exemplified in the context of bovine enamel restoration, the methodology may be more widely applicable to human enamel and other hard-tissue regenerative engineering. Statement of significanceIn this work we provide a new methodology for the mineralisation of dental hard tissues using femtosecond lasers and iron doped biomaterials. In particular, we demonstrate selective laser sintering of an iron doped fluorapatite on the surface of eroded enamel under low average power and mid-IR wavelength and the formation of a new layer to substitute the removed material. The new layer is evaluated through simulated brushing trials and nano-indentation. From the results we can conclude that is more acid resistant than natural enamel while, its mechanical properties are superior to that of current restorative materials. To the best of our knowledge this is the first time that someone demonstrated, laser sintering and bonding of calcium phosphate biomaterials on hard tissues. Although we here we discuss the case of dental enamel, similar approach can be adopted for other hard tissues, leading to new strategies for the fixation of bone/tooth defects.

Highlights

  • MethodsThe synthesis of the Fe containing fluorapatite followed the precipitation method described elsewhere [13]

  • We have demonstrated that calcium phosphate mineral (FAP) can be sintered and attached to dental enamel without inducing any significant thermal damage to the underlying tissue

  • The new layer is proven to be dense and compact to the extent that simulated brushing trials of 15-day duration show little or no mass loss compared to natural enamel

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Summary

Methods

The synthesis of the Fe containing fluorapatite followed the precipitation method described elsewhere [13]. 200 ml of a 0.1 M Ca(NO3)2 4H2O (Fisher Chemicals, CAS:13477-34-4) aqueous solution, containing 0.8 g Fe(NO3)3Á9H2O (Sigma Aldrich, CAS:7782-61-8) was prepared (solution A) and heated to 50 °C. 1 M (NH4)3PO4 (Acros Organics, CAS:778328-0) solution (200 ml) containing the appropriate mass of NH4F for stoichiometric fluorapatite, was introduced dropwise into the solution (A). The final mixture was continuously stirred at 50 °C for 2 h and left to settle for 1 h to allow precipitation. In these conditions we have the dehydration of the Fe(OH)y2Ày and the precipitation of hematite nanoparticles [14]. After drying the powder was heat treated to 400 °C for 3 h

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