Abstract

Despite increasing interest in the use of natural biomolecules for different applications, few attempts of coupling them to inorganic biomaterials are reported in literature. Functionalization of metal implants with natural biomolecules could allow a local action, overcoming the issue of low bioavailability through systemic administration. In the present work, gallic acid was grafted to a pre-treated Ti6Al4V in order to improve its biological response in bone contact applications. The grafting procedure was optimized by choosing the concentration of gallic acid (1 mg/mL) and the solvent of the solution, which was used as a source for functionalization, in order to maximize the amount of the grafted molecule on the titanium substrate. The functionalized surfaces were characterized. The results showed that functionalization with Simulated Body Fluid (SBF) as solvent medium was the most effective in terms of the amount and activity of the grafted biomolecule. A key role of calcium ions in the grafting mechanism is suggested, involving the formation of coordination compounds formed by way of gallic acid carboxylate and Ti–O− as oxygenated donor groups. Bioactive behavior and surface charge of the pre-treated Ti6Al4V surface were conserved after functionalization. The functionalized surface exposed a greater amount of OH groups and showed higher wettability.

Highlights

  • Polyphenols are organic molecules attracting more and more interest within the scientific community and their application is studied in different fields like medicine, pharmacology, packaging, food conservation and cosmetics

  • Simulated Body Fluid (SBF) as medium proved to be the most effective in terms of molecular amount and activity; the source solution and the uptake did not show evidence of degradation; no significant difference between the use of source solutions of different concentrations was registered

  • Bioactive behavior conferred to the titanium surface by the chemical pre-treatment was conserved after functionalization: Zeta potential measurements suggest a different kinetic of apatite precipitation, but this issue is still subjected to confirmation

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Summary

Introduction

Polyphenols are organic molecules attracting more and more interest within the scientific community and their application is studied in different fields like medicine, pharmacology, packaging, food conservation and cosmetics. Polyphenols have anti-inflammatory, antioxidant, anticancer and antibacterial effects [1,2,3] They can affect bone health, i.e., stimulating differentiation of healthy osteoblasts [4] and promoting the apoptosis of osteosarcoma cells [5]. Surface modifications of titanium and its alloys, in order to confer bioactive and antibacterial properties, are widely studied [31,32,33], but papers related to functionalization with natural biomolecules are very few in number. The following biomolecules were coupled to titanium or titanium dioxide substrates: Natural polyphenols and pyrogallol [28], quercetin [34], taxifolin [35], rhamnogalacturonan-Is (RG-Is) isolated from potatoes and apples [36], lignin [37] and gallic acid esters (namely, octyl-, decyl-, lauryl- and cetyl-gallate) [38]. Surface wettability and surface charge were evaluated by means of contact angle and zeta potential measurements, respectively

Surface Activation
Surface Functionalization
Detection of the Grafted Biomolecule
Contact Angle Measurements
Electro-Kinetic Measurements
Results and Discussion
Biomolecule Detection
In Vitro Apatite-Forming Ability Tests
Zeta Potential Measurements
Conclusions
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