Presented by Sean Day, Stanley Gelin, Kristin O Connor, Chris Sullivan, and Brian Wilson

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Different corrosive effects on hydroxyapatite nanocrystals and amine fluoride-based mouthwashes on dental titanium brackets: a comparative in vitro study Presented by Sean Day, Stanley Gelin, Kristin O Connor, Chris Sullivan, and Brian Wilson

About the Authors Alma Mater Studiorum, University of Bologna Department of Chemistry Bologna, Italy Marco Lelli Ismaela Foltran Giulia Montebugnoli Massimo Marcaccio Norberto Roveri University of Pisa Istituto Stomatologico Tirreno, Lido di Camaiore, Lucca, Italy Olivia Marchisio Annamaria Genovesi Ugo Covani

Key Terms Fluoridated Hydroxyapatite Fluoride attached calcium material used in dental enamel. SEM Scanning Electron Microscopy is a way to visualize the surface roughness of the material. AFM Atomic Force Microscopy is a way to visualize the surface roughness of the material. Biomemetic Any human made substance that is meant to imitate things naturally found in the body.

History of Dental Work Early History Mummified ancients with crude metal bands wrapped around individual teeth (catgut used as wire!). Hippocrates and Aristotle both ruminated about ways to straighten teeth.

History of Dental Work Important Breakthroughs In 1728 a French dentist used a Bandeau to help expand the arch In 1757 another French dentist perfected the Bandeau In 1819 Delabarre introduced the wire crip which marked the birth of contemporary orthodontics

History of Dental Work The First Metal Mouths In the early 1900s orthodontists used gold, platinum, silver, steel, gum rubber, and vulcanite. Why do you think titanium was eventually used over other materials or other metals?

Why use titanium? Low thermal conductivity. Has an appropriate modulus of elasticity, which helps bone to heal when in close contact. Highly ductile and resistant to cyclic forces in the oral environment. Considered to be biocompatible

Use of Dental Fluoride When exposed to fluoride in a mouthwash, the native hydroxyapatite will substitute a hydroxyl group for a fluoride ion. This modification promotes more enamel formation, higher crystallinity, and stronger mechanics Fluoride also inhibits bacterial metabolism in plaque formation

Alternative Treatment Fluoride is being replaced by biomimetic hydroxyapatite nanocrystals. Hydroxyapatite that is substituted by carbonate anions and zinc to mimic native dental HA Have been shown to be able to produce mineral deposition on enamel and dentin

Biomimetic CHA Images TEM images of zinc substituted carbonatehydroxyapatite nanocrystals 10

Effects of Fluoride Fluoride has a corrosive effect on titanium Titanium oxide layer destroyed At ph <3.5 and concentrations >30 ppm, fluoride degrades titanium and increases the surface roughness

Bracket Corrosion Corroding the titanium brackets changes the topology of the biomaterial The extra surface area allows for more adhesion by bacteria This can lead to oral diseases and decrease the effectiveness of the dental implant through What other methods besides modifying surface roughness could be used to prevent bacterial accumulation?

Purpose of Study Compare the corrosive effects on titanium by both fluoride mouthwash and CHA mouthwash Why? 13

METHODS: General Outline Four types of titanium were considered: 1. Polished 2. Blasted 3. Machined 4. Acid-etched Each type 3 mm thick and 6 mm diameter Each type had six in vitro test samples Each sample was dipped in mouthwash for 60 seconds two times a day for 30 days Titanium plates were rinsed after treatment

Discussion Question What do you think about the protocol that was used for dipping? Are there other variables that might make this experiment less realistic? 15

METHODS: In Vitro Test Polished titanium bracket samples were tested at room temperature A nanostructured microcrystal CHA-based mouthwash Composition of biomimetic CHA (active component): Ca (-x) Zn x (PO 4 ) (6-y) (CO 3 ) y (OH) 2 X = 0.1 Y=0.4 An amine fluoride F based mouthwash ph between 4.3 and 5.5

METHODS: Morphological Characterization SEM Scanning Electron Microscopy Carl-Zeiss EVO, 40 XVP (Oberkochen, Germany) with energy dispersive detector (EDAX) Inca 250 (Oxford, UL) Used secondary electrons at 25 KV and different magnifications Uses a beam of high energy electrons to scan and produces images of a sample Used to visualize the surface roughness of the titanium sample

METHODS: Morphological Characterization AFM Atomic Force Microscopy Digital Instruments Nanoscope IIIa Multiomode SPM (Digital Instruments, Santa Barbara, CA, USA) Superior multitasking control for scanning probe microscopes (SPMs) J scanner and silicon nitride tips (200 lm long with nominal spring constant 0.06 N/m) Uses SPMs in contact mode to produce images of the surface topography of a sample By recording height adjustments or changes in interatomic forces Used to visualize the surface roughness of the titanium sample

Discussion Question AFM and SEM are both good topographic techniques. How can these be supplemented to get chemical composition information?

RESULTS

SEM Images of Titanium Surfaces Polished Blasted Machine Treated Acid-Etched Discussion Question Polished titanium was chosen as the more suitable plates to be utilized in this study. How do these results support this selection? How might the results have been different if a different surface was used?

SEM images of titanium surfaces after mouthwash treatment Surface after fluoride-based mouth wash treatment Elementary analysis after fluoride-based mouth wash treatment Surface after CHA-based mouth wash treatment Elementary analysis after CHA-based mouth wash treatment

Discussion The zinc-substituted carbonate hydroxyapatite (CHA) based mouth wash had HA deposition filling the streaks on the titanium surface and therefore reducing surface roughness. The energy dispersive detector (EDAX) analysis revealed the presence of calcium and phosphorus which was characteristic of the CHA present in the mouthwash. Ca5(PO4)6(OH)2 Hydroxyapatite

Comparison of Pre and Post- Treatment SEM Images Original, Polished Titanium F and CHA treated Titanium

AFM Analysis 10 x 10 μm Section 100 x 100 μm Section

Discussion The treatment with amine the fluoride based mouthwash induced a roughness characterized by streaking with higher peaks and deeper valleys on the titanium bracket surface. Increased depth of the streaks encouraged bacterial growth, promoting infection and prosthesis contamination and mobility. Amine Fluoride

Discussion Treatment with the CHA-based mouthwash induced a roughness characterized by streaking with smoothed peaks and less deep valleys on the titanium bracket surface. Hydroxyapatite deposition protected against the surface oxidative process, which can damage the mechanical behavior of the titanium brackets.

Numerical Analysis From AFM Images

Discussion Question Using your knowledge of biomaterial surface properties, what are the advantages and disadvantages of using a ceramic implant?

Conclusion Determined the presence of F- in a mouthwash induces mechanical weakness in the metallic dental implant and bacterial contamination. Found that the presence of zinc-substituted CHA in a mouthwash prevents the deterioration of the metallic dental implant and contamination with bacteria.

Questions???