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[Rice Catalyst Issue 14]

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Figure 3: A comparison of the three 3D printing techniques discussed. A. Vat Polymerization generates a scaffold by using a DLP projector to<br />

harden a scaffold layer by layer, with a platform rising as the resin hardens. [20] B, C. Inkjet printing and extrusion both involve pushing out<br />

a scaffold through a nozzle that is able to be specific in size and shape. [26]<br />

of the non-HAp-immersed tooth (Figure<br />

2). These results together display evidence<br />

that the HAp powder had rehardening<br />

properties, with calcium ions adsorbing<br />

onto teeth, and phosphate ions acting as an<br />

agglomeration tool. [<strong>14</strong>]<br />

Yet another approach to covering enamel<br />

is to mimic the gel-like environment that<br />

surrounds the teeth during amelogenesis,<br />

which involves the transport of calcium<br />

and phosphate ions from ameloblasts into<br />

the enamel. [16] Unlike past experiments<br />

that were conducted in aqueous solutions,<br />

Cao et. al created an agarose-based<br />

calcium chloride hydrogel mat to provide<br />

a one-way transport of ions into damaged<br />

teeth. [17] The researchers treated 2 mmthick<br />

teeth samples with phosphoric acid<br />

for deterioration, then created a four-layer<br />

model by covering the damaged teeth<br />

slices with the calcium chloride hydrogel,<br />

an ion-free agarose gel, and a phosphate<br />

solution. Looking at SEM photographs,<br />

HAp crystals were visible after just two<br />

days of immersion for the treated teeth.<br />

Over the next few days, these rods<br />

organized themselves into one axis, and<br />

after six days, the gel that had previously<br />

been located between the crystals had<br />

been effectively eliminated. Furthermore,<br />

a nanohardness test demonstrated similar<br />

hardness values for the control and<br />

repaired teeth, with a hardness increase of<br />

3.04 ± 0.75 gigapascals (GPa)(p=.05) after 6<br />

days. [17] Although this gel can be cheaply<br />

produced, a limitation of the matrix<br />

formed is that it is inorganic, meaning<br />

that it is dissimilar to real enamel; further<br />

research can be done to explore how to<br />

embed enamel proteins like amelogenin<br />

and enamelin into the matrix without<br />

sacrificing low-cost.<br />

Although gel immersion may enhance<br />

dental enamel, its clinical roles are limited<br />

due to the difficulty of isolating individual<br />

teeth from patients for the sole purpose of<br />

enamel repair. Rather than immersing the<br />

entire tooth, Hontsu and his team at Osaka<br />

Dental University created a film of HAp that<br />

demonstrated evidence of tooth hardening.<br />

[18] To create this sheet, they deposited<br />

a film of HAp on a soluble substrate via<br />

pulsed laser deposition, after which the<br />

substrate is dissolved and the remaining<br />

flexible HAp sheet is collected. [18] To<br />

observe its ability to bind to the dentin<br />

and enamel layers of teeth, photographs<br />

provided evidence of sealing owing to the<br />

moisture content of the created layer.<br />

[18] However, research has yet to be<br />

done to demonstrate whether or not this<br />

protective coating demonstrates hardening<br />

capabilities. Overall, though, the techniques<br />

of powders, hydrogels, and mats have all<br />

provided possibilities for enamel repair<br />

and solutions to ailments like dentine<br />

hypersensitivity.<br />

3D PRINTING<br />

A more advanced method to produce<br />

synthetic grafts is through 3D printing<br />

biomimetic material, also known as<br />

biomanufacturing. The advantages of<br />

these 3D-printed scaffolds are that they<br />

are replicable, have great biocompatibility,<br />

and can be customized to individual<br />

needs. Though there are numerous<br />

ways to develop artificial HAp through<br />

3D printing, the ones that are successful<br />

must have certain traits. Notably, the<br />

HAp must be porous enough to allow<br />

for mass transport, strong enough to<br />

demonstrate hardening capabilities in<br />

enamel and prevent degradation in the<br />

mouth microenvironment, and nontoxic<br />

to ensure an absence of side effects. [19]<br />

Three methods of 3D printing are described<br />

in this discussion.<br />

Vat polymerization is a method of using<br />

UV light in Digital Light Processing (DLP) to<br />

manufacture a HAp scaffold synthetically.<br />

[20, 21] In this process, liquid resin inside<br />

of a large tank hardens due to UV light<br />

causing molecules to bond. By lifting a<br />

platform and exposing resin to light, the<br />

3D print is generated layer by layer [20]<br />

However, after the fabrication stage, the<br />

resin must be sintered, or burned, at a<br />

high temperature. To prevent cracks from<br />

forming, this must be done in a gradual<br />

process to an optimal temperature of 1250<br />

°C, with a high flexural and compressional<br />

strength compared to fabrication at 1200°<br />

C and 1300° C. [21] Although this method<br />

can create a scaffold that is accurate<br />

and specific for an individual tooth,<br />

the sintering process at extremely high<br />

temperatures leads to concerns about<br />

4 6 | C A T A L Y S T 2022-2023

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