Biomimetic Materials
Biomimetic Materials
A R T I C L E I N F O A B S T R A C T
Keywords: This review covers aspects of orthodontic materials, appliance fabrication and bonding, crossing scientific fields
Orthodontic and presenting recent advances in science and technology. Its purpose is to familiarize the reader with de
Biomaterials velopments on these issues, indicate possible future applications of such pioneering approaches, and report the
Biomimetic
current status in orthodontics. The first section of this review covers shape-memory polymer wires, several
Self-healing
Shape-memory
misconceptions arising from the recent introduction of novel three-dimensional (3D)-printed aligners (mistak
3D printed enly termed shape-memory polymers only because they present a certain degree of rebound capacity, as most
non-stiff alloys or polymers do), frictionless surfaces enabling resistance-less sliding, self-healing materials for
effective handling of fractured plastic/ceramic brackets, self-cleaning materials to minimize microbial attach
ment or plaque build-up on orthodontic appliances, elastomers with reduced force relaxation and extended
stretching capacity to address the problem of inadequate force application during wire-engagement in the
bracket slot, biomimetic (non-etching mediated) adhesive attachment to surfaces based on the model of the
gecko and the mussel, and command-debond adhesives as options for an atraumatic debonding. This review’s
second section deals with the recent and largely unsubstantiated application of 3D-printed alloys and polymers in
orthodontics and aspects of planning, material fabrication, and appliance design.
* Correspondence to: Clinic of Orthodontics and Pediatric Dentistry, Center of Dental Medicine, University of Zurich, Plattenstrasse 11, 8032 Zurich, Switzerland.
E-mail address: theodore.eliades@zzm.uzh.ch (T. Eliades).
https://doi.org/10.1016/j.jdsr.2023.10.005
Received 6 September 2023; Received in revised form 24 October 2023; Accepted 26 October 2023
1882-7616/© 2023 Published by Elsevier Ltd on behalf of The Japanese Association for Dental Science. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
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2.4. Self-cleaning materials involved the development of Titanium photocatalysis [12], which in
volves the coating of the bracket with a layer of Ti oxide that upon
2.4.1. Clinical challenge sunlight exposure releases reactive oxygen species or hydroxyl radicals,
Plaque accumulation on a biomaterial exposed to a biological system which have antimicrobial, odor-removing effects. However, such ap
is accompanied by the organization of a non-cellular biofilm by spon plications have yet to be widely employed in orthodontics.
taneous adsorption of extracellular macromolecules, composed mostly
of glycoproteins and proteoglycans. These films induce a conditioning
2.5. New elastomers
effect that modifies the biomaterial’s surface properties and alters both
the response of the subsequently attached cells and the interactions
2.5.1. Clinical challenge
occurring at the biomaterial-host interface. This conditioning effect is
The use of polyurethane-based elastomeric ligatures and modules in
based on the differing capacities of artificial surfaces to fractionate
engaging archwires and closing spaces in orthodontics is accompanied
proteins from biological fluids, such as saliva or blood, and the ability to
by a notable force relaxation that accounts for up to 40% of the initially
induce conformation and orientation changes of adsorbed proteins.
applied load. This effect is accentuated by the laborious and multi
The outcome of biofilm adsorption is dependent on the biological
perspective intraoral ageing pattern of these polymers that comprises of
fluid flow rate at the site of contact, the type of interfacial interactions
hydrolytic degradation, swelling, and softening, which further degrade
involved, and the attachment strength with the substrate. Under static
the mechanical properties and decrease the exerted forces from the
conditions or low flow rates, the biomaterial surface chemistry is the
material. At the same time, they favor plaque build-up and contribute to
fundamental factor affecting the composition and organization of ac
the microbial colonization of the bracket-wire-elastomer complex.
quired biofilms, whereas in environments with high flow rates, substrate
Elastomeric force relaxation derives from the material’s macroscopic
surface molecular motion and roughness are also important factors. In
degradation in the form of tearing of the structural surface and bulk
addition, with long exposure periods, material properties such as
structure, presenting discontinuities because of sustained load. Micro
porosity, sorption, corrosion, and biodegradation further modify
scopically, the extension of the molecular chains that, in some cases
biomaterial-host interactions. Finally, the material’s wettability is
fracture, leads the load to be exerted by fewer number of bearing units,
modulated by its critical surface tension and plays a significant role in
and as a result presenting higher deformation.
the development of adverse effects either on the tooth’s enamel (in the
Efforts to address this problem in the broader biomedical literature
form of white spot lesions) or periodontal inflammation.
have focused on increasing the crosslinking of chains or their length to
provide more area for load-distribution and longer chains. The problems
2.4.2. Available materials
arising from these approaches have to do with the increased initial
Most efforts in this field have concentrated around the alteration of
stiffness in the cases of fortifying the crosslinking (which would result in
the wetting characteristics of orthodontic materials such as brackets
increased exerted forces) and the entanglement in the scenario of
adhesives and elastomers. The problem with adhesives lies with the fact
incorporating much longer chains which cause the noodle effect–i.e. the
that a reduced wettability to disrupt the developed biofilm on the
increase in stiffness due to the perplexed structure and the entanglement
microbia-attracting adhesive margins, would also result in reduced
of chains.
wetting of the enamel etching-induced tags and projection of the resin in
Thus, ideally elastomers should maintain the applied load for at least
the enamel, thus adversely affecting the bond integrity of the bracket to
4–6 weeks, while they should be hydrophobic to reduce the attraction of
enamel.
species and be water tolerant.
Potential solutions for brackets or elastomers could be their
manufacturing with reduced wettability modelled by the lotus effect [8],
2.5.2. Available materials
which is based on the example of the synonymous plant that, through a
Elastomers used in industrial applications are structures with chains
dense network of hairs developed on its surface, allows the formation of
forming multi-dimensional networks [13,14]. As a result, these elasto
a large contact angle, which is indicative of reduced wetting (Fig. 1).
mers have much higher toughness and strength, producing extension
The formation of superhydrophobic surfaces has been adopted in
ranges in the order of 50 times the original length (in general rubber
medicine [9], dentistry [10], and everyday applications ranging from
elasticity refers to a property of a material to be capable of being
utility material surfaces, dishes, handles, car surface coatings of cars to
extended 10 times its size).
decrease dirt, and fabric repellant surfaces, among others.
An alternative approach could be engaging the wire tying a silk fiber
In orthodontics, the fabrication of self-healing brackets [11] has
around the bracket wings, as silk has remarkable properties [15] and has
recently been produced synthetically [16], leading to a product stronger
than Kevlar and more elastic than nylon.
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teeth. Anything else is not an active, but rather a passive appliance, concluded that the ability to change the thickness of printed aligners and
which is not meant to move teeth of its own (occlusal splints, metallic the change in force and moments, could be used to optimize the pre
appliances, customized brackets). For this reason, a directly printed scribed orthodontic movement while minimizing unwanted tooth
aligner is an appliance that needs to possess properties, which will movements. This opens new possibilities in the provision completely
enable adequate and efficient tooth movement in the desired direction. individualized mechanotherapy for each patient, according to the spe
On one side, the material properties are limiting the efficacy of the cific needs of each treatment phase.
movement, if inadequate, and on the other side the multistep workflow, As can be shown from the abovementioned studies, each step of the
which is not consistent, creates a non-stable and repeatable environment 3D printed aligners workflow, if not performed correctly, could alter the
that might pose threats in the demand to have every time the same final result. On the other hand, different printers, software, or curing
aligner quality. Briefly, the workflow of printed aligner manufacturing units currently available in the market could have a different effect on
includes 3D scanning, importing of the scans in a CAD software, where the finally printed aligner outcome in terms of their mechanical prop
setup and designing of the virtual aligners is performed, 3D printing erties, transparency, leaching, roughness, etc. For this reason, it is
using aligner resin, removing of the excess resin, and finally post essential to investigate what is the effect of using different printers on
printing curing of the aligners in order to give the aligner its final the final outcome. A recent study comparing the mechanical properties
properties. of directly printed aligners using five different 3D printers showed that
The last two years studies have been conducted to investigate many mechanical properties of 3D-printed orthodontic aligners are directly
aspects of directly printed aligners. One of the first available resins for dependent on the 3D printer used [36].
printed aligners that appeared in the market was made by Graphy As is well known, uncured resin (monomer/ oligomer) might exert
(Seoul, Korea), followed by 3Dresyns (Barcelona, Spain), Luxcreo possibly toxic and allergic side effects on human cells. It is possible that
(Luxmark, Belmont, USA) and Clear A (Senertek, Ismir, Turkey) . The incomplete post-printing cure can increase the chances of toxic or
first study concerning Graphy’s aligner resin investigated the properties allergic reactions to the patient and therefore, relevant studies on this
of printed aligners aged for one week of use in the mouth of patients issue should be carried out before such appliances see widespread use.
[27]. The results showed a non-significant decrease in all the mechanical Software for direct aligner printing resembles the ones for
properties of the aligners at the end of the week. Cytotoxicity and manufacturing of thermoformed aligners. The only difference is that the
estrogenicity are terms that are discussed in the community when it operator must design the virtual aligner on the 3D model that will be
comes to dental materials and units. In another study, no signs of later printed (Fig. 6). In addition, the operator must define the proper
cytotoxicity and estrogenicity were found in specimens of directly thickness and offset of the aligner, while in Deltaface (Coruo, Limoges,
printed aligners [28]. Leaching is similarly an important factor that can France) software there is an option, where the software detects the tooth
lead to problems with the appiance’s integrity and also to patient health movement prescribed in setup and adds more material on the opposite
hazards. In a recent study, urethane was detected in sets of printed side of the direction of tooth movement (from 0.1 mm to 0.9 mm ac
aligners [29]—even though the impact of urethane to humans is not cording to the operator’s wish) (Fig. 6). However, the usefulness of this
precisely known. Nevertheless, since aligners are the only appliances feature in achieving more predictable tooth movement needs to be
that are renewed every week, possible leaching phenomena of any clinically proven. Artificial intelligence (AI) is another feature that can
substance will be kept in constantly high levels in the patient’s mouth, be incorporated in such software to facilitate faster designing workflow
thereby creating potential health hazards to the patient. Roughness is at the steps of teeth segmentation and setup. In addition, a central
another property that should not be overlooked, especially in appliances server, where all the data will be gathered from multiple offices, can be
that are made of polymers. A study comparing Invisalign aligners and the center where AI analyzes and gives feedback to the orthodontist for
directly printed aligners revealed higher roughness values after one future aligner orthodontic treatment. Thus, more accurate and predict
week of wearing for the latter [30]. This could lead to easier aligner able results might be obtained with the help of big data analysis through
microfractures, loss of transparency, material leaching, and overall the use of AI.
deterioration of their mechanical properties. Nevertheless, the study
was done using the initial printed aligner manufacturing workflow and 2.10.2. Customized metallic appliances
this could have affected the final outcome. A new study with optimized CoCr is an alloy used for decades in dentistry for casting removable
protocols might have shown more favorable results for printed aligners. or fixed partial dentures. During the last decades, a novel 3D printing
Comparison of thermoformed and in-office directly printed aligners technology, called selective laser sintering, was introduced, allowing the
in terms of dimensional accuracy revealed higher accuracy for the latter, 3D printing of various metallic appliances in orthodontics. CoCr alloys
while there was also a 12% increase of the thickness and significant are used most of the time, while stainless steel, and titanium ones are
thickness decrease of thermoformed aligners. Due to the inconsistent
multistep procedure, which is prone to errors, a different workflow
configuration could present different results [31]. However, in another
study, printed aligners were found to apply a constant light force to the
teeth owing to their flexibility and viscoelastic properties [32]. The force
profile of printed aligners versus thermoformed was also studied from
another research team concluding that the forces delivered by printed
aligners in the vertical dimension were more consistent and of lower
magnitude compared to forces exerted from thermoformed ones [33].
Furthermore, a comparison of the mechanical properties between
printed and thermoformed aligners revealed a significant difference in
elastic modulus, ultimate tensile strength, and stress relaxation. In
addition, moisture of the simulated oral environment showed to have a
greater effect on the mechanical properties of the printed aligners
compared to the thermoformed ones, and this might affect printed
aligners’ ability to generate and maintain force levels appropriate for Fig. 6. Printed aligners are easily designed on the virtual model. Deltaface
tooth movement throughout their use [34]. software (Coruo, Limoges, France) offers the ability to increase the aligner
Increases in thickness of the directly printed aligners and their effect thickness on specific areas. This thickness increase is automatically added by
on tooth movement was investigated in a recent vitro study [35], which the software in places where movement of teeth is detected.
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also available but not used that often. Several companies have released customized orthodontic brackets. In both systems a 3D scanning is
in the market machines for metallic printing with different names and performed, which is then sent to the company to produce the customized
technology variations to manufacture metallic objects. However, their brackets. Such online CAD software enables the orthodontist to create a
big plethora and potentially hazardous materials used in the printing virtual setup, where customized brackets are designed, approved by the
procedure do not allow their installation in the average orthodontic orthodontist, and then printed by the company.
office. The development of this technology allowed the shift from the The evolution of 3D-technologies and competition between manu
manual designing and manufacturing of orthodontic appliances to a facturers enabled the development of faster, more accurate, and cheaper
digital one. Both techniques, analogue and digital, possess advantages 3D printers. New materials were invented and introduced to the market,
and disadvantages which should be taken into consideration when with CAD software being an integral part in the appliances’ design. The
manufacturing orthodontic appliances. Designing orthodontic appli last years, many orthodontic offices have installed all the necessary units
ances can be performed using dedicated CAD software such as 3Shape for designing and 3D printing, thus creating small digital laboratories of
ortho system software (3Shape, Copenhagen, Denmark), OnyxCeph their own and thermoformed or directly printed aligners, occlusal
(Chemnitz, Germany), Deltaface (Coruo, Limoges, France), etc. For the splints, indirect bonding trays, and dental models are nowadays often
skilled designing personnel, professional engineering CAD software manufactured within the orthodontic office.
(Meshmixer, Blender, etc) can also be used to design appliances. How Nevertheless, orthodontic treatment is mainly based on fixed appli
ever, the bigger disadvantage of CoCr alloys is the almost complete lack ances, the orthodontic brackets, which up to now could not be
of flexibility of the appliances. 3D-printed bands are rigid compared to adequately manufactured in the orthodontic office. 3D technology ad
commercially-available bands and cannot pass the maximum circum vancements enable the orthodontic office to become a small lab that can
ference of the molars, thereby creating retention problems. Several or print customized orthodontic brackets. Novel software called Ubrackets
thodontic appliances can be designed and printed such as maxillary- (Coruo, Limoges, France) enables the orthodontist to perform a digital
expanders, lingual arches, and distalizers (Fig. 7). Nevertheless, many setup of imported dental scans and automatically design customized
times an orthodontic technician must manually add pre-fabricated parts orthodontic brackets together with their customized archwires [24]. The
such as expander-screws, springs, or other parts for molar distalization, workflow of manufacturing customized brackets can be divided into the
because these cannot be printed. The behavior of CoCr alloy was eval designing and the printing part. At the designing part the operator
uated in a study examining CoCr-based orthodontic appliances placed separates the teeth from the gingiva in a stage called segmentation to
for 6 months in the oral environment. The results showed that intraoral perform the setup of the dental arches. At the next step the orthodontist
ageing did not influence the mechanical properties of the appliances, but chooses to design labial or lingual customized brackets which will be
the appliance showed degradation in the breakdown potential of the later printed. Following that, the brackets are automatically positioned
protective oxide layer, which results in pitting corrosion. Thus, it is on a flat rectangular archwire opposite the teeth’s surfaces and with
possible that Cobalt may be released in the patient’s mouth [37] and this special manipulators the operator positions the brackets on the desired
might be potentially detrimental to the patient’s health. place creating customized brackets where their bases are adapted to the
tooth surfaces (Fig. 8). The next step is to design indirect bonding trays
2.10.3. Customized orthodontic brackets or positioning keys for each bracket which will help the orthodontist
After introduction of the original Edgewise appliance by E.H. Angle bond them in an accurate way, and which should be easily removed after
[38], the development of the straight-wire appliance [39] was in fact the bonding. Customized archwires can also be exported as 3D files for an
first attempt to create customized orthodontic appliance (even if it was archwire bending robot or in a electronic drawing for manual plier
tailored simply to the average patient). A real need for completely bending. Maybe the most important issue to be solved is the material
customized brackets appeared when lingual orthodontic appliances that will be used to create the customized brackets. In the orthodontist’s
were introduced, due to the unique nature of the lingual surfaces of the armamentarium several printers can be found together with specialized
teeth. The following years, customized lingual appliances played a big software to solve the problem of designing and printing. Nevertheless,
role in orthodontic treatment, offering adequately predictable results, the key to creating good-quality brackets for orthodontic treatment is
even for difficult cases. the material. Attempts have been made to print customized brackets
It wasn’t until a few years ago that Ormco (Orange, Calif, USA) using hybrid ceramic permanent crown resins (Fig. 9), while the first
created its own series of labial customized brackets, while LightForce study to compare two resins, normally used for temporary and perma
(Burlington, Massach, USA) introduced its polycrystalline 3D-printed nent crown resins, to print brackets was published a few years ago [40].
The study concluded that there was no significant difference between
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T. Eliades et al. Japanese Dental Science Review 59 (2023) 403–411
Fig. 9. The picture presents the first attempt to print customized brackets using
permanent hybrid ceramic crown resin. Positioning keys placed on the teeth
cusps and incisal edges were designed in Ubrackets in order to facilitate ac
curate bonding.
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