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Polymer Chemistry

REVIEW

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Advances in polymeric materials for dental applications
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a,# b,# a b a
Received 00th January 20xx, Xinyuan Xu, Libang He, Bengao Zhu, Jiyao Li, Jianshu Li *
Accepted 00th January 20xx Over the past decade, polymeric materials for clinical dental applications have been developed with excellent properties
DOI: 10.1039/x0xx00000x and various functionalities. This review outlines the present understanding and design of polymeric dental materials based
on structure-property-function relationships. First, the chemistry/microstructure of polymeric materials will be reviewed.
www.rsc.org/ Then, the resultant properties such as mechanical, thermal, visco-elastic, and water solution properties, as well as
additional bio-functionalities such as antibacterial capabilities, remineralization, and bioactive -delivery properties, will be
reviewed for specific dental applications. Finally, perspectives and challenges regarding the rational design and application
of polymeric dental materials will be discussed.
impressions; and tissue-regenerative materials focus more directly
on in situ tissue regeneration and controlled delivery (Fig.1).

1. Introduction
In normal physiological activity, the soft and hard tissues of the
human oromaxillo-facial region are likely to become defective or
lost due to congenital disease, trauma, and biological degradation.
These deficiencies reduce the natural functions and aesthetics of
the soft/hard dental tissue. Hence, it is necessary to treat these
deficiencies. Dental materials have a very long history, beginning
with the Romans using gold for dental crowns and bridge
restorations. Since then, various metal and ceramic materials have
been researched and applied in dentistry, as well as vulcanized
rubber and celluloid that were made into denture bases in the
1860s. A synthetic polymer was first used in the field of oral
medicine in 1937, with the development of poly(methacrylic acid).
Polymers have aroused a vast and increasing interest in oral
medicine due to their excellent biocompatibility, satisfactory
mechanical properties, and processability. Polymers can be divided
into two classes, depending on their source: natural or synthetic.
The former includes chitosan, collagen, fibrin, and agar, while the
latter consists mainly of acrylic resin and its derivatives,
Fig.1 Schematic illustration of advanced polymeric materials in
polyetheretherketone (PEEK), dendrimer, polylactic acid, etc. In
dental applications. The center represents the two common
addition, polymers can be classified into restoration materials,
diseases in dentistry, and the surrounding figures describe different
accessory materials, tissue regeneration materials, etc., on the basis
devices, technologies and related materials in clinical setting or in
of their applications. Restoration materials are defined as materials
development. (Reproduced from ref. 24, copyright 2016, with
directly used for fabricating restorations and their applications in
permission from American Chemical Society; Reproduced from ref.
dentistry include composite resin restoration, soft/hard prostheses,
115, copyright 2015, with permission from Elsevier Ltd; Reproduced
and dental implants; accessory materials are used for supporting
from ref. 123, copyright 2013, with permission from Elsevier Ltd;
fabrication of restorations for indirect restorations, such as
Reproduced from ref. 144, copyright 2011, with permission from
Elsevier Ltd; Reproduced from ref. 155, copyright 2015, with
a
permission from American Chemical Society; Reproduced from ref.
College of Polymer Science and Engineering, State Key Laboratory of Polymer
Materials Engineering, Sichuan University, Chengdu, 610065, China. Fax:
157, copyright 2015, with permission from Nature Publishing Group;
86-28-85405402. E-mail: jianshu_li@scu.edu.cn (JS. Li). Reproduced from ref. 163, copyright 2010, with permission from
b
State Key Laboratory of Oral Diseases, West China Hospital of Stomatology, Elsevier Ltd).
Sichuan University, Chengdu, 610041, China.
#
These authors contributed equally to this work.

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Fig.2 The chemical structures of main polymeric materials described in this review.
Nowadays, new treatment concepts and higher clinical demands carbohydrates, while other dental diseases are caused by fungal
2, 3
are compelling the development of novel materials with excellent infection, such as Candida-associated denture stomatitis (CADS).
properties and techniques with high efficiency and accuracy to Therefore, enhancing antibacterial properties is very important for
improve the treatment of dental diseases. Minimally invasive most dental materials, such as the conventional acrylic resin-based
dentistry emphasizes the preservation of healthy, natural tooth dentures, composite resin, and adhesives. In order to improve the
1
structure as much as possible. In particular, caries control is closely antibacterial properties, an admixture of an antibacterial agent and
4,5
related to this concept, which includes early diagnosis, prevention, a surface modification are in process. In addition to the
and direct composite resin repair. The formation of dental caries is enhancement of antibacterial properties, the regeneration of
connected with acid-producing bacteria and fermentable hard/soft tissues has become another goal for dental materials.

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Polymers can induce in situ regeneration, not only through the This review focuses on the relationships between the structures
materials inherent properties, but also via the bioactive factors and properties of various polymers for different applications in
delivered from the materials. For instance, dendrimer, which is a dentistry.
class of three-dimensional highly symmetrical monodisperse
macromolecular compounds, can form in situ remineralization layer
6-8
on the surface of enamel and dentin. A poly(lactic-co-glycolic acid) 2. General requirements of polymeric dental
(PLGA) scaffold combined with tricalcium phosphate (TCP) is also materials
reported to be appropriate for the proliferation and differentiation
9 For polymeric dental materials, there are different performance
of cells and generates dentin- and pulp-like tissues.
requirements for specific applications, but the fundamental
Natural polymeric materials, including polysaccharide derivatives

Polymer Chemistry Accepted Manuscript


principle of biomaterials is consistent: excellent biocompatibility
(chitosan and cellulose) and protein derivatives (collagen and fibrin),
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and biological safety, coupled with appropriate biomechanical


also have wide applications in dentistry. There are several main
properties. The chemical structure of a polymer determines its
aspects: antibacterial properties, tissue engineering, drug delivery,
properties, and the properties are closely related to the clinical
etc. Chitosan is one of the most common used antibacterial natural
applications. Hence, to better understand the dental application of
polymers. It can also be used to fabricate tissue engineering
polymers, this review first explains the relation between structure
scaffold and release drugs. Le et al. demonstrated that low
and property. The chemical structures of the main materials
molecular weight chitosan nanoparticles had high antimicrobial
10 described in this review are shown in Fig. 2. Polyetheretherketone
effect. Kim et al. fabricated an alendronate-loaded chitosan
(PEEK), for example, is a high-performance thermoplastic polymer
scaffold to release alendronate to enhance osteoblast functions and
11 consisting of an aromatic backbone molecular chain, and is
inhibit osteoclast differentiation in vitro. Natural antimicrobial
interconnected by ketone and ether functional groups. It is the
agents can avoid side effects of many synthetic antimicrobial
12 structure that determines PEEKs excellent inherent performance,
agents. Cellulose, collagen, and fibrin are mainly used for tissue
such as its mechanical properties and its environmental stability.
engineering. Chatzistavrou et al. prepared collagen/fibrin
The combined structure of the rigid benzene ring and a flexible
microbeads containing silver doped bioactive glass (Ag-BG) and
ether linkage results in a broad range of mechanical behavior from
dental pulp stem cells (DPSCs), which were incorporated and
13 which to choose; in particular, its lower Youngs modulus is similar
proliferated within the microbeads.
to that for human bone. Meanwhile, the mechanical properties are
Excellent dental devices not only need satisfactory materials, but
influenced by synthetic processes and physical form. In addition,
also require precision manufacturing technology. Recently,
PEEK has good biocompatibility and compatibility with other
computer-aided design and computer-aided manufacturing
reinforcing materials, making for safer and more effective materials
(CAD/CAM) techniques and 3D-printing technology have aroused
in dental implants and denture prostheses.17 However, the opacity
interest for those working in the field of dentistry. Although a
and color prevent the use of PEEK fillings or crowns. The verneering
dental CAD/CAM system was applied in fabricating crowns and
resin is necessary for its potential application as a crown.18, 19
bridges with ceramics or metals in the early 1970s, only in the last
The polymerization methods of a polymer also affect its final
several years have polymer been used in CAD/CAM, due to the prior
14 properties. For instance, silicone synthesized by condensation
limitations of polymer properties. In contrast to the CAD/CAM
polymerization or addition polymerization defines a class of
technique, 3D-printing technology is fairly new. Polymers are more
synthetic elastomers with a molecular chain composed of
suitable as 3D-printing materials because they have excellent
alternating silicon and oxygen atom (-Si-O-Si-).20
versatility associated with in situ photo-polymerization, as well as a
Condensation-cured silicone is easy to use and can solidify directly
variety of preformed processable types, even though metals and
15 in the mouth. Compared to condensation-cured silicone,
ceramics can be used with 3D-printing technology. Further
addition-cured silicone dose not leak small molecules in the curing
descriptions and applications about both techniques will be
process and it possesses better dimensional stability. But the two
discussed later.
silicones both have inferior mechanical properties and bonding
Tissue engineering has received widespread attention for its in
strength, requiring further modifications.21 Additionally, the
situ regeneration capability. Tissue engineering includes three parts:
polymerization method has a considerable relation with the rate of
cells, growth factors and scaffolds. Polymers are mainly used for
monomer-polymer conversion.22 Composite restorative materials
fabricating scaffolds. Taking a PLGA scaffold as an example, Chen et
are polymerized by radical-mediated chain-growth, which is
al. fabricated three materials, aligned PLGA/Gelatin electrospun
incredible utility, but has an obvious volume reduction. Novel
sheet (APES), treated dentin matrix (TDM) and native dental pulp
polymerization mechanisms, including cationic polymerization,
extracellular matrix (DPEM) and combined them into three
ring-opening reaction, and step reaction, are beneficial to reduce
composites, APES/TDM, DPEM/TDM and APES/TDM/DPEM, aiming
the polymerization shrinkage. For example, restorative composites
to simulate an extracellular matrix for tooth root regeneration. The
with a specific methacrylate monomers, which can occur
results showed that both APES/TDM and DPEM/TDM facilitated the
phase-separation at high conversions, have low volume shrinkage
odontogenic differentiation of dental stem cells in vitro, while
but high conversions. Ring-opening polymerization have a nature
APES/TDM/DPEM generated tooth root-like tissues in vivo. All of
advantage over tradition photopolymerization because cyclic
the results indicated that APES and DPEM, when combined with
structures induce significantly less volume shrinkage when rings are
TDM, exhibited appropriate physicochemical properties and
16
biocompatibility, thus meeting the primary aim.

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opened. Another two polymerization mechanisms, thiol-ene can be used as coating to improve a metal materials antibacterial
polymerization and hybrid polymerization, also have great results. properties. For instance, chitosan can be used as coating for
implants due to its benefical drug delivery and antibacterial
properties. A methacrylic thermosets coated with silver-chitosan
nanocomposite can effectively kill both Gram+ and Gram- bacterial
strains, and the material does not have any significant cytotoxic
29
effects.
Other functions like fracture resistance and in situ regeneration
are also important, And they have similar modified approaches:
additives and surface modification. The additives used for

Polymer Chemistry Accepted Manuscript


enhancing physical and mechanical properties (polymerization
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shrinkage, linear expansion coefficient, water adsorption, tensile


strength, and viscidity) are called reinforcing fillers, which include
various types with different size (macro, micro, nano), shape
(particle, fiber, cluster), and component (glass, silicone, carbon).30, 31
The types, dosage, size, and shape of the filler should be taken into
Fig.3 General anticaries strategy using multiagents containing account for the final property. Nanofiller especially represents the
dental composite materials (Reproduced from ref. 24, copyright state-of-the-art in terms of filler formulation.32, 33 Uyar and Ben
2016, with permission from American Chemical Society). investigated the reinforcement effect of electrospun
polyvinylalcohol (PVA) nanofiber fillers and alumina whiskers for
Although materials properties have been greatly improved PMMA, respectively.34,35 Both reported improved mechanical
recently, there are several clinical problems that need to be solved properties of PMMA with the fillers. Besides the admixture of a
and higher functional requirements that need to be meet. The most single filler, the hybrid effect of multi-filllers is deserving of further
important function is that of antibacterial properties. Antibacterial exploration. When using reinforcing fillers, the strength of the bond
properties are very important for most polymeric dental materials between the composites and the fillers is still important, because
for three main reasons:23 The first reason is that the oral cavity is a it affects the abrasion resistance of the restorative composites. To
complex environment, rich in a variety of microorganisms; second, meet the demand, it is essential to silanize the fillers, called the
polymer tend to adsorb microorganisms because they can provide a silane coupling agent.36
source of carbon and oxygen; finally, microorganisms adsorbed on Another kind of additive can be added for improving a materials
the surface of materials might lead to certain diseases. (e.g., bioactivity, such as Ag nanoparticles for antibacterial properties,
cariogenic bacteria causes caries or secondary caries; Candida and TiO2 and hydroxyapatite (HA) for biocompatibility and cell
albicans causes periodontal inflammation). In order to improve interaction. TiO2, which is the main component of a Ti surface,
antibacterial properties, there are two routes: admixture of results in the exceptional anticorrosive and biocompatibility
antibacterial agents and surface modification . Antibacterial agents properties of Ti and the Ti alloy. It is reported that TiO2
include quaternary ammonium salt (QAMs), Ag nanoparticles, nanoparticles have a higher bioactivity than conventional partical
antibiotic and antibacterial drugs, etc., furthermore, using sizes because of the better dispersion of the former. N-TiO2/PEEK
multi-addition in a system become a trend. Melo et al.24 introduced composites showed more cell attachment and a higher percent of
multiagents, such as silver nanoparticles (NAg), amorphpus calcium bone volume value than pure PEEK, and the composites possess
phosphate nanoparticles (NACP), and dimethylaminohexadecyl great bioactivity, especially if they have a rough composite
methacrylate (DHAHAD), a kind of quaternary ammonium salt, into surface.37 HA is a constituent of living bone and teeth, and is
dental composite resin for reducing biofilm viability and improving considered to be a superb promoter for osteogenic differentiation
resistance to mechanical and acidic challenges (Fig. 3). Neverthless, of bone cells. To enhance bone regeneration, the porous collagen
some papers demonstrated that antibacterial agents may have side fibrils with nanometer-sized apatide hydroxyapatite (Col/HA)
effects, such as the water absorption increased with rising composite and Col/HA infused with polyethylene glycol hydrogel
concentration of QAMs and the toxicological properties of (Col/HA/PEG-hydrogel) were synthesised, and both scaffolds were
nanoparticles.25, 26 Surface modifications focus on the change of used to deliver non-glycosylated bone morphogenetic protein-2
roughness, hydrophobic and hydrophilic properties, and interface (BMP-2). The results showed that the Col/HA/PEG-hydrogel scaffold
energy by physical, chemical or mechanical methods.5 The initial was the most successful one in vivo.38
adhesion of microorganisms is associated with surface roughness Surface modification can be divided to two categories: direct
(Ra) and surface free energy (SFE). Reduced Ra and SFE are not surface modification and deposition methods, the latter introduces
beneficial for the attachment of microorganisms.27 Polishing and new material coating.39 Every category still can be divided to more
coating with a protective layer are typical clinical approaches to detailed types by different theories. In all these methods, the
reducing surface roughness. Trimethylchitosan (TMC) and sodium frequently used ones are plasm treatment, laser treatment, coating
alginate (SA) are coated onto the MMA-grafted PMMA via of hydroxyapatite or titanium or TiO2. Wakelin et al. utilized plasma
layer-by-layer self-assembly. The TMC/SA multilayer significantly immersion ion implantation (PIII) to modify the surface properties
40
reduces fungal adhesion due to the hydrophilicity of the surface and of PEEK. The treated surface layer had a higher value of Youngs
28
the antifungal activity of TMC. Otherwise, antibacterial polymers modulus and elastic recovery without compromising the bioactivity.

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Furthermore, surface treatments activated the PEEK surface and properties of composites, like radiopacity, abrasion resistance,
improved its bioactivity. Because the surface of PEEK is hydrophobic, intrinsic surface roughness, flexural modulus, coefficient of thermal
enhancing its wettability is important for improving cell interaction. expansion, and translucency. Fillers have been briefly reviewed in
There are a lot of papers on enhancing osteoblast responses by the previous section, but more contents can be found in other
32, 33, 45
many different direct surface modifications, leading to a positive papers. Polymerization efficiency is an important target for
influence on the cell adhesion, proliferation and metabolic activity composite resins, and polymerization efficiency is related to their
41-43
compared to the pristine PEEK. mechanical and physical properties, especially shrinkage and depth
51
of cure. Furthermore, the novel composites tend to increase the
3. Polymeric materials for dental applications depth of cure and reduce polymerization shrinkage stress.
Conventional composites have the highest thickness of 2 mm, while

Polymer Chemistry Accepted Manuscript


the bulk-fill resins enable increments of up to 4 mm to be
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3.1 Resin composite and adhesives materials


adequately cured. And bulk-fill resins have lower polymerization
Resin composite and adhesive systems have been widely used for 52, 53
shrinkage stress than traditional resin composites. Two
dental restoration due to their versatile properties, such as a fast
modifications can increase the penetration of visible light through
and on-demand setting processes, elastic quality, safety, and
materials. The first method is decreasing the filler content and
adequate mechanical properties. Adhesives, which include 54
increasing the filler size. The second method is novel
monomers, initiators, stabilizers, fillers and sometimes other 55
photoinitiators. Conventional resin composites are cured by using
additives, are designed to bond composite resins to enamel and
31 visible light photoinitiators, which is mainly camphorquinone/
dentin. Composites, which have the same component with
44 amines system (such as, CQ/DMAEMA). However, It has been
adhesives, are used to replace missing biological tissue. Moszner
demonstrated that the photo initiators will affect the mechanical
and Hirt articulated the new polymer-chemical developments of 56-59
properties and the color, and amines also have toxicity. Thus,
adhesives and composites, and future trends using new
45 amine-free photoinitiators (e.g. phosphine oxide and
components and procedures in exquisite detail. This section 55
benzoylgermanium derivatives) have been synthesized. Polymer
briefly introduces chemistry of adhesives and composites, advances
shrinkage reduces the dimensional stability of the restorative
in methacrylate monomers and photo-cure system, and
materials, thus it is not good for clinical use. Cramer et al. reviewed
modification on some clinical problem of adhesives and composites.
the effect of photoinitiator, methacrylate monomer, polymerization
The main component of adhesives and composites is the monomers, 22
method, and fillers for polymer shrinkage. In addition, a lot of
which are mostly methacrylate and its derivatives. Adhesives act as
papers in the last five years have reported some new monomers
the bridge to connect enamel/dentin and restorative composites,
and additions for improving the properties of resin composites.
which need to withstand mechanical forces and prevent leakage on
Dendritic compounds as alternative materials of conventional
the shrinkage of the restoration. Monomers in adhesives contain
resin-based restorative materials have been widely studied.
non-acidic functionalized monomers, acidic-functionalized
Compared to Bis-GMA-based resin, the resin with G-IEAM has a
monomers, and crosslink monomers. For example, hydroxyethyl
higher conversion rate, comparable or lower polymerization
methacrylate (HEMA) is used not only to ensure good wetting, but
shrinkage, water sorption, and lower water solubility. It also has
also improve the stability of solutions containing hydrophobic and
46 higher fracture toughness due to its higher fracture energies and
hydrophilic components. Methacryloyloxydecyl dihydrogen 60
plastic deformation prior to fracture. Polyhedral oligomeric
phosphate (MDP), one of the common acidic functionalized
silsesquioxane (POSS) is a nanocage consisting of an inner inorganic
monomethacrylates, can etch the enamel surface and bond with
47 framework of silicon and oxygen atoms, and an outer shell of
other methacrylate monomer. In addition, with the development
organic functional groups, which can be used for enhancing
of adhesive techniques, one-step self-etching adhesives are
mechanical properties and reducing the polymer shrinkage rate
prepared by adding acidic functional monomers into the system, 61, 62
(Fig. 4).
and achieve the function of conditioner, primer, and adhesive resin
Apart from mechanical and physical properties, antibacterial
in a single step, which obviously simplify the operation and lowering
properties, which are relate to secondary caries, are hopeful to be
technique sensitivity. 63
further improved. Quaternary ammonium monomers (QAMs)
Resin composites mainly imitate the appearance and functions of
with a double bond can react with resin monomers by
tooth hard tissue; therefore, resin composites should possess great
photopolymerization to build a cross-linked network structure,
optical and mechanical properties, such as wear resistance,
30 which is beneficial to maintain the resins mechanical properties
strength, and toughness. Monomers used for composites include
and increase its antibacterial properties. Longer chain length and
crosslinker, diluents, and functionalized monomers. Such as,
higher charge density of QAMs make for better antibacterial
bisphenol A-diglycidyl methacrylate (Bis-GMA), are used to provide 64, 65
capability within a certain range. Furthermore, an admixture of
mechanical properties in resin composites by forming densely
48 more than one filler is a universal approach to improving the
cross-linked polymeric networks.
performance of resin composites. Incorporation of QAMs and
Triethylene glycol dimethacrylate (TEGDMA), and urethane
nanoparticles, like nanosilver particles (NAg) or nanoparticles of
dimethacrylate (UDMA) are added as diluents, which all have a
49, 50 amorphous calcium phosphate (NACP), into resin composites
higher flexibility than Bis-GMA due to their long alkyl chain.
provides better performance than the pure QAM-containing
Compared to adhesives, composites have another important 66, 67
composites. Zhang et al. combined 2-methacryloyloxyethyl
component, fillers, which have a close relationship with the
phosphorylcholine (MPC) with dental composite and demonstrated

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that a composite with 3% MPC by mass can effectively reduce conduction of the artificial tooth, disperse occlusal forces and
protein adsorption and bacteria attachment, without compromising connect all parts of the denture into a whole. Reliner, which
68
mechanical properties. But all the antibacterial restorative improves the vertical dimension of the denture, resulting in a higher
materials just are used in laboratory due to their several side effcts retention of the denture, includes a soft denture liner and a hard
and expensive cost. The clinical products used for patients still need denture liner; the difference in the two devices is in the elasticity of
to be developed. the materials and clinical applicability. The most common polymer
for fabricating dentures is acrylic resin and its composites with
other additives like reinforcing filler, initiator, and pigment. The soft
denture-lining material most used is silicone as a substitute for
acrylic resins because of their instability in an oral environment.

Polymer Chemistry Accepted Manuscript


Crowns and fixed dental prostheses (FDPs) are mainly made of
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ceramic or composite resin, and the use of PEEK for these devices is
in process. However, the application of PEEK as FDPs is limited by its
grayish or whitish color and its low translucency.72 Dental veneer is
used to cover the shortage, but another difficulty occurs in the
adhesion between PEEK and veneering due to PEEKs low surface
energy. Some papers have reported that surface pre-treatment and
the application of an adhesive system are possible for enhancing
the binding strength of PEEK on the veneering layer. 72-74 Hence,
PEEK can be used under resin-composite as a coping materials/core.
Fig. 4 G-IEMA and POSS for dental applications (Reproduced from Dentures have several common requirements, such as
ref. 60, copyright 2014, with permission from Elsevier Ltd; satisfactory fracture resistance, excellent antibacterial property,
Reproduced from ref. 62, copyright 2005, with permission from radiodensity, and high color stability. Polymethyl methacrylate
Elsevier Ltd). (PMMA), the primary family of acrylic resins, has many virtues, such
as satisfying aesthetics, ease of laboratory and clinical
3.2 Prostheses/implant materials manipulation, favorable working characteristics, accurate fit,
Prostheses in dentistry are simply divided into dentures and stability in an oral environment, and efficient equipment
maxillofacial prostheses. The former, also known as false teeth, are demands.75 However, PMMA as a denture basis still have clinical
prosthetic devices constructed to replace missing teeth; they are problems of fracture and inflammation caused by the degradation
supported by the surrounding soft and hard tissues of the oral of materials and/or adhesion of micro-organism.76, 77 There are
cavity. The latter are used to repair the maxillofacial tissues defect three routes which have been investigated to improve the
and loss adopting the principle and method of denture restoration. performances of PMMA: the optimization of chemical structure, the
Prostheses have two retain method: implant-retained prostheses admixture with fillers, and alternative materials such as polyamide.
and adhesive-retained prostheses. Implants are usually made of The chemical modification through modifying the packing and
metal, and recently PEEK as a new implant material has been processing technique and copolymerization with several monomers
researched. Compared to adhesive for composite resin, the can achieve improvement of the mechanical properties.78, 79 Various
adhesive for metal and ceramic have more fillers and higher fillers possess of different functions. Reinforcement filler, such as
strength. The most common and effective adhesive is inorganic oxides and nanoparticles, is mixed with PMMA resin to
resin-modified glass-ionomer cement (RM-GIC). The other cements improve flexural strength and impact strength without
include zinc phosphate, polycarboxylate, and glass ionomer.
69 compromising other mechanical properties.80 Silver, zinc oxide, and
RM-GIC are hybrid, dual-phase materials, which contain the resin quaternary ammonium salt are famous for their excellent antibiotic
phase (an aqueous solution of polyalkenoic acids modified with properties, despite differing mechanisms. The results from various
pendant methacrylate groups) and the glass inomer phase research efforts show the composites with these additives have a
(fluoroaluminosilicate glass powder). The former polymerizes significant reduction of adhesion of microorganisms.81-83 Moreover,
quickly either by chemical or photoinitiation, while the latter surface reaction-type pre-reacted glass ionomer (S-PRG) filler
proceeds slowly toward normal maturation via an acid-base formed by an acid-base reaction of fluoroalumino-silicate glass with
reaction over an extended period of time. Some papers have polyacrylic acid is introduced to the PMMA matrix, which can
demonstrated that RM-GIC have high strength and chemical prevent dental plaque formation due to its ability to induce
bonding force, similar shrinkage with tooth, and no sensitization. mineralization.84 However, it is a great challenge to balance the
Additionally, RM-GIC can prevent caries through releasing performance of both fracture resistance and antibacterial
70, 71 properties, which still need to be further explored. Apart from
fluorine.
Dentures include removable dentures (partial removable conventional heat-polymerized PMMA resins, there are
dentures and complete dentures), fixed partial dentures (also injection-molded thermoplastic denture base resins, including
85
known as crown and bridge) and dental implants. Removable polyamide, polycarbonate and polyester materials. As the most
dentures are usually composed of three parts: the denture base, common material, polyamide has a better fracture resistance than
reliner, and crown. The denture base covers the alveolar ridge and PMMA but its other mechanical and thermal properties are inferior
hard palate in the edentulous area, which provide adhesion and to standard PMMA materials. Polyamide has excellent aesthetic

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properties, and is referred to as invisible dentures; however, it is stabillity. The materials used as maxillofacial prostheses to date
susceptible to discoloration. Furthermore, the chewing efficiency include acrylic resin and its composite, polyvinyl chloride and its
and occlusal forces of dentures made of polyamide are low because copolymers, chlorinated polyethylene, polyurethane, silicone and
104
of its lower modulus of elasticity. In general, polyamide may be a polyphosphazene. Silicone elastomer is currently the best
potential material as an alternative to denture bases, but will material available for maxillofacial prostheses. However, the
86-90
require modification to achieve better properties. longevity of silicone facial prostheses is 6-12 months due to
Silicone-based soft liners are susceptible to accumulating more discoloration or wear, which are related to the outdoor
105,106
microbes on their surface since their porous surfaces may promote weather. Matching the color of a prosthesis to human tissue
the adhesion of yeasts and the diffusion of yeast nutrients into the plays a key role in fabricating a successful maxillofacial prosthesis.
materials. Once this occurs, biofilm will develop into candidiasis, a Both intrinsic and extrinsic dyeing are feasible; however, the

Polymer Chemistry Accepted Manuscript


91, 92
significant clinical oral disease. Some studies have indicated addition of pigments or opacifier influences the mechanical
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107, 108
that the surface characteristics influence the adhesion of Candidia properties of silicone. A better method for color stability
albicans to denture lining materials.93 Chladek et al. added various should be researched.
amounts of silver nanoparticles (AgNPs) into soft liner materials;
the results showed that the antifungal efficacy increased with the
increase in the AgNP concentration, and the highest antifungal
efficacy was 52.2% at the AgNP concentration of 200 ppm.94 Garner
et al. synthesized antifungal dental silicones coated by
chlorhexidine-containing nanoparticles (CHX-NPs). CHX-NPs provide
the silicone surface with an effective antifungal capability without
compromising hydrophilicity by releasing low but clinically relevant
concentrations of chlorhexidine.95
Fiber-reinforced composite (FRC) have been used as posts for
endodontic treatment, however, its limited surface polishability
prevents its other applications such as crowns, inlay or fillings. The
FRC post has one prominent advantage over metal posts: its
stiffness property is close to that of dentin, while metal has around
10-17 times higher stiffness than dentin. The modulus mismatch Fig. 5 The preparation of glass fiber dental posts by pultrusion
between the dentin and the post can cause a stress concentration (Reproduced from ref. 101, copyright 2016, with permission from
at the root of the teeth.96 Madfa et al. demonstrated through the Elsevier Ltd).
finite element method that the carbon and glass fiber posts
reduced the stress distribution around the post when compared Dental implants are a type of restoration approach for missing
with the metal posts.97 In addition, aesthetics, lack of metal-based teeth that supports or fixes the upper dental restoration on the
allergies, corrosion resistance, and ease of handing are advantages basis of the lower part implanted in the bone tissue. The implant is
of FRC post. The component of the FRC post and the interface usually fabricated by metal materials. Recently, scientists found that
between the fiber and matrix influence the performance of the FRC PEEK modified through surface treatment or filler reinforcement can
post. The most common types of fiber are glass and carbon, while be used as dental implants. However, pure PEEK causes marginal
for matrixes, composite resin and epoxy are the most common.98 bone loss around the dental implants, a process termed stress
For flexural strength, the fibers aspect ratio is more important than shielding, due to the shielding of normal loads by the implant.109
volume loading, and short and very short glass fibers can Also, PEEK is bioinert and has inferior osteoconduction. It is
significantly reinforce the flowable dental composite.99 Lassila et al. important for successful bone regeneration that implants own
demonstrated that the use of different length scales of osseointegration, meaning integration of implants with the
discontinuous fiber fillers with a resin matrix improved mechanical surrounding bone. Hence, it is necessary to endow PEEK with
performance like fracture toughness and flexural strength.100 Fibers biomechanical and bioactive properties.110 The mechanical
mixed with matrix are pre-treated by a silane coupling agent and properties will change with the addition of fillers. The PEEK
FRC post is fabricated by pultrusion (Fig. 5).101 Using reinforced with 30% continuous carbon fibers by mass had a higher
high-performance poly-p-phenylene-2,6-benzobisoxazole (PBO) value of elastic modulus, elastic limit, and pressure strength than
fiber, which possesses a thermal stability, and specific tensile the specimens with TiO2.111 Schwitalla et al.112 evaluted the
stiffness and strength, provides a new avenue for intracanal post biomechanical behavior of a dental implant of carbon fiber
material.102 Almaroof et al. also developed a new intracanal post reinforced (CFR)-PEEK, a commercial powder-filled PEEK, and
made up of silanated hydroxyapatite (HA) and zirconium dioxide titanium, utilizing the present finite element analysis (FEA). All three
(ZrO2) filled low-density polyethylene (LDPE) composites.103 materials showed a minimum in safety factors regarding the yield
A maxillofacial prosthesis is used to repair missing facial parts strength of cortical bone and similar stress distributions. Otherwise,
which have been lost due to ablative surgery, congenital deformity, PEEK/CFR-PEEK coated with titanium and hydroxyapatite have great
113
or trauma. Desired maxillofacial prosthetic materials should have osteoconductive or osteoinductive properties. Simple PEEK/HA
long-term excellent physical/mechanical properties and biological binary mixtures showed better biocompatibility but a reduced
114
propertieslike high tensile strength, tear resistance, and color ultimate tensile strength, and a decreased fatigue limit. Hence, a

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new ternary composite may be helpful to biomechanics and electrostatic force and size exclusion effect, capture and stabilize
bioactivity. As shown in Fig. 6, Deng et al. fabricated a the metastable amorphous calcium phosphate (ACP)
polyetheretherketone/nano-hydroxyapatite/carbon ber nanoprecursors to promote the formation of intrafibrillar
(PEEK/n-HA/CF) composite, and the results showed that adhesion, mineralization, and finally form intrafibrillar mineralization along
123
proliferation and osteogenic differentiation of cells, as well as the the microfibrils. (Fig. 7) To enhance the binding strength at the
115
mechanical properties were greatly enhanced. remineralization layers, carboxyl-terminated poly(amido amine)
alendronate conjugate (ALN-PAMAM-COOH) was synthesized and
124
characterized. Phosphate-terminated dendrimer
(PAMAM-PO3H2) was also reported to tightly adsorb on the human
tooth enamel and dentin, and generated a thick HA layer of 11.23

Polymer Chemistry Accepted Manuscript


125, 126
m. Furthermore, some research obtained multifunctional
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dental materials with both remineralization and antibacterial


properties. For example, triclosan-loaded PAMAM-COOH was
prepared, which can not only induce in situ remineralization, but
can also release tricolosan for a long period.127 Zhang et al. reported
a peptide-conjugated oligomeric proanthocyanidins bioinspired
from salivary-acquired pellicles. This material can induce the in situ
Fig.6 The preparation and biological evalution of PEEK/n-HA/CF remineralization of enamel and resist bacterial at the same time.128
biocomposite (Reproduced from ref. 115, copyright 2015, with
permission from Elsevier Ltd).

3.3 Remineralization materials


Dental caries is caused by the acid produced by bacterial action on
dietary fermentable carbohydrates that diffuse into the tooth and
dissolve the carbonated hydroxyapatite mineral, a process called
demineralization. Remineralization, the replacement of minerals in
the partially demineralized regions of the carious lesion of enamel Fig.7 a) Bioinspired intrabrillar mineralization process induced by
or dentin, is one of the approaches to treat caries, as well as G4-COOH as articial proteins. b) Sample disk sutured to the cheek
inhibition of demineralization and inhibition of bacterial of rat (arrow). c) Mineralized collagen brils after mineralization for
enzymes.116 Fluoride is the most common material for 14 days. d) Scanning electron microscopy (SEM) micrographs of the
remineralization by adsorbing on the crystal surface and attracting ethylenediaminetetraacetic acid- (EDTA)-treated tooth dentine
calcium ions, followed by phosphate ions. However, high disks treated with G4-COOH for 5 min, after being implanted in rats
concentrations of fluoride can easily cause dental fluorosis.117 oral cavity for 14 days. (Insert: EDS of the mineral crystals deposited
Biomineralization, which utilizes protein or protein-like materials to on the surface of dentine, Ca/P ratio is 1.67). e) The fracture surface
induce the formation of hydroxyapatite-like structures, is therefore of d (Reproduced from ref. 123, copyright 2013, with permission
of great interest. The key point of biomimetic mineralization is from Elsevier Ltd).
stabilizing amorphous calcium phosphate (ACP), which can direct
the nucleation and growth of apatite within collagen fibrils. For 3.4 Tissue engineering materials
example, Liu et al. used small inorganic polyphosphate molecules to
Tissue engineering is used to restore or substitute the functions of
template hierarchical intrabrillar apatite assembly in reconstituted
defective tissue as a result of birth defects or acquired diseases. In
collagen in the presence of polyacrylic acid (PAA) to sequester
dentistry, the tissue can be hard or soft tissue, such as enamel,
calcium and phosphate into transient amorphous nanophases. The
dentin, cementum, periodontal ligament, and alveolar bone. Tissue
extrafibrillar precipitation is caused by the use of polyphosphate,
engineering includes three parts: cells, growth factors, and
while the intrafibrillar mineralization is caused by the use of PAA.118
scaffolds. Scaffolds, which provide not only the three-dimensional
Moradian-Oldak et al. reported a series of works on
templates for cell adhesion, growth, and proliferation, but also
amelogenin-mediated enamel mineralization.119-121 Amelogenin is
mimic extracellular matrix environments for tissue regeneration,
the major structural protein of the enamel organic matrix,
are usually fabricated by polymer or complexes. The scaffold
constituting more than 90% of the extracellular organic matrix. It
materials and fabrication methods have a great influence on the
can regulate the tooth enamel remineralization and control the
performance of the scaffold. The most commonly used materials
oriented growth of apatite crystals, which is related to its ability of
include natural polymers (chitosan, collagen, fiber, peptide, fibrin,
assembling into nanospheres and then forming a birefringent
and cellulose) and synthetic polymer (polylactic acid (PLA),
microribbon structure. Carboxyl terminated poly (amido amine)
poly(lactic-co-glycolic acid) (PLGA), and polyglycolide acid (PGA)).
(PAMAM) dendrimer (PAMAM-COOH) can self-assemble into
And the main fabrication methods are electrospinning,
macroscopic aggregates with a microribbon structure in aqueous 129
self-assembly, and phase separation.
solution, which is similar to that of the supramolecular assembly of
122 Huang et al. synthesized poly-D,L-lactide/glycolide scaffold
amelogenin. PAMAM-COOH can bind to collagen fibrils relying on
through gas foaming/particulate leaching process, then seeded

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stem/progenitor cells and dental pulp stem cells onto the scaffold micrographs of the functionally graded membrane (FGM) processed
130
to regenerate lost dental pulp and dentin. Galler et al. used a cell via multilayering electrospinning (Reproduced from ref. 144,
adhesive, an enzyme-cleavable hydrogel made from self-assembling copyright 2011, with permission from Elsevier Ltd).
peptide nanofibers, to encapsulate dental pulp stem cells (DPSCs)
and incorporated growth factors into the hydrogel via heparin Dental pulp tissue engineering fabricates the complete dental
131
binding. Compared with single scaffold, organic/inorganic root formation on the basis of tissue engineering and stem-cell
complex scaffolds have obtained more interest; e.g., a sodium technology. The clinical translation of dental pulp regeneration
139
hyaluronate/chitosan polyelectrolyte complex scaffold and requires the use of injectable scaffolds. Mosgaverinia et al.
collagen/fibrin microbeads containing silver-doped bioactive glass developed an injectable and biodegradable scaffold based on
13, 132
(Ag-BG) and DPSCs. Moreover, scaffold materials are supposed oxidized alginate microbeads encapsulating periodontal ligament

Polymer Chemistry Accepted Manuscript


140
to degrade in the human body, with a degradation rate close to the and gingival mesenchymal stem cells. Jang et al. prepared an
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tissue regeneration. PLA is a biodegradable material that degrades injectable solution consisting of human dental pulp stem cells
through simple hydrolysis of the ester bond at a slow degradation (hDPSCs) and a methoxy polyethylene glycol-polycaprolactone
rate of between 10 months and 4 years due to the hydrophobic block copolymer (PC), which can form hydrogel in no more than 10s
methyl group. Fibrin is mechanically weak and undergoes rapid in vivo.141
degradation. Modification with polyethylene glycol (PEG) can Guided tissue regeneration (GTR) and guided bone regeneration
decelerate the rapid degradation of fibrin, and the hybrid materials (GBR) membrane are critical for periodontal tissue regeneration. In
are used for cell delivery and provide the growth and differentiation clinical settings, the epithelial cells and fibroblasts tend to grow into
of dental stem cells.133 bone defects more than osteoblasts, so that the bone defects
Proper stem cells and effective cellular factors are vital factors cannot obtain the desired bone tissue. Hence, to resolve this
for successful tissue engineering.134 For example, enamel matrix problem, a GTR membrane will be placed into the defects for
derivative (EMD) contributes in mesenchymal progenitors to early hindering the non-bone structures grown into bone defects and
cells in the osteogenic lineage. Induced pluripotent stem (iPS) cells improving tissue regeneration. GTR membranes can be made up of
combined with EMD provide a valuable tool for periodontal tissue resorbable materials (e.g., PLA, PGA, collagen, and gelatin) and
engineering, by promoting the formation of new non-resorbable materials (mainly polytetrafluoroethylene
cementum, alveolar bone, and normal periodontal ligament.135 (PTFE)).142, 143 The polyester-based membranes have the advantages
Wang et al. isolated human periodontal ligament tissue stem cells of biodegradation, tissue integration, and ease of handling over
(PDLSCs) and jaw bone mesenchymal stem cells (JBMSCs), and non-resorbable membranes, but their poor cell response limits their
fabricated PDLSC sheet/PRF/JBMSC sheet composites. The results application. In contrast, collagen-based membranes have favorable
showed that the PDLSC sheets tended to develop into PDL-like regeneration but show insufficient mechanical properties, similar to
tissues, while the JBMSC sheets tended to produce predominantly PTFE. To improve the properties of the GTR membrane, Bottino et
bone-like tissues.136 Furthermore, novel tissue engineering is al. fabricated a multilayer membrane by electrospinning for
fabricated just through cell-based therapy without an extraneous periodontal regeneration. The membrane consists of a core layer
scaffold. Yamada et al. demonstrated that various stem cells from (CL) and two functional surface layers (SLs) interfacing with bone (
deciduous teeth had the ability to regenerate bone using loading of nano-hydroxyapatite, n-HAp) and epithelial (loading of
platelet-rich plasma as an autologous scaffold and signal metronidazole, MET), as shown in Fig. 8. The membrane possess
molecules.137 The complex of treated dentin matrix (TDM) as a appropriate mechanical integrity, biodegradation and
biological scaffold and dental follicle cells (DFCs) as the seeding cells cell-membrane interaction, and the functional surface of n-HA
has a possibility for the treatment of root or tooth defects.138 enhances osteoconductive behavior, while the MET combats
periodontal pathogens.144
Fibrin is synthesized from fibrinogen, which may be autologously
harvested from the human body. Its advantages for tissue
engineering include mimicking native tissue and enhancing the
mitogenic response of periosteum. Furthermore, fibrin can be
obtained from the patients own blood and used as an autologous
scaffold, and the technology of plasma rich in growth factors
(PRGF-Endoret) beginning with fibrin is gaining interest in
regenerative medicine due to its possibility of stimulating and
accelerating tissue healing and bone regeneration. PRGF-Endoret is
an endogenous therapeutic technology, which is designed for the in
situ delivery of multiple cellular modulators and the formation of a
fibrin scaffold.145, 146 The detailed process and application is shown
in Fig. 9. Anitua et al. evaluated the effects of a PRGF technology
Fig. 8 a) Schematic illustration of the spatially designed and treatment for five patients with bilateral sinus lift augmentation.
functionally graded periodontal membrane. b1-b4) Representative The area treated with PRGF had less inflammation and more new
147
SEM micrographs of the individual electrospun layers obtained vital bone than the control area.
during the optimization process. c1-c4) Cross-sectional SEM

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well-interconnected macroporous structure and is incorporated


with the PLGA nanospheres loaded with an antibiotic drug,
doxycycline (DOXY). The DOXY released from the PLLA scaffolds can
inhibit common bacterial growth for a prolonged duration and the
nano-fibrous scaffolds have a potential to deliver various substances
from the large molecules to small hydrophilic drugs.

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Fig.10 Structure and function of nanoparticles and properties of


used polymers for pH-activated system for controlled topical
delivery of farnesol to disrupt oral biolm virulence. (A) Depiction of
the chemistry and self-assembly of diblock copolymers. (B)
Structures of control polymers utilized to isolate required
physicochemical characteristics for binding to dental surfaces. (C)
Fig. 9. Above: Schematic illustration of PRGF-Endoret technology Proposed mode of action of pH-responsive nanoparticles for
and its application. A) the liquid plasma rich in growth factors prevention and/or treatment of biofilms (Reproduced from ref. 155,
(PRGF), B) the scaffold-like PRGF and C) the elastic and copyright 2015, with permission from American Chemical Society).
biocompatible brin. Below: The application of PRGF technology in
regenerative tissue. a) The regenerated bone covered nearly all the Keeping the drug concentration on the tooth surface is of vital
threads in the PRGF-treated implant. B) PRGF reduces the importance to treat biofilm. Chen et al. fabricated a tooth-binding
inammatory level (Reproduced from ref. 146, copyright 2010, with micellar drug delivery platform that would effectively bind to the
permission from Elsevier Ltd). tooths surface. They synthesized a biocompatible Pluronic
copolymer with the end group of alendronate, which showed a
3.5 Drug delivery materials great binding with hydroxyapatite (the main composite of tooth
The application of polymeric systems in the delivery of antibacterial surface) while the mixture of the Pluronic solution and farnesol can
drugs, biologically active agents, or different types of cells has form micelles. The results showed that the micelles were able to
gained worldwide attention by scientists engaged in material provide significantly stronger inhibition of biofilm formation than
sciences, as well as in the field of dentistry. For example, the control.153 The micelles also can be used for loading other drugs,
Chronopoulou et al. obtained chlorexidine dihydrochloride like triclosan.154 Furthermore, the oral cavity is a complicated,
(CHX)-loaded chitosan nanoparticles (CSNPs) with peptidomimetic versatile, and dynamic environment. Oral bacteria mostly produce
derivative glutathione (GSH). The carrier, which can be applied to acid, decreasing the pH to around 4.5. Horev et al. prepared
oral mucosa treatments, has sustained a release profile of CHX from pH-activated nanoparticles for controlled topical delivery of farnesol
CSNPs with strong cell adhesion and low cytotoxicity.148 However, (Fig. 10). The nanoparticles are formed from diblock copolymers
there is still a problem of control over this release. A novel chitosan and load farnesol owing to their hydrophobicity. The nanoparticles
coating modified with gelatin nanospheres was synthesized by Song can bind to the surface of HA, saliva-coated HA, and
et al.149 The coating can exert control over the release of antibiotics exopolysaccharides and undergo core destabilization at acidic pH to
to tune the antibacterial capacity of a metallic implant, and the release farnesol. Then the mechanical stability of the biofilm is
method provides a new approach to prevent orthopedic and dental compromised and the biofilm will be easily disrupted.155
implant infection.
PLA or PLGA can load different drugs or bioactive 3.6 CAD/CAM technique and 3D-printing technology for polymeric
macromolecules to cure different oral diseases and improve tissue dental materials
regeneration. The carriers can be fabricated into various shapes, CAD/CAM techniques and 3D-printing technology provide great
such as scaffolds, microspheres, nanoparticles, and fiber mats. PLA support for accurate device fabrication. CAD/CAM systems include
fiber mats can be fabricated by electrospinning, then load single three parts: a data acquisition unit through intraoral scanners or
drugs or dual-drugs to treat local periodontitis by controlled indirectly by means of a stone model, software for designing virtual
150, 151 152 156
release. Feng et al. fabricated a novel antibacterial restoration, and a computerized milling device. The term
nanofibrous poly(L-lactic acid) (PLLA) scaffold. It has a 3D-printing is generally used to describe a manufacturing approach

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162
that builds objects one layer at a time, adding multiple layers to differentiate into different tissues. Park et al. designed and
157
form an object. Although the two techniques look similar, they fabricated the hybrid scaffold through computational topology
are very different in processing formation. The former usually uses design and solid free-from fabrication technique. The results
cutting tools to remove unwanted materials, while the latter adds demonstrated that the composite hybrid polymeric scaffolds via
15
materials to form the desired shape. multi-scale computational design and fabrication can be applied for
targeted cell transplantation of genetically modied human cells for
the formation of human tooth dentin-ligament-bone complexes in
163
vivo (Fig. 11).

3.7 Other polymeric dental materials

Polymer Chemistry Accepted Manuscript


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Oral impression is a female die which is used to record the


appearance and relationships of oral soft or hard tissues. Its
accuracy is affected by the performance of the impression materials,
and impression techniques will influence the quality of the final
restorations. The most used impression materials are vinyl
polysiloxane (VPS) and polyether (PE), while the most common
techniques are the closed (transfer), the open (direct), and the
splinted techniques. Splinted techniques can obtain the most
consistent and accurate impression, followed by the direct
technique, and finally the indirect technique.164 The development of
digital impressions(intraoral scanners) simplifies the procedure and
overcomes the inherent accuracy problems of traditional impression
techniques.165 In addition, alginate and agar also can be used as
Fig. 11 a) Schematic illustration of the 3-D wax printing system and impression materials. According to their performance, alginate
dimension of the hybrid scaffold shows polymeric architecture impression is usually used in orthodontics, for complete dentures
manufacturing. b) The left is the 3-D-designed hybrid scaffold and and for partial dentures. Agar impression can be used in all aspects,
the right is the micro-CT scanned maps. The scale bar: 50 m but its operation is inconvenient because of the heat device and the
(Reproduced from ref. 163, copyright 2010, with permission from tray. To optimize the performance of agar impression materials,
Elsevier Ltd). alginate-impression materials are combined with agar.
Condensation silicone impression material is suitable for complete
CAD/CAM techniques are mainly used in the field of dentures, partial removable dentures and crown-bridge impressions,
prosthodontics and restorative dentistry, such as fixed dental especially for secondary impressions that can improve dimension
prostheses. The polymer includes a microfilled acrylic polymer block, stability of the condensation silicone rubber. Additionally, silicone
unfilled polymethyl methacrylate blocks, and PEEK, which are rubber and polyether rubber are both appropriate for crown, bridge,
158, 159 lay, veneer and occlusal registration.
usually used as fixed dental prostheses. 3D-printing
technology is mainly used in orthodontics, maxillofacial prosthetics, Owing to its superior mechanical properties and biocompatibility,
and fabrication of tissue engineering scaffold. Resin composite is a PEEK has also been explored as a removable prosthesis. So far,
great candidate for 3D-printing, but a functional 3D-printable denture clasps and obturator prostheses have been reported.
material remains lacking. Yue et al. fabricated Denture clasps connect removable dental prosthesese with the
diurethanedimethacrylate/glycerol dimethacrylate (UDMA/GDMA) patients teeth. To meet the demands of clinical application and
resin components with positively charged quaternary ammonium aesthetics, clasps need to have excellent properties, such as
groups by photocuring or prepolymerized as a linear chain for flexibility, retention, and fatigue resistance.166 An obturator
incorporation into a semi-interpenetrating polymer network by prosthesis is a device that separates the oral cavity from the nasal
light-induced polymerization. The composite resins can be made and/or antral cavities. The primary reason for using PEEK as an
out of a molar tooth and clear dental splint by 3D-printing and the obturator peosthesis is its low specific gravity (1.31 g/cm3, which is
devices have a great antibacterial property.160 Moreover, the dental important to keep the retention of the obturator prosthesis), and a
splints made by 3D-printing have very good market prospects. Youngs modulus close to that of bone, resistance to cracking,
167
Polylactic acid has been used as the key components of scaffold attractive biocompatibility, and machinability.
structures used for bioprinting, a popular area for research in Cellulose is the most abundant polysaccharide in nature.
tissue engineering.161 Lee et al. fabricated a Cellulose can be divided into two categories on the basis of source:
polycaprolactone-hydroxyapatite scaffold using 3D-printing, and bacterial cellulose (BC) and plant cellulose. They have different
the scaffold was composed of three phases and each phase loaded properties and characteristics, even though both possess similar
for connective growth factors designed for cementum/dentin chemical structures. Plant cellulose has excellent advantages of
interface, periodontal ligament, and alveolar bone, respectively. In biocompatibility, biodegradation, low water solubility and
this study, DPSC-seeded multiphase scaffolds can control a sustainability, while BC has a higher degree of crystallinity,
multi-protein role to induce a single/progenitor cell population to mechanical strength, and absorptive capacity. Olyveira et al.

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explored a series of BC scaffolds for tissue regeneration, including 4 H. J. Busscher, M. Rinastiti, W. Siswomihardjo and H. C. van
modification of the bacterial cellulose fermentation, composites of der Mei, J. Dent. Res., 2010, 89, 657-665.
otolith and bacterial cellulose to improve cell adhesion. In addition, 5 C. M. Bollen, P. Lambrechts and M. Quirynen, Dent. Mater.,
otoliths/bacterial cellulose nanocomposites can be used for direct 1997, 13, 258-269.
168, 169
dental pulp capping. Yoshino et al. applied bacterial cellulose 6 X. Yang, H. Shang, C. Ding and J. Li, Polym. Chem., 2015, 6,
as an alternative to paper points for dental canal treatment, 668-680.
because BC has excellent material and biological characteristics, 7 L. Chen, K. Liang, J. Li, D. Wu, X. Zhou and J. Li, Arch. Oral
such as solution absorption, expansion, tensile strength, drug Biol., 2013, 58, 975-980.
170
release and biocompatibility. 8 H. Zhang, J. Yang, K. Liang, J. Li, L. He, X. Yang, S. Peng, X.
Chen, C. Ding and J. Li, Colloids Surf., B, 2015, 128, 304-314.

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4. Conclusions and perspective 9 L. Zheng, F. Yang, H. Shen, X. Hu, C. Mochizuki, M. Sato, S.
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In summary, this review has talked about the structure, properties, Wang and Y. Zhang, Biomaterials, 2011, 32, 7053-7059.
and applications of various polymers in dentistry. All the materials 10 C. D. P. Le, A. Resin, K. A. Howard, D. S. Sutherland and P. L.
have to meet basic requirements, like satisfactory biocompatibility, Wejse, Appl. Environ. Microbiol., 2011, 77, 3892-3895.
appropriate biomechanical properties, and excellent antibacterial 11 S. E. Kim, D. H. Suh, Y. P. Yun, J. Y. Lee, K. Park, J. Y. Chung and D.
properties, and they also need to achieve further special functions W. Lee, J Mater Sci: Mater Med, 2012, 23, 2739-2749.
for clinical purposes. Conventional restoration focuses on the 12 O. O. Agboola, S. Oyedeji, J. O. Olowoyo, A. Ajao, O. Aregbesola,
enhancement of mechanical properties, such as the polymer J. Bioresour. Bioprod., 2016, 1, 169-176.
shrinkage rate and fracture resistance through an admixture of new 13 X. Chatzistavrou, R. R. Rao, D. J. Caldwell, A. W. Peterson, B.
monomers (e.g., dendritic macromolecular and POSS) and McAlpin, Y.-Y. Wang, L. Zheng, J. Christopher Fenno, J. P.
reinforcing fillers (macrofiller, microfiller, nanofiller, etc.). The Stegemann and P. Papagerakis, J. Non-Cryst. Solids, 2016, 432,
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This journal is The Royal Society of Chemistry 20xx Polym. Chem., 2016, 00, 1-3 | 15

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Polymer Chemistry Page 16 of 16
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DOI: 10.1039/C6PY01957A

Graphical and textual abstract

This review focuses on the relationships between the structures and properties of

various polymers for different applications in dentistry.

Polymer Chemistry Accepted Manuscript


Published on 09 December 2016. Downloaded by Fudan University on 13/12/2016 01:05:06.

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