Review on Emerging Applications of Nanobiomaterials in Dentistry and Orthopaedics.
Biomaterials may be defined as "materials which can be incorporated with the human body for evaluating, treating, or replacing tissue or for the functioning of the body" or can be defined as "any synthetic materials which is used to replace part of a human system or to function in close contact with the living tissue. Due to their very good physical and mechanical characteristics, nanobiomaterials have gained a greater interest among the researchers. Mostly because of the nanoparticle size and their peculiar characteristics, they enable defining of many physical applications . Nanomaterials that can be employed in bioengineering applications are referred as nanobiomaterials. There is an extensive ascent in the quantity of researches over the years, concentrating on the uses of nanobiomaterials in dental and orthopedic field. This paper intends to address these current advancements and is a push to bring ideas and research outputs in this interdisciplinary field all in one. The review is divided into number of sections to give the researchers an idea about the synthesis and application of nanobiomaterials in various dental disciplines like implant dentistry, preventive dentistry, dental tissue engineering, orthodontics and orthopaedics. Dental implants are subject to failure caused by a lack of adequate osseointegration . Early failures, defined as those occurring before prosthetic restoration, are typically caused by poor bone/implant contact. In fact, there has been an increase in the rate of clinical complications for dental implants in recent years . The most common causes of failures are peri-implantitis, implant overloading, and fracture . Peri-implantitis is a disease characterized by progressive loss of bone surrounding dental implants.
Bone repair is a major problem in orthopedic surgery due to various bone infections, bone abnormalities and bone loss by trauma. The conventional methods to treat bone abnormalities are autografts, allografts and xenografts. Autografts are susceptible to pathogenic infection whereas allografts and xenografts are rejected by an immunological barrier of the recipient . To overcome the drawbacks associated with traditional methods of treatment, the fabrication of an ideal nanobiomaterials should be devoted to dentistry and bone tissue engineering, in which ceramic scaffold (i.e., calcium phosphate), synthetic polymers (i.e., polyethylene, polyvinyl alcohol (PVA), poly-glycolic acid (PGA), poly-caprolactone and poly L-lactic acid (PLLA)), natural polymers (i.e., chitosan, collagen, gelatin, and cellulose), metallic materials or their composites is used to mimic the natural system of human to some extent . Classification of biomaterials with their main merits and demerits were given in the figure1. A comprehensive review which includes characteristics of biomaterials largely used in biomedical applications could be very valuable for gaining better insight into the advantages and shortcomings of a particular material.
Polymers are categorized as two divisions, based on the availability either it is natural or artificially synthesized. Natural polymers viz., chitosan, fibrin, collagen, agar etc., and synthetic polymers includes mainly acrylic resin and its derivatives, dendrimer, polyetheretherketone (PEEK), polylactic acid, etc. In addition, polymers further divided into restoration materials, tissue regeneration materials and accessory materials based on their application. Restoration materials are the materials which are directly employed in fabricating restorations and their usage in dental field include dental implants, composite resin restoration and soft/hard prostheses . Tissue regenerative materials are used more directly on in situ tissue regeneration and controlled delivery. Accessory materials are employed in supporting fabrication of restorations for indirect restorations, such as impressions.
Synthesis of Polymeric Nanomaterial
In polymer melting process better mixing of the polymer with nano materials is achieved when compared to solution blending method. First the polymer is melted to above recrystallizing temperature then nanomaterial is added to the polymer with stirring process. In this method, polymer/nano mixture is allowed to heat and then cooled slowly in atmospheric temperature, heating is usually done at the higher temperature than that of melting point of the polymer . The representation of steps involved in melting and blending method can be seen from figure 2.
Applications of Polymeric Nanomaterials
The applications, merits and demerits of polymeric biomaterials are listed in the table 1.
Polymeric Nanomaterial Applications in Dentistry
Polymeric materials can be easily produced in many conformations such as fibers, rods and viscous liquids. Thus, they are widely used as implantation material. Polymeric materials have been developed to equalize the mechanical strength of light metals but not the stiffness property. The polymers have excellent mechanical, chemical and thermal characteristics due to their coarse main backbone chains. Polyacetals and polysulfones can be used as implant materials. Recently, scientists found that PEEK have better application as dental implants after surface modification or filler reinforcement. However, while pure PEEK was used, it resulted in slight bone loss around the dental implants, a process termed stress shielding . Also, PEEK is bio-inactive and has poor quality of osteoconduction. These properties are very essential for desired bone regeneration and osseointegration of implants.
Polymeric Nanomaterial Applications in Orthopaedics
Chitosan (1-4, 2-amino-2-deoxy-b-D-glucan) is a deacetylated by-product of chitin (1-4, 2-acetamido-2-deoxy-b-D-glucan), is a linear form of polysaccharide compound usually present in the outer walls of some fungal cells, plankton and exoskeletons of arthropods. In a fascinating application, Kawai et al. analyzed the capacity of a chitosan powder coated on a non-woven polyester framework for bone binding of ligament implants . The authors disseminated a commercially available chitin/ chitosan powder  on the surface of the fabric to a thickness per area of 0.08 mg/[cm.sup.2]. Chitosan has been appeared to quicken wound mending, biodegradable, osteoconductive and biocompatible. These attributes are generally because of its physical and compound homology to hyaluronic acid and different proteoglycans found in extracellular lattices. In view of these properties, chitosan has been examined as a covering for implant materials to advance osseointegration . The coating of chitosan surface of the implantable device is succeeded by means of chemical reactions and electrodeposition systems and by different strategies, for example, submerged coating and layer by layer get together. Chitosan a biopolymer with biocompatibility, has received importance as a potential coating material in the production of dental and orthopedic implants due to its osteotissue generation, wound healing, biodegradable properties and flexibility in making process and modification
Metal Based Nanobiomaterial
Metallic materials have become an important role in orthopedic surgery, the main reason behind its role is most of the part used in orthopedic surgery are made of metallic materials only, which includes permanent implant devices (e.g. whole joint substitutions) and temporary implants (e.g. bone fixtures, bolts and nuts) . Simultaneously, metals as well got usage in dentistry and orthopedics, as fillers in tooth and roots. Notwithstanding an extensive count of metals and their alloys ready to be manufactured commercially, just a very less number of alloys are biocompatible and prepared to do long haul accomplishment as an implantable material. These materials can be classified as Co-based amalgams, SS, Ti-based compounds and varied other alloys (e.g. Mg Ta and Ni Ti alloys) . The use of silver metal is increasing around the world. The mechanical properties of metallic biomaterials were discussed in the Table 2.
Modulus of elasticity, UTS=Ultimate tensile strength, of = Fatigue limit, El= Elongation, FR=Fatigue ratio- ([[sigma].sub.f]/UTS), BF=Bio-functionality [[sigma].sub.f]/E.
Synthesis of Metal Based Nanomaterials
Several methods were adopted to synthesize metal based nanomaterials for biomedical applications. The squeeze casting technique is one of the methods used to fabricate metallic nanomaterials.
In Squeeze casting technique, first metal is molted in any furnace, then nano particles/nano fillers should be added into the molted metal. The liquid mixture of metal and nano particle/nano fillers is then poured into mold. Upper mold should be moved to give pressure for the metallic nanomaterial. Squeeze casting gives better mechanical properties when compared to other casting methods. The ejector pin is used to remove the casted metallic nanomaterial .
Applications of Metal Based Nanobiomaterials
The various merits and demerits of metallic nanobiomaterials were discussed in the Table 3.
Metallic Nanomaterials in Dentistry
Metallic nanobiomaterials are widely used in dentistry as metallic implants and in orthodontic surgery for positioning tooth and jaw in the correct place . Co alloys and Ti alloys were employed in substituting tooth roots. SS and Ni-Ti alloys are used as restorative archwires and mercury-silver-tin (Hg Ag Sn) amalgam is used as a restorative material. Mercury-silver-tin-copper (Hg Ag Sn Cu) combination has been used in as a restorative material in dentistry. Advantages of these materials include (i) Melting point is close to body temperature, (ii) It is simple to utilize, (iii) Easy to manipulate during fixation process, (iv) It remains delicate for a brief period, which also it to be utilized for stuffing any uneven gaps, after which it turns out to be hard compound, (v) It has agreeable durability and (vi) It is low cost. However, Hg Ag Sn Cu has been highly substituted by white tooth fillers and amalgamate resins, initially due to toxicity of Hg ions and for cosmetic reasons. The application of titanium-tantalum (Ti-Ta), titanium-niobium (Ti-Nb), titaniumzirconium (Ti-Zr) and nickel-tantalum (Ni-Ta) alloys in the dental field is initially propelled due to their good wear resistance. Dental materials are synthesized using the biocompatible metals like Ta, Zr and Nb alloying to Ti. The Ta-Ti alloys have better mechanical characteristics compared to Nb-Ti alloys . Zr-Ti alloy is having good biocompatible property when compared to other Ti alloy .
Metallic Nanomaterials in Orthopaedics
Philip Wiles (1958) was the first to apply Stainless steels in the manufacturing of hip replacement implants and Co-Cr alloys were insightfully selected by the researcher Austin Moore (1943). Yet stainless steels are scarcely used in dental implants due to their poor corrosion, weakness, low wear resistances and the subsequent issue of iron toxicity. Nowadays, the stem part of maximum implants is built of Orthinox steel, Co/Cr or Ti based alloys. Co-Cr based composites or ceramic materials (Zr[O.sub.2] or [Al.sub.2][O.sub.3]) are utilized in producing the ball part, which are smoothened to permit rotation effortlessly inside the acetabular socket. Metal with Ultra High Molecular Weight Poly Ethylene (UHMWPE) bearing surfaces are account for ~ 60%, ceramic with UHMWPE account for 20% and remaining 20% by metal-on-metal combination of all total hip replacement implants . Co alloys found enormous desirable usage in total hip replacement devices and also in other total knee and ankle joint replacements because of its good load-bearing property . Due to the brittle nature of ceramic, it is not preferred in producing knee and ankle joints which are incoherent in nature and consequently results in stress concentration due to their always changing work state. In case of knee implants Co-Cr alloys with Ti are broadly used due to their desirable mechanical characteristics such as strength and toughness . Co-based alloys are employed in making the tibial and femoral parts in knee joints, and talar and tibial parts of ankle joints, along with UHMWPE. Ta and Zr alloy is used in making knee prostheses. Though these alloys are better mechanical properties such as strength and toughness than bone in vitro, they have limited durability ~20-25 years, which is significantly less compared to the lifespan of humans .
Ceramics are inorganic and non-metallic compounds with a broad range of chemical composition. Over the past years, there is a significant development in the area of ceramic research which resulted in the production of ceramic nanobiomaterials for producing dental implant devices, total hip replacements and in tissue engineering. Ceramic materials that include hydroxyapatite, zirconia, alumina, silicon nitride and tricalcium phosphate have numerous desirable mechanical characteristics like, high resistance to wear potential, compound stability, low density and furthermore it has biocompatibility. Nanocrystalline hydroxyapatite (nHAp) was cited for various usages like coatings in implants to improve the biocompatibility of titanium alloy [37, 38] and as in fusible pastes for bone replacements with better osteoconductive characteristics . Bioactive glass-based ceramic was synthesized to obtain scaffolds with an optimized rate of degradation and show the best output in orthopedic applications .
Hydroxyapatite (HAp) is a biologically active calcium phosphate ceramic which is commonly used in surgery for replacing and mimicking bones and teeth. The bioactivity of HAp refers to its reliability to enhance bone growth along its layer. Due to the high density of ceramic nanobiomaterial it weighs highly. Brittleness property can lead to failure of the material when it is subject to a little bit higher load than the load it can withstand. A diversity of HAp based composites has been extensively used in medical applications as it biologically imitates several inorganic components present in the human body, particularly in bone, dental enamel . HAp is an ideal material for dental and orthopedic implants, but its use is restricted because of the low mechanical strength. According to the recent reports, nano- HAp is an ideal biomaterial because of its better osseointegration property and biocompatibility . In the study done by  Zhou and Lee, the importance of size, crystal structural control and composites of nano-HAp particles with other inorganic materials for the development of biomedical implant is highlighted. Graphene oxidehydroxyapatite (GO/HAp) composites have been reported to show higher osseointegration ability with surrounding tissues, superior induction of bone cell growth and better compatibility with living system. The ends of graphene oxide sheets are stick to the adjacent HAp nano-grains impeding the crack formation along the grain boundaries. This effect of grain bridging in GO-HAp composite, increases the elastic modulus 40% as compared to pure HAp. Unlike pure HAp, GO/HAp coated on Ti metal has improved binding strength, corrosion resistance and enhance the cell growth. Nanoscale HAp grain, which prevents the formation of cracks at the interface of HAp-GO and stacked structure of graphene flakes are the main strengthening factors of the GO-HAp composites . The results of cell culture and viability assays show that the addition of reduced graphene oxide (rGO) upgrades the proliferation and osteoblast adhesion. The cell proliferation and viability of osteoblasts properties are enhanced by combining rGO with the HAP nanoparticles . The rGO enhances cell conduct since it is biocompatible as well as the nearness of modest number of functional groups namely hydroxyl, epoxy and carbonyl in its basal plane and edges create an approach to outline bioactive nanomaterials with customized microstructure having improved mechanical properties .
Synthesis of Ceramic Nanobiomaterials
Chemically prepared ceramic powders and nanofillers with dispersant will be formed as slurry. The slurry can be introduced to ball milling process at a constant temperature. The slurry can be formed into ceramic by pressure molding. After pressure molding the ceramic can be heat treated to obtain optimum mechanical and desirable properties .
Applications of Ceramic Nanomaterials
Ceramics in Dentistry
In recent years, many researchers have investigated the synthesis and characterization of nano-structured glass ceramics, mainly calcium phosphates, as a potential alternative for hard tissue, in orthopedic and dental surgery . Denry et. al., (2015) studied the crystallization of a fluorapatite (Fap), [Ca.sub.5][(P[O.sub.4]).sub.3]F, glass ceramic. One of the merits of prepared glass ceramics in the previously mentioned research, besides their nano-scale structure, was their relatively high, approximately 20-30 Vol%, the content of the FAp crystal phase, making them suitable candidates for feasible applications in the fields such as biomedicine and dentistry. Bioactive glass nanoparticles have shown excellent biocompatibility in relation to bone derived cells and tooth-derived cells, such as odontoblasts and dental pulp cells . They dissatisfied mechanical properties, namely less tensile strength and more brittleness, and were difficult to process, which primarily confined their practical applications as scaffolds for dental tissue engineering . Nevertheless, the group of bioactive nanoceramic glass has a lot of merits such as osteoinductive characteristics and biocompatibility.
Bioactive ceramics compounds are osteoconductive, which act as a platform to improve bone cell generation on their surface layer. These ceramics are used as a coating on various substrates to repair bone defections. Due to its osteoconductive property, it can initiate osteogenesis only in an osseous condition, whereas osteoinductive materials can induce bone formation even in an extraosseous state . HAp and tricalcium phosphate (TCP) had a wide application in manufacturing orthopaedic implants. The main drawbacks of HAp are poor mechanical properties such as brittle nature and poor tensile property. This made its limited application in the clinical field as a bone-graft substitute . Accordingly, knowledge on the application of ceramic bone implants in clinical field is scanty. Yoru and Aydinoglu et al (2017) studied the reactant, mechanical, and biological properties of hydroxyapatite ceramics under biomimetic conditions (7.4 pH and 37[degrees]C and in the simulated environment of body fluid). Based on the results of cytotoxicity assays conducted in vitro, it was concluded that amorphous ceramics which are produced at low temperatures and which have chlorapatite structure are highly cytotoxic. It was also analyzed that ceramic samples which are highly crystalline were also highly cytotoxic even though they contained pure hydroxyapatite phase. In their study, it is observed that heat treated biomimetic hydroxyapatite ceramic samples, which contained only pure Na-Mg hydroxyapatite phase and which had almost 80% crystallinity, were sufficiently biocompatible .
Ceramics in Orthopaedics
Ceramics are commonly used in making femoral head part of total hip along with polyethylene and alumina-on-alumina as cups. Crack formation in ceramic femoral heads due to its brittle nature along with high manufacturing cost is the main reason for their restricted use world-wide . However, crack formation has been almost removed by the improvised manufacturing process along with increased density and purity of material, effective size and distribution of the material and good quality control. Also, critical stresses in the head portion are avoided by accurately fixing ceramic ball to the femoral stem. Dense alumina of the surgical grade is produced by subjecting the alumina powder to heat at the range of 1600 to 1800 [degrees]C and it has chemical inertness, superior resistance to corrosion and high thermal stability. Another widely used material Zirconia which is brittle in nature with good compression strength but less bending strength. Zirconia ceramic was used for the first time in the production of femoral heads for total hip implants. This is due to its high mechanical strength and toughness which would reduce the problem of fracturing. Pure form zirconia ceramic is found to be an unstable material which shows three various forms of crystalline phases such as monoclinic, cubic and tetragonal which leads to variation in volume and production of cracks. A novel grade of composite has been manufactured recently to syndicate the tribological characteristics of alumina powder and the mechanical properties of yttrium stabilized zirconia . These combined oxide forms of ceramics containing 40% to 80% zirconia have exhibited a higher degree of wear in vitro compared to alumina ceramic. Initial outputs in hip joint simulators are promising, yet further research is required to assess their longevity.
The application of nanobiomaterial is a new field in dentistry and orthopaedic research. Nanobiomaterials have the capability to develop new systems that resembles the complicated, hierarchical structure of the biological tissue. The initial researches on nanobiomaterials done so far suggest that these materials have greater potential to make better dental and orthopedic biomaterials and in the creation process of new tissue engineering. However, significant improvements are needed to extrapolate the full potential use of nanobiomaterials in medical field. In general, current improvements in the application of nanobiomaterial foreshadow a bright future in dentistry and orthopedic domain. It is important that a successful dental implant and bone transplant is not only to meet the mechanical properties of the teeth or bone but also biocompatibility of the implant with the body. Biocompatibility plays a major role in implants. Therefore, it is must to analysis in vitro and in vivo compatibility of nanobiomaterial before any implantation.
The authors wish to thankfully acknowledge the Management of VIT University, Chennai Campus for their constant encouragement and support to the finishing of this review work. The authors also acknowledge Karunya University, Coimbatore, Christ Institute of Technology (CIT), Puducherry, InCUBE-EngSciRes R&D, Udumalpet, Coimbatore, for providing technical and financial support to carry out this research work.
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R. Dinesh Babu (1,3) *, P. Prakash (2), D. Devaprakasam (1, 4)
(1) Department of Mechanical Engineering, School of Mechanical and Building Sciences, VIT University Chennai Campus, Chennai 600127, India
(2) Department of Nanotechnology, Karunya University, Coimbatore 641114, India.
(3) Christ Institute of Technology (CIT), Puducherry, 605502 India
(4) InCUBE-EngSciRes R&D, Alpha Academy Tech, Udumalpet, Coimbatore, 642126, India
Received 20 November 2017; Accepted 21 November 2017; Published online 31 December 2017
* Coresponding author: R. Dinesh Babu; rdineshbabupdv@gmail. com
Caption: Figure 1: Classification, merits and demerits of nanobiomaterials
Caption: Figure 2: Synthesis of polymeric nanomaterial
Caption: Figure 3: Fabrication of Metallic Nanobiomaterial/Nanocomposite
Caption: Figure 4: Fabrication of Ceramic Nanomaterial
Table 1: Applications, merits and demerits of polymers Polymers Applications Polypliosphazenes Tissue Engineering, Dental Applications Polyanhydrides Orthopedic and Dental Applications Polyacetals Dental and orthopedics Polycaprolaetone Biomedical applications Pharmaceutical and Polylaetide medical applications Polycarbonates Tissue Engineering: Fixators Preparation of denture m Polyamides dentistry Polymethylmeth-aciylate Bone repair materials Polymers Merits Polypliosphazenes Fire resistance: Flexible Mechanical Properties Suggestive Monomer Polyanhydrides Flexibility; Regulative Degradation Rates Mild pH Degradation Polyacetals Products: pH Sensitive Degradation Polycaprolaetone Highly Processable: Easily available Highly Processable; Polylaetide Many Commercial Vendors Available Polycarbonates Chemically dependent mechanical characteristics; Surface Eroding Biocompatible and Biodegradable Polyamides Polymethylmeth-aciylate Good resistance to abrasion; stiffness and hardness; Less water absorption Polymers Demerits Polypliosphazenes Synthesis is intricate  Low-molecular Polyanhydrides Weights; Weak Mechanical Properties  Low Molecular Polyacetals Weights; Complex Synthesis  Polycaprolaetone Restricted Degradation  Restricted Degradation; Highly Acidic Polylaetide Degradation Products  Polycarbonates Restricted Degradation; Copolymerization polymers is possible  Very less Degradation; Polyamides Charge Induced Toxicity  Resistance to solvent is Polymethylmeth-aciylate poor. Can be used in low temperature only. Fatigue resistance is poor.  Table 2: Mechanical properties of metallic biomaterials Metallic Materials UTS % [[sigma].sub.f] E [MPa) El CUPa) (GPa) Pure Titanium 940-1015 10-19 600-790 82-83 Stainless steel 450 40 250 210 Cobalt Chromium 500 E 300 200 Ti Alloy 900 13 550 105 Metallic Materials FR BF Pure Titanium 0.64-0.78 7.2-9 6  Stainless steel 0 56 L2  Cobalt Chromium 0 60 1.5  Ti Alloy 0.61 5.2  Table 3: Applications, merits and demerits of metals as nanobiomaterials Materials Applications Titanium and Surgery. Implants. Titanium alloys Femoral bone replacements. Dental Stainless steel Implants. Fixtures Cobalt Hip implants Chromium Materials Merits Titanium and Chemical resistant. Hish Titanium alloys strength to weight ratio replacements. Dental Stainless steel High strength. High corrosion resistance Cobalt Low wear rate, highly Chromium resistance to corrosion Materials Demerits Titanium and Hiah reactivity. Hiah production cost. Titanium alloys hard on tooling  replacements. Dental Stainless steel Reactive to chemicals. Need replacement after a tune period  Cobalt Early high loosening rate and Limited Chromium for use  Table 4: Mechanical Properties of Ceramic Nanomaterials Material Density lTS(MPa) E(GPa) Hydroxyapatite 3.05-6.15 40-300 70-120  Alumina 3.5-4.1 210-290 220-370  Zirconia 5.7 to 6.0 190-200 410-450  Table 5: Applications, merits and demerits and of various ceramic biomaterials Material Merits Hydroxyapatite Low processing temperatures, Can coat complex shapes, Thin coatings Alumina High biocompatibility, hardness, wettability, fluid film lubrication Zirconia Highly compatible, Easy to process, Unbreakable Silica Biocompatibility Material Demerits Hydroxyapatite Expensive raw material, Requires controlled atmosphere Alumina Alumina head fracture and the resultant difficult revision surgery Zirconia Abrasion causes loosen the implant Silica Decay cause to fall from dental crown Material Applications Hydroxyapatite Biomaterial coating  Alumina Total hip arthroplasty  Zirconia orthopedic and dental applications  Silica Bone repairing and drug delivery 
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|Author:||Babu, R. Dinesh; Prakash, P.; Devaprakasam, D.|
|Publication:||Trends in Biomaterials and Artificial Organs|
|Date:||Oct 1, 2017|
|Previous Article:||Advances in Wear and Tribocorrosion Testing of Artificial Implants and Materials: A Review.|