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Makanjuola, J.; Deb, S. Chemically Activated Glass-Ionomer Cements as Bioactive Materials. Encyclopedia. Available online: (accessed on 19 June 2024).
Makanjuola J, Deb S. Chemically Activated Glass-Ionomer Cements as Bioactive Materials. Encyclopedia. Available at: Accessed June 19, 2024.
Makanjuola, John, Sanjukta Deb. "Chemically Activated Glass-Ionomer Cements as Bioactive Materials" Encyclopedia, (accessed June 19, 2024).
Makanjuola, J., & Deb, S. (2023, March 29). Chemically Activated Glass-Ionomer Cements as Bioactive Materials. In Encyclopedia.
Makanjuola, John and Sanjukta Deb. "Chemically Activated Glass-Ionomer Cements as Bioactive Materials." Encyclopedia. Web. 29 March, 2023.
Chemically Activated Glass-Ionomer Cements as Bioactive Materials

Glass-ionomer cement (GIC) is a long-established restorative dental material with several clinical applications that have remained relevant because of the chemical adhesive bond it forms at the tooth-restoration interface and its fluoride-releasing and recharging properties. It was invented by Wilson and Kent in 1969 and successfully introduced into clinical practice in 1972. Chemically activated GICs, commonly referred to as conventional GICs, typically consist of ion-leachable glasses based on calcium or strontium alumino-fluorosilicate and weak polymeric water-soluble acids of polyacrylic acid (PAA) homopolymer, or acrylic acid, maleic/itaconic acid copolymer. They set by an acid-base reaction, and the setting reaction is initiated by mixing glass powder and polymeric acids. 

glass-ionomer cements remineralisation bioactive glasses ion

1. Remineralisation Properties of GIC

Calcium and phosphate ions play an important role in the balance of the HA mineral phase of dental hard tissues, and under mildly acidic conditions, they can promote tooth remineralisation [1]. Due to the ability of GIC to exchange ions with the surroundings, which is also applicable to tooth tissue, an ion-rich layer is formed over time at the GIC-tooth interface, which is resistant to acid attack, therefore reducing the incidence of secondary caries [1].
The mineralisation potential of GIC is a desirable property, which has prompted researchers to explore different ways to enhance the bioactivity of GIC by exploring the chemistry and developing new routes to glass synthesis and, more commonly, modification of the GIC-matrix by incorporating bioactive glasses (BAG), hydroxyapatite (HA), beta-tricalcium phosphate (β-TCP), casein phosphopeptide–amorphous calcium phosphate, and other bioactive materials into the glass-ionomer powder and/or the liquid phases [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23].
Since its introduction in 1969 by Larry Hench [24], BAG has widely been used in dental materials such as gutta percha, dental adhesives, GIC and composite resins, pulp protective dressings, endodontic sealants, and orthodontic cements [9]. The combination of BAG and GIC has benefits, with a significant increase in remineralisation capacity; however, the effect of BAG on the mechanical properties and setting kinetics of GIC are often contradictory [6][8][14][15][16][17][18][19][25][26][27][28][29][30][31][32][33]. This is in agreement with other studies reporting that higher amounts of BAG additives in GIC cements compromise the mechanical properties, which are attributed to the partial replacement of the fluoro-alumino silicate glass powder phase. This results in a decrease in the amount of Al3+ in the glass, resulting from its replacement of Na+ in BAG, and a reduction in the bond strength between PAA and the ions released [6][34][35]. The addition of Al3+ to the BAG composition has been reported to be beneficial in improving the strength of BAG-GIC composites, but this decreases bioactivity [6][34][35]. The inclusion of nano-sized particles of BAG into glass-ionomers is also believed to at least reduce the likelihood of the extent of compromise in mechanical properties. The BAG nanoparticles may occupy the voids between the larger glass-ionomer particles and act as additional PAA bonding sites, thereby improving the mechanical properties [16]. The reactivity of the BAG nanoparticles with the GI matrix is higher, and the pH rapidly increases, which could further develop the silica gel and apatite layer formed [6][36]. The incorporation of BAG nanoparticles into GICs can enhance their odontogenic and osteogenic properties for clinical applications such as root surface fillings and bone regeneration [16].
β-TCP contains a significant amount of calcium and phosphate, which can promote remineralisation of enamel when incorporated into the glass phase of GIC [37]. A recent report has shown that the addition of fortilin (which is also referred to as ‘translationally controlled tumour protein’) to β-TCP as a GIC additive further promotes odontogenic differentiation and mineral deposition in human dental pulp stem cells (hDPSCs) [23]. HA nanoparticles are widely used in dentistry because they are biocompatible bio-ceramics that promote enamel remineralisation and have superior osseointegration properties [38][39]. Numerous studies have revealed that the incorporation of hydroxyapatite nanoparticles into GIC can significantly improve the interfacial bond strength, improve marginal adaptation to tooth tissue, enhance the mechanical properties, reduce cytotoxicity, and leave the sustained release of fluoride unaffected [38][40][41][42]. Forsterite (Mg2SiO4) has been reported to be more effective as nanoparticles in promoting bioactivity and enhancing the mechanical properties of GIC. This is attributed to the higher surface energy and increased reactivity [18][21]. Wollastonite (also known as calcium silicate) is another material known to promote bioactivity. It is available in nature or can be synthesised from mine-silica and limestone. Its inclusion into the powder phase of GIC reinforces the mechanical properties, reduces cracks, and decreases shrinkage, due to its acicular nature [34][43]. Wollastonite has been reported to promote the formation of an apatite layer on the surface of powder in simulated body fluid [44]. Published data related to the combination of wollastonite with GICs are limited, but it has been reported that the incorporation of wollastonite into GIC promotes the bioactivity without compromising compressive strength [11]. Casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) nanocomplexes have been shown to prevent enamel demineralisation and promote the remineralisation of carious enamel [21][45]. The incorporation of CPP-ACP into the glass phase has been found to enhance the anticariogenic properties of GIC. This is because of the localisation of casein phosphopeptide to amorphous calcium phosphate at the tooth surface, which results in a prolonged state of supersaturation of the tooth mineral [45][46]. CPP-ACP as GIC additives has shown to increase the release of calcium, phosphate, and fluoride ions from the cement, and this leads to increased protection of the adjacent dentine from acid demineralisation [47]. In addition, CPP-ACP interacts with fluoride ions released from GIC to form a stabilised amorphous calcium fluoride phosphate complex, and this further augments its anticariogenic potential [45][46][47].

2. Antibacterial Properties

With an increasing clinical demand for tooth-coloured materials with superior mechanical properties, wear resistance, remineralisation, and antibacterial effects, improvements to these properties in GIC have gained the interest of researchers. The low pH during the initial setting of GIC, the fluoride-releasing properties of GIC, as well as its ability to leach other therapeutic ions such as strontium and zinc, have all been suggested to play a role in the antibacterial property of GIC; however, these effects are minimal [48][49][50][51][52][53].
The slight antimicrobial properties displayed by unmodified GIC are attributed to the fluoride ions that are released, which have therapeutic benefits against bacteria remnants at the restoration-dentine interface following excavation of infected dentine [54]. The fluoride release has been shown to encourage the remineralisation process in addition to the formation of low-soluble fluorapatite (FAp), which is more resistant to demineralisation [48][49][50][55][56][57][58][59]. FAp formation disrupts ionic bonding to the tooth surface during pellicle and plaque formation, reduces the bacteria’s acidogenicity, and slows down bacterial metabolic activities [48][49][50][55][56][57][58][59]. However, it has been reported that fluoride release most likely has minimal antibacterial effects and that this antibacterial property ceases after the GIC hardens since it is attributed to the low pH of the GIC setting reaction [52][53][60][61].
In addition to its mechanical, remineralising, and adhesive properties, improvements in GIC’s antibacterial properties would be highly beneficial in treating residual cariogenic bacteria and preventing the recurrence of caries. This ultimately is expected to increase the clinical survival rates when used as restorative dental material and improve its efficacy as a lining material by serving as an antibacterial seal under restorations and as a fissure sealant over the occlusal surfaces of teeth highly susceptible to caries [62][63]. Enhancing antibacterial activity would be particularly useful in ART, which involves the removal of carious lesions and placement of HVGIC with the use of manual instruments only. ART is usually performed in constrained environments where functional dental equipment is lacking or in cases of uncooperative patients, such as special needs patients, where it is difficult to manage the patient and when it is unlikely to completely remove infected caries [62][63][64].
The limited antibacterial activity of GICs has led to studies to augment this property by the addition of a range of antimicrobial agents to the powder or liquid phase of GIC that can interfere with metabolic activity and inhibit biofilm formation and the adherence of cariogenic bacteria [3][34][52][54][65][66]. Enhancement of the antibacterial activity of GIC is largely dependent on the concentration and type of antimicrobial agent used as an additive and its release rate from the cement surface layer [3][34][52]. However, it is of utmost importance that if the inclusion of these antimicrobial additives into glass-ionomer fillers or liquids does not improve the physical properties, fluoride release, and adhesive properties of the cement, it should at least not compromise these properties for it to remain clinically relevant [3][34][52]. So far, the incorporation of these antibacterial modifiers into conventional GICs has led to promising results, with the potential for these modified GICs to be more clinically beneficial [3][34][52][54][65][66][67].
Some of the additives that have been explored are natural products such as graphene, chitosan, propolis, turmeric, and epigallocatechin-3-gallate; antibiotics such as metronidazole, ciprofloxacin, and minocycline; antiseptics such as chlorhexidine (CHX) [CHX diacetate and CHX digluconate], triclosan, quaternary ammonium salts such as cetrimide, benzalkonium chloride, and cetyl pyridinium chloride; and metallic dopants such as silver, zinc, magnesium, and titanium [3][34][52][54][65][66][67].
Chlorhexidine (CHX) has a wide spectrum of activity against Gram-positive bacteria, especially mutans streptococci, Gram-negative, aerobic and facultative anaerobic bacteria, and fungi. Whilst some studies have reported that the incorporation of CHX salts into GIC increases their antimicrobial activity without compromising their physical properties, other studies have reported that CHX additives negatively impart mechanical properties, fluoride release, and biocompatibility at high doses. Following extensive research, it has been suggested that an addition of not more than 1% of CHX into GIC provides optimal antibacterial activity without compromising the physical properties [62][68][69][70][71]. A higher concentration of CHX is not contributory to the formation of the glass-ionomer network and would weaken the scaffold, thereby affecting the physical properties of GICs [34][72]. CHX has also been reported to have long-term antibacterial properties because of its substantivity effect by binding to hydroxyapatite. This leads to a gradual release of CHX over an extended period [68][73][74]. The addition of quaternary ammonium salts as well as antibiotics have also been reported to be dose-dependent in order to be effective without compromising physical properties [60][64][73][75][76][77][78][79]. Polyhexamethylene biguanide (PHMB) is another broad-spectrum bactericidal agent that has recently been explored as a glass-ionomer additive. It has been widely used in trauma treatment, ophthalmic disinfection, and many other biomedical fields. PHMB eliminates bacteria by binding protonated groups to the anionic membrane of bacteria, which results in a leak in the cytoplasm. Unlike chlorhexidine and quaternary ammonium compounds, PHMB not only has superior antibacterial activity but has also been reported to be biocompatible at high concentrations [38][80].
Chitosan is a natural biopolymer that is relevant in the dental (or biomedical) field due to its biocompatibility, natural adhesive properties, and antibacterial properties [7][19]. It acts as a physical or chemical binder between the glass filler and matrix in GIC, thereby improving the mechanical properties [7]. Epigallocatechin-3-gallate (EGCG) is another antibacterial agent that is worth exploring as an additive. It is a major polyphenol present in green tea, and it has been reported to be effective against both Gram-positive and Gram-negative bacteria [34][81]. It destroys the cellular structures, inhibits cellular enzymes, and causes intracellular oxidative stress in the bacteria [82][83]. A study has shown that the inclusion of EGCG into GICs at low concentration improved the antibacterial activity and some mechanical properties of GICs [84]. The strength enhancement is attributed to an increase in crosslinking and a high degree of poly-salt bridging [34][85][86]. Another natural product that can serve as an antibacterial additive is propolis. It is a natural resin sourced from honeybees. Ethanolic extracts of propolis (EEP) are the most used form for antibacterial activity [87]. The mechanism of its antibacterial property is associated with its activity against cariogenic bacteria and inhibition of glucosyltransferase activity [88]. Despite its well-known antimicrobial activity against oral microorganisms, only a few studies have investigated the effect on the physical properties of GIC when EEP is used as an additive [89][90]. The paucity of data investigating the effect of EGCG and EEP on GIC properties shows that more in vitro studies still need to be carried out before it can be used for clinical applications.
Ionic dopants such as magnesium, zinc, silver, copper, and titanium are of interest for use in biomaterials due to their antimicrobial properties against bacteria, spores, and viruses [91][92]. Most nano-metallic dopants such as these have been reported to be cytotoxic as the concentration increases. Despite the mechanical reinforcement observed when nano-metallic dopants such as zinc, silver, copper, and titanium oxides are incorporated into GIC, there have been reports of cytotoxicity, discolouration, poor marginal adaptation, and decreased interfacial bonding following an increase in concentration [22][38][48][93][94][95][96][97][98]. On the other hand, magnesium nanoparticles have been reported to be biocompatible and thermally stable; however, they compromise the physical properties of GIC when added in high concentrations [66][99][100]. Little research has been performed on investigating the effects of fluorinated graphene (FG) (a derivative of graphene). FG can serve as an antibacterial material since graphene has been reported to be effective against bacteria [48]. FG has been reported to be a biocompatible material because it enhances the proliferation and polarisation of mesenchymal stem cells and the neuro-induction of stem cells [48][101][102]. The inclusion of FG in GIC has been reported to be highly beneficial for the property enhancement of GIC. Studies have shown that it significantly improves the mechanical and antibacterial properties of GIC without interfering with fluoride release [48][103].


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