In vitro investigation of aluminum and fluoride release from compomers,conventional and resin-modified glass-ionomer cements: A standardized approach

The amount of fluoride release from dental cements necessary for an anticariogenic effect is not established; moreover, the possible toxic effects due to high fluoride and aluminum release are not well known and the results are still controversial. The aim of our study was to evaluate fluoride (F) and aluminum (Al) release from dental cements using a 'standardized approach' according to the end-use of the materials, i.e. biocompatibility testing. Two polyacid-modified resin composites of recent application, commonly called compomers (Dyract® and Dyract Cem®), were compared with two conventional acid-based (Fuji I?, Ketac-Cem®) and two resin-modified (Vitremer?, Vitrebond?) glass-ionomer cements (GICs). All types of cement are used in dentistry and are commercially available. Extracts of the cements into minimum essential medium, after setting over a 1-h (group A) and 1-week (group B) period, were performed. The extraction conditions were rigorously standardized. Mean values +/- standard deviation of F- and Al-levels in such extracts were measured and were expressed as μg g^-1 (micrograms of ions per gram of cement). A great difference in the amount of ion release, both F and Al, was shown among the tested materials. The GICs, as well as Ketac-Cem®, released more F and Al than the compomers. All of the materials released the greatest proportion of ions when the extraction was performed in the first hour after mixing (group A). Al- and F-values showed a highly significant positive correlation, independently from the curing time. We conclude that the biological assessment of dental cements can be performed only if a preevaluation of the leachables is obtained by applying a standardized protocol which allows a useful comparison between the different materials.     

FTIR investigation of monomer polymerisation and polyacid neutralisation kinetics and mechanisms in various aesthetic dental restorative materials

Diamond ATR FTIR has been used to quantify light catalysed polymerisation and polyacid neutralisation rates in various glass ionomer cements (GIC), resin-modified GICs (RMGIC) and compomers. At 150s after the start of light exposure, levels of methacrylate polymerisation on the lower surfaces of 1mm thick specimens were 97% and 98% for the RMGIC, Vitremer and Fuji II LC and 47% and 37% for the compomers, Compoglass and Dyract. After light exposure, polymerisation rates for the compomers decreased linearly with inverse time. By 50,000s Compoglass and Dyract were 62% and 51% polymerised. Initial rate of polyacid neutralisation in the GIC Shofu HIFI was 0.32 times that of Fuji IX GIC. Those in Vitremer, Fuji II LC, Compoglass and Dyract were 0.16, 0.09, 0.004 and 0.004 times that of Fuji IX. Excluding short initial periods, log of neutralisation rates decreased linearly with log-time. Average gradients were -1.35 for the GIC, -0.80 for the RMGIC and -0.59 for the compomers. By 50,000s, polyacid salt concentrations for the RMGIC and compomers were 0.41 and 0.016 times that of the GIC. Reaction mechanisms have been discussed and used to help interpret material mechanical properties, fluoride release rates and adhesion to tooth structure.     

Short-term fluoride and cations release from polyacid-modified composites in a distilled water,and an acidic lactate buffer

Fluoride and various cations release from three commercial compomers (Dyract, Dyract AP and Compoglass-F) and a resin-modified glass ionomer (Fuji-II LC) as a control were measured up to 7 days in distilled water and 0.01M lactate buffer solution with pH 4.1. The surface morphological change before and after the release experiment was observed with a scanning electron microscopy. Fluoride, aluminum and strontium ions were released from Dyract, Dyract AP and Fuji-II LC much more in the lactate buffer than in the distilled water. With compoglass-F containing barium instead of strontium, barium was released in the same way. X-ray diffraction analysis confirmed that fluoride release from Dyract and Dyract AP was derived mainly from SrF(2) contained in Dyract and Dyract AP. However, fluoride release from Compoglass-F was derived from glassy phase though it contained much fluoride as YbF(3). Cumulative release amount of each species versus square root of time plot showed good linearity, indicating that the dissolution was controlled by the diffusion mechanism. The surface characteristics of disks for each material, which were immersed in the lactate buffer, were quite different from the surface before and after immersion in deionized water, especially with Dyract. After immersion in the lactate buffer, many voids which were left after dissolution of the filler particle, were seen obviously on the surface of Dyract.     

Long-term effects of four extraction media on the fluoride release from four polyacid-modified composite resins (compomers) and one resin-modified glass-ionomer cement.

It was the aim of the present experiments to evaluate the fluoride leaching of four compomers and one resin-modified glass-ionomer cement (gic) into aqueous media over a 1-year period. Various extraction/equilibrium solutions were applied to simulate important intraoral parameters. Specimens of Dyract, Compoglass F, F2000, one experimental compomer, and the resin-modified gic Fuji II LC were stored for 366 days in distilled water (I), acidic medium (pH 4.2) (II), neutral medium (pH 7.0) (III), or solution III supplemented with 1.6 u/mL porcine liver esterase (IV). Equilibrium media were changed and fluoride concentration was measured every 48 h (first 30 d), thereafter each week (twice), then every 14 d (three times), and finally every 28 d up to a total period of 1 year. Data were statistically analyzed for significant differences by means of Scheffe' tests (p < 0.05). The gic and the compomers leached significantly more fluoride into the acidic solution in the initial phase compared to the other media (p < 0.05). Cumulative fluoride release from all materials (except experimental compomer) was elevated because of esterase activity (p <0.05). Measurable but low quantities of fluoride were segregated into all media during the 1-year period. But no significantly different long-term fluoride release into the various media from the investigated materials was found. The data indicate that plaque-associated organic acids or salivary hydrolases may increase initial fluoride release from resin-modified gics or compomers in the oral cavity. Because long-term fluoride release from all materials decreased to low concentrations within a 30-day period, their caries preventive effect remains questionable.     

Compressive strength,fluoride release and recharge of fluoride-releasing materials

The compressive strength, fluoride releases and recharge profiles of 15 commercial fluoride-releasing restorative materials have been studied. The materials include glass ionomers (Fuji IX, Ketac Molar, Ketac Silver, and Miracle Mix), resin-modified glass ionomers (Fuji II LC Improved, Photac-Fil, and Vitremer), compomers (Compoglass, Dyract AP, F2000, and Hytac) and composite resins (Ariston pHc, Solitaire, Surefil and Tetric Ceram). A negative linear correlation was found between the compressive strength and fluoride release (r(2)=0.7741), i.e., restorative materials with high fluoride release have lower mechanical properties. The fluoride-releasing ability can be partially regenerated or recharged by using a topical fluoride agent. In general, materials with higher initial fluoride release have higher recharge capability (r(2)=0.7088). Five equations have been used in curve fitting to describe the cumulative fluoride release from different materials. The equation [F](c)=[F](I)(1-e(-bt))+betat best describes the cumulative fluoride release for most glass ionomers, resin-modified glass ionomers, and some high fluoride-releasing compomers and composites, whereas [F](c)=[F](I)/(t(1/2)+t)+alphat best describes the cumulative fluoride release for most compomers and composite resins. The clinic applications of different fluoride-releasing materials have also been discussed.     

Effect of bleaching agents on the fluoride release and microhardness of dental materials

The use of bleaching agents has become a popular procedure for whitening teeth. Recently introduced polyacid-modified composite resins (compomers) have several favorable features, such as improved physical properties and fluoride release. Because these two materials have many possibilities to interact in the oral cavity during dental treatment, it is necessary to understand such interaction. To evaluate the effect of a bleaching agent on dental restoratives, three compomers were photopolymerized and then bleached for 1, 2, 3 and 5 days with the use of 30% hydrogen peroxide. Fluoride release, surface microhardness, and surface modifications were evaluated. It was found that the cumulative fluoride release was found to be linearly correlated to the tested periods of bleaching in all compomers. Among the tested compomers, F2000 showed the highest cumulative fluoride release. Bleached compomers became soft because of surface degradation, so the surface microhardness decreased. F2000 showed an apparent crack formation that was not observed in other compomers. The nearly linear correlation between the filler content and microhardness was found in the control samples. However, the same correlation was not observed after the compomers were stored in a bleaching agent or distilled water.     

Kinetics of fluoride release from zinc oxide-based cements

Considerable attention has been given to the release of the cariostatic fluoride ion from glass-based dental cements (dental silicate and glass ionomer). In these, the total available fluoride content is not precisely known since fluorine is distributed between the cross-linked aqueous salt matrix, partially dissolved glass, and undissolved glass. In analogous cements based on zinc oxide the fluoride is added as highly soluble SnF2. The object of this study is to compare the F- ion release profiles of commercial zinc polycarboxylate and zinc phosphate containing 4.4 and 3.6% SnF2, respectively. Mixed cements were clamped in split ring moulds to produce discs of 10 mm x 1 mm after storage at 37 degrees C for 1 h. Each was weighed and immersed in 10 ml of deionised water. When this changed, at 13 time intervals up to 98 days, the fluoride content was measured using an ion selective electrode. The mean (N = 3) values obtained were expressed cumulatively [F] in micromol F ion/g cement. The total [F] released was 111 for the zinc polycarboxylate and 286 for zinc phosphate compared with total F in the cements of 561 and 464, respectively. When the cumulative [F] was plotted versus t(1/2) close associations were found for both cements. For the polycarboxylate the regression line [F] = 10.6t(1/2) + 9.9 fitted well over the whole 98 days (R = 0.997). For the phosphate a better fit regression line was obtained using results up to 32 days only; [F] = 36.8t(1/2) - 8.4 (R = 0.999). For t > 32 days results increasingly deviated from this line. These results fitted a regression line of the form [F] = 81.7log(e) t - 87.3 (R = 0.9997). Comparisons are made with data from previous authors both for zinc phosphate cement and glass-based cements and with diffusion theory of F ion release. It is concluded that zinc-based cements provide some indications of how glass-based cements may behave over long periods of release and that zinc phosphate is the material of clinical choice for orthodontic cementation if maximal fluoride release is the prime criterion.     

The effects of adding fluoride compounds to a fluoride-free glass ionomer cement on subsequent fluoride and sodium release

Studies have shown that ions in a glass ionomer matrix are 1-10% of the amounts present in the original glass. To measure more precisely the release from a cement matrix, known amounts of ions were added to LG30 glass which was fluoride and sodium-free. Cement without additions acted as the control. 1.4-1.6% of each of sodium, calcium and aluminum fluorides were added to three portions of control blend. The sodium and fluoride release into deionised water from five discs of each cements blend was measured for 8 months. This represented complete release for sodium but not for fluoride. Traces of fluoride and sodium in the glass produced low but measurable amounts indicating about a third of the fluoride and substantially all sodium present in LG30 was released. The addition of calcium fluoride had no significant effect on sodium or fluoride release and aluminium fluoride minimal effects. Adding sodium fluoride significantly enhanced release of both ions although fluoride release was less than from a glass containing 5% fluoride. Only small proportions of the additions, 2-5% of the fluoride and 13% of sodium, were released. Sodium and fluoride appeared to be released independently. For LG30 cements additives were poor at supplying extra ions.     

Zinc ion release from novel hard tissue biomaterials

Zinc polyalkenoate cements (ZPCs) and glass polyalkenoate cements (GPCs) are used routinely in dentistry, but have potential for orthopaedic applications as they set at body temperature without shrinkage or significant heat evolution. However, the materials have drawbacks; ZPCs are biocompatible in implant studies, but a fibrous collagen capsular layer forms adjacent to the cement. GPCs are bioactive in the bone environment as a result of the release of calcium, phosphate and fluoride ions, as well as the formation of a silicious gel phase, but research has shown that aluminum ions released result in defective bone mineralisation and as a consequence the ability of these cements to chemically bond to bone is lost. Two approaches have been developed to overcome these problems. The ZPC route considers a ZnO : hydroxyapatite (HA) : poly(acrylic acid) (PAA) mixture, the HA incorporated to improve bioactivity. The GPC route employs a calcium zinc silicate glass; the zinc taking the role that aluminum plays in conventional GPCs. This study has shown that cements can be formulated by an acid base reaction between PAA and both calcium zinc silicate glasses (GPCs) and a mixture of hydroxyapatite and zinc oxide (ZPCs). The moduli of these cements are comparable to both bone and conventional acrylic cements, highlighting their potential for biomedical applications. Unfortunately, both materials have previously been shown to be toxic by cell culture methods, as a result of high zinc ion release, and so it is necessary to study ion release profiles of the cements in order to determine the magnitude of this release. Considering the ZPCs, the modulus of the cement has an inversely proportional relationship to the zinc ion release. From the data presented it is clear that increases in polymer concentration results in lower amounts of zinc ions being released, whilst molar mass of the PAA has no influence. Therefore it would appear that polymer concentration has a significant influence over ion release. Generally, the amount of Zn(2+) released decreases with increasing HA content and/or decreasing ZnO content. Considering the GPCs, the materials are all seen to release large amounts of the active ion, when compared to the commercial versions. The extent of this release increases with temperature and agitation. The release could be minimised by an increased P : L mixing ratio, and an increased PAA concentration, which would produce a more cross-linked cement matrix. Minimising the release of the active ion should improve the in vitro bioactivity of both materials. However, for a full understanding of the clinical benefits of such materials, an in vivo study would be required.     

Effect of maturation on the fluoride release of resin-modified glass ionomer and polyacid-modified composite resin cements

The effect of an early water contact on the fluoride release is studied for the resin-modified glass ionomer cements (RM-GIC) GC Lining LC, PhotacBond, Vitremer and Vitrebond and for the polyacid-modified composite resins (PAM-C) Variglass and Dyract. Six months fluoride release profiles were determined in regularly renewed water (37 degrees C), for the products directly after light curing and after 24 h maturation in a humid atmosphere (85% RH). ANOVA shows that both the short-term and the long-term fluoride release of a RM-GIC are influenced by this maturation. This indicates that direct water contact for this material should be avoided. For the RM-GIC a correlation is found between the initial fluoride release process and the long-term process. For the PAM-C materials, no differences in the fluoride release are found as a function of maturation, indicating that early water contact has no effect. The amounts of fluoride released by PAM-C are low compared to RM-GIC, which can affect their caries preventive potential. The results are explained on the basis of the setting reaction of both types of materials.     

The effect of temperature on viscoelastic properties of glass ionomer cements and compomers

The objective of this study was to determine the viscoelastic properties of different types of glass ionomer cements (GICs) and compomers under varying temperature conditions found in the mouth. The materials tested were a conventional GIC (Aqua Ionofil U), a resin modified GIC (Fuji II LC), a highly viscous GIC (Voco Ionofil Molar), and two polyacid modified composite resins/compomers (Glasiosite and Dyract Flow). Six groups of four specimens were prepared from each material. One group was stored dry for 24 h and was subsequently tested dry at 21 degrees C. Each of the remaining five groups was stored for 24 h in distilled water at the temperatures 21, 30.5, 37, 43.5, and 50 degrees C, respectively, and was subsequently tested at that temperature. Shear storage modulus and loss tangent were determined by conducting dynamic torsional loading. Static shear moduli were determined by applying a constant torque (below the proportional limit of the materials) for 10 s and recording the angular deformation of the specimens. Data were analyzed by ANOVA and Duncan's test (alpha= 0.05). It was found that the viscoelastic properties varied significantly (p < 0.05) across the different materials. The compomer Glasiosite, with the highest filler content, and the highly viscous GIC Voco Ionofil Molar exhibited the highest elastic moduli and lowest loss tangents. Viscoelastic properties varied also significantly (p < 0.05) with temperature levels, but changes in the tested region were not indicative of a glass transition. Dynamic shear storage moduli were highly correlated to the static ones. Storage in water lowered the values of elastic moduli.     

In vitro effects of ascorbate and Trolox on the biocompatibility of dental restorative materials

Previous in vitro studies on the cytotoxicity of eight dental restorative materials including composites, compomers, resin-modified glass ionomer cements and glass ionomer cements have demonstrated a depletion of intracellular glutathione in gingival fibroblasts incubated with eluates of these materials and a protective effect of N-acetylcysteine. In the present study, we investigate the effects of two other antioxidants: ascorbate and Trolox. It was found that Trolox reduced the cytotoxicity induced by resin-based biomaterial eluates. In contrast, ascorbate increased in a dose-dependent manner the toxic effect of all eluates except for Z100 MP and Tetric flow (composites). The effect of D-mannitol was studied for GC FUJI II and was found to neutralize the additional toxic effect of ascorbate. Ascorbate increased the depletion of intracellular glutathione of these dental material eluates (between 17% and 24%, depending on the material). Quantification of metal ions in the dental material eluates showed the presence of significant amounts of aluminum and iron in GC FUJI II > photac fil > GC FUJI II LC > F2000. The mechanism of this increased cytotoxicity could be explained by the Fenton reaction resulting from the pro-oxidant effect of ascorbate in the presence of iron (transition metal ions) and/or aluminum.     

Effect of a neutral citrate solution on the fluoride release of resin-modified glass ionomer and polyacid-modified composite resin cements

The effect of 0.01 mol/l citrate solution at pH = 7 on the fluoride release is compared for the resin-modified glass ionomer cements (RM-GIC) GC Lining LC, PhotacBond, Vitremer and Vitrebond and for the polyacid-modified composite resins (PAM-C) Variglass and Dyract by means of the six-month fluoride release profiles at 37 degrees C. The fluoride release of both RM-GIC and PAM-C increases in the neutral citrate solution as compared to water, which can be explained by the ability of citrate to complex metal ions and hence to degrade the glass as well as the polysalt matrix of the cement. Although RM-GIC release more fluoride than PAM-C in water as well as in citrate solution, the relative increase in fluoride release upon immersion in citrate solution is most pronounced for PAM-C. Whereas for the latter citrate affects both the short-term and long-term fluoride release, for RM-GIC only the long-term fluoride release is affected. This suggests that the action of citrate increases with decreasing importance of the polysalt formation in the hardening of the material. This could be explained on the basis of the difference in the chemical properties of the cement matrix.     

Degradative analysis of glass ionomer polyelectrolyte cements

As part of a detailed investigation of the setting mechanisms of dental polyelectrolyte cements, the Al3+, Ca2+, and Na+ concentrations in the matrix phase of glass ionomer cements were measured as a function of the cements age by use of a selective degradation technique. In the early stages of cement formation, all three cations were rapidly released from the glass, and it is inferred that both Ca2+ and Al3+ are responsible for gelation. Even after 5 X 10(4) min, the reaction was incomplete and still continuing.     

The physico-mechanical consequences of exposing glass ionomer cements to water during setting

The effect of exposing glass ionomer cement to water during the first 48 hours after mixing was studied. The strength of the set cement was only reduced if exposure to water occurred within the first hour after mixing. The gel matrix formed during the setting reaction was shown to be the source of fluoride ions released when glass ionomer cement is placed in water. The degree of hydration, rate of fluoride release, and degree of cross-linking of the gel matrix were all shown to be affected by the water ingress during the setting reaction. Finally the fluoride release from the cements was found to cease within six months of exposure to water indicating that only fluoride ions released into the gel matrix during the setting reaction are available to protect surrounding tooth structure.     

Release profile of antimicrobial agents from alpha-tricalcium phosphate cement.

A new method for treating carious dentine with alpha-tricalcium phosphate (alpha-TCP) dental cement containing antimicrobial agents has been recently introduced. However, the release behavior of antimicrobial agents from this cement has not yet been clarified. The aim of this study is therefore to examine the release profile of the antimicrobial agents from the alpha-TCP cement. Three kinds of antimicrobial agents (metronidazole, cefaclor and ciprofloxacin) were added to two commercially available alpha-TCP cements (new apatite liner type I and type II). The set cements were then immersed in water at 37 degrees C and the released antimicrobial agents and Ca ion were determined at regular intervals for three months. In addition, scanning electron microscopic observations were conducted before and after immersion for three months. The release profile of the cements containing antimicrobial agents varied depending on the types of antimicrobial agents. The incorporation of antimicrobial agents affected the setting reaction of the cements. The release behavior of the drugs also varied depending on the types of the cements. The differences in the release profile between type I and type II cements reflected the structures and compositions of their matrices.     

Release of silica, calcium, phosphorus, and fluoride from glass ionomer cement containing bioactive glass

The aim of this study was to examine the release of silica (Si), calcium (Ca), phosphorous (P), and fluoride (F) from conventional glass ionomer cement (GI) and resin-modified glass ionomer cement (LCGI), containing different quantities of bioactive glass (BAG). Further aim was to evaluate in vitro biomineralization of dentine. The release of Si increased with the increasing immersion time from the specimens containing BAG, whereas the amount of Ca and P decreased indicating in vitro bioactivity of the materials. LCGI with 30wt% of BAG showed highest bioactivity. It also showed CaP-like precipitation on both the surface of the test specimens and on the dentin discs immersed with the material. Within the limitations of this study, it can be concluded that a dental restorative material consisting of glass ionomer cements and BAG is bioactive and initiates biomineralization on dentin surface in vitro.     

A preliminary comparison of the mechanical properties of chemically cured and ultrasonically cured glass ionomer cements, using nano-indentation techniques

There is a requirement for a dental cement with properties comparable or superior to conventional glass ionomer cements (GICs) but with the command set properties of the resin-modified GICs. The objective of this work was to show that the application of ultrasound to conventional Fuji IX commercial glass ionomer cement imparts a command set, whilst improving the short-term surface mechanical properties. Nano-indentation techniques were employed to highlight the improvements in hardness and creep resistance imparted to the cement through the application of ultrasound. The instant set imparted by the application of ultrasound provides improved surface hardness and creep, particularly within the first 24 h after setting. The surface hardness of the chemically cured Fuji IX (176 M Pa) increased by an order of magnitude when set ultrasonically (2620 M Pa), whilst creep reduced to a negligible amount. Rapid setting allows for shorter chair time and an improved clinical technique, making restorations more convenient for both the patient and clinician.     

Fluoride release profiles of mature restorative glass ionomer cements after fluoride application

This study investigates the fluoridation of four conventional glass ionomer cements (GIC) (ChemFil Superior encapsulated, Fuji Cap II, Ketac-Fil and Hi Dense) and three resin-modified GIC (RM-GIC) (Fuji II LC encapsulated, Photac-Fil and Vitremer). The fluoride release of matured restorative GIC was measured as a function of time, after four repeated fluoridations in a 2% NaF aqueous solution for 1 h. This release was corrected for the intrinsic release as determined with a control group. It was demonstrated that application of fluoride is capable of recharging GIC but the subsequent high fluoride release only lasts for one or a few days. Moreover, the fluoride release behaviour depends on the cement formulation. Comparable to the intrinsic release, the net fluoride release after fluoridation is composed of a short- and a long-term process, the former being predominant after fluoridation. The total amount of fluoride released according to the short-term process increases with consecutive fluoridations. This is especially pronounced for the RM-GIC, who exhibit a relatively slow release after fluoridation as compared to the conventional GIC. An explanation for these results is suggested on the basis of the physicochemistry of the setting reaction of the cements and of the fluoridation process.     

Effect of fluoride from glass ionomer on discoloration and corrosion of titanium

The objective of the study was to examine the effects that fluoride ions released from different dental glass ionomer cements may have on titanium. The study included determination of the amounts of released ions and measurement of the color changes on titanium plates cemented with four kinds of commercial glass ionomer cements due to immersion of such “sandwich specimens” in 1% saline (NaCl) solution. The discoloration of titanium in the presence of glass ionomer cements was observed. In addition, for specimens cemented with two of the cements titanium ions were found in the solution after immersion. The results of the present study show that a low concentration of released fluoride ions and other elements from glass ionomer cements may cause aesthetic problems of discoloration of titanium restorations and appliances.