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Biomineralisation is a well-regulated process mediated by extracellular matrix proteins. Biomimetic remineralisation strategies should reproduce the dimension and structural hierarchy of apatite deposits within a demineralised collagen matrix. Interfibrillar and intrafibrillar remineralisation of phosphoric acid-etched human dentine was demonstrated in this study using a Portland cement/phosphate-containing fluid system in the presence of polyacrylic acid and polyvinylphosphonic acid as respective calcium phosphate- and collagen-binding matrix protein analogues. Metastable amorphous calcium phosphate nanoprecursors were generated when polyacrylic acid was included in the phosphate-containing fluid. When both polyvinylphosphonic acid and polyacrylic acid were included, these nanoprecursors were attracted to the acid-demineralised collagen matrix and transformed into polyelectrolyte-stabilised apatite nanocrystals that assembled along the microfibrils (intrafibrillar remineralisation) and surface of the collagen fibrils (interfibrillar remineralisation). Transition from nanocrystals to larger apatite platelets probably occurred via the formation of mesocrystal intermediates. Guided tissue remineralisation is potentially useful in the remineralisation of acid-etched dentine that is incompletely infiltrated by dentine adhesives, as well as partially demineralised caries-affected dentine.

It is well understood that the application of a self-etching primer enhances the bonding at the resin-teeth interface. In this study, we designed a self-etching primer consisting of N-methacryloyl glycine (NMGly) and N-methacryloyl-2-aminoethyl phosphonic acid (NMEP). The demineralization effects on the hydroxyapatite or dentin by the carboxylic acid in the NMGly and by the phosphonic acid in the NMEP and their effects on the bond strength of the resin to the tooth were examined. The application of the NMGly-NMEP solution to the enamel resulted in an increase in the bond strength when additional amounts of NMEP were added to the NMGly aqueous solution. This increase was due to the phosphonic acid in the NMEP demineralizing the enamel. Conversely, the addition of the NMEP to the NMGly solution resulted in a decrease in the bond strength to the dentin. The optimal concentration of the NMEP in the NMGly-NMEP solution resulted in bond strengths of over 20 MPa for both the enamel and dentin.

Glass ionomer cements (GIC) can potentially be used as matrices for the slow release of active species, as has been shown previously for fluoride ions. This study investigated the use of an experimental GIC as a carrier for the release of chlorhexidine acetate (CHA) at included concentrations ranging from 0.5% to 13.0% of CHA by weight. Release into water was examined using high-performance liquid chromatography. All measurable chlorhexidine was released within 22 h1/2, however this was less than 10% of the total mass incorporated in the specimens. An increased percentage of CHA incorporated into the powder gave an increased release into the surrounding water. The bulk of the CHA was retained within the cement. For comparison, the surface chemistry of a CHA-containing GIC was examined using X-ray photoelectron spectroscopy before and after prolonged immersion in water. This confirmed retention of a large amount of CHA. Spectra after leaching appeared very similar to those from a CHA-free GIC after immersion in a CHA solution. In order to explore the effect of CHA-inclusion on the cement properties, compressive strengths, working and setting times were also measured. In general, compressive strengths were found to be decreased in direct proportion to the quantity of CHA added, while working and setting times increased.

Tensile strength tests of restorative resins bonded to dentin, and the resultant strengths of interfaces between the two, exhibit wide variability. Many variables can affect test results, including specimen preparation and storage, test rig design and experimental technique. However, the more fundamental source of variability, that associated with the brittle nature of the materials, has received little attention. This paper analyzes results from micro-tensile tests on unfilled resins and adhesive bonds between restorative resin composite and dentin in terms of reliability using the Weibull probability of failure method. Results for the tensile strengths of Scotchbond Multipurpose Adhesive (3 M) and Clearfil LB Bond (Kuraray) bonding resins showed Weibull moduli (m) of 6.17 (95% confidence interval, 5.25–7.19) and 5.01 (95% confidence interval, 4.23–5.8). Analysis of results for micro-tensile tests on bond strengths to dentin gave moduli between 1.81 (Clearfil Liner Bond 2 V) and 4.99 (Gluma One Bond, Kulzer). Material systems with m in this range do not have a well-defined strength. The Weibull approach also enables the size dependence of the strength to be estimated. An example where the bonding area was changed from 3.1 to 1.1 mm diameter is shown. Weibull analysis provides a method for determining the reliability of strength measurements in the analysis of data from bond strength and tensile tests on dental restorative materials.

Effects of the granularity of the raw materials on the hydration and hardening process of calcium phosphate cement (CPC) composed of equimolar tetracalcium phosphate (TECP) and dicalcium phosphate anhydrous (DCPA) were investigated systematically. The variation of pH value in CPC slurry indicated that the control step of CPC hydration was the dissolution of DCPA under these experimental conditions. Reducing the particle size of DCPA could accelerate the hydration rate, and decreasing the particle size of TECP would expedite the dissolution of DCPA, which would obviously result in a faster hydration rate. The results of isothermal conduction calorimetry showed that reducing the particle size of TECP could increase the conversion ratio of starting materials to hydration products, which would lead to an increase in the compressive strength of the hardened body of CPC. The sample composed of the smallest particle size of DCPA and TECP obtained the compressive strength of 41 MPa, which would not attain the highest compressive strength, 49 MPa. The smaller the particle size of either DCPA or TECP, the shorter the setting time was. During the setting process of CPC, the microstructure progresses from a gel structure to an agglomeration-crystallization structure. The calculated values of setting time from the rheological model coincided with the experimental data very well. The parameters of AC impedance spectroscopy were closely correlated with the mean pore diameter and porosity of the CPC hardened body. The results of AC impedance spectroscopy further verified that a small particle size of raw materials could result in high hydration rate and the compressive strength of 49.1 MPa.

Previously, we introduced a methodology to determine the chemical bonding potential of polyalkenoic acids to mineralized tissues through quantification of the degree of ionic bond formation between the carboxyl groups of a polyalkenoic acid with calcium of hydroxyapatite. In a continuation of that study, we now investigated in how far the chemical bonding potential to synthetic hydroxyapatite is influenced by the molecular structure of the polyalkenoic acid and if this also may affect the self-adhesiveness to enamel and dentin. X-ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectrometry were used to quantitatively analyze the chemical bonding efficacy of a polyalkenoic acid consisting of acrylic acid units (PAA) to synthetic hydroxyapatite (HAp) in comparison to the chemical bonding potential of the previously investigated synthesized polyalkenoic acid (s-PA) co-polymer consisting of 90w/w% acrylic and 10w/w% maleic acid units. In addition, the analysis was carried out for enamel and dentin samples. PAA revealed a significantly lower bonding effectiveness with only half of its carboxyl groups bonded to HAp versus about two-third of the carboxyl groups of s-PA. The difference in bonding potential was confirmed by the considerably lower adhesiveness of PAA to enamel and dentin as compared to that of s-PA The present findings indicate that the molecular structure of the polyalkenoic acid significantly influences the chemical bonding efficacy to Hap-based substrates.

Calcium phosphate cement (CPC) sets to form hydroxyapatite and has been used in medical and dental procedures. However, the brittleness and low strength of CPC prohibit its use in many stress-bearing locations, unsupported defects, or reconstruction of thin bones. Recent studies incorporated fibers into CPC to improve its strength. In the present study, a novel methodology was used to combine the reinforcement with macroporosity: large-diameter resorbable fibers were incorporated into CPC to provide short-term strength, then dissolved to create macropores suitable for bone ingrowth. Two types of resorbable fibers with 322 microm diameters were mixed with CPC to a fiber volume fraction of 25%. The set specimens were immersed in saline at 37 degrees C for 1, 7, 14, 28 and 56d, and were then tested in three-point flexure. SEM was used to examine crack-fiber interactions. CPC composite achieved a flexural strength 3 times, and work-of-fracture (toughness) nearly 100 times, greater than unreinforced CPC. The strength and toughness were maintained for 2-4 weeks of immersion, depending on fiber dissolution rate. Macropores or channels were observed in CPC composite after fiber dissolution. In conclusion, incorporating large-diameter resorbable fibers can achieve the needed short-term strength and fracture resistance for CPC while tissue regeneration is occurring, then create macropores suitable for vascular ingrowth when the fibers are dissolved. The reinforcement mechanisms appeared to be crack bridging and fiber pullout, the mechanical properties of the CPC matrix also affected the composite properties.

Frequently, bone cement strengths are evaluated from uniaxial tests, such as three- or four-point flexure. Measurement of material strength in this manner may not provide an accurate characterisation of a bone cements true load-bearing capacity. In most orthopaedic applications, there exists a state of biaxial stress and so biaxial strength information is most useful. To address this issue, the biaxial flexure strength of two polymethylmethacrylate orthopaedic (PMMA) bone cements and two glass-ionomer dental cements have been determined. The biaxial strength of orthopaedic bone cements have been compared to the three-point bending strength. Furthermore, the calculated theoretical biaxial strength was compared with a value of biaxial strength utilising the finite element method. For all materials tested the calculated biaxial strength is significantly greater than the three-point bending strength. The biaxial test offers several advantages over three-point bending because it critically explores surface flaws — as it does not matter in which orientation the crack lies. However, it does minimise the volume or surface area investigated and also the edge effect. The difference in strength calculated for the two testing methods can be explained quantitatively in terms of the volume of material under stress. This work has demonstrated that the biaxial flexure test can be used for the testing of orthopaedic bone cements.

This work focuses on the chemical alterations occurring on the dentin surface on treatment with sodium hypochlorite (NaOCl), a known deproteinating agent. In addition, sequential treatment with both acid and NaOCl are characterized. Modifications are evaluated using photoacoustic FTIR (PA-FTIRS), a surface-sensitive spectroscopy. Spectra of NaOCl-treated dentin samples show a slow and heterogeneous removal of its organic phase, leaving calcium hydroxyapatite and carbonate apatite unchanged. Spectra of this deproteinated surface resemble those of apatites synthesized at low temperatures and having very high-surface areas. A combined sequential 2-min treatment of dentin with both maleic acid and NaOCl indicates that this treatment can produce a surface region which is neither significantly demineralized nor deproteinated. This sequential treatment can be used to remove the smear layer and restore the dentin surface to its natural composition.

The rate of change of pH of aqueous lactic acid at pH 4.2-4.5 (i.e. a little below that of active caries in vivo) in contact with disks of various commercial glass-ionomer cements has been determined in two configurations. In the first of them, a thin film set-up, 20 microl of solution was spread across the surface of a cement disk (diameter: 13 mm), and its pH determined by pressing a flat-ended electrode against the film at varying time intervals. In the second, a similar disk was immersed in 1.5 ml of solution, removed after varying time intervals, after which the pH of the solution was measured using a round-ended electrode. The latter measurement was more reliable, in that the pH electrode had time to equilibrate, whereas the former was more realistic because the film was approximately the same thickness as that of saliva on a tooth surface. Both series of experiments showed measurable differences in pH after only 30 s, with the thin-film configuration showing a range of pH changes of 0.5-1.2 units depending on the cement and the small volume configuration showing a range of 0.1-0.5 units, also depending on the cement. After 10 min, in the small volume experiments, the pH had generally increased further. The extent and speed of the change in pH led to the conclusion that ability of glass-ionomers to increase pH is likely to be an important mechanism of caries protection under clinical conditions.

Raman spectra of various combinations of glass-ionomer cement components have been compared with those of the reactants and the salts of polyacrylic and tartaric acids. The components consisted of a fast-setting acid-degradable dental glass (containing, inter alia, oxides of Si, Al, Ca, Ba and Na), polyacrylic acid (PAA) and/or tartaric acid (TA). On the addition of water to the glass and tartaric acid, Raman spectroscopy indicated loss of acid and production of tartrate salts within seconds of mixing. Mixtures containing the glass, PAA and water in mass ratios 2:1:(0.1-4) reacted to form polyacrylate salts. The maximum fraction of unreacted PAA was found to decrease linearly with initial water/PAA mass ratio to a minimum of approximately 20% when this ratio exceeds 1.5. The data are consistent with 5.6 moles of water being required when each mole of acidic groups is neutralised. In newly prepared cements containing glass, water, polyacrylic and tartaric acids, polyacrylic acid and its salts, in both ionised and solid state form, can be detected. After about 1 h, however, Raman peaks associated with ionised species disappear.

The fluoride release from a commercial, restorative glass ionomer cement was found to be strongly dependent on sample surface area rather than volume. This was noted for disc, cylindrical- and bar-shaped specimens over periods ranging from 1 day to 3 yr. Release from all shapes of specimen followed the established pattern of an initial non-linear region followed by one where release was proportional to the square root of time. If fluoride levels in the cement matrix of specimens were artificially increased by incorporation during the mixing then the release pattern during the first few months was altered. The initial release increased for some specimen sizes and decreased for others. The dependency on surface area was greatly reduced for several months. By the time a year had elapsed the correlation between fluoride ion release and surface area had been re-established. The influence of additional fluoride during setting can therefore act to perturb the normal release pattern and may in some instances reduce the initial fluoride release. Release should be quoted in terms of, or with measurements of, the surface area of specimens under investigation.

Aims: The study aims to directly measure uptake of Na and F ions by glass ionomer cement from dilute NaF solution and compare this with the subsequent re-release of these ions into water. In addition, the effect of the presence or absence of Na and/or F as a component of the glass is evaluated. Materials and methods: The four glass ionomers used differed only in glass composition; AH2 contained both Na and F, LG26 contained F, MP4 contained Na and LG30 contained neither Na nor F. Discs of cement were set in moulds at 37°C for 1 h and matured in water at 37°C for 3 days. Test discs were immersed in 0.2% NaF solution for 24 h, control discs in water. Discs were subsequently immersed in water which was changed regularly. Ion-selective electrode measurements (F and Na) and atomic absorption spectrometry (Na) were used to determine uptake (change in immersion solution concentration) and re-release into water. Results: All cements took up large quantities of Na and F ions (range 95–336 μmol g -1 ). This resulted in internal ion concentrations from 16 to 56 times higher than the immersing solution. All re-release was complete within 97 days. No cement re-released more ion than taken up. Glass ionomers containing fluoride took up more Na and F than fluoride-free ones and then re-released a lower percentage of these ions. The cements all took up Na and F ions in equimolar proportions, but initially re-released more F than Na with F-free cement results tending to unity by 97 days. Conclusions: Glass ionomer cements take up Na and F ions from NaF solution in large quantities and in equimolar proportion. This is re-released either wholly or in part in 97 days by which time the release does not differ from the controls. The presence or absence of F in the cement composition markedly influences both uptake and re-release. Fluoride/hydroxyl interchange does not appear to play an important role in uptake.

The addition of potassium and fluoride ions to a water-admixed glass ionomer cement initially free from either ion was accomplished either by addition via the mixing water or by immersing mixed set cement in a solution of the ions in water. In both cases the aqueous concentration of ions was the same. The release of both potassium and fluoride was measured for 500 days. Ion release from immersed specimens was some 20-fold higher than from the other method indicating enhanced concentration of ions inside the cement. This calculation assumes that the ions resided in the aqueous phase. Ions added by mixing appeared to follow the release pattern shown by glass ionomers containing intrinsic fluoride; ions added by immersion did not. As specimens matured the amount which could be taken up by immersion was reduced. Potassium release was still continuing at 500 days whereas fluoride release was complete.

One cause of arthroplasty failure is the brittle mechanical behavior of bone cements. However, the improvement of cement formulations must also be accompanied by the maintenance of a wide variety of characteristics. New bone cements were obtained by the substitution of high percentages, up to 60% (v/v), of methyl methacrylate (MMA) by a higher molecular weight and more hydrophilic monomer, ethoxytriethyleneglycol methacrylate (TEG). The essential advantages of these materials were the decrease of maximum temperature together with a decrease in the residual monomer content with respect to conventional cement formulations. The water absorption process obeyed diffusion laws and the equilibrium water content increased by the introduction of higher percentages of the hydrophilic component. This characteristic had an appreciable effect on the viscoelastic behavior analyzed by DMTA. These modified bone cements had reduced polymerization shrinkage and similar levels of porosity. Tensile test revealed that the introduction of TEGMA gave rise to an important modification of the mechanical behavior, with a noticeable increase in the fracture strain. This fact was also confirmed by means of the analysis of the fracture surfaces by SEM.

Glass–ionomer cements, both self-hardening and resin-modified, have been shown to increase the pH of lactic acid solutions in which they are stored. Similar results have been obtained for a zinc phosphate and a zinc polycarboxylate cement. The pH was increased over a period of 7 days by between 1.54 and 2.65 pH units from an initial value of pH of 2.60, depending on the cement. It is concluded that, as a result of this ability to neutralize surrounding aqueous solutions, these materials may have the beneficial effect in vivo of inhibiting caries development. In the case of glass–ionomers, this mechanism might complement that of fluoride release.

Anti-washout-type fast-setting calcium phosphate cement using chitosan (aw-FSCPC(chi)), conventional CPC (c-CPC), CPC mixed with citric acid (CPC(citric)) and CPC mixed with polyacrylic acid (CPC(acrylic)) were implanted subcutaneously in rats immediately after mixing to shed some light on the understanding of the appearance of excellent tissue response to CPC. CPC(citric) and CPC(acrylic) set quickly, similar to aw-FSCPC(chi), but the former two stopped their transformation to apatitic minerals. The c-CPC, which required a long setting time, was found to be crumbled, but the other CPCs maintained the shape at implantation. The aw-FSCPC(chi) and CPC(citric) showed no inflammatory response whereas c-CPC and CPC(acrylic) showed an inflammatory response one week after implantation. A component of the aw-FSCPC(chi) and c-CPC was an apatitic mineral whereas CPC(citric) and CPC(acrylic) showed no transformation to apatite. We concluded that the non-crumbling property plays a more dominant role in the appearance of excellent tissue response to CPC than the transformation to apatite. Also, a non-crumbling property is not a sufficient condition, but a necessary condition for the appearance of the excellent tissue response to CPC.

Materials that augment bone cell proliferation and osteogenic activity have important therapeutic implications for bone regeneration and for use in skeletal reconstruction and joint replacement. We have studied the growth and interactions of human bone marrow cells on a variety of new cement composites in vitro. These cement materials are composed of calcium-deficient hydroxyapatites, carbonated apatite and amorphous calcium phosphate. Cell proliferation was significantly reduced and cell differentiation increased in the presence of these cements compared with cells cultured on tissue culture plastic. Alkaline phosphatase, one of the markers of the osteoblast phenotype, was dramatically stimulated by 3 of the 4 cements examined between day 4 and day 10, above levels observed following culture of human osteoblasts on plastic alone. Photomicroscopic examination demonstrated growth and close integration of bone marrow cells and 3 of the composites. Longer term marrow cultures (15 day) on the cements confirmed the stimulation of cell differentiation over proliferation. From these studies, enhanced osteoblastic differentiation was observed on a 70% carbonated apatite, which has a composition similar to bone mineral, whereas, cell toxicity was observed on cells grown on amorphous calcium phosphate. This in vitro culture system demonstrates the use of human bone marrow cells for the potential evaluation of new biomaterials and the development of a novel carbonated apatite that may be of potential use in orthopaedic implants.

This paper is a summary of already published papers on the bioactive bone cement (BA cement) which consists of CaO–SiO2–P2O5–MgO–CaF2 (AW glass–ceramic) powder and bisphenol-a-glycidyl methacrylate (Bis-GMA) resin. Two types of BA cement, dough and injection type, were prepared by changing their chemical compositions slightly. They harden in a few minutes exhibiting much lower curing temperature than PMMA cement. They have significantly higher compressive, bending, and tensile strengths than PMMA cement and have a character of bonding directly with bone in 4–8 weeks in vivo. Intercalary prosthetic replacement of the femur and total prosthetic replacement of the hip were performed in dogs using either PMMA cement or BA cement. Mechanical tests demonstrated that fixation strengths of these prostheses with BA cement increased with time and were significantly greater than those with PMMA cement tested at any time. Results of histological examinations showed direct bonding between BA cement and bone, and that the bone trabeculae around BA cement mantle grew with time, while with PMMA cement an intervening soft tissue layer was always observed at the cement–bone interface. BA cement was used in a few aged patients to instal a hip prosthesis either in cases of revision or femoral neck fracture. The longest follow-up period of the patient is 4 yrs. The patients have been doing well with no adverse effect of the cement to date.

The influence of substituting sodium for calcium on the properties of glass polyalkenoate cements was investigated. Two series of glass compositions based on PSiO2 x QAl2O3 x 0.75P2O5 x (1 - Z)CaO x XCaF2ZNa2O were studied. The fluorine content was fixed at X = 0.50 and 0.75 and the sodium content varied by altering Z. The glass polyalkenoate cements formed from these glasses were characterized using a linear elastic fracture mechanics (LEFM) approach. In addition, compressive strengths of the cements were determined. The properties of the cements based on the high fluorine content glasses (X = 0.75) were relatively insensitive to sodium content. The Young's modulus, un-notched fracture strength and fracture toughness of the cements produced with the lower fluorine content glasses (X = 0.5) reduced with sodium content, which was consistent with sodium acting to disrupt ionic cross-linking in the polyacrylate matrix. The compressive strength was not as dependent on sodium content as the LEFM parameters.

Synopsis This study aimed to develop techniques to allow dynamic imaging of a cavity before, during and after placement of glass-ionomer restorative materials. Cavities were cut in recently extracted third molars and the teeth longitudinally sectioned. Each hemisected tooth surface was placed in green modelling compound at 90° to the optical axis of the microscope. The cavity surface was imaged using a video rate confocal microscope in conjunction with an internally focusable microscope objective. The sample on the stage was pushed up to the objective lens which ‘clamped’ the cover glass onto it. Water, glycerine or oil was placed below the coverglass, with oil above. Internal tooth structures were imaged by changing the internal focus of the objective. The restorative material was then placed into the cavity. Video images were stored either onto video tape or digitally, using a frame grabber, computer and mass memory storage. Software controls produced time-lapse recordings of the interface over time. Preliminary experiments have examined the placement and early maturation of conventional glass-ionomer cements and a syringeable resin-modified glass-ionomer cement. Initial contact of the cement matrix and glass particles was visible as the plastic material rolled past the enamel and dentine, before making a bond. Evidence for water movement from the dentine into the cement has also been seen. After curing, the early dimensional changes in the cements due to water flux were apparent using the time-lapse facility. This new technique enables examination of developing tooth/restoration interfaces and the tracking of movement in materials.

The basic properties of calcium phosphate cement (CPC) containing atelocollagen, the main component of the organic substrate in bone, were studied in an initial evaluation for the fabrication of modified CPC. The setting time of conventional CPC (c-CPC) was prolonged to over 100 min when c-CPC contained 1% or more atelocollagen. The diametral tensile strength (DTS) of c-CPC decreased linearly with the collagen content, descending to below the detection limit when the c-CPC contained 3% or more atelocollagen. Therefore, use of c-CPC as the base cement seems inappropriate for the fabrication of atelocollagen-containing CPC. In contrast, the cement set at 9–34 min when fast-setting CPC (FSCPC) was used as the base cement and contained 1–5% atelocollagen, respectively. Although addition of atelocollagen resulted in the decrease of DTS of the set mass, the DTS was approximately the same, 6–8 MPa, at contents of atelocollagen between 1% and 5%. When atelocollagen was added to FSCPC, the handling property was improved significantly. The paste also became more adhesive with increase in atelocollagen content. These properties are desirable for its use in surgical procedures since, for example, bony defects can be filled easily and without a space interposed between the bone and cement paste. Although there are some disadvantages for the addition of atelocollagen to CPC, it can be accepted as long as FSCPC was used as the base cement. We conclude that further evaluations of the effects of atelocollagen, such as biocompatibility, bone synthesis, and bone replacement behaviour should be done, using FSCPC as the base cement.

Studies of the setting of glass-ionomer cements have been carried out for over twenty years, and there is now a considerable body of information concerning the steps that lead to the conversion of a freshly mixed cement paste into a solid, durable dental restorative. This paper reviews these studies, paying particular attention to more recent work. The conclusion is that glass-ionomers consist of interpenetrating networks of inorganic and organic components forming a matrix in which particles of unreacted glass are embedded. However, there remain uncertainties over aspects of the setting chemistry, for example over the role of (+)-tartaric acid in the setting reaction, and over the nature of the fluoride species which form during the reaction. The chemistry of resin-modified glass-ionomers is also discussed and shown to be more complex than that of the simple cements. The presence of the resin component slows down the ionic cure reaction of the conventional cement, and leads to both a significant exotherm and a set material capable of absorbing water reversibly. The paper concludes that the microstructure of the set cement depends completely on chemical composition and the kinetics of the setting process, and that an understanding of the setting chemistry of these materials is thus important for optimal clinical use.

In the 1960s the idea of positive physico-chemical adhesion with tooth substance resulted in the invention of polyacrylic acid-based cements, first the zinc polycarboxylate and, subsequently, the glass-ionomer cements. These materials were shown to undergo specific adhesion with hydroxyapatite and proved to have properties satisfactory for a variety of clinical applications. The key properties of the glass-ionomer cements--fluoride release over a prolonged period and specific adhesion to enamel and dentine coupled with aesthetic qualities are related to their characteristics as aqueous polyelectrolyte systems. In order to improve toughness, speed of setting and resistance to dehydration, hybrid materials in which some of the water content of the glass-ionomer system was replaced by water-soluble polymers or monomer systems capable of ambient polymerization were formulated in the late 1980s. These materials, which have been termed resin-modified glass-ionomer cements, involve, ideally, the formation of an interpenetrating polymer network combining the acid-base cross-linking reaction of the metal ion-polyacid with the cross-linking polymerization of the monomer system or additive action of the polymers. In the predominantly resin materials there is little polyelectrolyte character and it is controversial whether such materials should be categorized as glass-ionomer cement systems. The specific advantages of these materials over traditional glass-ionomer systems and over composite restorative systems remain to be fully documented. Studies of adsorption to hydroxyapatite of typical monomers using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF SIMS) indicate that resistance to water displacement decreases as hydrophobicity increases.

The strength of dental glass-ionomer cements will be influenced by defects present within its structure. This study measured the surface area porosity, percentage surface area porosity, and mean surface area of small bubbles (

alpha-Tricalcium phosphate (alpha-TCP)/dicalcium phosphate dibasic (DCPD)/tetracalcium phosphate monoxide (TeCP) cement was implanted in paste form into soft tissue (rate subcutaneous sockets) and bone tissue (defects in rabbit mandibles) to evaluate the setting behaviour of the cement and tissue responses to the cement. A histological study of the soft tissue implants revealed thin fibrous capsule formation, the appearance of multinucleated giant cells on and close to the cement surface, and small clusters of the cement near the main part of the set cement which were formed by the migration of the paste while setting. X-ray diffraction (XRD) analysis of the implanted cement showed peaks for hydroxyapatite (HA) which increased as the implant period increased. Histology and microradiography of the bone tissue implants showed well-set cement without migration, active bone formation around the cement and direct bone union to it. However, the cement disappeared from the implant site in 4 of 16 specimens where intense bleeding seemed to wash away the implants while setting. From the results of the present study, we concluded that the cement is well tolerated, especially by bone tissue. This may be related to the fact that the cement sets producing HA. The cement is a promising material as a bone substitute; however, there is a problem of migration while setting in soft tissue and of exclusion from the bone defects by intense bleeding.

The comparative reactivity of new tertiary amine activators with the basic chemical structure of N,N-dimethyl-4-toluidine, but reduced toxicity, is analysed. The leaching of the amine compounds from cured cements was studied by analysis of the concentration of the corresponding amine in a physiological saline solution after 3 months of immersion, giving lower values for the new amine compounds as compared to N,N-dimethyl-4-toluidine. The acute toxicity was determined by intravenous injection of saline solutions of the corresponding chlorhydrates in mice and the cytotoxicity by the evolution of specific culture media. The results obtained demonstrate a lower acute toxicity and cytotoxicity of the new activators, even with a noticeable antiseptic action, which makes these materials very interesting from a practical point of view as activators of the curing process of acrylic bone cements for orthopaedic surgery and dentistry.

Previous studies have shown that glass-ionomers made from acrylic/maleic copolymers stored in water reach a maximum strength at about 1 week, and after 4 months have become significantly weaker. This finding, which contrasts with the behaviour of glass-ionomers based on poly(acrylic acid), was originally attributed to hydrolytic instability. This interpretation has been tested in the current work. Specimens of glass-ionomer prepared from acrylic/maleic acid copolymer have been stored for up to 4 months in different media, namely deionized water, dry air and vegetable oil, then tested for compressive strength. Specimens were in the form of cylinders of dimensions 6 mm high x 4 mm diameter, and storage temperature was 37 degrees C. Data were analysed using two-way analysis of variance (ANOVA) and in all three media specimens became weaker at 4 months than they had been at 1 week (P < 0.05). However, for the specimens stored in dry air and in water, the 1-week values were not the maximum. The fact that there was a loss of strength under all conditions led to the conclusion that it is not, after all, due to hydrolysis.

Prehardened calcium phosphate cement consisting of alpha-tricalcium phosphate (alpha-TCP), dicalcium phosphate dibasic (DCPD) and tetracalcium phosphate monoxide (TeCP) was implanted in rabbit mandibles and back muscles, and studied histologically and microradiographically. In the mandibles, new bone formation occurred around the implants and increased in quantity the longer the implant period lasted. Histology, microradiography and scanning electron microscopy (SEM) demonstrated direct contact of bone and cement. Bone response to this cement was essentially the same as to hydroxyapatite (HA) ceramics, known as a biocompatible bone substitute. Material resorption was recognized, which increased with the implant period and was greater in the surface bound by soft tissue than the surface bound by bone tissue. In the back muscles, however, no calcified tissue formation occurred. Resorption proved to be faster than in the case of the mandible implants. It was concluded that the cement, in prehardened form, has good biocompatibility and is a promising material as a bone substitute.

Organic compounds of phosphorus have been developed for a range of applications in clinical dentistry. These include dentine bonding agents, restorative materials and therapeutic agents, such as active ingredients in anticaries mouthwashes. A characteristic feature of all of these applications is the good bonding of the phosphorus compound to the tooth. This review highlights the progress that has been made to date in preparing functional and durable organophosphorus bonding agents and cements, and includes coverage of recent synthetic work aimed at preparing improved organophosphorus molecules for this application. The review concludes that this remains a promising field of chemistry to explore in the search for improved, clinically useful dental materials.

The purpose of this study was to quantify and compare the amount of water absorbed by six commercially available resin-modified glass ionomer cements and to investigate the possible influence of time and resin content on water sorption. The materials evaluated included Variglass used as a restoration, base and liner; Fuji II LC; Fuji Liner; Vitrebond; Vitremer and Photac-Bond. Z100, a composite resin, was used as control. All specimens were manipulated according to manufacturers' instructions and then subjected to a water sorption test based on the ISO 4049 requirements. Storage in water was further extended to 1 month to evaluate the effects of time and indirectly cement maturity on water sorption. Data were subjected to one-way ANOVA and Duncan's test at 0.05 significance level. Results show that the composite resin control had significantly less water sorption than all the resin-modified polyalkenoate cements evaluated. Variglass when used as a base or restorative had the least water sorption after both 1 week and 1 month storage in water. The degree of water sorption was product dependent and appeared to be influenced by the resin (HEMA) content. The results also reflect a potential relationship between time (cement maturity) and water sorption.

Although glass ionomer cements are generally considered to be tissue-compatible, it has been suggested that unreacted components or setting reaction by-products can affect cell metabolism. The current study examined the effects of constituents leached out of three glass ionomer cements on growth and metabolism of oral epithelial cells. Aseptically prepared discs of Ketac-Cem Radiopaque (KCR), Ketac-Cem Maxicap (KCM) and Fuji I were incubated in Dulbecco's medium for 10 d, with daily medium changes. Cultures of hamster cheek pouch (HCP) cells, a line of hamster buccal pouch epithelial cells, were incubated in control or eluate-containing media for 24 h. Viable cell numbers were determined by the colorimetric MTS assay, and DNA and RNA syntheses were assessed using [3H]thymidine and [3H]uridine incorporation, respectively. Responses to materials were determined by comparison of cell numbers and radioisotope incorporation (counts per minute (cpm) per 1000 cells). Results were analysed by ANOVA and Duncan's multiple range test, then converted to percent control for comparison. The eluates of all three materials from the first 24 h of soaking inhibited HCP cell growth. The number of cells in cultures exposed to Fuji were 88% of control cultures, while those exposed to KCR and KCM were 58% and 59% of control, respectively. The difference between Fuji-exposed and control cultures was significant (P < 0.05). The two Ketac cements were different from Fuji-exposed and control cultures (P < 0.05) but not from each other. All of the materials caused significant increases in labelling of DNA compared to control cultures (P < 0.05) when calculated on a per cell basis, but the materials did not differ from each other. Both Ketac cements also significantly stimulated labelling of RNA per cell compared to control cultures (P < 0.05). All effects of the material decreased over time. Results suggest that leachable components of the materials may affect the rate of progression of HCP cells through the cell cycle, rather than overt toxicity that results in cell death.

The release of methylene blue from glass-ionomer cements based on a commercial glass powder and partly hydrolysed poly(acrylic acid-co-vinyl alcohol) has been studied. A series of random copolymers were synthesized from acrylic acid and vinyl acetate monomers, using feed ratios of 10–90 mol % acrylic acid. The acetate group was hydrolysed using sodium hydroxide. According to proton nuclear magnetic resonance analysis, the degree of hydrolysis was about 40%. The residual Na + content in the samples after hydrolysis was in the vicinity of 3 mmol g −1 polymeric sample. The viscosity average molecular weight of the copolymers was the region of 60 000 g mol −1 for samples with low acrylic acid content and in the region of 300 000 g mol −1 for samples with a larger fraction of acrylic acid. Cement sample discs were prepared and the porosity of the cement was determined using N 2 adsorption-desorption isotherms. The specific surface area was 10 m 2 g −1 , and the volume of the pores ( 3 g −1 . The swelling indices and the release rates in two different buffers, pH 2.0 and pH 7.4, were determined for fresh and dried samples. An acidic environment did not bring about significant swelling in the samples and release of the model agent at pH 2.0 was limited. At a physiological pH value the cements swelled in a hydrogel manner and the fractional release of model agent increased.

The purpose of this study was to observe the effect of different conditions of storage on the surface and in the depth of luting glass ionomer cement by measuring microhardness. The hardness of a glass ionomer cement was measured after storage in wet and dry conditions and in an atmosphere of 80% relative humidity, for times up to 1000 h. Storage in distilled water produced a softening effect, but the depth hardness increased progressively. The penetration of the water is a surface phenomenon and does not affect the depth of the cement. However, the cement is vulnerable to moisture to a depth of 600 μm and marginal gaps evolve in the range of 40 to 80 μm when the luting cement at the tooth crown margin is always destroyed.

Conventional glass ionomer cements are known to release fluoride ions to the surroundings. Recently, resin-modified glass ionomer cements have been produced. These have differing chemical formulations and this may affect their ability to release fluoride ions. The study evaluates both the fluoride release and compressive strength of one conventional and four resin-modified glass ionomer cements with respect to time. The results showed that the formulation of the resin-modified materials influenced the fluoride release. One resin-modified glass ionomer (PhotacFil) released more fluoride than all other materials, while Vitremer, Fuji II LC and Chemfil Superior release similar amounts. Variglass had a very much smaller elution of fluoride ions. This suggests that there is considerable variation in fluoride release between materials of similar generic origin. The compressive strength of these materials was not affected with time.

A method has been developed which enables an in situ analysis of the degree of polymerization of bone cement. The concentration of monomeric double bond is monitored continuously during the entire curing process and hence the method can be used for quantitative studies of polymerization kinetics. In this study, Fourier Transform Raman (FTR) spectroscopy was utilized to investigate the degree of polymerization of a novel bone cement in situ, and the results are compared with the thermal profile obtained for polymerization.

The cytotoxicity of a range of dental restorative cements was assessed by continuous observation of cultures with inverted microscopy and by light microscopic study of fixed preparations, using an in vitro model with cultured test cells derived from human periodontal ligament. The sequential morphological changes observed over a seven day period showed different degrees of cell loss and patterns of injury in response to different restorative materials, reflecting primarily either nuclear or cytoplasmic damage. Attempts at recovery were frequently identified as the culture period was extended and were characterized by recolonization of denuded areas of the culture well. It was concluded that differing dental cements damage cells through a variety of mechanisms and that the test cells exhibit differing degrees of susceptibility to injury. Assays based on short-term cultures may overestimate cytotoxicity by not allowing for cell recovery from reversible injury or repopulation of monolayers by proliferation of resistant cells.

This study reports the effect of varying the thickness of a commercial zinc polycarboxylate dental cement on its adhesion in a metal-to-metal single lap joint. The thickness was controlled externally in a specially designed apparatus, rather than by the inclusion of isodimensional glass spheres, as has been done previously. The results show that both the tensile shear bond strength and the mode of failure of the cement are influenced by the thickness of the cement layer in the bonded joints. Hence, these results confirm previous findings that there is an optimum thickness for the zinc polycarboxylate layer. They also show that failure is more likely to be cohesive with thicker layers. The optimum thickness of the adhesive layer was 205 μm for the particular cement studied, PolyF Plus (De Trey, Dentsply, Weybridge, Surrey, UK), for which the average shear bond strength was found to be 4.03 MPa. Using stress analysis, the maximum shear and tensile stresses, τ 12(max) and σ 11(max) , have also been obtained. These analyses showed that joints failed at the interface between the cement layers and the lap joint at adhesive layer thicknesses of below 100 μm. This resulted from the high stress concentrations in bonded joints with thin adhesive layers. On the other hand, thicker joints failed cohesively within the adhesive layer because of greater contributions from tensile stresses in these joints.

Powdered zinc silicate glasses were investigated for cement formation with aqueous poly(acrylic acid). Alkali metal zinc silicate glasses and calcium zinc silicate glasses gave polyalkenoate cements which were hydrolytically unstable, whilst alumino-zinc-silicate glasses gave hydrolytically stable cements with short setting times (under 10 min) and high compressive strengths (above 90 MPa). The aluminium to silicon ratio was not important in determining the cement forming ability of the glass. The ability to form a cement was, instead, determined largely by the network connectivity of the glass.

The lactic acid jet test erosion rates were measured for 13 radiopaque glass ionomer dental materials obtained from a number of manufacturing sources. The erosion rate was compared with that found for the non-radiopaque restorative from the same manufacturer to determine whether the addition of an extra element had affected the resistance to erosion. Six materials were not significantly affected, six showed a significant increase in erosion rate. Only one material showed a reduced erosion rate. Materials containing a high proportion of any additive could show an increased erosion rate. Glass ionomer cements with or without radiopacifying elements had low erosion rates compared with other dental materials.

A study has been made on the release of fluoride from three glass-ionomer cements. The effect of the maturity of cements at the time of immersion and powder/liquid ratio were examined. It was found that fluoride release from immature cements was dependent on cement and powder/ liquid ratio and that the effect was permanent. The effect of cement type and powder/liquid ratio lessened as cements were allowed to mature prior to immersion. It appeared that fluoride release was dependent on the strength and maturity of the cement matrix and not fluoride content. It was concluded that the rate of fluoride release would depend largely on clinical factors rather than cement type.

The fracture toughness and yield stress values of model zinc polycarboxylate and glass polyalkenoate cements have been used to calculate plastic zone sizes. The size of the plastic zone at the crack tip in these materials has been used to predict whether cement layer thickness is likely to influence the adhesive bond strength. In the model zinc polycarboxylate cement studied, the plastic zone size was comparable to the cement layer thickness and had a pronounced influence on the shear bond strengths obtained. In contrast, the plastic zone sizes obtained for the glass polyalkenoate cements were much smaller and the shear bond strengths were found to be much less dependent on cement layer thickness.

When zinc phosphate cement was immersed in 0.1 M acetic and lactic acid buffer solutions adjusted to pH 4.1, its dissolution rate was determined by chemical analysis. The eroded surface of the cement was examined by X-ray diffraction and SEM observation. The dissolution process of the cement immersed in the acetic acid buffer solution was mainly controlled by the diffusion of releasing species through the cement matrix and that of the cement immersed in the lactic acid buffer solution by the decomposition of the cement matrix at the surface.

An investigation was made into the effect of structure and functionality of aromatic carboxylates on their adsorption on to hydroxyapatite (HAP) with a view to identifying factors affecting the adhesion of polyacrylate cements to tooth materials. In general, the amount of carboxylate adsorbed was found to increase with the number of groups contained in the molecule. The arrangement of these groups around the benzene ring also affected adsorption. These results suggested that adsorption was the result of a cooperative effect between carboxylate groups. An adsorption isotherm for mellitate on to HAP was constructed.

Light curable antibacterial, dental composite restoration materials, consisting of 80wt% of a strontium fluoroalummosilicate glass dispersed in methacrylate monomers have been produced. The monomers contained 40-100wt% of a 10wt% chlorhexidine diacetate (CHXA) in hydroxyethylmethacrylate (HEMA) solution and 60-0wt% of a 50150 mix of urethane dimethacrylate (UDMA) and triethyleneglycol dimethacrylate (TEGDMA). On raising HEMA content, light cure polymerisation rates decreased. Conversely, water sorption induced swelling and rates of diffusion controlled CHXA release from the set materials increased. Experimental composites with 50 and 90wt% of the CHXA in HEMA solution in the monomer were shown, within a constant depth film fermentor (CDFF), to have slower rates of biofilm growth on their surfaces between I and 7 days than the commercial dental composite Z250 or fluoride-releasing dental cements, Fuji II LC and Fuji IX. When an excavated bovine dentine cylinder refilled with Z250 was placed for 10 weeks in the CDFF, both bacteria and polymers from the artificial saliva penetrated between the material and dentine. With the 50wt% experimental HEMA/CHXA formulation, this bacterial microleakage was substantially reduced. Polymer leakage, however, still occurred. Both polymer and bacterial microleakage were prevented with a 90 wt% HEMA/CHXA restoration in the bovine dentine due to swelling compensation for polymerisation shrinkage in combination with antibacterial release. (c) 2005 Elsevier Ltd. All rights reserved.

Previous studies have shown that methacrylated beta-cyclodextrins (MCDs) can be used as comonomers in resin-based dental composites. These MCDs by virtue of having several polymerizable methacrylate groups and hydrophilic hydroxyl groups, may also promote bonding of dental composites to dentin. This study evaluated MCDs as adhesive comonomers, and optimized comonomer and polymerization initiator concentrations for maximum shear bond strength (SBS). Experimental MCD-based bonding formulations in acetone were prepared by mixing 33 mass fraction % MCDs with (10, 20, 30, 40, or 50) mass fraction % of 2-hydroxyethyl methacrylate (HEMA). The MCD/HEMA-based solutions were activated with varied amounts of camphorquinone (CQ) and ethyl 4-dimethylamino benzoate (4E). Samples for SBS were prepared by bonding a composite resin to acid-etched dentin surfaces of extracted human molars with the experimental bonding solutions. The specimens were immersed in 37 degrees C water for 24 h and bond strengths were determined in shear mode. With increasing HEMA concentration, the SBS values of MCD-bonding solutions increased to 16 MPa at a composition of 33% MCD, 30% HEMA, and 37% acetone by mass. Also, SBS values of MCD-bonding solutions varied as a function of the CQ and 4E concentrations and passed through a maximum SBS at 21 MPa, which was comparable to that of a commercial control. This preliminary study indicated that nonacidic MCD monomers could be used as an adhesion-promoting comonomer. Additional modification of MCDs having both polymerizable groups and anionic ligand groups, e.g., polymerizable acidic cyclodextrin derivatives should increase the SBS even further.

The bonding effectiveness of restorative materials to tooth tissue is typically measured statically. Clinically tooth/composite bonds are however subjected to cyclic sub-critical loads. Therefore, in vitro fatigue testing of dental adhesives should predict better the in vivo performance of adhesives. The objective of this study was to determine the fatigue resistance of two representative adhesives, a self-etch and an etch&rinse adhesive, bonded to enamel and dentin. Therefore, tooth/composite interfaces were cyclically loaded using a miniaturized version of a rotating beam fatigue testing device. Subsequently, the load at which 50% of the specimens fail after 10 5 cycles, was determined as the median micro-rotary fatigue resistance (μRFR). For both adhesives, the μRFR was about 30–40% lower than the corresponding micro-tensile bond strength (μTBS) to both enamel and dentin. Analysis of the fracture surfaces by Feg-SEM revealed typical fatigue fracture patterns. It is concluded that resin/tooth interfaces are vulnerable to progressive damage by sub-critical loads, with the 3-step etch&rinse adhesive being more resistant to fatigue than the 2-step self-etch adhesive.

Utilizing scanning electron microscope, X-ray diffraction (XRD) and microhardness tests, we evaluated how various physiological environments affect the hydration behavior and physical properties of mineral trioxide aggregate (MTA). We found that the microstructure of hydrated MTA consists of cubic and needle-like crystals. The former comprised the principal structure of MTA, whereas the later were less prominent and formed in the inter-grain spaces between the cubic crystals. MTA samples were hydrated in distilled water, normal saline, pH 7, and pH 5. However, no needle-like crystals were observed in the pH 5 specimens, and erosion of the cubic crystal surfaces was noted. XRD indicated a peak corresponding to Portlandite, a hydration product of MTA, and the peak decreased noticeably in the pH 5 group. The pH 5 specimens' microhardness was also significantly weaker compared to the other three groups (p