Novel rechargeable calcium phosphate dental nanocomposite.

OBJECTIVES: Calcium phosphate (CaP) composites with Ca and P ion release can remineralize tooth lesions and inhibit caries. But the ion release lasts only a few months. The objectives of this study were to develop rechargeable CaP dental composite for the first time, and investigate the Ca and P recharge and re-release of composites with nanoparticles of amorphous calcium phosphate (NACP) to achieve long-term inhibition of caries. METHODS: Three NACP nanocomposites were fabricated with resin matrix of: (1) bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) at 1:1 mass ratio (referred to as BT group); (2) pyromellitic glycerol dimethacrylate (PMGDM) and ethoxylated bisphenol A dimethacrylate (EBPADMA) at 1:1 ratio (PE group); (3) BisGMA, TEGDMA, and Bis[2-(methacryloyloxy)ethyl] phosphate (BisMEP) at 2:1:1 ratio (BTM group). Each resin was filled with 20% NACP and 50% glass particles, and the composite was photo-cured. Specimens were tested for flexural strength and elastic modulus, Ca and P ion release, and Ca and P ion recharge and re-release. RESULTS: NACP nanocomposites had strengths 3-fold of, and elastic moduli similar to, commercial resin-modified glass ionomer controls. CaP ion recharge capability was the greatest for PE group, followed by BTM group, with BT group being the lowest (p<0.05). For each recharge cycle, CaP re-release reached similarly high levels, showing that CaP re-release did not decrease with more recharge cycles. After six recharge/re-release cycles, NACP nanocomposites without further recharge had continuous CaP ion release for 42 d. SIGNIFICANCE: Novel rechargeable CaP composites achieved long-term and sustained Ca and P ion release. Rechargeable NACP nanocomposite is promising for caries-inhibiting restorations, and the Ca and P ion recharge and re-release method has wide applicability to dental composites, adhesives, cements and sealants to achieve long-term caries-inhibition.

Polymeric dental composites based on remineralizing amorphous calcium phosphate fillers.

For over two decades we have systematically explored structure-composition-property relationships of amorphous calcium phosphate (ACP)-based polymeric dental composites. The appeal of these bioactive materials stems from their intrinsic ability to prevent demineralization and/or restore defective tooth structures via sustained release of remineralizing calcium and phosphate ions. Due to the compositional similarity of the ACP to biological tooth mineral, ACP-based composites should exhibit excellent biocompatibility. Research described in this article has already yielded remineralizing sealants and orthodontic adhesives as well as a prototype root canal sealer. Our work has also contributed to a better understanding on how polymer matrix structure and filler/matrix interactions affect the critical properties of these polymeric composites and their overall performance. The addition of antimicrobial compounds to the formulation of ACP composites could increase their medical and dental regenerative treatment applications, thereby benefiting an even greater number of patients.

Novel Dental Cement to Combat Biofilms and Reduce Acids for Orthodontic Applications to Avoid Enamel Demineralization.

Orthodontic treatments often lead to biofilm buildup and white spot lesions due to enamel demineralization. The objectives of this study were to develop a novel bioactive orthodontic cement to prevent white spot lesions, and to determine the effects of cement compositions on biofilm growth and acid production. 2-methacryloyloxyethyl phosphorylcholine (MPC), nanoparticles of silver (NAg), and dimethylaminohexadecyl methacrylate (DMAHDM) were incorporated into a resin-modified glass ionomer cement (RMGI). Enamel shear bond strength (SBS) was determined. Protein adsorption was determined using a micro bicinchoninic acid method. A dental plaque microcosm biofilm model with human saliva as inoculum was used to investigate metabolic activity, colony-forming units (CFU) and lactic acid production. Incorporating 3% of MPC, 1.5% of DMAHDM, and 0.1% of NAg into RMGI, and immersing in distilled water at 37 °C for 30 days, did not decrease the SBS, compared to control (p > 0.1). RMGI with 3% MPC + 1.5% DMAHDM + 0.1% NAg had protein amount that was 1/10 that of control. RMGI with triple agents (MPC + DMAHDM + NAg) had much stronger antibacterial property than using a single agent or double agents (p < 0.05). Biofilm CFU on RMGI with triple agents was reduced by more than 3 orders of magnitude, compared to commercial control. Biofilm metabolic activity and acid production were also greatly reduced. In conclusion, adding MPC + DMAHDM + NAg in RMGI substantially inhibited biofilm viability and acid production, without compromising the orthodontic bracket bond strength to enamel. The novel bioactive cement is promising for orthodontic applications to hinder biofilms and plaque buildup and enamel demineralization.

Structural and dynamical studies of acid-mediated conversion in amorphous-calcium-phosphate based dental composites.

OBJECTIVE: To investigate the complex structural and dynamical conversion process of the amorphous-calcium-phosphate (ACP)-to-apatite transition in ACP based dental composite materials. METHODS: Composite disks were prepared using zirconia hybridized ACP fillers (0.4 mass fraction) and photo-activated Bis-GMA/TEGDMA resin (0.6 mass fraction). We performed an investigation of the solution-mediated ACP-to-apatite conversion mechanism in controlled acidic aqueous environment with in situ ultra-small angle X-ray scattering based coherent X-ray photon correlation spectroscopy and ex situ X-ray diffraction, as well as other complementary techniques. RESULTS: We established that the ACP-to-apatite conversion in ACP composites is a two-step process, owing to the sensitivity to local structural changes provided by coherent X-rays. Initially, ACP undergoes a local microstructural rearrangement without losing its amorphous character. We established the catalytic role of the acid and found the time scale of this rearrangement strongly depends on the pH of the solution, which agrees with previous findings about ACP without the polymer matrix being present. In the second step, ACP is converted to an apatitic form with the crystallinity of the formed crystallites being poor. Separately, we also confirmed that in the regular Zr-modified ACP the rate of ACP conversion to hydroxyapatite is slowed significantly compared to unmodified ACP, which is beneficial for targeted slow release of functional calcium and phosphate ions from dental composite materials. SIGNIFICANCE: For the first time, we were able to follow the complete solution-mediated transition process from ACP to apatite in this class of dental composites in a controlled aqueous environment. A two-step process, suggested previously, was conclusively identified.

Evaluation of three-dimensional biofilms on antibacterial bonding agents containing novel quaternary ammonium methacrylates.

Antibacterial adhesives are promising to inhibit biofilms and secondary caries. The objectives of this study were to synthesize and incorporate quaternary ammonium methacrylates into adhesives, and investigate the alkyl chain length effects on three-dimensional biofilms adherent on adhesives for the first time. Six quaternary ammonium methacrylates with chain lengths of 3, 6, 9, 12, 16 and 18 were synthesized and incorporated into Scotchbond Multi-Purpose. Streptococcus mutans bacteria were cultured on resin to form biofilms. Confocal laser scanning microscopy was used to measure biofilm thickness, live/dead volumes and live-bacteria percentage vs. distance from resin surface. Biofilm thickness was the greatest for Scotchbond control; it decreased with increasing chain length, reaching a minimum at chain length 16. Live-biofilm volume had a similar trend. Dead-biofilm volume increased with increasing chain length. The adhesive with chain length 9 had 37% live bacteria near resin surface, but close to 100% live bacteria in the biofilm top section. For chain length 16, there were nearly 0% live bacteria throughout the three-dimensional biofilm. In conclusion, strong antibacterial activity was achieved by adding quaternary ammonium into adhesive, with biofilm thickness and live-biofilm volume decreasing as chain length was increased from 3 to 16. Antibacterial adhesives typically only inhibited bacteria close to its surface; however, adhesive with chain length 16 had mostly dead bacteria in the entire three-dimensional biofilm. Antibacterial adhesive with chain length 16 is promising to inhibit biofilms at the margins and combat secondary caries.

Effects of dual antibacterial agents MDPB and nano-silver in primer on microcosm biofilm, cytotoxicity and dentine bond properties.

OBJECTIVES: The objective of this study was to investigate the effects of dentine primer containing dual antibacterial agents, namely, 12-methacryloyloxydodecylpyridinium bromide (MDPB) and nanoparticles of silver (NAg), on dentine bond strength, dental plaque microcosm biofilm response, and fibroblast cytotoxicity for the first time. METHODS: Scotchbond Multi-Purpose (SBMP) was used as the parent bonding agent. Four primers were tested: SBMP primer control (referred to as "P"), P+5% MDPB, P+0.05% NAg, and P+5% MDPB+0.05% NAg. Dentine shear bond strengths were measured using extracted human teeth. Biofilms from the mixed saliva of 10 donors were cultured to investigate metabolic activity, colony-forming units (CFU), and lactic acid production. Human fibroblast cytotoxicity of the four primers was tested in vitro. RESULTS: Incorporating MDPB and NAg into primer did not reduce dentine bond strength compared to control (p>0.1). SEM revealed well-bonded adhesive-dentine interfaces with numerous resin tags. MDPB or NAg each greatly reduced biofilm viability and acid production, compared to control. Dual agents MDPB+NAg had a much stronger effect than either agent alone (p<0.05), increasing inhibition zone size and reducing metabolic activity, CFU and lactic acid by an order of magnitude, compared to control. There was no difference in cytotoxicity between commercial control and antibacterial primers (p>0.1). CONCLUSIONS: The method of using dual agents MDPB+NAg in the primer yielded potent antibacterial properties. Hence, this method may be promising to combat residual bacteria in tooth cavity and invading bacteria at the margins. The dual agents MDPB+NAg may have wide applicability to other adhesives, composites, sealants and cements to inhibit biofilms and caries.

Effect of amorphous calcium phosphate and silver nanocomposites on dental plaque microcosm biofilms.

A dental composite containing amorphous calcium phosphate nanoparticles (NACP) was developed that released calcium (Ca) and phosphate (PO(4)) ions and possessed acid-neutralization capability. There has been little study on incorporation of antibacterial agents into calcium phosphate composites. The objective of this study was to investigate the effect of silver nanoparticle (NAg) mass fraction in NACP nanocomposite on mechanical properties and dental plaque microcosm biofilm for the first time. NACP nanoparticles of 116 nm were synthesized via a spray-drying technique. NAg nanoparticles were synthesized using Ag 2-ethylhexanoate and 2-(tert-butylamino)ethyl methacrylate, yielding NAg of particle size of 2.7 nm that were well-dispersed in the resin. Five NACP nanocomposites were fabricated with NAg mass fractions of 0, 0.028, 0.042, 0.088, and 0.175%, respectively. Mechanical properties of NACP nanocomposites containing 0-0.042% of NAg matched those of a commercial composite without antibacterial activity. Live/dead assay of dental plaque microcosm biofilms showed complete coverage with live bacteria on commercial composite. However, there were increasingly more dead bacteria with higher NAg content in the NACP nanocomposite. Colony-forming unit (CFU) counts for total microorganisms, total streptococci, and mutans streptococci for NACP nanocomposite with 0.042% NAg were about 1/4 those of commercial composite. Lactic acid production on NACP nanocomposite with 0.042% NAg was 1/3 that on commercial composite. In conclusion, novel NACP-NAg nanocomposites were developed which possessed good mechanical properties and potent antibacterial properties, with substantially reduced biofilm viability and lactic acid production. Hence, the NACP-NAg nanocomposites are promising for dental restorations with remineralizing and antibacterial capabilities.

Long-term mechanical durability of dental nanocomposites containing amorphous calcium phosphate nanoparticles.

Half of all dental restorations fail within 10 years, with secondary caries and restoration fracture being the main reasons. Calcium phosphate (CaP) composites can release Ca and PO(4) ions and remineralize tooth lesions. However, there has been no report on their long-term mechanical durability. The objective of this study was to investigate the wear, thermal-cycling, and water-aging of composites containing amorphous calcium phosphate nanoparticles (NACP). NACP of 112-nm and glass particles were used to fabricate four composites: (1) 0% NACP+75% glass; (2) 10% NACP+65% glass; (3) 15% NACP+60% glass; and (4) 20% NACP+50% glass. Flexural strength and elastic modulus of NACP nanocomposites were not degraded by thermal-cycling. Wear depth increased with increasing NACP filler level. Wear depths of NACP nanocomposites after 4 × 10(5) cycles were within the range for commercial controls. Mechanical properties of all the tested materials decreased with water-aging time. After 2 years, the strengths of NACP nanocomposites were moderately higher than the control composite, and much higher than the resin-modified glass ionomers. The mechanism of strength loss for resin-modified glass ionomer was identified as microcracking and air-bubbles. NACP nanocomposites and control composite were generally free of microcracks and air-bubbles. In conclusion, combining NACP nanoparticles with reinforcement glass particles resulted in novel nanocomposites with long-term mechanical properties higher than those of commercial controls, and wear within the range of commercial controls. These strong long-term properties, plus the Ca-PO(4) ion release and acid-neutralization capability reported earlier, suggest that the new NACP nanocomposites may be promising for stress-bearing and caries-inhibiting restorations.

Ultra-small-angle X-ray scattering-X-ray photon correlation spectroscopy studies of incipient structural changes in amorphous calcium phosphate-based dental composites.

The local structural changes in amorphous calcium phosphate (ACP)-based dental composites were studied under isothermal conditions using both static, bulk measurement techniques and a recently developed methodology based on combined ultra-small angle X-ray scattering-X-ray photon correlation spectroscopy (USAXS-XPCS), which permits a dynamic approach. While results from conventional bulk measurements do not show clear signs of structural change, USAXS-XPCS results reveal unambiguous evidence for local structural variations on a similar time scale to that of water loss in the ACP fillers. A thermal-expansion-based simulation indicates that thermal behavior alone does not account for the observed dynamics. Together, these results suggest that changes in the water content of ACP affect the composite morphology due to changes in ACP structure that occur without an amorphous-to-crystalline conversion. It is also noted that biomedical materials research could benefit greatly from USAXS-XPCS, a dynamic approach.

Antibacterial amorphous calcium phosphate nanocomposites with a quaternary ammonium dimethacrylate and silver nanoparticles.

OBJECTIVES: Calcium and phosphate ion-releasing resin composites are promising for remineralization. However, there has been no report on incorporating antibacterial agents to these composites. The objective of this study was to develop antibacterial and mechanically strong nanocomposites incorporating a quaternary ammonium dimethacrylate (QADM), nanoparticles of silver (NAg), and nanoparticles of amorphous calcium phosphate (NACP). METHODS: The QADM, bis(2-methacryloyloxyethyl) dimethylammonium bromide (ionic dimethacrylate-1), was synthesized from 2-(N,N-dimethylamino)ethyl methacrylate and 2-bromoethyl methacrylate. NAg was synthesized by dissolving Ag 2-ethylhexanoate salt in 2-(tert-butylamino)ethyl methacrylate. Mechanical properties were measured in three-point flexure with bars of 2 mm×2 mm×25 mm (n=6). Composite disks (diameter=9 mm, thickness=2 mm) were inoculated with Streptococcus mutans. The metabolic activity and lactic acid production of biofilms were measured (n=6). Two commercial composites were used as controls. RESULTS: Flexural strength and elastic modulus of NACP+QADM, NACP+NAg, and NACP+QADM+NAg matched those of commercial composites with no antibacterial property (p>0.1). The NACP+QADM+NAg composite decreased the titer counts of adherent S. mutans biofilms by an order of magnitude, compared to the commercial composites (p<0.05). The metabolic activity and lactic acid production of biofilms on NACP+QADM+NAg composite were much less than those on commercial composites (p<0.05). Combining QADM and NAg rendered the nanocomposite more strongly antibacterial than either agent alone (p<0.05). SIGNIFICANCE: QADM and NAg were incorporated into calcium phosphate composite for the first time. NACP+QADM+NAg was strongly antibacterial and greatly reduced the titer counts, metabolic activity, and acid production of S. mutans biofilms, while possessing mechanical properties similar to commercial composites. These nanocomposites are promising to have the double benefits of remineralization and antibacterial capabilities to inhibit dental caries.

Synthesis and characterization of dimethacrylates containing quaternary ammonium functionalities for dental applications.

OBJECTIVES: The widespread incidence of recurrent caries highlights the need for improved dental restorative materials. The objective of this study was to synthesize low viscosity ionic dimethacrylate monomers (IDMAs) that contain quaternary ammoniums groups (antimicrobial functionalities) and are compatible with existing dental dimethacrylate-based monomers. Such monomers have the potential to copolymerize with other methacrylate monomers and produce antibacterial polymers. METHODS: Two monomers (IDMA-1 and IDMA-2) were synthesized using the Menschutkin reaction and incorporated at 0-30% (by mass) into a 1:1 (by mass) bisphenol A glycerolate dimethacrylate (BisGMA):triethylene glycol dimethacrylate (TEGDMA) resin. Resin viscosity was quantified using rheology, and polymer degree of conversion (DC) and surface charge density were measured using Fourier transform infrared spectroscopy (FTIR) and fluorescein binding, respectively. Effects of IDMA-1 on initial attachment of Streptococcus mutans and on viability and metabolic activity (via reductase enzymes) of RAW 264.7 macrophage-like cells were quantified. RESULTS: IDMA-1 and IDMA-2 were prepared and characterized. IDMA-1 was miscible with BisGMA:TEGDMA and slightly increased the resin viscosity and DC. As expected, polymeric surface charge density increased with increasing IDMA-1. Incorporation of 10% IDMA-1 into BisGMA:TEGDMA reduced bacterial colonization without affecting viability or metabolic activity of mammalian cells. Increasing IDMA-1 up to 30% had no additional effect on bacterial coverage, but ≥20% IDMA-1 significantly reduced macrophage density, viability, and metabolic activity. Leachables from polymers containing IDMA-1 were not cytotoxic. SIGNIFICANCE: The Menschutkin reaction provides a facile, convenient means to synthesize new monomers with quaternary ammonium groups for dental and medical applications.

Bioactive polymeric composites for tooth mineral regeneration: physicochemical and cellular aspects.

Our studies of amorphous calcium phosphate (ACP)-based dental materials are focused on the design of bioactive, non-degradable, biocompatible, polymeric composites derived from acrylic monomer systems and ACP by photochemical or chemically activated polymerization. Their intended uses include remineralizing bases/liners, orthodontic adhesives and/or endodontic sealers. The bioactivity of these materials originates from the propensity of ACP, once exposed to oral fluids, to release Ca and PO(4) ions (building blocks of tooth and bone mineral) in a sustained manner while spontaneously converting to thermodynamically stable apatite. As a result of ACP's bioactivity, local Ca- and PO(4)-enriched environments are created with supersaturation conditions favorable for the regeneration of tooth mineral lost to decay or wear. Besides its applicative purpose, our research also seeks to expand the fundamental knowledge base of structure-composition-property relationships existing in these complex systems and identify the mechanisms that govern filler/polymer and composite/tooth interfacial phenomena. In addition to an extensive physicochemical evaluation, we also assess the leachability of the unreacted monomers and in vitro cellular responses to these types of dental materials. The systematic physicochemical and cellular assessments presented in this study typically provide model materials suitable for further animal and/or clinical testing. In addition to their potential dental clinical value, these studies suggest the future development of calcium phosphate-based biomaterials based on composite materials derived from biodegradable polymers and ACP, and designed primarily for general bone tissue regeneration.

Analyses of a cantilever-beam based instrument for evaluating the development of polymerization stresses.

OBJECTIVE: This investigation was to generate (1) guidelines for designing a tensometer that satisfies the necessary accuracy and sensitivity requirements for measuring polymerization stress (PS), and (2) a formula for calculating PS. Polymerization stress remains one of the most critical properties of polymeric dental materials, yet methods that can accurately quantify PS have been limited in part due to the complexity of polymerization, and in part due to the instrumentation itself. METHOD: In this study, we performed analytical and finite element analyses on a cantilever-beam based tensometer that is used to evaluate shrinkage stresses during the polymerization of dental restorative composites. RESULTS: The PS generated by a commercial dental composite determined using our new tensometer agrees with the predicted trend when the beam length and/or specimen height is varied. SIGNIFICANCE: This work demonstrates the importance of beam dimension and component relative rigidity to the accuracy of PS evaluation. An analytical solution is also derived for the vertical beam deflection, which can be used for any combination of bending and shearing to properly calculate the PS. In addition, an easy-to-conduct calibration procedure is provided that is desirable for periodic tensometer recalibration.

In situ formation of silver nanoparticles in photocrosslinking polymers.

Nanocomposites of cross-linked methacrylate polymers with silver nanoparticles have been synthesized by coupling photoinitiated free radical polymerization of dimethacrylates with in situ silver ion reduction. A polymerizable methacrylate bearing a secondary amino functional group was used to increase the solubility of the silver salt in the hydrophobic resin system. Fourier transform infrared spectroscopy (FTIR) revealed that the silver ion reduction had no significant effect on the degree of vinyl conversion of the methacrylate. X-ray photoelectron spectroscopy (XPS) measurements showed an increased silver concentration at the composite surface compared to the expected concentration based on the total amount of silver salt added. Furthermore, the surface silver concentration leveled off when the silver salt mass fractions were 0.08% or greater. Composites with low concentrations of silver salt (< 0.08% by mass) exhibited comparable mechanical properties to those containing no silver. Transmission electron microscopy (TEM) confirmed that the silver nanoparticles formed within the polymer matrix were nanocrystalline in nature and primarily ≈ 3 nm in diameter, with some large particle aggregates. Composites containing silver nanoparticles were shown to reduce bacterial colonization with as little as 0.03% (by mass) silver salt, while additional amounts of silver salt did not further decrease their surface colonization. With a substantial effect on bacterial growth and minimal effects on mechanical properties, the in situ formation of silver nanoparticles within methacrylate materials is a promising technique for synthesizing antibacterial nanocomposites for biomedical applications.

NMR characterization of the formation kinetics and structure of di-O-benzylidene sorbitol gels self-assembled in organic solvents.

The molecule 1,3:2,4-di-O-benzylidene sorbitol (DBS) is a common "gelator" that forms thermally reversible gels in diverse organic solvents. Solid-state (13)C and (1)H NMR techniques, along with electron microscopy, are utilized in an exploratory study of DBS in the gelled state where we consider both in situ and dried gels. The gels were formed in either acetone or benzene, with the former being a better solvent for DBS. We find the in situ or dried DBS gels to be composed of rigid twisted nanofibrils (∼15 to 21 nm in diameter). The fibrils show local molecular ordering, but not crystalline order, and they contain no trapped solvent. The molecular mobility at the fibril surface is modestly enhanced, and all the free hydroxyl groups of the sorbitol moiety are involved in strong hydrogen bonding. We also attempted to find a truly crystalline form of DBS whose structure, as judged by the similarity of (13)C spectra, is close to that of the fibrils. We partially succeeded in this quest, employing melt crystallization followed by slow cooling. However, this sample was a mixed crystal having small domains, where only one type of domain was structurally similar to the fibrils. We also investigated the long-time evolution of the in situ DBS gel network. Specifically, high-resolution NMR kinetic studies were performed over periods of days where the residual concentration of DBS in acetone solution was monitored during and after gel formation. The DBS concentration on these long timescales evolved slowly, and we introduce a simple mathematical model and equation to describe this phenomenon.

Fine-Tuning of Polymeric Resins and Their Interfaces with Amorphous Calcium Phosphate. A Strategy for Designing Effective Remineralizing Dental Composites.

For over a decade our group has been designing, preparing and evaluating bioactive, remineralizing composites based on amorphous calcium phosphate (ACP) fillers embedded in polymerized methacrylate resin matrices. In these studies a major focus has been on exploring structure-property relationships of the matrix phase of these composites on their anti-cariogenic potential. The main challenges were to gain a better understanding of polymer matrix/filler interfacial properties through controlling the surface properties of the fillers or through fine-tuning of the resin matrix. In this work, we describe the effect of chemical structure and composition of the resin matrices on some of the critical physicochemical properties of the copolymers and their ACP composites. Such structure-property studies are essential in formulating clinically effective products, and this knowledge base is likely to have strong impact on the future design of therapeutic materials, appropriate for mineral restoration in defective tooth structures.

Polymerization stress development in dental composites: Effect of cavity design factor.

The objective of the study was to assess the effect of the cavity design factor (C-factor) on polymerization stress development (PSD) in resin composites. An experimental resin (BT resin) was prepared, which contained 2,2-bis[p-(2'hydroxy-3'-methacryloxypropoxy)phenylene]propane (B) and triethylene glycol dimethacrylate (T) in 1:1 mass ratio, and an activator for visible light polymerization. Also an experimental composite with demonstrated remineralizing potential was formulated by inclusion into the BT resin of zirconia-hybridized amorphous calcium phosphate (ACP) filler at a mass fraction of 40 % (BT/ACP composite). A commercial glass-filled composite (TPH) was used as a control. To assess the effect of the test geometry on PSD, C-factor was systematically varied between 0.8 and 6.0 by varying the height of the cylindrical composite specimens. The measured PSD values obtained by cantilever beam tensometry for specimens with variable C-factors were normalized for mass to specimens with a C-factor of 1.33 (h=2.25 mm) as controls to give calculated PSD values. Degrees of vinyl conversions (DC) attained in the TPH control and in the experimental BT/ACP composites were measured by near-infrared spectroscopy. In both the TPH and BT/ACP composite series, PSDcalc increased with the increasing C-factor, confirming the hypothesis that the C-factor value influences PSD values. The higher PSDmeas and PSDcalc values for the experimental BT/ACP composite compared to the commercial TPH composite probably reflect differences in the type and mass of the resin and filler phases in the two types of composite. These differences also account for the observed variation (21 %) in DC attained in a BT/ACP composite 2 h after cure (69.5 %) and in the DC of the TPH composite (57.5 %) having the same C-factor. The cavity design factor seems to play a key role in influencing the PSD of bonded composites, but other factors such as composite mass and composition also must be considered for their effects on PSD.

Structure-Composition-Property Relationships in Polymeric Amorphous Calcium Phosphate-Based Dental Composites.

Our studies of amorphous calcium phosphate (ACP)-based materials over the last decade have yielded bioactive polymeric composites capable of protecting teeth from demineralization or even regenerating lost tooth mineral. The anti-cariogenic/re-mineralizing potential of these ACP composites originates from their propensity, when exposed to the oral environment, to release in a sustained manner sufficient levels of mineral-forming calcium and phosphate ions to promote formation of stable apatitic tooth mineral. However, the less than optimal ACP filler/resin matrix cohesion, excessive polymerization shrinkage and water sorption of these experimental materials can adversely affect their physicochemical and mechanical properties, and, ultimately, limit their lifespan. This study demonstrates the effects of chemical structure and composition of the methacrylate monomers used to form the matrix phase of composites on degree of vinyl conversion (DVC) and water sorption of both copolymers and composites and the release of mineral ions from the composites. Modification of ACP surface via introducing cations and/or polymers ab initio during filler synthesis failed to yield mechanically improved composites. However, moderate improvement in composite's mechanical stability without compromising its remineralization potential was achieved by silanization and/or milling of ACP filler. Using ethoxylated bisphenol A dimethacrylate or urethane dimethacrylate as base monomers and adding moderate amounts of hydrophilic 2-hydroxyethyl methacrylate or its isomer ethyl-α-hydroxymethacrylate appears to be a promising route to maximize the remineralizing ability of the filler while maintaining high DVC. Exploration of the structure/composition/property relationships of ACP fillers and polymer matrices is complex but essential for achieving a better understanding of the fundamental mechanisms that govern dissolution/re-precipitation of bioactive ACP fillers, and, ultimately, the suitability of the composites for clinical evaluation.

Adhesion of amorphous calcium phosphate composites bonded to dentin: a study in failure modality.

AIMS: As a bioactive filler capable of remineralizing tooth structures, the main disadvantage of as-made amorphous calcium phosphate (am-ACP) are its large agglomerates. The objective of this study was to mill ACP, and compare the adhesive strength with dentin, work to fracture, and failure modes of both groups to glass-filled composites and one commercial compomer after 24 h, 1 week, 1, 3, and 6 months of exposure to simulated saliva solution (SLS). Flat dentin surfaces were acid-etched, primed, and photopolymerized. Composites were applied, photo-cured, and debonded in shear. The resin used in each composite was identical: ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, and methacryloxyethyl phthalate. Fillers consisted of am-ACP and milled ACP (m-ACP), and a strontium-containing glass (Sr-glass) at respective mass fractions of (40, 60, and 75%). FINDINGS: Ninety percent of the fracture surfaces in this study showed adhesive failure, with most of these occurring at the dentin/primer interface. Fifty-two percent of failures after 24-h immersion occurred at the primer/composite interface. After 6 months of SLS exposure, 80% of specimens failed at the dentin/primer interface, with a 42% overall reduction in bond strength. CONCLUSIONS: Milled ACP composites showed initial mechanical advantages over am-ACP composites and the compomer, and produced a higher incidence of a failure mode consistent with stronger adhesion. Evidence is provided which suggests that milled ACP composites may offer enhanced potential in clinical bonding applications.