Electron Paramagnetic Resonance Characterization of Sodium- and Carbonate-Containing Hydroxyapatite Cement.

Ionizing radiation-induced paramagnetic defects in calcified tissues like tooth enamel are indicators of irradiation dose. Hydroxyapatite (HA), the principal constituent in these materials, incorporates a variety of anions (CO32-, F-, Cl-, and SiO44-) and cations (Mn2+, Li+, Cu2+, Fe3+, Mg2+, and Na+) that directly or indirectly contribute to the formation of stable paramagnetic centers upon irradiation. Here, we used an underexploited synthesis method based on the ambient temperature setting reaction of a self-hardening calcium phosphate cement (CPC) to create carbonate-containing hydroxyapatite (CHA) and investigate its paramagnetic properties following γ-irradiation. Powder X-ray diffraction and IR spectroscopic characterization of the hardened CHA samples indicate the formation of pure B-type CHA cement. CHA samples exposed to γ-radiation doses ranging from 1 Gy to 150 kGy exhibited an electron paramagnetic resonance (EPR) signal from an orthorhombic CO2•- free radical. At γ-radiation doses from 30 to 150 kGy, a second signal emerged that is assigned to the CO3•- free radical. We observed that the formation of this second species is dose-dependent, which provided a means to extend the useful dynamic range of irradiated CHA to doses >30 kGy. These results indicate that CHA synthesized via a CPC cement is a promising substrate for EPR-based dosimetry. Further studies on the CHA cement are underway to determine the suitability of these materials for a range of biological and industrial dosimetry applications.

Iron oxide nanoparticle-calcium phosphate cement enhanced the osteogenic activities of stem cells through WNT/ß-catenin signaling.

Calcium phosphate cement (CPC), functionalized with iron oxide nanoparticles (IONP), is of great promise to promote osteoinduction and new bone formation. In this work, the IONP powder was added into the CPC powder to fabricate CPC + IONP scaffolds and the effects of the novel composite on bone matrix formation and osteogenesis of human dental pulp stem cells (hDPSCs) were explored. A series of CPC + IONP magnetic scaffolds with different IONP contents (1%, 3% and 6%) were fabricated using 5% chitosan solution as the cement liquid. Western blotting and RT-PCR were used to analyze the signaling pathway. The IONP incorporation substantially enhanced the performance of CPC + IONP, with increases in both mechanical strength and cellular activities. The IONP addition greatly promoted the osteogenesis of hDPSCs, elevating the ALP activity, the expression of osteogenic marker genes and bone matrix formation with 1.5-2-fold increases. The 3% IONP incorporation showed the most enhancement among all groups. Activation of the extracellular signal-related kinases WNT/ß-catenin in DPSCs was observed, and this activation was attenuated by the WNT inhibitor DKK1. The results indicated that the osteogenic behavior of hDPSCs was likely driven by CPC + IONP via the WNT signaling pathway. In conclusion, incorporate IONP into CPC scaffold remarkably enhanced the spreading, osteogenic differentiation and bone mineral synthesis of stem cell. Therefore, this method had great potential for bone tissue engineering. The novel CPC + IONP composite scaffolds with stem cells are promising to provide an innovative strategy to enhance bone regenerative therapies.

Effect of calcium phosphate nanocomposite on in vitro remineralization of human dentin lesions.

OBJECTIVE: Secondary caries is a primary reason for dental restoration failures. The objective of this study was to investigate the remineralization of human dentin lesions in vitro via restorations using nanocomposites containing nanoparticles of amorphous calcium phosphate (NACP) or NACP and tetracalcium phosphate (TTCP) for the first time. METHODS: NACP was synthesized by a spray-drying technique and incorporated into a resin consisting of ethoxylated bisphenol A dimethacrylate (EBPADMA) and pyromellitic glycerol dimethacrylate (PMGDM). After restoring the dentin lesions with nanocomposites as well as a non-releasing commercial composite control, the specimens were treated with cyclic demineralization (pH 4, 1h per day) and remineralization (pH 7, 23h per day) for 4 or 8 weeks. Calcium (Ca) and phosphate (P) ion releases from composites were measured. Dentin lesion remineralization was measured at 4 and 8 weeks by transverse microradiography (TMR). RESULTS: Lowering the pH increased ion release of NACP and NACP-TTCP composites. At 56 days, the released Ca concentration in mmol/L (mean±SD; n=3) was (13.39±0.72) at pH 4, much higher than (1.19±0.06) at pH 7 (p<0.05). At 56 days, P ion concentration was (5.59±0.28) at pH 4, much higher than (0.26±0.01) at pH 7 (p<0.05). Quantitative microradiography showed typical subsurface dentin lesions prior to the cyclic demineralization/remineralization treatment, and dentin remineralization via NACP and NACP-TTCP composites after 4 and 8 weeks of treatment. At 8 weeks, NACP nanocomposite achieved dentin lesion remineralization (mean±SD; n=15) of (48.2±11.0)%, much higher than (5.0±7.2)% for dentin in commercial composite group after the same cyclic demineralization/remineralization regimen (p<0.05). SIGNIFICANCE: Novel NACP-based nanocomposites were demonstrated to achieve dentin lesion remineralization for the first time. These results, coupled with acid-neutralization and good mechanical properties shown previously, indicate that the NACP-based nanocomposites are promising for restorations to inhibit caries and protect tooth structures.

Calcium phosphate cements for bone engineering and their biological properties.

Calcium phosphate cements (CPCs) are frequently used to repair bone defects. Since their discovery in the 1980s, extensive research has been conducted to improve their properties, and emerging evidence supports their increased application in bone tissue engineering. Much effort has been made to enhance the biological performance of CPCs, including their biocompatibility, osteoconductivity, osteoinductivity, biodegradability, bioactivity, and interactions with cells. This review article focuses on the major recent developments in CPCs, including 3D printing, injectability, stem cell delivery, growth factor and drug delivery, and pre-vascularization of CPC scaffolds via co-culture and tri-culture techniques to enhance angiogenesis and osteogenesis.

Rechargeable calcium phosphate orthodontic cement with sustained ion release and re-release.

White spot lesions (WSL) due to enamel demineralization are major complications for orthodontic treatments. Calcium phosphate (CaP) dental resins with Ca and P ion releases are promising for remineralization. However, previous Ca and P releases lasted for only weeks. Experimental orthodontic cements were developed using pyromellitic glycerol dimethacrylate (PMGDM) and ethoxylated bisphenol A dimethacrylate (EBPADMA) at mass ratio of 1:1 (PE); and PE plus 10% of 2-hydroxyethyl methacrylate (HEMA) and 5% of bisphenol A glycidyl dimethacrylate (BisGMA) (PEHB). Particles of amorphous calcium phosphate (ACP) were incorporated into PE and PEHB at 40% filler level. Specimens were tested for bracket-enamel shear bond strength, water sorption, CaP release, and ion recharge and re-release. PEHB+40ACP had higher bracket-enamel bond strength and ion release and rechargeability than PE+40ACP. ACP incorporation into the novel orthodontic cement did not adversely affect the bracket-enamel bond strength. Ion release and re-release from the novel ACP orthodontic cement indicated favorable release and re-release patterns. The recharged orthodontic cement could release CaP ions continuously for four weeks without further recharge. Novel rechargeable orthodontic cement containing ACP was developed with a high bracket-enamel bond strength and the ability to be repeatedly recharged to maintain long-term high levels of CaP ion releases.

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.

Injectable nanoamorphous calcium phosphate based in situ gel systems for the treatment of periapical lesions.

Nonsurgical local treatment of a periapical lesion arising from trauma or bacterial infection is a promising innovative approach. The present study investigated the feasibility of developing injectable amorphous calcium phosphate nanoparticles (ACP NPs) and ACP NPs loaded with an anti-inflammatory drug; ibuprofen (IBU-ACP NPs) in the form of thermoreversible in situ gels to treat periapical lesions with the stimulation of bone formation. NPs were produced by a spray-drying technique. Different formulations of Poloxamer 407 were incorporated with/without the produced NPs to form injectable gels. A drug release study was carried out. A 3 month in vivo test on a dog model also was assessed. Results showed successful incorporation of the drug into the NPs of CP during spray drying. The particles had mean diameters varying from 100 to 200 nm with a narrow distribution. A drug release study demonstrated controlled IBU release from IBU-ACP NPs at a pH of 7.4 over 24 h. The gelation temperature of the injectable in situ gels based on Poloxamer 407 was measured to be 30 °C. After 3 months of implantation in dogs, the results clearly demonstrated that the inclusion of ACP NPs loaded with IBU showed high degrees of periapical bone healing and cementum layer deposition around the apical root tip.

Oral fluoride levels 1 h after use of a sodium fluoride rinse: effect of sodium lauryl sulfate.

Increasing the concentration of free fluoride in oral fluids is an important goal in the use of topical fluoride agents. Although sodium lauryl sulfate (SLS) is a common dentifrice ingredient, the influence of this ion on plaque fluid and salivary fluid fluoride has not been examined. The purpose of this study was to investigate the effect of SLS on these parameters and to examine the effect of this ion on total (or whole) plaque fluoride, an important source of plaque fluid fluoride after a sufficient interval following fluoride administration, and on total salivary fluoride, a parameter often used as a surrogate measure of salivary fluid fluoride. Ten subjects accumulated plaque for 48 h before rinsing with a 12 mmol/l NaF (228 µg/g F) rinse containing or not containing 0.5% (w/w) SLS. SLS had no statistically significant effect on total plaque and total saliva fluoride but significantly increased salivary fluid and plaque fluid fluoride (by 147 and 205%, respectively). These results suggest that the nonfluoride components of topical agents can be manipulated to improve the fluoride release characteristics from oral fluoride reservoirs and that statistically significant change may be observed in plaque fluid and salivary fluid fluoride concentrations that may not be observed in total plaque and total saliva fluoride concentrations.

Development of a novel fluorapatite-forming calcium phosphate cement with calcium silicate: in vitro and in vivo characteristics.

Aim of this study was to develop a novel fluorapatite-forming calcium phosphate cement (FA-CPC) with tricalcium silicate (TCS) for endodontic applications and to examine its in vitro and in vivo characteristics. The FA-CPC powder consisted of 62.8% CaHPO4, 30.8% CaCO3, and 6.4% NaF. One part of TCS was combined with 9 parts of FA-CPC powder (FA-CPC with TCS). A 1.5 M phosphate solution was used as cement liquid. Setting time (ST), diametral tensile strength (DTS), phase composition by X-ray diffraction (XRD), and cement alkalinity were analyzed. Cement biocompatibility was assessed using rat subcutaneous model. Cement ST was 10.3±0.6 min and DTS was 3.89±0.76 MPa. XRD patterns showed that highly crystalline apatitic material was the only significant phase present and pH value was approximate 11.0. FA-CPC with TCS demonstrated similar biocompatibility as that of mineral trioxide aggregate control. These results suggest that FA-CPC with TCS may be useful for endodontic applications.

In-situ hybridization of calcium silicate and hydroxyapatite-gelatin nanocomposites enhances physical property and in vitro osteogenesis.

Low mechanical strengths and inadequate bioactive material-tissue interactions of current synthetic materials limit their clinical applications in bone regeneration. Here, we demonstrate gelatin modified siloxane-calcium silicate (GEMOSIL-CS), a nanocomposite made of gelatinous hydroxyapatite with in situ pozzolanic formation of calcium silicate (CS) interacting among gelatin, silica and Calcium Hydroxide (Ca(OH)2). It is shown the formation of CS matrices, which chemically bonds to the gelatinous hydroxyapatite, provided hygroscopic reinforcement mechanism and promoted both in vitro and in vivo osteogenic properties of GEMOSIL-CS. The formation of CS was identified by Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction. The interfacial bindings within nanocomposites were studied by FTIR and thermogravimetric analysis. Both gelatin and CS have been found critical to the structure integrity and mechanical strengths (93 MPa in compressive strength and 58.9 MPa in biaxial strength). The GEMOSIL-CS was biocompatible and osteoconductive as result of type I collagen secretion and mineralized nodule formation from MC3T3 osteoblasts. SEM and TEM indicated the secretion of collagen fibers and mineral particles as the evidence of mineralization in the early stage of osteogenic differentiation. In vivo bone formation capability was performed by implanting GEMOSIL-CS into rat calvarial defects for 12 weeks and the result showed comparable new bone formation between GEMOSIL-CS group (20%) and the control (20.19%). The major advantage of GEMOSIL-CS composites is in situ self-hardening in ambient or aqueous environment at room temperature providing a simple, fast and cheap method to produce porous scaffolds.

A New Bioactive Polylactide-based Composite with High Mechanical Strength.

A new bioresorbable polylactide/calcium phosphate composite with improved mechanical strengths and a more basic filler, tetracalcium phosphate (TTCP), was prepared by melt compounding. N-(2-aminoethyl)-3-aminoproplytrimethoxysilane (AEAPS) and pyromellitic dianhydride (PMDA) were used to improve the interfacial adhesion between TTCP and polylactide (PLA). While AEAPS improved the dispersion of TTCP in the matrix, PMDA might react with the terminal hydroxyl group of PLA and the amino group on the surface of AEAPS modified TTCP, which could further enhance the interfacial strength. The tensile strength was improved to 68.4 MPa for the PLA/TTCP-AEAPS composite from 51.5 MPa for the PLA/TTCP composite (20 wt% of TTCP). Dynamic mechanical analysis suggested that there was a 51 % improvement in storage modulus compared to that of PLA alone, when PMDA (0.2 wt% of PMDA) was incorporated into the PLA/TTCP-AEAPS composite (5 wt% of TTCP). Using this new bioresorbable PLA composite incorporated with a more basic filler for biomedical application, the inflammation and allergic effect resulted from the degraded acidic product are expected to be reduced.

Antibacterial activity and ion release of bonding agent containing amorphous calcium phosphate nanoparticles.

OBJECTIVE: Recurrent caries at the margins is a primary reason for restoration failure. The objectives of this study were to develop bonding agent with the double benefits of antibacterial and remineralizing capabilities, to investigate the effects of NACP filler level and solution pH on Ca and P ion release from adhesive, and to examine the antibacterial and dentin bond properties. METHODS: Nanoparticles of amorphous calcium phosphate (NACP) and a quaternary ammonium monomer (dimethylaminododecyl methacrylate, DMADDM) were synthesized. Scotchbond Multi-Purpose (SBMP) primer and adhesive served as control. DMADDM was incorporated into primer and adhesive at 5% by mass. NACP was incorporated into adhesive at filler mass fractions of 10%, 20%, 30% and 40%. A dental plaque microcosm biofilm model was used to test the antibacterial bonding agents. Calcium (Ca) and phosphate (P) ion releases from the cured adhesive samples were measured vs. filler level and solution pH of 7, 5.5 and 4. RESULTS: Adding 5% DMADDM and 10-40% NACP into bonding agent, and water-aging for 28 days, did not affect dentin bond strength, compared to SBMP control at 1 day (p>0.1). Adding DMADDM into bonding agent substantially decreased the biofilm metabolic activity and lactic acid production. Total microorganisms, total streptococci, and mutans streptococci were greatly reduced for bonding agents containing DMADDM. Increasing NACP filler level from 10% to 40% in adhesive increased the Ca and P ion release by an order of magnitude. Decreasing solution pH from 7 to 4 increased the ion release from adhesive by 6-10 folds. SIGNIFICANCE: Bonding agents containing antibacterial DMADDM and remineralizer NACP were formulated to have Ca and P ion release, which increased with NACP filler level from 10% to 40% in adhesive. NACP adhesive was "smart" and dramatically increased the ion release at cariogenic pH 4, when these ions would be most-needed to inhibit caries. Therefore, bonding agent containing DMADDM and NACP may be promising to inhibit biofilms and remineralize tooth lesions thereby increasing the restoration longevity.

Effects of Inorganic Fillers on the Thermal and Mechanical Properties of Poly(lactic acid).

Addition of filler to polylactic acid (PLA) may affect its crystallization behavior and mechanical properties. The effects of talc and hydroxyapatite (HA) on the thermal and mechanical properties of two types of PLA (one amorphous and one semicrystalline) have been investigated. The composites were prepared by melt blending followed by injection molding. The molecular weight, morphology, mechanical properties, and thermal properties have been characterized by gel permeation chromatography (GPC), scanning electron microscope (SEM), instron tensile tester, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). It was found that the melting blending led to homogeneous distribution of the inorganic filler within the PLA matrix but decreased the molecular weight of PLA. Regarding the filler, addition of talc increased the crystallinity of PLA, but HA decreased the crystallinity of PLA. The tensile strength of the composites depended on the crystallinity of PLA and the interfacial properties between PLA and the filler, but both talc and HA filler increased the toughness of PLA.

Immobilization of Xanthate Agent on Titanium Dioxide and Surface Initiated RAFT Polymerization.

Surface modification of titanium dioxide (TiO2) nanoparticle is essential to control its surface properties, thereby to enhance its cell penetration capability, reduce its cytotoxicity, or improve its biocompatibility. In order to graft polyvinyl acetate onto TiO2 nanoparticles, xanthate was chemically immobilized on the surface of TiO2 by acylation followed by nucleophilic substitution with a carbodithioate salt. Reversible addition fragmentation chain transfer polymerization was conducted to graft vinyl acetate onto the surface of TiO2. Both the TiO2-xanthate and TiO2-polyvinyl acetate hybrids were characterized by UV-Vis spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The chemical immobilization of xanthate on the surface of TiO2 and the subsequent controlled polymerization provide useful insight for decoration and modification of TiO2 and other nanoparticles.

Nanofiber scaffold gradients for interfacial tissue engineering.

We have designed a 2-spinnerette device that can directly electrospin nanofiber scaffolds containing a gradient in composition that can be used to engineer interfacial tissues such as ligament and tendon. Two types of nanofibers are simultaneously electrospun in an overlapping pattern to create a nonwoven mat of nanofibers containing a composition gradient. The approach is an advance over previous methods due to its versatility - gradients can be formed from any materials that can be electrospun. A dye was used to characterize the 2-spinnerette approach and applicability to tissue engineering was demonstrated by fabricating nanofibers with gradients in amorphous calcium phosphate nanoparticles (nACP). Adhesion and proliferation of osteogenic cells (MC3T3-E1 murine pre-osteoblasts) on gradients was enhanced on the regions of the gradients that contained higher nACP content yielding a graded osteoblast response. Since increases in soluble calcium and phosphate ions stimulate osteoblast function, we measured their release and observed significant release from nanofibers containing nACP. The nanofiber-nACP gradients fabricated herein can be applied to generate tissues with osteoblast gradients such as ligaments or tendons. In conclusion, these results introduce a versatile approach for fabricating nanofiber gradients that can have application for engineering graded tissues.

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.

Nanocomposite containing CaF(2) nanoparticles: thermal cycling, wear and long-term water-aging.

OBJECTIVES: Fluoride (F) releasing dental restoratives are promising to promote remineralization and combat caries. The objectives of this study were to develop nanocomposite containing calcium fluoride nanoparticles (nCaF(2)), and to investigate the long-term mechanical durability including wear, thermal-cycling and long-term water-aging behavior. METHODS: Two types of fillers were used: nCaF(2) with a diameter of 53 nm, and glass particles of 1.4 µm. Four composites were fabricated with fillers of: (1) 0% nCaF(2)+65% glass; (2) 10% nCaF(2)+55% glass; (3) 20% nCaF(2)+45% glass; (4) 30% nCaF(2)+35% glass. Three commercial materials were also tested. Specimens were subjected to thermal-cycling between 5°C and 60°C for 10(5) cycles, three-body wear for 4×10(5) cycles, and water-aging for 2 years. RESULTS: After thermal-cycling, the nCaF(2) nanocomposites had flexural strengths in the range of 100-150 MPa, five times higher than the 20-30 MPa for resin-modified glass ionomer (RMGI). The wear scar depth showed an increasing trend with increasing nCaF(2) filler level. Wear of nCaF(2) nanocomposites was within the range of wear for commercial controls. Water-aging decreased the strength of all materials. At 2 years, flexural strength was 94 MPa for nanocomposite with 10% nCaF(2), 60 MPa with 20% nCaF(2), and 48 MPa with 30% nCaF(2). They are 3-6 fold higher than the 15 MPa for RMGI (p<0.05). SEM revealed air bubbles and cracks in a RMGI, while composite control and nCaF(2) nanocomposites appeared dense and solid. SIGNIFICANCE: Combining nCaF(2) with glass particles yielded nanocomposites with long-term mechanical properties that were comparable to those of a commercial composite with little F release, and much better than those of RMGI controls. These strong long-term properties, together with their F release being comparable to RMGI as previously reported, indicate that the nCaF(2) nanocomposites are promising for load-bearing and caries-inhibiting restorations.

A new approach to prepare well-dispersed CaF(2) nanoparticles by spray drying technique.

Previously, nano-sized calcium fluoride (CaF2) particles were prepared using a spray drying method by simultaneously feeding Ca(OH)2 and NH4F solutions to a two-liquid nozzle. The aim of the present study was to prepare better-dispersed nano-CaF2 particles by co-forming a soluble salt, sodium chloride (NaCl). NaCl of various concentrations were added to the NH(4) F solution, leading to formation of (CaF2 +NaCl) composites with CaF2 /NaCl molar ratios of 4/1, 4/4, and 4/16. Pure nano-CaF2 was also prepared as the control. Powder X-ray diffraction analysis showed that the products contained crystalline CaF2 and NaCl. Scanning electron microscopy examinations showed that both the CaF2 /NaCl composite and pure CaF2 particles were about (50-800) nm in size and consisted of primary CaF2 particles of < 50 nm in size. BET surface area measurements showed similar primary particle sizes for all samples. Dynamic light scattering measurements showed that the washed (CaF2+NaCl) particles were much smaller than the pure CaF2 as the dissolution of NaCl "freed" most of the primary CaF2 particles, leading to a greater degree of particle dispersion. The well-dispersed nano-CaF2 may be expected to be a more effective anticaries agent than NaF by providing longer lasting elevations of fluoride concentrations in oral fluids.

Mechanical and acid neutralizing properties and bacteria inhibition of amorphous calcium phosphate dental nanocomposite.

Dental composites do not hinder bacteria colonization and plaque formation. Caries at the restoration margins is a frequent reason for replacement of existing restorations, which accounts for 50 to 70% of all restorations. The objectives of this study were to examine the filler level effect on nanocomposite containing nanoparticles of amorphous calcium phosphate (NACP) and investigate the load-bearing and acid-neutralizing properties and bacteria inhibition. NACP with 116-nm particle size were synthesized via a spray-drying technique and incorporated into a resin. Flexural strength of nanocomposite with 10 to 30% NACP fillers matched the strength of a commercial hybrid composite (p > 0.1). Nanocomposite with 40% NACP matched the strength of a microfill composite, which was 2-fold that of a resin-modified glass ionomer. Nanocomposite with 40% NACP neutralized a lactic acid solution of pH 4 by rapidly increasing the pH to 5.69 in 10 min. In contrast, the commercial controls had pH staying at near 4. Using Streptoccocus mutans, an agar disk-diffusion test showed no inhibition zone for commercial controls. In contrast, the inhibition zone was (2.5 ± 0.7) mm for nanocomposite with 40% NACP. Crystal violet staining showed that S. mutans coverage on nanocomposite was 1/4 that on commercial composite. In conclusion, novel calcium-phosphate nanocomposite matched the mechanical properties of commercial composite and rapidly neutralized lactic acid of pH 4. The nanocomposite appeared to moderately reduce the S. mutans growth, and further study is needed to obtain strong antimicrobial properties. The new nanocomposite may have potential to reduce secondary caries and restoration fracture, two main challenges facing tooth cavity restorations.

Nanocomposite containing amorphous calcium phosphate nanoparticles for caries inhibition.

OBJECTIVES: The main challenges facing composite restorations are secondary caries and bulk fracture. The objectives of this study were to synthesize novel nanoparticles of amorphous calcium phosphate (NACP), develop NACP nanocomposite with calcium (Ca) and phosphate (PO(4)) ion release to combat caries, and investigate the effects of NACP filler level and glass co-filler reinforcement on composite properties. METHODS: NACP (diameter=116 nm) were synthesized via a spray-drying technique for the first time. Since the local plaque pH in the oral cavity can decrease to 5 or 4, photo-activated composites were tested with immersion in solutions of pH 7, 5.5, and 4. Composite mechanical properties as well as Ca and PO(4) ion release were measured vs. pH and filler level. RESULTS: Increasing the NACP filler level increased the ion release. At 28 d and pH 4, the Ca release was (4.66±0.05)mmol/L at 20% NACP, much higher than (0.33±0.08) at 10% NACP (p<0.05). Decreasing the pH increased the ion release. At 20% NACP, the PO(4) release at 28 d was (1.84±0.12)mmol/L at pH 4, higher than (0.59±0.08) at pH 5.5, and (0.12±0.01) at pH 7 (p<0.05). However, pH had little effect on composite mechanical properties. Flexural strength at 15% NACP was (96±13)MPa at pH 4, similar to (89±13)MPa at pH 5.5, and (89±19)MPa at pH 7 (p>0.1). The new NACP nanocomposites had strengths that were 2-fold those of previous calcium phosphate composites and resin-modified glass ionomer control. SIGNIFICANCE: NACP composites were developed for the first time. Their strengths matched or exceeded a commercial composite with little ion release, and were 2-fold those of previous Ca-PO(4) composites. The nanocomposite was "smart" as it greatly increased the ion release at a cariogenic pH 4, when these ions would be most needed to inhibit caries. Hence, the new NACP composite may be promising for stress-bearing and caries-inhibiting restorations.