Monocalcium Phosphate Monohydrate Research Articles

Self-sealing ability of OCP-mediated cement as a deciduous root canal filling materia

The densification process and canal sealing ability of octacalcium phosphate (OCP)-mediated cement were investigated for developing biocompatible and biodegradable root canal filling material for deciduous root. The results of the characterization revealed that the starting paste, which consisted of monocalcium phosphate monohydrate, calcium carbonate, and α-tricalcium phosphate, gradually transformed into carbonate apatite for 6 weeks of immersion in medium with 30% fetal bovine serum (MEM30). The canal sealing ability was estimated by dye penetration test. Three kinds of conditions were chosen for the test: one was the cement just after filling the single-rooted extracted human roots; the others were the cement aged in MEM30 for 1 and 6 weeks after filling, respectively. All roots were then immersed in India ink for 3 days. The penetration depth of OCP-mediated cement decreased significantly with time. This demonstrates that OCP-mediated cement has self-sealing ability.

Loading and release of doxycycline hyclate from strontium-substituted calcium phosphate cement

Novel Sr-substituted calcium phosphate cement (CPC) loaded with doxycycline hyclate (DOXY-h) was employed to elucidate the effect of strontium substitution on antibiotic delivery. The cement was prepared using as reactants Sr-substituted β-tricalcium phosphate (Sr-β-TCP) and acidic monocalcium phosphate monohydrate. Two different methods were used to load DOXY-h: (i) the adsorption on CPC by incubating the set cement in drug-containing solutions; and (ii) the use of antibiotic solution as the cement liquid phase. The results revealed that the Sr-substituted cement efficiently adsorbs the antibiotic, which is attributed to an enhanced accessibility to the drug-binding sites within this CPC. DOXY-h desorption is influenced by the initial adsorbed amount and the cement matrix type. Furthermore, the fraction of drug released from CPCs set with DOXY-h solution was higher, and the release rate was faster for the CPC prepared with 26.7% Sr-β-TCP. The analysis of releasing profiles points to Fickian diffusion as the mechanism responsible for antibiotic delivery. We can conclude that Sr substitution in secondary calcium phosphate cements improves their efficiency for DOXY-h adsorption and release. The antibiotic loading method provides a way to switch from rapid and complete to slower and prolonged drug release.

Reactive calcium-phosphate-containing poly(ester- co-ether) methacrylate bone adhesives: Chemical, mechanical and biological considerations

A poly(propylene glycol- co-lactide) dimethacrylate adhesive with monocalcium phosphate monohydrate (MCPM)/β-tricalcium phosphate (β-TCP) fillers in various levels has been investigated. Water sorption by the photo-polymerized materials catalyzed varying filler conversion to dicalcium phosphate (DCP). Polymer modulus was found to be enhanced upon raising total calcium phosphate content. With greater DCP levels, faster release of phosphate and calcium ions and improved buffering of polymer degradation products were observed. This could reduce the likelihood of pH-catalyzed bulk degradation and localized acid production and thereby may prevent adverse biological responses. Bone-like MG-63 cells were found to attach, spread and have normal morphology on both the polymer and composite surfaces. Moreover, composites implanted into chick embryo femurs became closely apposed to the host tissue and did not appear to induce adverse immunological reaction. The above results suggest that the new composite materials hold promise as clinical effective bone adhesives.

Characterization of calcium phosphate cements modified by addition of amorphous calcium phosphate

In this study the influence of amorphous calcium phosphate (ACP) on the setting of, and the formed apatite crystallite size in, a calcium phosphate cement (CPC) based on α-tricalcium phosphate (α-TCP) or tetracalcium phosphate (TTCP)/monocalcium phosphate monohydrate (MCPM) was investigated. Setting times at 22 °C were measured in air atmosphere; those at 37 °C were measured at 100% relative humidity. The phase composition of the set cements was investigated after 1 week using X-ray diffractometry and infrared spectroscopy and the morphology was investigated using scanning electron microscopy. The compressive strength (CS) of the set CPCs was measured after 1 day. Viability of MC3T3-E1 cells on the CPCs was analyzed after 7, 14 and 21 days of incubation using the CellTiter 96 ® Aqueous Non-Radioactive Cell Proliferation Assay. The α-TCP-based cement exhibited long setting times, a high CS and was converted to a calcium-deficient hydroxyapatite (CDHAp). The TTCP/MCPM-based CPC was only partly converted to CDHAp, produced acceptable setting times and had a low CS. Addition of ACP to these two CPCs resulted in cements that exhibited good setting times, CS suitable for non-load-bearing applications and a full conversion to nanocrystalline CDHAp. Moreover, the ACP containing CPCs demonstrated good cell viability, making them suitable candidates for bone substitute materials.

Effect of silica gel on the cohesion, properties and biological performance of brushite cement

The cohesion of calcium phosphate cements can be improved by the addition of substances to either the solid or liquid phase during the setting reaction. This study reports the effect of silica gel on brushite cement cohesion. The cement was prepared using a mixture of β-tricalcium phosphate (β-TCP) and monocalcium phosphate monohydrate as the solid phase, while the liquid phase comprised carboxylic acids silica gel. This cement presents a shorter final setting time (FST), better cohesion and higher amount of unreacted β-TCP than the cement prepared without silica gel. Furthermore, in vivo experiments using rabbits as an animal model showed that after 8weeks of implantation cements modified with silica gel showed a similar new bone formation volume and more remaining graft in comparison with unmodified cements. Thus, the silica gel could be efficiently applied to reduce cement disintegration and to decrease the resorption rate of brushite cements.

β-TCP/MCPM-based premixed calcium phosphate cements

Novel premixed calcium phosphate cements (CPCs) were prepared by combining cement liquids comprised of glycerol or polyethylene glycol with CPC powders that consisted of β-tricalcium phosphate (β-TCP) and monocalcium phosphate monohydrate (MCPM). Changing the powder to liquid mass ratio enabled the setting time to be regulated, and improved the compressive strength of the CPCs. Although some ratios of the new premixed CPCs had long setting times, these ranged from 12.4 to 27.8 min which is much shorter than the hour or more reported previously for a premixed CPC. The premixed CPCs had tolerable washout resistance before final setting, and the cements had strengths matching that of cancellous bone (5–10 MPa); their maximum compressive strength was up to 12 MPa. The inflammatory response around the premixed CPCs implanted in the subcutaneous tissue in rabbits was more prominent than that of apatite cement. These differences might be due to the much faster resorption rate of the premixed CPCs.

31P Solid‐State NMR study of the chemical setting process of a dual‐paste injectable brushite cements

The composition and evolution of a brushite-type calcium phosphate cement was investigated by Solid-State NMR and X-ray during the setting process. The cement is obtained by mixing beta-tricalcium phosphate [Ca(3)(PO(4))(2), beta-TCP] and monocalcium phosphate monohydrate [Ca(H(2)PO(4))(2).H(2)O, MCPM] in presence of water, with formation of dicalcium phosphate dihydrate or brushite [CaHPO(2).2H(2)O, DCPD]. Analysis of the initial beta-TCP paste has shown the presence of beta-calcium pyrophosphate [Ca(2)P(2)O(7), beta-CPy] and that of the initial MCPM a mixture of MCPM and dicalcium phosphate [CaHPO(4), DCP]. Follow-up of the chemical composition by (31)P Solid-State NMR enables to show that the chemical setting process appeared to reach an end after 20 min. The constant composition observed at the end of the process was similarly determined.

The effect of hyaluronic acid on brushite cement cohesion

The improvement of calcium phosphate cement (CPC) cohesion is essential for its application in highly blood perfused regions. This study reports the effectiveness of hyaluronic acids of different molecular weights in the enhancement of brushite cement cohesion. The cement was prepared using a powder phase composed of a mixture of β-tricalcium phosphate and monocalcium phosphate monohydrate, whereas the liquid phase was formed by 0.5 M citric acid solution modified by the addition of hyaluronic acid of different molecular weights. It was found that medium and high molecular weight hyaluronic acid enhances the cement cohesion and scarcely affects the cement mechanical properties. However, concentrations >0.5% (w/v) were less efficient to prevent the cement disintegration. It is concluded that hyaluronic acid could be applied efficiently to reduce brushite cement disintegration.

Characterization of dicalcium phosphate dihydrate cements prepared using a novel hydroxyapatite-based formulation

Dicalcium phosphate dihydrate (DCPD) cements are typically prepared using β-tricalcium phosphate (β-TCP) as the base component. However, hydroxyapatite (HA) is an interesting alternative because of its potential for reducing cement acidity, as well as modulating cement properties via ionic substitutions. In the present study, we have characterized DCPD cements prepared with a novel formulation based on monocalcium phosphate monohydrate (MCPM) and HA. Cements were prepared using a 4:1 MCPM:HA molar ratio. The reactivity of HA in this system was verified by showing DCPD formation using poorly crystalline HA, as well as highly crystalline HA. Evaluation of cements prepared with poorly crystalline HA revealed that setting occurs rapidly in the MCPM/HA system, and that the use of a setting regulator is necessary to maintain workability of the cement paste. Compressive testing showed that MCPM/HA cements have strengths comparable to what has previously been published for DCPD cements. However, preliminary in vitro analysis of cement degradation revealed that conversion of DCPD to HA may occur much more rapidly in the MCPM/HA system compared to cements prepared with β-TCP. Future studies should investigate this property further, as it could have important implications for the use of HA-based DCPD cement formulations.

Development of remineralizing, antibacterial dental materials

Light curable methacrylate dental monomers containing reactive calcium phosphate filler (monocalcium phosphate monohydrate (MCPM) with particle diameter of 29 or 90 μm) and β-tricalcium phosphate (β-TCP) at 1:1 weight ratio in a powder:liquid ratio (PLR) of 1:1 or 3:1 and chlorhexidine diacetate (0 or 5 wt.%), were investigated. Upon light exposure, approximately 90% monomer conversion was gained irrespective of the formulation. Increasing the PLR promoted water sorption by the set material, induced expansion and enhanced calcium, phosphate and chlorhexidine release. Concomitantly, a decline in compressive and biaxial flexural strengths occurred. With a reduction in MCPM particle diameter, however, calcium and phosphate release was reduced and less deterioration in strength observed. After 24 h, the remaining MCPM had reacted with water and β-TCP, forming, within the set materials, brushite of lower solubility. This provided a novel means to control water sorption, component release and strength properties. Measurable chlorhexidine release was observed for 6 weeks. Both diffusion rate and total percentage of chlorhexidine release decreased with lowering PLR or by adding buffer to the storage solutions. Higher chlorhexidine release was associated with reduced bacterial growth on agar plates and in a biofilm fermenter. In cell growth media, brushite and hydroxyapatite crystals precipitated on the composite material surfaces. Cells spread on both these crystals and the exposed polymer composite surfaces, indicating their cell compatibility. These formulations could be suitable antibacterial, biocompatible and remineralizing dental adhesives/liners.

Novel bioactive composite bone cements based on the β-tricalcium phosphate–monocalcium phosphate monohydrate composite cement system

Bioactive composite bone cements were obtained by incorporation of tricalcium silicate (Ca 3SiO 5, C 3S) into a brushite bone cement composed of β-tricalcium phosphate [β-Ca 3(PO 4) 2, β-TCP] and monocalcium phosphate monohydrate [Ca(H 2PO 4) 2·H 2O, MCPM], and the properties of the new cements were studied and compared with pure brushite cement. The results indicated that the injectability, setting time and short- and long-term mechanical strength of the material are higher than those of pure brushite cement, and the compressive strength of the TCP/MCPM/C 3S composite paste increased with increasing aging time. Moreover, the TCP/MCPM/C 3S specimens showed significantly improved in vitro bioactivity in simulated body fluid and similar degradability in phosphate-buffered saline as compared with brushite cement. Additionally, the reacted TCP/MCPM/C 3S paste possesses the ability to stimulate osteoblast proliferation and promote osteoblastic differentiation of the bone marrow stromal cells. The results indicated that the TCP/MCPM/C 3S cements may be used as a bioactive material for bone regeneration, and might have significant clinical advantage over the traditional β-TCP/MCPM brushite cement.

Strontium modified biocements with zero order release kinetics

Strontium-substituted β-TCP with the general formula Ca (3− x) Sr x (PO 4) 2 (0 < x < 1) was synthesized by calcination of powder mixtures with the appropriate stoichiometry and reacted with acidic monocalcium phosphate monohydrate (MCPM) to form a cementitious matrix of secondary calcium phosphates. The use of Sr-substituted β-TCP as a reactant not only induced strontium substitution in the setting products but surprisingly it also favoured the formation of monetite (CaHPO 4) as setting product, whereas Sr-free cements set to brushite (CaHPO 4·2H 2O). Release experiments under dynamic conditions for up to 15 days revealed the release of Sr 2+ ions at dose ranges of 12–30 ppm with zero order release kinetic. Cement cytocompatibility was investigated by culturing human osteoblast cell line hFOB1.19 on cement surfaces whereas Sr-containing cements were as good as Sr-free cements in providing a template for cell growth and function.

Electrochemical depositions of calcium phosphate film on commercial pure titanium and Ti–6Al–4V in two types of electrolyte at room temperature

Electrochemical depositions of calcium phosphate film on commercially pure titanium (cp-Ti) and Ti–6Al–4V in two types of electrolytes, mono-calcium phosphate monohydrate (MCPM) based aqueous solution and supersaturated calcium phosphate solution (SCPS), were carried out by the cathodic polarization. The calcium phosphate coating layer was successfully deposited on cp-Ti and Ti–6Al–4V under 3 mA/cm 2 current density for 45 min. The major phases that appeared in the film were DCPD (brushite) co-existed with octa-calcium phosphate (OCP). After soaking in revised simulated-body-fluid (r-SBF), the amorphous bone-like apatite became a single phase within a day for the specimen obtained from MCPM electrolyte. The specimens obtained from SCPS electrolyte took a week to complete the apatite precipitation in r-SBF. From the scratch test, the highest critical load of 87.2 N was obtained from the as-deposited rod-like DCPD on cp-Ti substrate. The critical load was decreasing almost 50% for all of the specimens after apatite precipitation in r-SBF. The decrease of critical load might result from loosening of the film structure during immersion of the specimens in r-SBF. The thickness of the films was 44–55 μm in average, which satisfied the qualification for using as an implant material.

In vitro Study of Root Fracture Treated by CO 2 Laser and DP-bioactive Glass Paste

An ideal material has yet to be discovered that can successfully treat vertical root fracture. Therefore, the purpose of this study was to use a continuous-wave CO2 laser of medium-energy density to fuse DP-bioactive glass paste (DPGP) to vertical root fracture. The DP-bioglass powder was based on a Na2O-CaO-SiO2-P2O5 system and it was mixed with phosphoric acid (65% concentration) with a powder/liquid ratio of 2 g/4 mL to form DPGP. The interaction of DPGP and dentin was analyzed by means of X-ray diffractometer (XRD) and differential thermal analysis/thermogravimetric analysis (DTA/TGA). Root fracture line was filled with DPGP followed by CO2 laser irradiation and the result was examined by scanning electron microscopy (SEM). The main crystal phase of DPGP was monocalcium phosphate monohydrate (Ca(H2PO4)2.H2O) and the phase transformed to dicalcium phosphate dihydrate (CaHPO4.2H2O) after mixing DPGP with dentin powder (DPG-D). Additionally, gamma-Ca2P2O7 and beta-Ca2P2O7 were identified when DPG-D was lased by CO2 laser. The reaction temperature was between 500 degrees C and 1100 degrees C. SEM results demonstrated that the fracture line was effectively sealed by DPGP. The chemical reaction of DPGP and dentin indicated that DPGP combined with CO2 laser is a potential regimen for the treatment of vertical root fracture.

Thermal reactions of brushite cements

The thermal reactions of a brushite cement made of beta-tricalcium phosphate (beta-TCP), monocalcium phosphate monohydrate (MCPM), and an aqueous solution were followed in situ with an isothermal calorimeter at 37 degrees C. The investigated parameters were the beta-TCP/MCPM weight ratio, the liquid-to-powder ratio, the synthesis route and milling duration of the beta-TCP powder, as well as the presence of sulfate, citrate, and pyrophosphate ions in the mixing liquid. The thermograms were complex, particularly for mixtures containing an excess of MCPM or additives in the mixing solution. Results suggested that the endothermic MCPM dissolution and the highly exothermic beta-TCP dissolution occurred simultaneously, thereby leading to the formation of a large exothermic peak at early reaction time. Both reactions were followed by the exothermic crystallization of brushite and in the presence of an excess of MCPM by the endothermic crystallization of monetite. Additives generally widened the main exothermic reaction peak, or in some cases with pyrophosphate ions postponed the main exothermic peak at late reaction time. Generally, the results could be well explained and understood based on thermodynamic and solubility data.

Preparation and characterization of calcium phosphate biomaterials

Calcium phosphate cement (CPC) samples have been prepared with a mixture of monocalciumphosphate monohydrate (MCPM) and calcium carbonate (CC) powders, in stechiometric moles ratio 1:2.5 to obtain a Ca/P ratio of about 1.67 typical of hydroxyapatite (HAp), with or without addition of HAp. All specimens are incubated at 30 degrees C in a steam saturated air environment for 3, 6 and 15 days respectively, afterwards dried and stored under nitrogen. The calcium phosphate samples have been characterized by X-ray diffraction (XRD), Vickers hardness test (HV), diametral compression (d.c.), strength compression, and porosity evaluation. MCPM/CC mixture has a 30% HAp final concentration and is characterized by higher porosity (amount 78%) and mechanical properties useful as filler in bone segments without high mechanical stress.

Brushite Cements from Polyphosphoric Acid, Calcium Phosphate Systems

Brushite cement is more soluble than apatitic cement under physiological conditions. Thus, brushite cement may be resorbable in vivo when used as a bone substitute material. Our group has previously reported the formation of brushite cement from orthophosphoric acid and several calcium phosphates such as β‐tricalcium phosphate or nanocrystalline hydroxyapatite. In this study, polyphosphoric acid was investigated as a calcium phosphate cement component. We found that brushite cement was not formed when polyphosphoric acid was mixed with β‐tricalcium phosphate but instead monocalcium phosphate monohydrate (MCPM) was formed. Although stronger in compression when tested dry, MCPM is readily soluble under physiological conditions and cement loses structural integrity within hours of aging in water. However, by varying the solid component phases, we have discovered a new route to the formation of brushite cement. The mixture of polyphosphoric acid, water, and tetracalcium phosphate yielded cement composed predominantly of brushite. The mechanical performance, microstructure, and setting time of this cement appeared to be dependent on the composition of the set cement, which in turn was determined by the composition of cement reactants in the cement slurry.

Novel Antibacterial Calcium Phosphate Cement

The antibacterial brushite-forming calcium phospahte cements (CPC) were prepared using an equimolar mixture of β-tricalcium phosphate (β-TCP) and monocalcium phosphate monohydrate (MCPM) with chlorine dioxide (ClO2) generating powders (sodium chlorite and mixed acid activator). The effect of ClO2 on cement setting time, compressive strength, and antibacterial property of novel antibacterial CPC was investigated. The use of 0.3M citric acid solutions as liquid phase enabled final setting times of 5~10 min. The setting time of antibacterial cement systems was prolonged with increasing the amount of antibiotic used. Dry compressive strength was found to be in the range between 9~15 MPa and increased with addition of ClO2 generating powders. Wet compressive strength was slightly decreased compared to dry compressive strength after immersion of cement samples in water for 24 h. The antimicrobial potency of the different cement formulations was investigated using the agar diffusion method. The acidic brushite cement itself showed the inhibitory effect for Streptococcus mutans. The inhibition zone was increased with the amount of ClO2 generating powders. These results indicate that our novel antibacterial CPC have the great potential to avoid the development of infections for preventive antibiotic therapy.

Novel tricalcium silicate/monocalcium phosphate monohydrate composite bone cement

In this paper, we obtained a novel bone cement composed of tricalcium silicate (Ca(3)SiO(5); C(3)S) and monocalcium phosphate monohydrate (MCPM). The weight ratio of MCPM in the cement is 0, 10, 20, and 30%. The initial setting time was dramatically reduced from 90 min to 30 min as the content of MCPM reached 20%. The workable paste with a liquid/powder (L/P) ratio of 0.8 mL/g could be injected for 2-20 min (nozzle diameter 2.0 mm). The pH variation of the composite cement in simulated body environment was obviously lowered. The compressive strength of the composite cement after setting for 4-28 days was slightly lower than that of the tricalcium silicate paste. The in vitro bioactivity was investigated by soaking in simulated body fluid for 7 days. The result showed that the novel bone cement had good bioactivity and could degrade in tris-(hydroxymethyl)-aminomethane-hydrochloric-acid (Tris-HCl) solution. Our result indicated that the Ca(3)SiO(5)/MCPM paste had good hydraulic properties, bioactivity, and degradability. The novel bone cement could be a potential candidate as bone substitute.

Effects of incorporating nanosized calcium phosphate particles on properties of whisker-reinforced dental composites.

Clinical data indicate that secondary caries and restoration fracture are the most common problems facing tooth restorations. Our ultimate goal was to develop mechanically-strong and caries-inhibiting dental composites. The specific goal of this pilot study was to understand the relationships between composite properties and the ratio of reinforcement filler/releasing filler. Nanoparticles of monocalcium phosphate monohydrate (MCPM) were synthesized and incorporated into a dental resin for the first time. Silicon carbide whiskers were fused with silica nanoparticles and mixed with the MCPM particles at MCPM/whisker mass ratios of 1:0, 2:1, 1:1, 1:2, and 0:1. The composites were immersed for 1-56 days to measure Ca and PO4 release. When the MCPM/whisker ratio was changed from 0:1 to 1:2, the composite flexural strength (mean +/- SD; n = 5) decreased from 174 +/- 26 MPa to 138 +/- 9 MPa (p < 0.05). A commercial nonreleasing composite had a strength of 112 +/- 14 MPa. When the MCPM/whisker ratio was changed from 1:2 to 1:1, the Ca concentration at 56 days increased from 0.77 +/- 0.04 mmol/L to 1.74 +/- 0.06 mmol/L (p < 0.05). The corresponding PO4 concentration increased from 3.88 +/- 0.21 mmol/L to 9.95 +/- 0.69 mmol/L (p < 0.05). Relationships were established between the amount of release and the MCPM volume fraction v(MCPM) in the resin: [Ca]= 42.9 v(MCPM) (2.7), and [PO4] = 48.7 v(MCPM) (1.4). In summary, the method of combining nanosized releasing fillers with reinforcing fillers yielded Ca- and PO4-releasing composites with mechanical properties matching or exceeding a commercial stress-bearing, nonreleasing composite. This method may be applicable to the use of other Ca-PO4 fillers in developing composites with high stress-bearing and caries-preventing capabilities, a combination not yet available in any dental materials.