Calcium Phosphates

DENTAL RESEARCH HIGHLIGHTS

CALCIUM PHOSPHATES

Application of Calcium Phosphate Chemistry to Biomineralization Research L.C. CHOW Proceedings, 2003 Asian Bioceramics Symposium, Kyushu University, Fukuoka, Japan November 18-20, 2003 Archives of Advanced Bioceramics Research (Special Asian edition) Calcium phosphate chemistry encompasses a broad range of studies including crystal structures, solid-solution equilibria, coupled dissolution-diffusion processes, simultaneous dissolution-reprecipitation phenomena, lattice-surface interactions, and solid-state reactions. Through laboratory methods, knowledge derived from these studies can be applied to many areas in biomineralization research such as dental caries mechanism, tooth remineralization, normal and pathological mineralization, calcium phosphate biomaterials, etc. This presentation will provide an overview of application of calcium phosphate chemistry to several areas of biomineralization research, with special focus on development of cements that form different calcium phosphate phases, including stoichiometric HA, Ca-deficient HA, Carbonated HA, octacalcium phosphate and dicalcium phosphate dihydrate, as products. Physical and dissolution properties of these cements are discussed. Supported by USPHS NIDCR Grant DE11789 and the ADAHF.

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DENTAL RESEARCH HIGHLIGHTS

CALCIUM PHOSPHATES

Properties of Nanometer Sized Hydroxyapatite Prepared by Spray Drying Methods L.C. CHOW, L. SUN and B. HOCKEY Journal of Dental Research 83 (Special Issue A); IADR CD-ROM Abstract No. 3492, 2004 Journal of Research of the National Institute of Standards and Technology (accepted)

Previous studies have reported preparation of nanometer hydroxyapatite (HA) by sol-gel or precipitation methods, where the products were washed by aqueous or non-aqueous liquids that may modify the properties of the nano particles. Objective: This study evaluated properties of nano HA prepared by a spray drying method where the HA product was not exposed to any liquid after its formation. Methods: The spray drying apparatus comprised of a nozzle that sprayed a calcium phosphate solution in the form of a fine mist into a stream of heated air flowing though a glass column. The water in the mist was evaporated by the time the mist reached the end of the column and an electrostatic precipitator collected the fine particles. The nano HA products were characterized by powder X-ray diffraction (XRD), high resolution transmission electron microscopy (TEM), Fourier transfer infrared (FTIR) spectroscopy, and solubility measurements. Results: XRD patterns suggested the material was amorphous, exhibiting a single broad peak at 30.5 2. However, TEM analysis showed that the particles, some of which were 5 nm in size, exhibited well ordered HA lattice fringes and small area diffraction patterns were indicative of HA. FTIR showed patterns of typical of HA with small amounts of HPO42-. The thermodynamic solubility product of the nano HA (given as pKsp) was 103 4 in the pH range of 5 to 6 which is significantly more soluble than the value of 118 for crystalline HA. Conclusion: HA particles as small as 5 nm in size, prepared by a spray drying method, showed amorphous XRD patterns but exhibited well-defined lattice fringes in TEM. The nano HA was significantly more soluble than conventional crystalline HA. Supported by NIDCR Grant DE11789, NIST and the ADAF.

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DENTAL RESEARCH HIGHLIGHTS

CALCIUM PHOSPHATES

Preparation and Comprehensive Characterization of a Calcium Hydroxyapatite Reference Material M. MARKOVIC, B.O. FOWLER and M.S. TUNG Journal of Research of the National Institutes of Standards and Technology (in press) Numerous biological and chemical studies involve the use of calcium hydroxyapatite (HA), Ca10(PO4)6(OH)2. In this study detailed physicochemical characterization of HA, prepared from an aqueous solution, was carried out employing different methods and techniques: chemical and thermal analyses, X-ray diffraction, infrared and Raman spectroscopies, scanning and transmission microscopies, and Brunauer, Emmett, and Teller (BET) surface-area method. The contents of calcium (Ca2+), phosphate (PO43-), hydroxide (OH-), hydrogenphosphate (HPO42-), water (H2O), carbonate (CO32-), and trace constituents, the Ca/P molar ratio, crystal size and morphology, surface area, unit-cell parameters, crystallinity, and solubility of this HA were determined. This highly pure, homogeneous, and highly crystalline HA is certified as a National Institute of Standards and Technology (NIST) standard reference material, SRM 2910. Supported by Grant DE11789, NIST and the ADAF.
1.4

Fig. 1. Infrared absorbance spectrum of the v3 PO4 mode of HA-SRM (dashed line) and second derivative of the absorbance spectrum (solid line). The second derivative spectrum ordinate scale, not shown, is arbitrary. The second derivative spectrum was adjusted to full ordinate range and the minima denoted by numbers identify band positions in the absorbance spectrum.

Absorbance

1.0

10
0.6

12 9 11

8 7

0.2

3 5
1110 1060

1
1010

Wavenumber (cm-1)

Fig. 2. Infrared absorbance spectrum of the 4 PO4 mode of HA-SRM (dashed line) and second derivative of the absorbance spectrum (solid line). The absorbance band at 633 cm-1 and second derivative band at 633 cm-1 derive from the OH librational mode. The description of the second derivative spectrum is the same as that given in Fig. 1.

1.4

Absorbance

1.0

3 2 5

0.6

0.2 650

4
Wavenumber (cm-1)
600

1
550

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DENTAL RESEARCH HIGHLIGHTS Effect of Glycerol and Sorbitol on formation of Calcium Phosphates M.S. TUNG and D. SKRTIC

CALCIUM PHOSPHATES

Journal of Dental Research 83 (Special Issue A); IADR CD-ROM Abstract No. 3598, 2004 Polyhydric alcohols have excellent humectant properties. Triol - glycerol and hexitol - sorbitol also exhibit resistances to bacterial action and are important ingredients in dental products. Objective: To study the effect of these additives on the formation, growth and/or transformation of calcium phosphates (CaPs). Methods: The effect of glycerol and sorbitol was investigated in spontaneously precipitating systems and as the carriers for calcium and phosphate salts. CaP precipitation at 22 C was initiated by simultaneously mixing equal volumes of Ca- and PO4- reactant solution without or with glycerol and/or sorbitol. The polyalcohols were added to both Ca (11mmol/L) and PO4 ( 370mmol/L) reactants at the mass fractions of 14 to 45 %. Precipitation kinetics were followed by the changes in solution pH, calcium, fluoride and phosphate concentration. Solid phase(s) were isolated at different time intervals and identified by X-ray diffraction, FT-infrared spectroscopy and optical microscopy. Results: At high concentrations ((Ca+2)3(PO4-3)210-21.2), amorphous calcium phosphate (ACP) formed initially in solution containing glycerol or sorbitol and then converted to apatites and/or dicalcium phosphate dihydrate depending on the pH of the solutions and the presence of fluoride. Glycerol and sorbitol decreased while fluoride and lower pH increased the hydrolysis rate of ACP to crystalline phases. The mixtures of soluble calcium and phosphate salts converted to calcium phosphates when in contact with water or humidity, yet were stable in the pure glycerol. Conclusion: These alcohols do not adversely affect the initial formation of ACP from solutions and calcium phosphates are less reactive in their presence. This is attributed to the lower dielectric constants of glycerol and sorbitol, resulting in decrease in solubility of calcium phosphates. Supported by NIST and the ADAF.

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