Apatite, hydroxyapatite

Hydroxyapatite, Ca2Q(PO (OH)2, may be regarded as the parent member of a whole series of stmcturaHy related calcium phosphates that can be represented by the formula M2q(ZO X2, where M is a metal or H O" Z is P, As, Si, Ga, S, or Cr and X is OH, F, Cl, Br, 1/2 CO, etc. The apatite compounds all exhibit the same type of hexagonal crystal stmcture. Included are a series of naturally occurring minerals, synthetic salts, and precipitated hydroxyapatites. Highly substituted apatites such as FrancoHte, Ca2Q(PO (C02) (F,0H)2, are the principal component of phosphate rock used for the production of both wet-process and furnace-process phosphoric acid. 

Phosphorus is the eleventh element in order of abundance in crustal rocks of the earth and it occurs there to the extent of 1120 ppm (cf. H 1520 ppm, Mn 1060 ppm). All its known terrestrial minerals are orthophosphates though the reduced phosphide mineral schrieber-site (Fe,Ni)3P occurs in most iron meteorites. Some 200 crystalline phosphate minerals have been described, but by far the major amount of P occurs in a single mineral family, the apatites, and these are the only ones of industrial importance, the others being rare curiosities. Apatites (p. 523) have the idealized general formula 3Ca3(P04)2.CaX2, that is Caio(P04)6X2, and common members are fluorapatite Ca5(P04)3p, chloroapatite Ca5(P04)3Cl, and hydroxyapatite Ca5(P04)3(0H). In addition, there are vast deposits of amorphous phosphate rock, phosphorite, which approximates in composition to fluoroapatite. " These deposits are widely... 

By far the most abundant phosphate mineral is apatite, which accounts for more than 95% of all P in the Earth s crust. The basic composition of apatite is listed in Table 14-2. Apatite exhibits a hexagonal crystal structure with long open channels parallel to the c-axis. In its pure form, F , OH , or Cl occupies sites along this axis to form fluorapatite, hydroxyapatite, or chlor-apatite, respectively. However, because of the "open" nature of the apatite crystal lattice, many minor substitutions are possible and "pure" forms of apatite as depicted by the general formula in Table 14-2 are rarely found. 

It is probable that the prevalent oxidation states of phosphorus on the young Earth were lower than they are today, so calcium salts with a much better solubility than that of apatite could have been formed. As Glindemann et al. (1999) were able to show in model experiments, up to 11 % of the starting material could be converted to phosphite in CH4/N2 atmospheres (10% CH4) using Na2HP04, hydroxyapatite or fluoroapatite sources. Similar processes cannot be excluded for the primeval Earth, for example, under the influence of electrical discharges. 

Fig. 1.6 (A and B) Scanning electron micro- implantation in the bone marrow showing for-graphs of the porous hydroxyapatite-collagen mation of new bone (white asterisk) attached nanocomposite scaffolds at different magnifi- directly to the nanocomposite (asterisk). Arrows cations. Arrowheads in B indicate the hydroxy- indicate cuboidal osteoblasts on the surface of apatite nanocrystals on the collagen fibrils. new bone. Adapted from [94], reproduced by Histology at (C) 1 week and (D) 4 weeks after permission of Wiley-VCH.

The collagen fibers leave small compartments where apatite nanocrystals are deposited during a controlled biomineralization process [20]. The collagen acts as a structural framework in which plate-like nanocrystals of carbonated hydroxyapatite (CHA) are embedded to strengthen the bone. The chemical formula of biological CHA can be represented as follows ... 

The estimation of the crystallinity index (Cl) of bone is based on one of the four vibrational modes associated with the apatite phosphate group. In amorphous calcium phosphate, the absorption band at 550-600 cm-1 appears as a single broad peak, whilst in hydroxyapatite it is split into bands of unequal intensity by the apatite crystal field (Sillen and Parkington 1996). Based on the splitting factor introduced by Termine and Posner (1966), Weiner and Bar-Yosef (1990) proposed the use of a crystallinity index to measure the crystallinity of bone mineral. As illustrated in Fig. 4.7, the Cl is estimated by drawing a base line from 750 to 495 cm 1 and measuring the heights of the absorption peaks at 603 cm-1 (measurement a), 565 cm 1 (measurement b) and the distance from the base line to the lowest point between the two peaks (c). Cl is calculated from the formula ... 

Bone and teeth in mammals and bony fishes all rely on calcium phosphates in the form of hydroxyapatite [Ca5(P04)30H]2, usually associated with around 5% carbonate (and referred to as carbonated apatite). The bones of the endoskeleton and the dentin and enamel of teeth have a high mineral content of carbonated apatite, and represent an extraordinary variety of structures with physical and mechanical properties exquisitely adapted to their particular function in the tissue where they are produced. We begin by discussing the formation of bone and then examine the biomineralization process leading to the hardest mineralized tissue known, the enamel of mammalian teeth. 

Most calcium, containing apatites in nature are heavily carbonated. The only exception is formed by the mineral in the surface of tooth enamel which consists mainly of hydroxyapatite (Ca5(P04)30H). 

The logarithm of the solubility product for hydroxyapatite is -58.6 and that of fluorapatite (CajtPO jF) is -60.6 (57), and thus, D = 0.01 in favour of fluoride incorporation into the solid apatite precipitate. Accordingly, it should be difficult to prepare solid solutions of these compounds by precipitation from aqueous solution and if prepared batchwise, they are expected to contain logarithmic gradients in their internal composition. Yet, Moreno et al.(M3) report linear changes in the lattice parameters of such solid solutions. They also determined their solubility behavior. 

In conclusion, the solubility data indicate that upon precipitation from aqueous solutions which have a F/OH molar ratio less than a certain value, slightly fluoridated hydroxyapatites will be formed (x .0.15), and above that ratio nearly pure fluor-apatite will be formed. Usually the F/OH ratio varies so that intimate mixtures of hydroxyapatite and fluorapatite will result (64). The effect of fluoride on teeth and bones are discussed elsewhere (52, 57). 

Once calcium deficient hydroxyapatite DOHA (between pH 6.8 and 8.2) is formed, a metastable equilibrium is created with the aqueous solution which may last indefinitely at room or body temperature.If carbonate ions are present in addition the apatite preferably formed is... 

Despite the importance of the precipitation of calcium phosphates, there is still considerable uncertainty as to the nature of the phases formed in the early stages of the precipitation reactions under differing conditions of supersaturation, pH, and temperature. Although thermodynamic considerations yield the driving force for the precipitation, the course of the reaction is frequently mediated by kinetic factors. Whether dicalcium phosphate dihydrate (CaHPO HoO, DCPD), octacalcium phosphate (Ca HfPO, 2.5 H20, OCP), hydroxyapatite (Cag (PO fOH), HAP), amorphous calcium phosphate (ACP), or a defect apatite form from aqueous solution depends both upon the driving force for the precipitation and upon the initiating surface phase. Thermodynamically, the relative supersaturation, o, is given by... 

Interest in the nature of interactions between shortchain organic surfactants and large molecular weight macromolecules and ions with hydroxyapatite extends to several fields. In the area of carles prevention and control, surfactant adsorption plays an important role in the Initial states of plaque formation (1-5) and in the adhesion of tooth restorative materials ( ). Interaction of hydroxyapatite with polypeptides in human urine is important in human biology as hydroxyapatite has been found as a major or minor component in a majority of kidney stones ( 7). Hydroxyapatite is used in column chromatography as a material for separating proteins (8-9). The flotation separation of apatite from... 

Only a few systematic studies have been carried out on the mechanism of interaction of organic surfactants and macromolecules. Mishra et al. (12) studied the effect of sulfonates (dodecyl), carboxylic acids (oleic and tridecanoic), and amines (dodecyl and dodecyltrimethyl) on the electrophoretic mobility of hydroxyapatite. Vogel et al. (13) studied the release of phosphate and calcium ions during the adsorption of benzene polycarboxylic acids onto apatite. Jurlaanse et al.(14) also observed a similar release of calcium and phosphate ions during the adsorption of polypeptides on dental enamel. Adsorption of polyphosphonate on hydroxyapatite and the associated release of phosphate ions was investigated by Rawls et al. (15). They found that phosphate ions were released into solution in amounts exceeding the quantity of phosphonate adsorbed. 

Apatites are complexes of cationic Ca " matched by HP04, COa ", OH , or F as anions. Depending on the counter-ion, apatite can occur in the forms carbonate apatite Caio(P04)6C03, as hydroxyapatite Caio(P04)e (0H)2, or fluoroapatite Caio(P04)6F2. In addition, alkaline earth carbonates also occur in bone. In adults, more than 1 kg calcium is stored in bone. 

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