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Calcium orthophosphates

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Abstract

The present overview is intended to point the readers’ attention to the important subject of calcium orthophosphates. This type of materials is of the special significance for the human beings because they represent the inorganic part of major normal (bones, teeth and antlers) and pathological (i.e. those appearing due to various diseases) calcified tissues of mammals. For example, atherosclerosis results in blood vessel blockage caused by a solid composite of cholesterol with calcium orthophosphates. Dental caries and osteoporosis mean a partial decalcification of teeth and bones respectively that results in replacement of a less soluble and harder biological apatite by more soluble and softer calcium hydrogenphosphates. Therefore, the processes of both normal and pathological calcifications are just an in vivo crystallization of calcium orthophosphates. Similarly, dental caries and osteoporosis might be considered as in vivo dissolution of calcium orthophosphates. Conversely, due to a great chemical similarity with the biological calcified tissues, many calcium orthophosphates possess remarkable biocompatibility and bioactivity. Materials scientists extensively use this property to construct artificial bone grafts that are either entirely made of or only surface-coated by the biologically relevant calcium orthophosphates. For example, self-setting hydraulic cements made of calcium orthophosphates are helpful in bone repair, while titanium substitutes covered by a surface layer of calcium orthophosphates are used for hip joint endoprostheses and tooth substitutes. Porous scaffolds made of calcium orthophosphates are very promising tools for tissue engineering applications. In addition, calcium orthophosphates of a technical grade are very popular mineral fertilizers. There is a great significance of calcium orthophosphates for the humankind and, in this paper, an overview on the current knowledge on this subject is provided. To assist and guide the readers, a great number of references to the related publications detalizing various specific aspects of the matter has been collected.

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Notes

  1. As a mineral species, apatite was first recognized by the father of German geology Abraham Gottlob Werner (1750–1817) in 1786 and named by him from the Greek απατώ (apato)—“to mislead” or “to deceive”, because it had previously been mistaken for other minerals, such as beryl, tourmaline, chrysolite, amethyst, fluorite, etc.

  2. Occasionally “biological apatite” is called “bioapatite” [23–25].

  3. There are reports that dahllite belongs to the francolite group. Natural dahllite might be a rock forming mineral. For example, it is found in some phosphorite concretions of Podolia. In addition, it is found in both massive and accretionary crustal phosphorites [15].

  4. Collagens are fibrous, insoluble proteins found in the connective tissues, including skin, bone, ligaments and cartilage.

  5. In literature occasionally one might find brief notes on the 12th calcium orthophosphate, namely oxyapatite (Ca10(PO4)6O). A mixture of oxyapatite and HA might be prepared by dehydration of HA at temperatures exceeding ∼900°C (e.g., during plasma-spray of HA) only in the absence of water vapor [5, 6, 30]. It also might be crystallized in glass-ceramics [31]. Oxyapatite is very reactive and transforms to HA in contact with water vapor [30]. Oxyapatite is still very poorly known; however, the following data on the solubility constant (K s ∼ 10–69 at 25°C) and crystal structure (hexagonal, P63/62) are available [5].

  6. Biocompatibility is the ability of a material to perform with an appropriate host response in a specific application [41].

  7. To honor Prof. George Jarvis Brush (1831–1912), an American mineralogist, Yale University, New Haven, Connecticut, USA.

  8. For Moneta (now Monito) Island, which contains a notable occurrence.

  9. In 1941, to honor Mr. Herbert Percy Whitlock (1868–1948), an American mineralogist, the curator of the American Museum of Natural History, New York City, New York, USA, the term whitlockite was coined as a synonym for β-TCP identified by its X-ray diffraction pattern in phosphate rocks [77]. Therefore, strictly speaking, β-TCMP should be called as a “magnesium whitlokite”. An iron-containing whitlockite with chemical formula Ca9(Mg, Fe2+)(PO4)6(PO3,OH) exists in nature: is a relatively rare natural mineral but is found in granitic pegmatite and has also been found in meteorites. It can form small, but distinct and well-formed crystals [78, 79].

  10. In some research papers, CDHA is defined as “precipitated HA” [126–128].

  11. It is worth noting that the chemically correct name would be hydroxylapatite (perhaps, hydroxidapatite would be even better because it relates to calcium hydroxide) while by the medical and material communities it is usually called as hydroxyapatite.

  12. The amount of fluorides on the very surface of dental enamel might be increased by using fluoride-containing toothpastes and mouthwashes [208–211]. Fluoride-containing toothpastes and mouthwashes are widely used in practice due to the well-known anti-cariogenic effect of fluorides that is related to the solubility decreasing [212, 213].

  13. Due to the nanoscopic dimensions, biological apatite is occasionally called “nano-apatite” [231].

  14. Strictly speaking, there are some differences. For example, the hardness of live dentin is less than that of enamel but is greater than that of bone or cementum. When pulp of the tooth dies or is removed by a dentist, the properties of dentin change: it becomes brittle, liable to fracture and looses a reparative capability.

  15. In addition, there is a cementum-enamel junction (CEJ), which is quite similar to DEJ.

  16. Bioactivity is defined as the property of the material to develop a direct, adherent and strong bonding with bone [175, 176].

  17. Osteoconductivity is the ability to provide a scaffold or template for the formation of new bone on its surface by attachment, migration, proliferation, and differentiation of bone-forming cells [406].

  18. The term “biomimetics” (“the mimicry of life”) was coined by an American inventor, engineer, and biophysicist Otto Herbert Schmitt (1913–1998) in the 1950s.

  19. In 2003, the NSF published a report titled: “The emergence of tissue engineering as a research field”, which provides a thorough description of the history of this field [545].

  20. For multiphase compositions of various calcium orthophosphates, the problem of accurate phase quantification often arises. The problem is usually solved by the Rietveld refinement and the readers are referred to a very recent paper on this subject [612].

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Acknowledgments

I would like to thank Prof. Dr. Matthias Epple for providing some technical assistance, literature search and a financial support in the past.

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    Sergey V. Dorozhkin

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Dorozhkin, S.V. Calcium orthophosphates. J Mater Sci 42, 1061–1095 (2007). https://doi.org/10.1007/s10853-006-1467-8

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