Description
The chemical properties of microcalcifications within the body have been shown to provide a keen insight into the disease state of various cancers.[1] In their invasive form, these microcalcifications exist predominantly as the common calcium phosphate mineral hydroxyapatite. Being a biomineral, these apatites readily incorporate amounts of common biological ions which also have been shown in the literature to be key markers of disease state.[2] Current clinical techniques are dominated by X-Ray imaging which are incapable of resolving chemical information. Consequently, lab-based analysis is required to achieve a diagnosis. However, only around 20% of microcalcificaitons analysed turn out to be malignant, giving justification for the exploration of alternative diagnosis techniques.[3]
Low-wavenumber Raman spectroscopy is a rapid and non-destructive technique that has a evolving track record in the analysis of both minerals and biological materials. This technique is highly suited to probe the long-range intermolecular lattice modes of materials that are prevalent in repeating structures such as hydroxyapatite.[4] Given that the coordination of the rather heavy Calcium cations plays a key role in dictating these lattice modes, low-wavenumber Raman spectroscopy should be especially sensitive to the presence of substituting ions.
In this work, a set of synthetic substituted apatites, dictated by a design of experiments approach are analysed by both low-wavenumber and traditional Raman spectroscopy with insight given to the spectral changes due to substitution. Complementary THz IR data, collected at the Australian synchrotron is also leveraged with DFT calculations utilised to determine the most likely substitution mechanisms in each sample.
1 Gosling, S. et al. Journal of Mammary Gland Biology and Neoplasia 24 (2019).
2 Scott, R. et al. Scientific Reports 7, 136 (2017).
3 Evans, et al.Clinical Radiology 54, 644-646 (1999).
4 Kirkham, J. et al. Crystal Growth & Design 23, 5748-5761 (2023).
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