6 research outputs found
A time-course Raman spectroscopic analysis of spontaneous in vitro microcalcifications in a breast cancer cell line
Microcalcifications are early markers of breast cancer and can provide valuable prognostic information to support clinical decision-making. Current detection of calcifications in breast tissue is based on X-ray mammography, which involves the use of ionizing radiation with potentially detrimental effects, or MRI scans, which have limited spatial resolution. Additionally, these techniques are not capable of discriminating between microcalcifications from benign and malignant lesions. Several studies show that vibrational spectroscopic techniques are capable of discriminating and classifying breast lesions, with a pathology grade based on the chemical composition of the microcalcifications. However, the occurrence of microcalcifications in the breast and the underlying mineralization process are still not fully understood. Using a previously established model of in vitro mineralization, the MDA-MB-231 human breast cancer cell line was induced using two osteogenic agents, inorganic phosphate (Pi) and β-glycerophosphate (βG), and direct monitoring of the mineralization process was conducted using Raman micro-spectroscopy. MDA-MB-231 cells cultured in a medium supplemented with Pi presented more rapid mineralization (by day 3) than cells exposed to βG (by day 11). A redshift of the phosphate stretching peak for cells supplemented with βG revealed the presence of different precursor phases (octacalcium phosphate) during apatite crystal formation. These results demonstrate that Raman micro-spectroscopy is a powerful tool for nondestructive analysis of mineral species and can provide valuable information for evaluating mineralization dynamics and any associated breast cancer progression, if utilized in pathological samples
First Principles NMR Study of Fluorapatite under Pressure
NMR is the technique of election to probe the local properties of materials.
Herein we present the results of density functional theory (DFT) \textit{ab
initio} calculations of the NMR parameters for fluorapatite (FAp), a calcium
orthophosphate mineral belonging to the apatite family, by using the GIPAW
method [Pickard and Mauri, 2001]. Understanding the local effects of pressure
on apatites is particularly relevant because of their important role in many
solid state and biomedical applications. Apatites are open structures, which
can undergo complex anisotropic deformations, and the response of NMR can
elucidate the microscopic changes induced by an applied pressure. The computed
NMR parameters proved to be in good agreement with the available experimental
data. The structural evaluation of the material behavior under hydrostatic
pressure (from --5 to +100 kbar) indicated a shrinkage of the diameter of the
apatitic channel, and a strong correlation between NMR shielding and pressure,
proving the sensitivity of this technique to even small changes in the chemical
environment around the nuclei. This theoretical approach allows the exploration
of all the different nuclei composing the material, thus providing a very
useful guidance in the interpretation of experimental results, particularly
valuable for the more challenging nuclei such as Ca and O.Comment: 8 pages, 2 figures, 3 table
Three Structural Roles for Water in Bone Observed by Solid-State NMR
Hydrogen-bearing species in the bone mineral environment were investigated using solid-state NMR spectroscopy of powdered bone, deproteinated bone, and B-type carbonated apatite. Using magic-angle spinning and cross-polarization techniques three types of structurally-bound water were observed in these materials. Two of these water types occupy vacancies within the apatitic mineral crystal in synthetic carbonated apatite and deproteinated bone and serve to stabilize these defect-containing crystals. The third water was observed at the mineral surface in unmodified bone but not in deproteinated bone, suggesting a role for this water in mediating mineral-organic matrix interactions. Direct evidence of monohydrogen phosphate in a (1)H NMR spectrum of unmodified bone is presented for the first time. We obtained clear evidence for the presence of hydroxide ion in deproteinated bone by (1)H MAS NMR. A (1)H-(31)P heteronuclear correlation experiment provided unambiguous evidence for hydroxide ion in unmodified bone as well. Hydroxide ion in both unmodified and deproteinated bone mineral was found to participate in hydrogen bonding with neighboring water molecules and ions. In unmodified bone mineral hydroxide ion was found, through a (1)H-(31)P heteronuclear correlation experiment, to be confined to a small portion of the mineral crystal, probably the internal portion