Raman spectroscopic detection of changes in bioapatite in mouse femora as a function of age and in vitro fluoride treatment.

Laser Raman microprobe spectroscopy, which characterizes the molecular structure of a mineral, was used to analyze microscopically small regions of bioapatite in mouse femora in order to study the effect of mouse age and in vitro fluoride treatment on the bone mineral (i.e., mineral identity and degree of crystallinity). Both femora that had and those that had not undergone in vitro NaF treatment underwent point analysis of 1 micron spots in the center of the compact bone's cross-section. The Raman spectra of bones treated with fluoride showed a peak up-shift of the PO4 vibration mode from 961 to 964 delta cm-1 indicating a conversion from a carbonated hydroxylapatitic to a carbonated fluorapatitic mineral phase. The spectral band width of the 961 delta cm-1 PO4 vibration in femora of 4-, 10-, and 24-week-old mice showed that aging, as well as in vitro treatment with 1.5 M NaF for 12 hours, significantly increases the degree of crystallinity of the bioapatite. In vitro fluoridation of 10-week-old mouse femora increased the bioapatite's degree of crystallinity to about the same degree as did aging to 24 weeks. Four-point bending tests indicated that the age-related increase in crystallinity of untreated bones was associated with decreased deformation to failure, i.e., increased brittleness. In contrast, the increased crystallinity following fluoridation of 10-week-old bones was associated with increased deformation, i.e., increased ductility, perhaps due to the altered mineral composition. This study shows that the laser Raman microprobe readily detects the conversion of carbonated hydroxylapatite to carbonated fluorapatite, as well as changes in crystallinity of either mineral phase, in microscopically small regions of a bone sample.

A post-stishovite SiO2 polymorph in the meteorite Shergotty: implications for impact events.

Transmission electron microscopy and electron diffraction show that the martian meteorite Shergotty, a shocked achondrite, contains a dense orthorhombic SiO2 phase similar to post-stishovite SiO2 with the alpha-PbO2 structure. If an SiO2 mineral exists in Earth's lower mantle, it would probably occur in a post-stishovite SiO2 structure. The presence of such a high-density polymorph in a shocked sample indicates that post-stishovite SiO2 structures may be used as indicators of extreme shock pressures.

Analysis of breast implant capsular tissue for crystalline silica and other refractile phases.

This study questions previous reports of the presence of micrometer-sized areas of crystalline silica in pathologic tissue sections that are based exclusively on polarized-light microscopy. By using optical principles, it can be argued that it is impossible to identify unambiguously or to detect the birefringence of crystalline silica in 5-microm-thin sections. To clarify whether silicone, amorphous silica, or crystalline silica occurs in micrometer-sized moieties in standard 5-microm-thick tissue sections, one needs to apply a structural means of analysis in addition to optical microscopy. This study recommends the use of the laser Raman spectroscopic technique, which is very well suited to clarify this highly controversial issue in future pathologic studies.

Interstellar polycyclic aromatic hydrocarbons and carbon in interplanetary dust particles and meteorites.

Both interplanetary dust particles (IDP(s)) and meteorites may contain material that is similar to polycyclic aromatic hydrocarbons(PAH(s)). The Raman spectra of IDP(s) and meteorites show features that are similar in position and relative strength to interstellar infrared emission features that have been attributed to vibrational transitions in free, molecular-sized PAH(s). The Raman spectra of some IDP(s) also show red photoluminescence that is similar to the excess red emission seen in some astronomical objects and that has also been attributed to PAH(s) and hydrogenated amorphous carbon. Moreover, a part of the carbonaceous phase in IDP(s) and meteorites contains deuterium to hydrogen ratios that are greater than those for terrestrial samples. Deuterium enrichment is expected in small free PAH(s) that are exposed to ultraviolet radiation in the interstellar medium. Taken together, these observations suggest that some of the carbonaceous material in IDP(s) and meteorites may have been produced in circumstellar dust shells and only slightly modified in interstellar space.