Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) spectra of salivary glands carcinoma, tumor and healthy tissues and their homogenates analyzed by chemometry: Towards development of the novel tool for clinical diagnosis.

In this study, two approaches to salivary glands studies are presented: Raman imaging (RI) of tissue cross-section and surface-enhanced Raman spectroscopy (SERS) of tissue homogenates prepared according to elaborated protocol. Collected and analyzed data demonstrate the significant potential of SERS combined with multivariate analysis for distinguishing carcinoma or tumor from the normal salivary gland tissues as a rapid, label-free tool in cancer detection in oncological diagnostics. Raman imaging allows a detailed analysis of the cell wall's chemical composition; thus, the compound's distribution can be semi-quantitatively analyzed, while SERS of tissue homogenates allow for detailed analysis of all moieties forming these tissues. In this sense, SERS is more sensitive and reliable to study any changes in the area of infected tissues. Principal component analysis (PCA), as an unsupervised pattern recognition method, was used to identify the differences in the SERS salivary glands homogenates. The partial least squares-discriminant analysis (PLS-DA), the supervised pattern classification technique, was also used to strengthen further the computed model based on the latent variables in the SERS spectra. Moreover, the chemometric quantification of obtained data was analyzed using principal component regression (PCR) multivariate calibration. The presented data prove that the PCA algorithm allows for 91% in seven following components and the determination between healthy and tumor salivary gland homogenates. The PCR and PLS-DA methods predict 90% and 95% of the variance between the studied groups (in 6 components and 4 factors, respectively). Moreover, according to calculated RMSEC (RMSEP), R2C (R2P) values and correlation accuracy (based on the ROC curve), the PLS-DA model fits better for the studied data. Thus, SERS methods combined with PLS-DA analysis can be used to differentiate healthy, neoplastic, and mixed tissues as a competitive tool in relation to the commonly used method of histopathological staining of tumor tissue.

Metal fluoride nanotubes featuring square-planar building blocks in a high-pressure polymorph of AgF2.

At a pressure of ca. 15 GPa, AgF2 transforms to an unprecedented orthorhombic polymorph featuring an array of tubular subunits which are built of corner sharing [AgF4] squares. This seems to be the first type of a metal fluoride nanowire and also the only one showing rigid square planar rather than common hexagonal or octahedral moieties.

Lone-pair interactions and photodissociation of compressed nitrogen trifluoride.

High-pressure behavior of nitrogen trifluoride (NF3) was investigated by Raman and IR spectroscopy at pressures up to 55 GPa and room temperature, as well as by periodic calculations up to 100 GPa. Experimentally, we find three solid-solid phase transitions at 9, 18, and 39.5 GPa. Vibrational spectroscopy indicates that in all observed phases NF3 remains in the molecular form, in contrast to the behavior of compressed ammonia. This finding is confirmed by density functional theory calculations, which also indicate that the phase transitions of compressed NF3 are governed by the interplay between lone­pair interactions and efficient molecule packing. Although nitrogen trifluoride is molecular in the whole pressure range studied, we show that it can be photodissociated by mid-IR laser radiation. This finding paves the way for the use of NF3 as an oxidizing and fluorinating agent in high-pressure reactions.