Snezana Uskokovic-Markovic

Study of the decomposition pathway of 12-molybdophosphoric acid in aqueous solutions by micro Raman spectroscopy.

Micro Raman spectroscopy was applied to investigate the speciation of heteropoly and isopoly molybdates in 0.05 and 0.005 M aqueous solutions of 12-molybdophosphoric acid at pH values between 1 and 6. For comparative purposes, (31)P NMR spectroscopy was applied too. It is shown that stability of Keggin anion is influenced both by pH and concentration of solution. The Keggin structure is stable in acidic solutions (pH<1.6) while defective Keggin structures are formed with further alkalization (up to pH5.6). Monolacunary anion PMo11O(39)(7-) is the main component in the pH region from 1.6 to 3.4. Further removal of molybdenyl species causes the appearance of other vacant Keggin structures such as PMo9O31(OH)(3)(6-) and PMo6O(25)(9-) at about pH4. At pH5.0, anion PMo6O(25)(9-) is the main species. In solutions with pH greater than 5.0, heteropolymolybdates disappear completely and isopolymolybdates Mo7O(24)(6-) and MoO(4)(2-) are formed in higher amounts. In more diluted solution of 0.005 M, the decomposition scheme of 12-molybdophosphoric acid solution with increasing of pH takes place without observation of significant amounts of Mo7O(24)(6-) species. If alkalinization is performed with 0.5 M instead of 5 M NaOH, there are no significant changes in the Raman spectra of solutions. It is shown that the spectra of evaporated samples may be used for the identification of molecular species in corresponding concentrated solutions. However, Raman spectra of dry residues of more diluted solutions differ from spectra of corresponding solutions due to the reactions performed during the process of drying and cannot be used for unambiguous identification of species in solution. Acidification of 0.05 M solution of Na2MoO4 shows that at pH>5.6, molybdate anion MoO(4)(2-) dominates, while in the pH range between 5.6 and 1, heptamolybdate anion Mo7O(24)(6-) is preferentially formed.

Spectroscopic analysis of XIV century wall paintings from Patriarchate of Peć Monastery, Serbia

The Church of the Holy Mother of God Hodegetria in Peć is decorated with wall paintings that date from the beginning of the 14th century. In terms of style they correspond to Byzantine wall paintings from the epoch of Paleologos. The painting technique and pigment pallete has been examined on micro fragments in thin cross-sections by means of optical microscopy (OM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) and micro- Raman spectroscopy. Use of the fresco technique and two supporting plaster layers was noted on the majority of samples, while in large blue painted areas, a combination of fresco and secco techniques was used. The SEM-EDS results showed the presence of Ca as the main component of plaster besides the traces of Si and Mg. In some samples egg white as a binder was identified. The paint film is often multilayered. Twelve pigments were identified, mainly natural earth pigments such as red ochre, yellow ochre and green earth. A mixture of pigments was used for attaining desirable optical and aesthetical impressions. As decay product only weddelite was detected in many preparatory and painted samples.

Surface-Enhanced Raman Scattering (SERS) Biochemical Applications

Surface-enhanced Raman scattering (SERS) is achieved when an analyte is adsorbed onto or in close proximity to a prepared roughened metal surface (primarily gold or silver) in a process which greatly enhances the Raman emission. SERS provides high sensitivity, selectivity, and specificity to the field of biomolecule detection and identification, and a range of diseases can be detected. Of particular interest is the development of SERS tags for cancer detection, as well as SERS-labeled antibodies in SERS immunoassays for protein localization in blood plasma/serum or tissue. The suitability of SERS for biochemical diagnostics and future implementation in a clinical practice is promising.