The altar wall paintings of the catholicon "The Nativity of the Virgin", Rila Monastery, Bulgaria: Identification of the painting materials by means of vibrational spectroscopic techniques complemented by EDX, XRD and TGA analysis.

The purpose of the present study is to deepen our knowledge about the painting materials and technology characteristics of iconography during the Bulgarian National Revival. Our efforts have focused on studying the murals in the catholicon (main church) "The Nativity of the Virgin" of the Rila Monastery, which is one of Bulgarian leading historical monuments. A series of micro samples from the altar mural paintings were analyzed by a combination of attenuated total reflectance Fourier transform infrared (ATR-FTIR), micro-Raman spectroscopy, scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Optical microscopy (OM). The data analysis showed that the painter's palette is made up of nine mineral pigments: smalt, chrome yellow, emerald green, vermilion, red lead, green earths, yellow ochre, sienna and calcite. The impression of rich colorful palette was achieved by using various pigment mixtures. The presence of egg binder in many paint samples suggested that the murals were executed by the traditional egg tempera technique, with the only exception of the smalt paint of the background where carbohydrate glue is present as binder.

Analytical studies of the Alexandrovo Thracian tomb wall paintings.

A profound study of samples obtained from Thracian tomb wall paintings at Alexandrovo, Bulgaria (dating back to the fourth century BC) were carried out by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and Attenuated Total Reflectance Fourier transform infrared spectroscopy (ATR FTIR), high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS). The current work provides a glimpse of the ingenious construction and painting techniques used in Thracian tomb at Alexandrovo. The results suggest that beeswax was used as a paint binder and also revealed presence of various nano-materials.

IR spectral and structural changes caused by the conversion of 3-methoxy-4-hydroxybenzaldehyde (vanillin) into the oxyanion.

The spectral and structural changes, caused by the conversion of the vanillin molecule into the corresponding oxyanion have been studied by IR spectra and normal coordinate calculations within the Onsager self-consistent reaction field (SCRF) model, using a density functional theory (DFT) method at the Becke3LYP/6-31+G** level. Structures of all conformational isomers of vanillin and of its anion have been located, as well as their total and relative energies have been determined. The conversion leads to geometry changes in the whole species, due to the strong O-/acceptor polar resonance through the para phenylene ring. The conversion causes a 41 cm(-1) decrease in the frequency of the carbonyl stretching band nu(C=O), strong intensity increases (1.6 - 7.2-fold) of the aromatic skeletal nu8 and nu19 as well as formyl nu(CH) bands. According to the calculations the oxyanionic charge is delocalized over aldehyde group (0.25 e-), phenylene ring (0.13 e-), methoxy group (0.07 e-) and oxyanyonic center (0.55 e-).

IR spectral and structural changes caused by the conversion of 3-hydroxybenzaldehyde into the oxyanion.

The spectral and structural changes, caused by the conversion of the 3-hydroxybenzaldehyde molecule into the corresponding oxyanion have been studied by IR spectra, and MP2 and DFT force field calculations. The conversion causes a 13 cm(-1) decrease in the frequency of the carbonyl stretching band nu(Cz=O), a 1.3-fold increase in its integrated intensity, strong intensity increases (2.1-5.3-fold) of the aromatic skeletal nu8 and nu19 as well as formyl nu(CH) bands. According to the calculations the oxyanionic charge is delocalized over aldehyde group (0.37 e-), phenylene ring (0.12 e-) and oxyanionic center (0.52 e-). The conversion into the oxyanion leads to geometry changes in the whole species, but it remains planar.