Hematite colour revisited: Particle size and electronic transitions.

Hematite has been used as a pigment since ancient times, due to its natural abundance and colour that ranges from vivid red to purple. Caput mortuum is a purple α-Fe2O3 whose colour has been ascribed as originating from particle size. In this work, submicrometric synthetic, natural and commercial hematites were investigated by diffuse reflectance spectroscopy (DRS), scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and Raman microscopy aiming to clarify the origin of the purple colour. From the results it was concluded that the purple colour is associated with crystallinity, that promotes a significant decrease in absorption below 500 nm and, simultaneously, an increase in the 6A1(6S) → 4T1(4G) d-d transition at ca. 880 nm. The behaviour of the ca. 880 nm band can be explained by the more extensive magnetic interaction between adjacent Fe3+ ions in crystalline samples but cannot explain the spectral behaviour in the green-blue region considering only the d-d transitions. A plausible explanation is that in the distorted FeO6 octahedra, both the Fe-O distances and the Fe-O-Fe angles area are affected, thus interfering in the low energy oxygen-to-iron charge transfer transition, whose tail span the 400 nm - 500 nm region and is more intense than the d-d transitions in hematite nanoparticles, nanofilms and defective (red) Fe2O3 samples. The decrease in the intensity of the charge transfer band as a consequence of the FeO6 octahedral distortion is yet to be confirmed by further experiments, but the experimental results clearly show that the purple colour of hematite is due to a decrease in optical absorption below 500 nm.

A definitive analytical spectroscopic study of Indian yellow, an ancient pigment used for dating purposes.

The Raman spectrum of tartrazine has been mistakenly reported as being that of Indian yellow in the literature, which has serious consequences for the identification of this pigment in art works regarding their authentication. Unlike tartrazine, Indian yellow (a natural mixture of the magnesium and calcium salts of euxanthic acid) exhibits in its Raman spectrum a strong fluorescent background when visible excitation is used, however, excitation in the near infrared (1064nm) permitted the observation of the Raman bands from the raw pigment with the main features placed at 1346, 1368, 1425, 1441 and 1626cm-1. Indian yellow identification was assured by 1H and 13C Nuclear Magnetic Resonance characterization and the complete assignment of the proton and carbon resonances was accomplished using heteronuclear single quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), nuclear overhauser effect spectroscopy (NOESY) and 1H-1H correlation spectroscopy (COSY). Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray fluorescence (XRF) analyzes were also conducted on a genuine sample of this historical pigment.

Fake turquoises investigated by Raman microscopy.

Turquoise is frequently adulterated by unscrupulous dealers and, not rarely, simulants are commercialized as true stones. On the other hand, turquoise is a cryptocrystalline mineral and its use in adornments commonly demands some kind of treatment to facilitate its manipulation, such as impregnation using oil or fats, consolidation with resin and stabilization or reconstitution made with resins. In this work, Raman microscopy was employed in the investigation of turquoise adornments aiming to differentiate processed turquoise from fakes or simulants. Only one out of the five adornment objects analyzed was truly stabilized turquoise (powdered turquoise aggregated with a resin). Another one was constituted of turquoise, calcium carbonate, phthalocyanine blue and resin; the other objects were dyed minerals.

Investigation on the hazing of a Brazilian contemporary painting.

A whitish crystalline-like coating was observed on the surface of the painting "Incêndio", 1990, produced by Emmanuel Nassar and awarded at the 6th Biennial of Cuenca. This work belongs to the Contemporary Art Museum of the University of São Paulo (MAC-USP) and such coating modified the artwork characteristics, causing an unpleasant effect and compromising its exhibition. The choice of the proper conservation and restoration strategies involves the understanding of the degradation process, demanding the identification of the chemical compounds formed on the painting surface, as well as of the other components in the painting. The results here obtained from Raman and optical microscopies, FTIR-ATR, SEM-EDS and GC-MS, revealed that the efflorescence chemical composition is almost only palmitic acid, with minor contents of stearic acid and their methyl esters, and that the paints are composed by chrome yellow, amorphous carbon and toluidine red pigment; an aluminum silicate filler in the black paint applied on the aluminum ground was also detected. Hierarchical Cluster Analyses (HCA) of the Raman spectra also revealed that the concentration of the efflorescence minor components depends on the paint composition. It was suggested, therefore, that the degradation process resulted from segregation and migration of mainly palmitic acid from the dried paints. Restoration methodologies used in similar cases, as well as factors that contribute to this process, were discussed.

Molecular modeling and UV-vis spectroscopic studies on the mechanism of action of reversed chloroquine (RCQ).

Reversed chloroquine (RCQ) is a multiple ligand compound active against chloroquine-sensitive and resistant falciparum malaria. It is composed by a 4-aminoquinoline moiety (like that present in chloroquine (CQ)) joined to imipramine (IMP), a modulating agent that also showed intrinsic antiplasmodial activity against Brazilian Plasmodium falciparum isolates resistant to CQ. Molecular modeling and ultraviolet-visible spectroscopy (UV-vis) studies strongly suggest that the interaction between RCQ and heme is predominant through the quinoline moiety in a mechanism of action similar to that observed for CQ.

Raman spectroscopic analysis of a tembetá: a resin archaeological artefact in need of conservation.

The Raman spectroscopic analysis of a Brazilian tembetá, a lip-plug which signifies the attainment of manhood in tribal cultures, and dated to about 1600 years BP is reported. Tembetá are usually made of wood or stone but this lip-plug is very rare in that it is made of resin, which has been severely degraded in the burial environment; the brownish-red fragmented remains are in an extremely fragile condition and information about the chemical composition was required before urgent conservation was undertaken. Raman spectra excited at 1064 nm showed the presence of triterpenoid materials in the main body of the artefact, and indicated that the red-brown coating was not iron(III) oxide as suspected but rather degraded resin. Comparison with contemporary resins has facilitated the partial identification of the material in this important artefact as a triterpenoid-rich material, which is closely similar to the Pistacia species. A possible archaeological link to the Jatobá do Cerrado (Hymenaea stigonocarpa Mart.) resin has been excluded as the Raman spectra of this resin specimen and the tembetá do not match; indeed, the Jatobá do Cerrado resin specimen belongs to a diterpenoid-rich classification as befits its Hymenaea species.