Luiz Fernando C. de Oliveira

Vibrational spectroscopic study of brazilin and brazilein, the main constituents of brazilwood from Brazil

Abstract In this work, the vibrational spectra (FT-Raman and infrared spectra) of brazilin, the major component of brazilwood Caesalpinia echinata (from Bahia, Brazil), and brazilein, the oxidised pigment, are investigated. The FT-Raman spectra of the compounds show different patterns in the carbonyl stretching region, where brazilein presents a Raman feature at 1697xa0cm −1 that is tentatively assigned to a coupled vibrational mode described by Cue605O and aromatic Cue605C stretching. Infrared measurements are used to support this assignment. The spectral region between 1700 and 1500xa0cm −1 is also proposed as a fingerprint for brazilin and brazilein. Comparisons with some quinones and polyalcohols as parent molecules and other deep red resin pigments such as “dragon’s blood” are undertaken to assist the vibrational assignment. As a test of the spectroscopic protocol for the identification of these pigments in natural brazilwoods, an 80-year-old archival specimen of Caesalpinia echinata was analysed non-destructively and the feature of brazilein shown from the Raman spectrum.

Spectroscopic and theoretical study of the "azo"-dye E124 in condensate phase: evidence of a dominant hydrazo form.

Spectroscopic techniques, including Raman, IR, UV/vis, and NMR were used to characterize the samples of the azo dye Ponceau 4R (also known as E124, New Coccine; Cochineal Red; C.I. no. 16255; Food Red No. 102), which is 1,3-naphthalenedisulfonic acid, 7-hydroxy-8-[(4-sulfo-1-naphthalenyl) azo] trisodium salt in aqueous solution and solid state. In addition, first principle calculations were carried out for the azo (OH) and hydrazo (NH) tautomers in order to assist in the assignment of the experimental data. The two intense bands observed in the UV/vis spectrum, centered at 332 and 507 nm, can be compared to the calculated values at 296 and 474 nm for azo and 315 and 500 nm for hydrazo isomer, with the latter in closer agreement to the experiment. The Raman spectrum is quite sensitive to tautomeric equilibrium; in solid state and aqueous solution, three bands were observed around 1574, 1515, and 1364 cm(-1), assigned to mixed modes including deltaNH + betaCH + nuCC, deltaNH + nuC horizontal lineO + nuC horizontal lineN + betaCH and nuCC vibrations, respectively. These assignments are predicted only for the NH species centered at 1606, 1554, and 1375 cm(-1). The calculated Raman spectrum for the azo (OH) tautomer showed two strong bands at 1468 (nuN = N + deltaOH) and 1324 cm(-1) (nuCC + nuC-N), which were not obtained experimentally. The (13)C NMR spectrum showed a very characteristic peak at 192 ppm assigned to the carbon bound to oxygen in the naphthol ring; the predicted values were 165 ppm for OH and 187 for NH isomer, supporting once again the predominance of NH species in solution. Therefore, all of the experimental and theoretical results strongly suggest the food dye Ponceau 4R or E124 has a major contribution of the hydrazo structure instead of the azo form as the most abundant in condensate phase.

Raman spectroscopic analysis of dragon's blood resins—basis for distinguishing between Dracaena(Convallariaceae), Daemonorops(Palmae) and Croton(Euphorbiaceae)

Dragon[prime or minute]s blood is the name applied to the deep-red coloured resin obtained from various plants. The original source in Roman times, used by many cultures and esteemed for its depth of colour and mystical association, was the dragon tree Dracaena cinnabari(Convallariaceae), found only on the Indian Ocean island of Socotra, (Yemen). Additional sources emerged later, including another species of Dracaena, D. draco, from the Canary Islands and Madeira, and species in the genera Daemonorops(Palmae) from South East Asia and Croton(Euphorbiaceae) from tropical parts of both the New and Old Worlds. In this study, examples of dragons blood resins from the Economic Botany Collections at the Royal Botanic Gardens, Kew, dating from 1851 to 1993, have been analysed non-destructively using Raman spectroscopy. The Raman spectra of well-documented, provenanced specimens have been used to establish the source of specimens of questionable or unknown origin. It has also been possible from the Raman spectra to indicate whether processing of the resins has been undertaken in the preparation of the specimens before their deposition at Kew.

Romano-British wall-painting fragments: a spectroscopic analysis

Raman spectroscopic analyses of fragmented wall-painting specimens from a Romano-British villa dating from ca. 200 AD are reported. The predominant pigment is red haematite, to which carbon, chalk and sand have been added to produce colour variations, applied to a typical Roman “limewash” putty composition. Other pigment colours are identified as white chalk, yellow (goethite), grey (soot/chalk mixture) and violet. The latter pigment is ascribed to “caput mortuum”, a rare form of haematite, to which kaolinite (possibly from Cornwall) has been added, presumably in an effort to increase the adhesive properties of the pigment to the substratum. This is the first time that kaolinite has been reported in this context and could indicate the successful application of an ancient technology discovered by the Romano-British artists. Supporting evidence for the Raman data is provided by X-ray diffraction and SEM-EDAX analyses of the purple pigment.

Carotenoids and β-cyclodextrin inclusion complexes: Raman spectroscopy and theoretical investigation.

In the present study, the inclusion processes of β-carotene, astaxanthin, lycopene, and norbixin (NOR) into the β-cyclodextrin (β-CD) cavity were investigated by means of Raman spectroscopy and quantum mechanics calculations. The Raman ν(1) band assigned to C═C stretching was sensitive to the host-guest interaction and in general undergoes a blue shift (3-13 cm(-1)) after inclusion takes place, which is the consequence of the localization of single and double bonds. This is supported by the molecular modeling prediction, which inclusion complexes show the ν(1) band blue shifted by 1-8 cm(-1). The calculated complexation energies was small for most of derivatives and was found to be -11.1 kcal mol(-1) for inclusion of AST and +0.27 kcal mol(-1) for NOR. The stability order was qualitatively correlated to topological parameters accounting for the opening angle of the chain. This means that after inclusion the guest molecules assume a slightly more extended conformation, which enhances the host-guest contact, improving the interaction energy. The results discussed here clearly demonstrate the matrix effect on the carotenes spectroscopic profile and should contribute to fully characterize the raw samples.

Caput mortuum: spectroscopic and structural studies of an ancient pigment

The use of a pigment variously described as caput mortuum, usta or ostrum to provide a deep purple colour in ancient wall-paintings was highly prized, despite the technical difficulties associated with its application. With the Raman spectroscopic characterization of pigments in ancient frescoes and wall-paintings becoming more widespread, it is timely to consider the identification of this material either as a generic haematite alone or in admixture with contemporary blue pigments. Here, Raman and infrared spectroscopic, X-ray diffractometric and scanning electron microscopic structural studies have been undertaken to characterize caput mortuum and to identify a specimen of Roman wall-painting dating from the 3rd century.

Fourier-transform Raman characterization of brazilwood trees and substitutes

In this work we have applied Fourier-transform Raman spectroscopy to the analysis of several archival samples of brazilwoods from different geographical origins and of different ages. Samples of Caesalpinia echinata Lam. (from Brazil, South America), Caesalpinia sappan L. (East Indies, Asia), Haematoxylum brasiletto Karsten (Central America) and Haematoxylum campechianum L. (North America) were analysed in order to isolate key Raman biomarker bands which could provide the basis for an identification protocol. Previously recorded Raman spectra of brazilin and brazilein pigments extracted from genuine brazilwood of Brazilian origin provided a foundation for the nondestructive spectral discrimination between a sample of false brazilwood, which consisted of an inferior wood substratum stained with genuine pigment, and the true specimens. The provision of well-documented specimens of determinable age from the archival collection facilitated the evaluation of the effects of temporal degradation on the observed spectra, which could be used to further test the experimental protocols for nondestructive verification of samples in the archive with questionable assignment or provenance.

Raman spectroscopy of coloured resins used in antiquity: dragon's blood and related substances.

Dragons blood is a deep red resin which has been used for centuries by many cultures and much prized for its rarity, depth of colour and alchemical associations. The original source of dragons blood resin is believed to be Dracaena cinnabari from Socotra in Africa, but since mediaeval times there have been several alternatives from different geographical locations from the Canary Islands to the East Indies. Here, the Raman spectra of dragons blood resins from Dracaena draco Liliacae trees growing in several different locations bordering the Mediterranean and Middle East are compared with the resins from alternative botanical sources such as Daemonorops draco, Dracaena cinnabari and Eucalyptus terminalis, which all generically come under the description of dragons blood. Key vibrational spectroscopic marker bands are identified in the Raman spectra of the resins, which are suggested for adoption as a protocol for the identification of the botanical and possible geographical sources of modern dragons blood resins. The Raman spectra of materials, which are falsely attributed to dragons blood resin are also shown for comparison and identification purposes. Changes in the Raman spectra of genuine dragons blood resin specimens arising from simple processing treatment during the preparation of the resins for sale are also identified, which suggests a possible attribution characteristic for unknown samples.

Role of the Substituent Effect over the Squarate Oxocarbonic Ring: Spectroscopy, Crystal Structure, and Density Functional Theory Calculations of 1,2-Dianilinosquairane

This work presents the crystal structure and the investigation under a supramolecular perspective of a squaric acid derivative obtained from the replacement of the hydroxyl groups by anilines. The squaraine obtained (1,2-dianilinesquaraine) crystallizes in the Pbcn space group, in a unit cell with a = 26.5911(8) Å, b = 6.1445(10) Å, and c = 7.5515(5) Å. The bond lengths in the oxocarbon ring, squarate-N and C−O bonds present the character of double bonds. Also the difference between the longer and shorter C-C bond in the four-membered ring (ΔCC) is 0.0667 Å, showing a good degree of equalization of these bond lengths. The phenyl rings are slightly distorted in relation to the squarate ring, and the angle measured between the best plane fitted in each ring is 37.2(9)°. Each molecule is connected to the other through a hydrogen bond involving the N-H···O moieties, where the donor···acceptor distance is 2.826(1) Å, forming ribbons in a unidimensional arrangement C(5)R22(10) along the b axis. These structures are mutually connected by π-stacking interactions extending the supramolecular structure in a two-dimensional fashion. Besides, an interesting crossed structure can be easily identified in the formed sheets that are built through the C-H/π interactions. DFT calculations at the B3LYP/6-311++G(d,p) level of theory show an approximately planar molecular structure for the isolated molecule. However, when a dimer model built from hydrogen bonds is considered, the optimized structure presents considerable torsion between the phenyl and squarate rings, as observed in the experimental data. The electronic spectrum shows a strong absorption band at 341 nm that is red-shifted compared to the squarate maximum absorption (290 nm), indicating a more effective electronic delocalization. The most characteristic vibrational modes of the oxocarbon species were used as spectroscopic probe to understand how the substituent groups affect the oxocarbon moiety and, consequently, the vibrational spectra. The analysis shows that the modes associated with the C-Cox bonds are the most affected. Also the character of the double bond of squarate-N and the single bond for the phenyl-N are easily identified. In a general form, the calculated vibrational modes of the dimer model were in better accordance with the experimental data, mainly when the mode has a contribution from the acceptor molecule in the intermolecular interaction.

Fourier Transform Raman Spectroscopy of Honey

In this work we present the Fourier transform Raman spectra of several commercial samples of honey in different states, comprising nine crystallized and three fluid samples. The measured water content of the specimens bears no relationship to their fluid behavior. The relative intensities of the vibrational bands in the C–H stretching region of the FT-Raman spectra are found to be sensitive to the observed physical states of the specimens. Several observed vibrational bands in the region 500–1800 cm−1 could be identified as fingerprints of the two major components in honey, fructose, and glucose, and at least one vibrational band was characteristic of sucrose. A relationship between the bandshape of the C–H stretching bands of honey specimens and their fluid properties was noted; crystallized samples show a well-resolved distinctive spectrum in this region, whereas the fluid samples do not exhibit this pattern. Some minor differences in the FT-Raman spectra of the honey specimens are discussed in terms of composition (saccharides and water) and the fluid state of the samples.