Chemical Characterization and Molecular Dynamics Simulations of Bufotenine by Surface-Enhanced Raman Scattering (SERS) and Density Functional Theory (DFT).

Bufotenine (5-hydroxy-N,N-dimethyltryptamine) is a natural tryptamine derivative with hallucinogenic activity. In this paper, we present novel chemical and molecular conformational analyses of bufotenine based on an experimental and theoretical approach integrating surface-enhanced Raman scattering (SERS) and density functional theory (DFT). For the first time, low concentrations of bufotenine in acetonitrile solutions were analyzed by SERS using two types of silver nanoparticle substrates synthesized via one- or two-step reduction processes. The vibrational characteristics of this molecule were verified by molecular dynamics simulations of Raman bands based on DFT. Here we demonstrate the potential of this integrated approach for the identification of bufotenine, a prominent hallucinogenic agent, establishing an innovative rapid and accurate sensing and characterization method of the identification of controlled substances at trace amounts.

Acquisition of High Spectral Resolution Diffuse Reflectance Image Cubes (350-2500 nm) from Archaeological Wall Paintings and Other Immovable Heritage Using a Field-Deployable Spatial Scanning Reflectance Spectrometry Hyperspectral System.

There is growing interest in bringing non-invasive laboratory-based analytical imaging tools to field sites to study wall paintings in order to collect molecular information on the macroscale. Analytical imaging tools, such as reflectance imaging spectrometry, have provided a wealth of information about artist materials and working methods, as well as painting conditions. Currently, scientific analyses of wall paintings have been limited to point-measurement techniques such as reflectance spectroscopy (near-ultraviolet, visible, near-infrared, and mid-infrared), X-ray fluorescence, and Raman spectroscopy. Macroscale data collection methods have been limited to multispectral imaging in reflectance and luminescence modes, which lacks sufficient spectral bands to allow for the mapping and identification of artist materials of interest. The development of laboratory-based reflectance and elemental imaging spectrometers and scanning systems has sparked interest in developing truly portable versions, which can be brought to field sites to study wall paintings where there is insufficient space or electrical power for laboratory instruments. This paper presents the design and testing of a simple hyperspectral system consisting of a 2D spatial spot scanning spectrometer, which provides high spectral resolution diffuse reflectance spectra from 350 to 2500 nm with high signal to noise and moderate spatial resolution (few mm). This spectral range at high spectral resolution was found to provide robust chemical specificity sufficient to identify and map many artists' materials, as well as the byproducts of weathering and conservation coatings across the surface of ancient and Byzantine Cypriot wall paintings. Here, we present a detailed description of the hyperspectral system, its performance, and examples of its use to study wall paintings from Roman tombs in Cyprus. The spectral/spatial image processing workflow to make maps of pigments and constituent painting materials is also discussed. This type of configurable hyperspectral system and the imaging processing workflow offer a new tool for the field study of wall paintings and other immovable heritage.

Carminic Acid Based Red Dye from Scale Insects Detected in Red Ruby-Crowned Kinglet Feathers by Surface-Enhanced Raman Scattering.

In most birds, red feather color is linked to diet and attributed to carotenoids contained in plants and fruits. In the red crown feathers of the Ruby-crowned Kinglet (Regulus calendula), a new biopigment was identified based on carminic acid, the main coloring compound of cochineal (Dactylopius coccus) and other scale insects. This has revealed a potential new class of carminic acid-based biopigments, not previously identified in feathers. In this research, red crown feathers of a Ruby-crowned Kinglet were analyzed by surface-enhanced Raman scattering (SERS) employing synthesized silver star-shaped colloids as the nanoplasmonic platform. Results indicated peaks at 450, 670, 1290-1312, 1355, 1410, 1570, 1620 cm-1 in the feather SERS spectra characteristic of carminic acid. SERS has proven to be an extremely sensitive, non-destructive technique for the identification of different feather biopigments, even at trace quantities and in the presence of other predominant coloring substances.

Archaeometric data from the Via dei Sepolcri ceramic workshop in Pompeii (Southern Italy).

The present article provides chemical, paleontological and mineralogical data obtained during an archaeometric characterization of 40 samples (33 pottery sherds, 5 clay samples, 1 sand sample and 1 red earth pigment) collected in the Via dei Sepolcri ceramic workshop in Pompeii, Italy. The workshop was still active during the 79 CE eruption of Mt. Vesuvius and the archaeometric data obtained in our investigation reveal distinct differences between pottery and geological raw materials belonging to an early 'Phase 1' production (from the beginning of the 1st century CE to the 62 CE earthquake) and a subsequent 'Phase 2' production (from the 62 CE earthquake to the 79 CE eruption). These data inform the discussions and interpretations presented in the article entitled "A pottery workshop in Pompeii unveils new insights on the Roman ceramics crafting tradition and raw materials trade", edited by Grifa et al. [1].

Macroscale multimodal imaging reveals ancient painting production technology and the vogue in Greco-Roman Egypt.

Macroscale multimodal chemical imaging combining hyperspectral diffuse reflectance (400-2500 nm), luminescence (400-1000 nm), and X-ray fluorescence (XRF, 2 to 25 keV) data, is uniquely equipped for noninvasive characterization of heterogeneous complex systems such as paintings. Here we present the first application of multimodal chemical imaging to analyze the production technology of an 1,800-year-old painting and one of the oldest surviving encaustic ("burned in") paintings in the world. Co-registration of the data cubes from these three hyperspectral imaging modalities enabled the comparison of reflectance, luminescence, and XRF spectra at each pixel in the image for the entire painting. By comparing the molecular and elemental spectral signatures at each pixel, this fusion of the data allowed for a more thorough identification and mapping of the painting's constituent organic and inorganic materials, revealing key information on the selection of raw materials, production sequence and the fashion aesthetics and chemical arts practiced in Egypt in the second century AD.

Distribution and chemical speciation of arsenic in ancient human hair using synchrotron radiation.

Pre-Columbian populations that inhabited the Tarapacá mid river valley in the Atacama Desert in Chile during the Middle Horizon and Late Intermediate Period (AD 500-1450) show patterns of chronic poisoning due to exposure to geogenic arsenic. Exposure of these people to arsenic was assessed using synchrotron-based elemental X-ray fluorescence mapping, X-ray absorption spectroscopy, X-ray diffraction and Fourier transform infrared spectromicroscopy measurements on ancient human hair. These combined techniques of high sensitivity and specificity enabled the discrimination between endogenous and exogenous processes that has been an analytical challenge for archeological studies and criminal investigations in which hair is used as a proxy of premortem metabolism. The high concentration of arsenic mainly in the form of inorganic As(III) and As(V) detected in the hair suggests chronic arsenicism through ingestion of As-polluted water rather than external contamination by the deposition of heavy metals due to metallophilic soil microbes or diffusion of arsenic from the soil. A decrease in arsenic concentration from the proximal to the distal end of the hair shaft analyzed may indicate a change in the diet due to mobility, though chemical or microbiologically induced processes during burial cannot be entirely ruled out.