Novel Probe for Thermally Controlled Raman Spectroscopy Using Online IR Sensing and Emissivity Measurements.

Temperature rise during Raman spectroscopy can induce chemical alterations of the material under analysis and seriously affect its characterization. Thus, such photothermal side effects can represent a serious problem to be carefully controlled in order to safeguard the integrity of the material and its spectral features. In this work, an innovative probe for thermally controlled portable Raman spectroscopy (exc. 785 nm) equipped with infrared sensing lines was developed. It included an infrared source and two thermopile sensors, which allowed to perform real-time measurements of the local emissivity of the material surface under laser excitation. The emissivity, which is needed in order to monitor the temperature of the irradiated surface through infrared radiation measurements, represents the complementary component of the reflectance in the radiative energy balance. Thus, total reflectance, temperature measurements and Raman spectroscopy were integrated in the present probe. After independently assessing the reliability of the former in order to derive the emissivity of variety of materials, the probe was successfully applied on pigments, paint layers, and a painting on canvas. The results achieved evidence the significant exploitation potential of the novel tool.

Quantitative Compositional Analyses of Calcareous Rocks for Lime Industry Using LIBS.

Here, the potential of laser-induced breakdown spectroscopy (LIBS) in grading calcareous rocks for the lime industry was investigated. In particular, we developed a system equipped with non-intensified detectors operating in scanning mode, defined a suitable data acquisition protocol, and implemented quantitative data processing using both partial least squares regression (PLS-R) and a multilayer perceptron (MLP) neural network. Tests were carried out on 32 samples collected in various limestone quarries, which were preliminarily analyzed using traditional laboratory X-ray fluorescence (XRF); then, they were divided into two groups for calibration and validation. Particular attention was dedicated to the development of LIBS methodology providing a reliable basis for precise material grading. The congruence of the results achieved demonstrates the capability of the present approach to precisely quantify major and minor geochemical components of calcareous rocks, thus disclosing a concrete application perspective within the lime industry production chain.

Nanoscopic insights into the surface conformation of neurotoxic amyloid ß oligomers.

Raman spectroscopy assisted by localized plasmon resonances generating effective hot spots at the gaps between intertwined silver nanowires is herein adopted to unravel characteristic molecular motifs on the surface of Aß42 misfolded oligomers that are critical in driving intermolecular interactions in neurodegeneration.

Red lakes from Leonardo's Last Supper and other Old Master Paintings: Micro-Raman spectroscopy of anthraquinone pigments in paint cross-sections.

The analysis of red particles in paint cross-sections from Leonardo da Vinci's Last Supper, Masolino da Panicale's wall painting Beheading of St. John the Baptist in Castiglione Olona, Tintoretto's The Discovery of the Body of Saint Mark and Paolo Veronese's Supper in the House of Simon has been carried out with micro-Raman measurements. Subtracted shifted Raman spectroscopy methods have been employed to resolve the signals in the presence of fluorescence. Taking advantage of the vibrational assignments based on recent ab initio calculations of aluminum-complexes of anthraquinones, the approach allowed the discriminate between anthraquinone dyes and lakes based on kermesic and carminic acids present in the studied samples for the first time without heavy sample treatment.

Raman spectrometer for the automated scan of large painted surfaces.

In this work, a novel Raman scanner capable of performing point-to-point mapping of relatively large surface of paintings is presented. This device employs an excitation wavelength of 1064 nm, and it is equipped with a high efficiency probe in order to collect the back-scattered light from each point of analysis. The use of long depth-of-field optics as well as an autofocus system allowed maintaining the best conditions for the Raman signal acquisition during the scanning, regardless of the surface irregularities. The small dimension of the optical components and the reasonable size of mechanical parts made this instrumentation particularly suitable for on-site measurements. Finally, the Raman scanner was also equipped with an online temperature control using a thermal sensor, which allows modulating automatically the output power of the laser source in order to prevent overheating and alteration effects during the scanning process. The capabilities of the Raman scanner were evaluated scanning two valuable paintings one attributed to Ambrogio Lorenzetti and the other to Duccio da Buoninsegna of the fourteenth century.

A remote scanning Raman spectrometer for in situ measurements of works of art.

In conservation science, one of the main concerns is to extract information from an artistic surface without damaging it. Raman spectroscopy has emerged in recent years as a reliable tool for the non-destructive analysis of a wide range of inorganic and organic materials in works of art and archaeological objects. Nevertheless, the technique is still mainly limited to the analysis of micro-samples taken from artistic surfaces. The development of an instrument able to perform non-contact analysis of an area of a few square centimeters aims to further increase the employment of this technique. This paper describes the development of a prototype Raman scanning spectrometer based on a diode laser, a 2D scanning mirror stage and a custom optical system, which can map a surface of 6 cm in diameter at a working distance of 20 cm. The device exhibits collecting optics with a depth of field close to 6 cm, which makes the Raman system suitable for the analysis of non-flat surfaces and three-dimensional objects. In addition, the overall dimensions and weight of the instrument have been limited in order to make the device transportable and, in principle, usable for in situ measurements. Details on the design of the device, with particular emphasis on the collecting optical system, and on results of the characterization tests carried out to assess its performances are reported. Finally, an example of an application involving the identification of pigments from a model painting is presented.

Assessment of the ageing of triterpenoid paint varnishes using fluorescence, Raman and FTIR spectroscopy.

The assessment of the influence of natural and artificial ageing on the spectrofluorescence of triterpenoid varnishes dammar and mastic is the focus of this work. Both Fourier transform infrared (FTIR) microscopy using attenuated total reflectance and Raman spectroscopy have been employed for complementary molecular analysis of samples. Synchronous fluorescence spectroscopy, excitation emission spectroscopy, and statistical analysis of data have been used to monitor changes in the optical properties of varnish samples. Assessment of naturally and artificially aged samples using excitation emission spectroscopy suggests that extensive exposure to visible light does not lead to easily appreciable differences in the fluorescence of mastic and dammar; cluster analysis has been used to assess changes, which occur with artificial ageing under visible light, indicating that differences in the fluorescence spectra of aged triterpenoids may be insufficient for their discrimination. The results highlight significant differences between the initial fluorescence of films of dammar and mastic and the fluorescence, which develops with ageing and oxidation, and specific markers, which change with ageing in FTIR and Raman spectra, have been identified.

An optimization of parameters for application of a laser-induced breakdown spectroscopy microprobe for the analysis of works of art.

Laser-induced breakdown spectroscopy (LIBS) provides many advantages for analysis of works of art. Both qualitative and semi-quantitative information about the elemental composition of an object can be rapidly obtained using LIBS. The time of response is on the order of a few seconds and no sample preparation is required. The possibility of performing analysis in museums and archeological sites makes LIBS particularly important; the combination of laser ablation and analysis as encountered in LIBS provides means to effectively carry out depth profiling of samples. By combining the use of a microscope, the dimension of the spot of the laser used to carry out analysis can be reduced and the spatial resolution highly improved; in this way, a very small area of the sample (on the order of 10 miccrom) can be analyzed. The aim of this work is to investigate the best working conditions in order to obtain the least amount of material removal during analysis, and, at the same time, the best quality in the spectral response for rapid and reliable identification of the elemental composition of an object. First, investigations were undertaken using metal alloys; second, the optimized LIBS conditions were used for analysis of models of painting layers prepared in the laboratory. Finally, a painting cross-section and a 19th century painted icon were analyzed using the micro-LIBS setup.

Shift-excitation Raman difference spectroscopy-difference deconvolution method for the luminescence background rejection from Raman spectra of solid samples.

The feasibility of the shift-excitation Raman difference spectroscopy-difference deconvolution (SERDS-DDM) method for fluorescence suppression from Raman spectra of solid samples is discussed. For SERDS measurements a tunable diode laser source with an emission band centered at 684 nm is coupled to a conventional micro-Raman apparatus and a monochromator device is used for checking the excitation frequency stability. The shifted Raman spectra are then mathematically treated and a deconvolution procedure is used to reconstruct the Raman spectrum devoid of fluorescence. Two different cases are presented. In the first one, fluorescence is intrinsic to the sample and the Raman spectrum of cinnabar pigment is finally reconstructed. In the second, the presence of an external luminescence background in the spectrum of a pure sulfur crystal is considered. The SERDS-DDM reconstructed spectra are compared with spectra obtained via multi-point baseline subtraction and a significant improvement in the detection of weak bands is demonstrated. Practical insights for the application of this method are presented as well.

Raman spectra of proteinaceous materials used in paintings: a multivariate analytical approach for classification and identification.

This work presents Raman spectra obtained from thin films of protein materials which are commonly used as binding media in painted works of art. Spectra were recorded over the spectral range of 3250-250 cm(-1), using an excitation wavelength of 785 nm, and several bands have been identified in the fingerprint region that correspond to the various proteins examined. Differences in the C-H vibrations located between 3200 and 2700 cm(-1) can be accounted for with reference to the amino acid composition of the protein-based binding media as well as the presence of fatty acid esters, in the case of egg yolk. In addition, the discrimination of different proteins on the basis of variations in spectra between 3200 and 2700 cm(-1) can be achieved following multivariate analysis of a large data set of spectra, providing a novel and nondestructive alternative based on Raman spectroscopy to other methods commonly used for the analysis of proteins.