A multidisciplinary research carried out on the Solutrean points of El Buxu cave is presented in this paper. The technological and functional analysis of this small but diverse assemblage of lithic points has established that all the pieces had been intentionally discarded on site; one of them broke up while being used, the others were left behind as they did not reach optimal functionality due to manufacturing mistakes. Traces of some kind of glue were identified on the tang dorsal face of the shouldered point that had been used (Layer 2). In order to avoid damage to these valuable samples Raman and IR microscopies, two non-destructive techniques, have been applied for the analyses. A collection of natural adhesives possibly used to join the lithic points to the shaft have also been studied by these techniques. The use of a mixture of resin and wax for this purpose is suggested. Haematite, Fe2O3, impregnate the residues of this adhesive. & alpha;- Quartz, & alpha;-SiO2, is the principal component of the rock from which these lithic pieces have been made. This is the first evidence of remains of adhesive in this type of Solutrean point. We believe that the unusability of all Solutrean points from El Buxu is related to the territory exploitation strategies of the hunter-gatherer groups during the LGM.

Three Transylvanian fragments of some 18th century Saxon tiles obtained from excavations in the Central Railway Station Square in Sibiu (Romania) have been studied by Raman microscopy, FTIR, SEM-EDX and XRF techniques. A lead-rich aluminosilicate was found to have been used as enamel/glaze for the tile fragments. An analysis of the band components of the Raman spectra of the enamel of one fragment in the 400-1200 cm(-1) spectral region indicates that their processing temperature was in the 600-800 degrees C range, in good agreement with the temperature obtained from FTIR spectra of the other two tile fragments.

Three Transylvanian fragments of some 18th century Saxon tiles obtained from excavations in the Central Railway Station Square in Sibiu (Romania) have been studied by Raman microscopy, FTIR, SEM-EDX and XRF techniques. A lead-rich aluminosilicate was found to have been used as enamel/glaze for the tile fragments. An analysis of the band components of the Raman spectra of the enamel of one fragment in the 400–1200 cm− 1 spectral region indicates that their processing temperature was in the 600–800 °C range, in good agreement with the temperature obtained from FTIR spectra of the other two tile fragments.

Abstract Three Transylvanian fragments of some 18th century Saxon tiles obtained from excavations in the Central Railway Station Square in Sibiu (Romania) have been studied by Raman microscopy, FTIR, SEM-EDX and XRF techniques. A lead-rich aluminosilicate was found to have been used as enamel/glaze for the tile fragments. An analysis of the band components of the Raman spectra of the enamel of one fragment in the 400–1200 cm − 1 spectral region indicates that their processing temperature was in the 600–800 °C range, in good agreement with the temperature obtained from FTIR spectra of the other two tile fragments.

Dynamical properties of functional groups in 2-deoxyadenosine-5-monophosphate (dAMP) compound, were identified by UV resonance Raman spectroscopy (UVRR), upon varying nucleotide concentration in aqueous solution (200-600 μM). The studied full-widths at half-maximum (fwhms) were found between 13 - 21 cm-1 and the corresponding global relaxation times were faster than 0.817 ps and slower than 0.506 ps. Also, the band around 1430 cm-1 (C4N9-δC8H) in the UV resonance Raman spectrum of dAMP molecule at 400 μM concentration in aqueous solution, was selected for vibrational band shape analysis through time correlation function (CF) concept. Current theories developed for vibrational dephasing (Kubo-Rothschild and Oxtoby) have been applied to this profile and relevant relaxation parameters have been obtained and discussed. The best fit parameters for this dissipation channel of the vibrational excitation energy were established. To our knowledge this is the first UVRR study on nucleotide vibrational band shape analysis through time correlation function concept.

The interpretation of vibrational spectra is often complex but a detailed knowledge of the normal modes responsible for the experimental bands provides valuable information about the molecular structure of the sample. In this work we record and assign in detail the infrared (IR) spectrum of the benzylic amide [2]catenane, a complex molecular solid displaying crimped mechanical bonds like the links of a chain. In spite of the large size of the unit cell, we calculate all the vibrational modes of the catenane crystal using quantum first-principles calculations. The activity of each mode is also evaluated using the Born effective charges approach and a theoretical spectrum is constructed for comparison purposes. We find a remarkable agreement between the calculations and the experimental results without the need to apply any further empirical correction or fitting to the eigenfrequencies. A detailed description in terms of the usual internal coordinates is provided for over 1000 normal modes. This thorough analysis allows us to perform the complete assignment of the spectrum, revealing the nature of the most active modes responsible for the IR features. Finally, we compare the obtained results with those of Raman spectroscopy, studying the effects of the rule of mutual exclusion in vibrational spectroscopy according to the different levels of molecular symmetry embedded in this mechanically interlocked molecular compound.

Se cuestiona la adscripción contemporánea de la figura de estilo paleolítico existente en El Portalón de Cueva Mayor, dentro del complejo kárstico de la Sierra de Atapuerca en Burgos. Se plantea una revisión crítica de los argumentos utilizados en un estudio anterior y se valoran nuevas evidencias y datos disponibles desde entonces. Las conclusiones se ven apoyadas por la realización de estudios gráficos sustentados en una metodología específica y por análisis de muestras del pigmento mediante microespectroscopía Raman que detectó micropartículas de hematites y carbón amorfo. Este hallazgo posibilitó la datación por radiocarbono (AMS 14C) de la muestra. Aunque el resultado parece estar alterado, se abren nuevas expectativas para la revisión y la autentificación de estas manifestaciones. _____________________________________________ The contemporaneous ascription of the paleolithic style painting existing in El Portalón de Cueva Mayor, within the karstic complex of the Sierra de Atapuerca (Burgos), is questioned. A critical review of the arguments used in a previous study is proposed and new evidence and data collected since then are valued. The partial conclusions are reinforced by the data obtained through graphical studies supported by a specific methodology and by the analysis of the paint by Raman microspectroscopy that reveals that it is formed by microparticles of hematite and amorphous carbon. This finding has allowed the radiocarbon dating (AMS 14C) of the painting, although the result of this dating seems to be altered, new expectations open up for the revision and authentication of these manifestations.

In this work, we use Raman spectroscopy and quantum first-principles calculations to unveil the experimental spectrum of a complex molecular solid-like benzylic amide [2]catenane, a representative example of a mechanically interlocked molecular architecture. We use large-scale density functional theory calculations to obtain the complete set of vibrational normal modes of the catenane crystal, whose unit cell contains 544 atoms. Subsequently, we demonstrate that these calculations are able to accurately reproduce the experimental Raman spectrum of this molecular compound, without introducing any empirical corrections or fittings in the calculated eigen frequencies. Thanks to the good agreement between the experimental and theoretical spectra, it is possible to carry out the complete assignment of the main vibrational modes responsible for the whole spectrum. A detailed description in terms of the usual internal coordinates is given for all of these representative modes. This description, rather difficult from the experimental point of view, provides valuable information about the molecular structure of this compound, compatible with experimental evidences reported in the literature.

Rock paintings of two recent discovered rock shelters, Galb Budarga and Tuama Budarga, from the southeastern area of the Western Sahara, Sahrawi Arab Democratic Republic, have been studied by micro-Raman spectroscopy and scanning electron microscopy coupled with energy dispersive X-ray spectrometry in order to characterize the composition of the materials present in the painting panels. An unusual white pigment has been used in the zoomorphic pictographs of the Galb Budarga shelter which main components are the anhydrite (CaSO4) polymorphs I and II. Red and orange zoomorphic figures and ancient Berber scripts have been painted in the Tuama Budarga rock shelter. Haematite (α-Fe2O3) is the main component of the paints used; amorphous carbon and different manganese oxides have also been detected. Accretions of gypsum (CaSO4·2H2O) and anhydrite have been observed on the shelter wall used to paint. α-Quartz (α-SiO2), albite (NaAlSi3O8), dolomite, CaMg(CO3)2, calcite (CaCO3) and traces of hydroxylapatite (Ca10(PO4)6(OH)2) have been identified in the rocks supporting the paintings of both sites. Layers of calcium oxalates, whewellite (CaC2O4·H2O) and weddellite (CaC2O4·(2+x)H2O, x≤0.5) cover the pictorial panels of these rock shelters. A microestratrigraphic study of the paint used in the Tuama Budarga shelter revealed that the pigment layer is bracketed between oxalate layers.

The Fourier transform infrared spectra of Transylvanian pottery fragments from XVI-XVIII centuries and the identification of their vibrational frequencies and curve fitting of the 1400-800 cm(-1) spectral massif have allowed to determine the chemical and mineralogical composition of the fragments and their firing temperature. A pottery vessel was restored in a virtual environment by using 3D laser scanning and computer aided design software. An additive manufacturing solution was used for 3D printing of the inner pottery support to reassemble the fragments in order to assist classical restoration activities. The digital restoration allows for correct spatial positioning of the ceramic vessel fragments and 3D modelling of the vessel shape using the profile obtained after matching the fragments.

Vibrational band shape analysis through time correlation function concept is widely used to obtain experimental information on the molecular dynamics of medium-size molecules in different environments. Interesting details are revealed by extending this technique to biomolecules such as functional groups of the nucleic acids in media approaching the physiological conditions. In this work a study into the UV resonance Raman (UVRR) vibrational half bandwidths of functional groups in LacDNA, upon lowering the pH (pH 6.4, pH 3.45) and in the presence of Mn2+ and Ca2+ ions, respectively, was of interest. The corresponding global relaxation times have been derived. Also, the 793 cm-1 UVRR band, corresponding to ν (backbone O-P-O, dT) oscillator of LacDNA in aqueous solutions, was selected for band shape-analysis. Vibrational relaxation appears as the dominant relaxation process for this mode, with vibrational dephasing being the most efficient for this oscillator. Current theories developed for vibrational dephasing have been applied to this profile, and relevant relaxation parameters have been obtained and discussed. To our knowledge this is the first study on DNA oligomers vibrational band shape analysis through time correlation function concept.

Prehistoric paintings from the El Reno cave, Guadalajara (Spain) have been studied by μ-Raman spectroscopy. Goethite (α-FeOOH) and haematite (α-Fe2O3) have been used as pigments in this exceptional Palaeolithic site. Dolomite (CaMgCO3), anatase (TiO2), α-quartz (α-SiO2), hydromagnesite and the calcium carbonate (CaCO3) polymorphs calcite and aragonite have also been detected in the studied paint specimens. Clay minerals of the marl supporting the paintings could be the origin the significant spectral background of fluorescence radiation observed in the Raman spectra. The use of a pictorial recipe mixing haematite and amorphous carbon (charcoal or soot) to prepare the paint of a pictograph is proposed.

A series of rock art pictographs in the form of hand stencils discovered in two sites of the Yabrai Mountain, Inner Mongolia Autonomous Region (China) has been studied by micro-Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electronic microscopy combined with energy dispersive X-ray spectroscopy for the first time. These studies have made possible to characterise the materials present. The minerals α-quartz, phlogopite, albite and microcline have been identified in the granitic rocks supporting the paintings. Calcite and dolomite micro-particles detected on the rock surface have been attributed to desert dust. Accretions of gypsum, anhydrite and whewellite have also been identified on the rock surface. Haematite is the pigment used in the red pictographs, whereas well-crystallised graphite has been used in the black ones. The use of crystalline graphite instead of amorphous carbon (charcoal, soot or bone black) as a black pigment in rock art is an interesting novelty. Overlapped hands are proposed as a new type of hand stencils to make an unusual pictorial symbol in rock art that has been found in these sites.

Remains of pictorial decorations in a series of six representative megalithic monuments of Brittany (France) and two French stelae have been studied by micro‐Raman spectroscopy for the first time. Fungal colonies on the painted orthostats made it difficult to obtain in situ Raman spectra of the paint components. Nevertheless, paint micro‐specimens studied in the laboratory by micro‐Raman spectroscopy, X‐ray photoelectron spectroscopy and scanning electronic microscopy combined with energy dispersive X‐ray spectroscopy have made possible to characterise the materials present. The minerals α ‐quartz, albite, microcline, muscovite, phlogopite, celadonite, beryl and anatase have been identified in the granitic rocks supporting the paintings, while dolomite and calcite are dominant in the calcareous rocky substrata. Haematite is the main component of the red pictographs, whereas amorphous carbon and manganese oxides/oxihydroxides have been used in the black ones. Calcite, gypsum and amorphous carbon have been detected as additional components of the paint in some cases. Contamination with modern tracing materials (polystyrene and ε ‐copper‐phthalocyanine blue) has been detected in several cases. The presence of pigments as decorative elements in megalithic monuments of Western France and its possible relation with those of the Iberian Peninsula create interesting expectations for the knowledge of the European megalithic culture. Copyright © 2015 John Wiley & Sons, Ltd.

In situ micro‐Raman spectroscopy ( μ ‐RS) of rock art paintings in open‐air rock shelters entails several difficulties: sunlight, wind, dust and crusts that mask Raman signals from the pigments and any other component of the paint recipe. These problems have been considered in the present work. Special attention has been devoted to the presence of crusts. Five rock art sites in the eastern Iberian Peninsula with outstanding difficulties to be analysed by this technique have been the object of this study. In situ energy dispersive X‐ray fluorescence and diffuse reflectance infrared Fourier transform spectroscopy using portable instruments have provided important help. Moreover, microstratigraphic studies by μ ‐RS and scanning electronic microscopy combined with energy dispersive X‐ray spectroscopy of micro‐specimens from the painting panels have revealed the distribution of the different components. Dolomite and calcite are dominant minerals in the rock substrata. Whewellite, gypsum, calcite, clay, dolomite, α ‐quartz, anatase and haematite have been found on the surface of the painting panels or forming stratified layers in the crusts. Haematite and amorphous carbon have been detected in red and black pictographs, respectively. Copyright © 2014 John Wiley & Sons, Ltd.

An in situ study of post-Palaeolithic blackish pictographs found in an open air rock-shelter, Los Chaparros site (Albalate del Arzobispo, Teruel province, Spain), was carried out to identify the black pigments used. The composition of the pigments was analyzed by means of non-invasive instrumentation, such as a portable Raman spectrometer (RS) and a hand-held energy dispersive X-ray fluorescence (EDXRF) analyzer. In addition, some black natural deposits with a dendritic pattern, typical of manganese compounds, were also in situ analysed with the aforementioned techniques to explore the possibility that post-Paleolithic people used minerals from the surroundings of the Los Chaparros rock-shelter to elaborate the paintings. The results obtained by the EDXRF analyses of black pigments showed differences in composition between a black Levantine deer, in which manganese was present as the main element, and a deep red Schematic pictograph that included manganese as the secondary element. The results of Principal Component Analysis (PCA) of collected EDXRF spectra showed similarities in the elemental composition between the manganese dendrite formations present in the rock-shelter and the black deer. In order to confirm this, the in situ analytical campaign was completed with some analysis in the laboratory by using micro-RS (mu-RS) and X-ray diffraction (XRD) on mineral samples having black crystallisations. Two specimens were taken, one from the black dendrite present in the same rock-shelter and the other from the Los Mases de Crivillen mining area (which is near to Los Chaparros). These analyses revealed that the characteristic bands of Mn-O and Mn-OH bending and stretching vibrations obtained in situ on the black pictograph were the same as those observed in the Raman spectra of the dendrite mineralization of Los Chaparros obtained in the laboratory by mu-RS.

We report on the preparation and characterization of magnetically oriented single-walled carbon nanotube arrangements as novel nanoprobes to enhance anisotropically water relaxation as detected by magnetic resonance imaging methods. SWCNT suspensions immobilized in agarose gels showed evident magnetic anisotropy with significantly longer T-2 in the parallel than in the perpendicular orientations.