Study of a tabernacle with a remarkable architectural structure: In situ examination using Raman spectroscopy

In order to characterize ornamental stones and gemstones from the monstrance ‘Tabernáculo de la Colegiata de S. Pedro’ in Lerma, Burgos, a Raman spectroscopy in situ non‐destructive study has been performed on these materials. The Raman spectra obtained correspond to cornalline‐like chalcedony, nephrite jade, quartz veinlets, agates with moganite and jasper, together with goethite showing several degrees of alteration. Various types of marble and lapis lazuli were identified. The lapis lazuli samples show different Raman spectra depending on the blue–white chromatic gradient, due to the variations in the sulfur concentration. Raman spectroscopy allows for the correlation of the presence of radical molecular ions S₂⁻, S₃⁻ and SO₄²⁻, with the colour centres and colouration of lapis lazuli. Two varieties of marble are present, one of brown tones with greyish‐white incrustations and another with alternating white and black veinlets with yellow inclusions. In the former, white masses of microcrystalline calcite appear together with quartz inclusions, around which brown halos of goethite develop as an alteration product. In the latter, they show calcite in the white veinlets and calcite with graphite in the black ones. The mineralogical analysis of ornamentals stones on art objects allows determining their degree of conservation and the extension of the deterioration, in order to establish strategies for the cleaning and restoration. These results are an important factor to date the object and for shedding light about its authorship. Furthermore, it could eventually help to establish connections between the tabernacle‐monstrance and other tabernacles in Castilla y León. Copyright © 2013 John Wiley & Sons, Ltd.     

Study of Raman spectrum of uranium using a surface‐enhanced Raman scattering technique

Raman spectroscopic investigation on weak scatterers such as metals is a challenging scientific problem. Technologically important actinide metals such as uranium and plutonium have not been investigated using Raman spectroscopy possibly due to poor signal intensities. We report the first Raman spectrum of uranium metal using a surface‐enhanced Raman scattering‐like geometry where a thin gold overlayer is deposited on uranium. Raman spectra are detected from the pits and scratches on the sample and not from the smooth polished surface. The 514.5‐ and 785‐nm laser excitations resulted in the Raman spectra of uranium metal whereas 325‐nm excitation did not give rise to such spectra. Temperature dependence of the B_3g mode at 126 cm⁻¹ is also investigated. Copyright © 2011 John Wiley & Sons, Ltd.     

First and second‐order Raman scattering of B6O

First and second‐order Raman spectra of B₆O and their dependence on the wavelength of the excitation line from IR (infrared) to deep UV (ultraviolet) has been studied. The first‐order Raman spectra contain 11 well‐resolved lines of the 12 expected modes 5 A_1g + 7 E_g (space group R‐3m, point group D_3d). The second‐order Raman spectra contains eight lines that are resolved only in the case of the 244‐nm excitation line. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational spectroscopy and DFT calculations of N,N′‐dicyclohexylcarbodiimide

Infrared (IR) and Raman spectra were obtained for N,N′‐dicyclohexylcarbodiimide (DCC) in the solid state and in CHCl₃ solution. Structures and vibrational spectra of isolated, gas‐phase DCC molecules with C₂ and C_i symmetries, computed at the B3‐LYP/cc‐pVTZ level, show that the IR and Raman spectra provide convincing evidence for a C₂ structure in both the solid state and in CHCl₃ solution. Using a scaled quantum‐chemical force field, these density functional theory calculations have provided detailed assignments of the observed IR and Raman bands in terms of potential energy distributions. Comparison of solid‐state and solution spectra, together with a Raman study of the melting behaviour of DCC, revealed that no solid‐state effects were evident in the spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural analysis of xCsCl(1−x)Ga2S3 glasses by means of DFT calculations and Raman spectroscopy

The alkali metal halide doping of gallium‐sulfide glasses yields improvements in the optical, thermal and glass forming properties. To understand these improvements, the short‐range order of xCsCl(1 − x)Ga₂S₃ glasses was probed by Raman spectroscopy. Raman spectra have been interpreted using density functional theory (DFT) harmonic frequency calculations on specific clusters of GaS₄H₄ and/or GaS₃H₃Cl tetrahedral subunits. The assignment of the observed vibrational bands confirms the main structural conclusions obtained with X‐ray and neutron diffraction experiments and gives some new insights into the gallium‐network present in the xCsCl(1 − x)Ga₂S₃ glasses. At the lowest concentration, the observed spectrum may be interpreted with small clusters such as dimers and trimers connected by corner‐sharing (CS) GaS₄H₄ tetrahedral subunits. The vibrational fingerprints of tri‐clusters with three‐fold coordinated sulfur atoms have also been identified; however, no Raman signature of chlorine‐doped subunits has been found to be caused by their insufficient intensity. For higher CsCl concentrations, distinct spectral features corresponding to chlorine‐doped clusters appear and are increasing in intensity with x. In other words, undoped and Cl‐doped tetrahedra coexist in the xCsCl(1 − x)Ga₂S₃ glasses. The added chlorine atoms induce a fragmentation of the glass network and replace the sulfur atoms in the CS tetrahedral environment. The comparison of the observed spectra with theoretical predictions and diffraction data favoured one‐fold coordinated chlorine atoms in the glass network. Copyright © 2009 John Wiley & Sons, Ltd.     

Visible,near‐infrared,and ultraviolet laser‐excited Raman spectroscopy of the monocytes/macrophages (U937) cells

Raman spectra of the monocytes were recorded with laser excitation at 532, 785, 830, and 244 nm. The measurements of the Raman spectra of monocytes excited with visible, near‐infrared (NIR), and ultraviolet (UV) lasers lad to the following conclusions. (1) The Raman peak pattern of the monocytes can be easily distinguished from those of HeLa and yeast cells; (2) Positions of the Raman peaks of the dried cell are in coincidence with those of the monocytes in a culture cell media. However, the relative intensities of the peaks are changed: the peak centered around 1045 cm⁻¹ is strongly intensified. (3) Raman spectra of the dead monocytes are similar to those of living cells with only one exception: the Raman peak centered around 1004 cm⁻¹ associated with breathing mode of phenylalanine is strongly intensified. The Raman spectra of monocytes excited with 244‐nm UV laser were measured on cells in a cell culture medium. A peak centered at 1485 cm⁻¹ dominates the UV Raman spectra of monocytes. The ratio I₁₅₇₄/I₁₆₁₃ for monocytes is found to be around 0.71. This number reflects the ratio between proteins and DNA content inside a cell and it is found to be twice as high as that of E. coli and 5 times as high as that of gram‐positive bacteria. Copyright © 2009 John Wiley & Sons, Ltd.     

Correlations between Raman parameters and elemental composition in lead and lead alkali silicate glasses

This article examines the influence of the composition on the Raman spectra of lead silicate glass. Modern and historic lead alkali glasses and high‐lead glazed ceramics were analysed complementarily by Raman spectrometry and elemental techniques, either electron microprobe, proton induced X‐ray emission (PIXE) or scanning electron microscope with energy dispersive spectrometry (SEM‐EDS). The results showed that lead alkali silicate and high‐lead silicate glasses can be easily distinguished from their Raman spectra profile. In lead alkali silicate glasses, continuous variations were observed in the spectra with the compositional change. In particular, the position of the intense peak around 1070 cm⁻¹ was linearly correlated to the lead content in the glass. A unique decomposition model was developed for the spectra of lead alkali silicate glasses. From the combination of the Raman and elemental analyses, correlations were established between the spectral components and the composition. These correlations permitted to interpret the spectra and access additional compositional information, such as the lead content from area ratio A₉₉₀/A_900–1150, the total alkali + alkaline‐earth content from the area ratio A₁₁₀₀/A_900–1150 or the silica content from the area ratio A₁₁₅₀/A_900–1150. In lead silicate glass containing over 25 mol% PbO, the compositional variation induced no variation in the SiO₄ network region of the Raman spectra [150–1350 cm⁻¹], therefore no correlations and compositional information could be gained from the glass spectra in this range of composition. This new development of Raman spectroscopy for the analyses of glass will be very valuable for museums to not only access compositional information non‐destructively but also to understand the structural changes involved with their alteration. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman identification of lonsdaleite in Popigai impactites

Micro‐Raman spectroscopy and X‐ray diffraction method (XRD) were used to characterize impact carbonaceous rocks excavated from the Popigai crater (Siberia). The deconvolution of the first‐order Raman spectra of the rocks containing different amounts of carbon phases (diamond, lonsdaleite and graphite) allowed the identification of lonsdaleite spectrum. The most intensive band at 1292–1303 cm⁻¹ was ascribed to A_1g vibration mode of lonsdaleite, whereas the less intense band at 1219–1244 cm⁻¹ was attributed, in agreement with previously reported ab initio calculations, to E_2g vibration mode. The established correlation between the intensities of Raman and XRD peaks permits a rough estimation of lonsdaleite/diamond phase ratio in the impact rocks using micro‐Raman measurements. The second‐order Raman spectra of lonsdaleite–diamond rocks were recorded. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and Raman investigation of sol–gel‐derived relaxor ferroelectric thin films

Pb(Fe_2/3W_1/3)O₃ (PFW) thin films were deposited on platinized silicon substrate by a chemical solution deposition technique. Room‐temperature X‐ray diffraction (XRD) revealed a pure cubic crystal structure of the investigated material. The microstructure indicated good homogeneity and density of the thin films. A Raman spectroscopic study was carried out on PFW to study the polar nano‐regions in the temperature range 85–300 K. The Raman spectra showed a change in the peak intensity and a shift towards the lower wavenumber side with temperature. The Raman spectra also revealed the transition from the relaxor to the paraelectric state of PFW. There was no evidence of a soft mode in the low‐temperature region, in contrast to the normal ferroelectric behavior. The polar nano‐regions tend to grow and join at low temperatures (∼85 K), which become smaller with increase in temperature. The presence of strong Raman spectra in the cubic phase of the material is due to the presence of distributed Fm3m(Z = 2) symmetry nano‐ordered regions in the Pm3m(Z = 1) cubic phase. Copyright © 2007 John Wiley & Sons, Ltd.     

Temperature‐dependent vibrational studies of [N(C2H5)4]2MnCl4

Room‐temperature polarized Raman spectra of a single crystal and IR spectra of a polycrystalline sample were measured for [N(C₂H₅)₄]₂MnCl₄ and the assignment of the observed bands to the respective modes has been proposed. Temperature‐dependent Raman and far‐IR studies were also performed for the polycrystalline sample in order to obtain information on changes occurring in this material as a result of phase transitions at T₁ = 227 K and at T₂ = 199 K. These studies revealed that the higher‐temperature ferroelastic phase transition is associated with significant modification of vibrational properties due to ordering of tetraethylammonium groups. The lower‐temperature phase transition does not lead to any clear changes in the spectra. However, our results suggest that disorder of MnCl₄²⁻ ions decreases with decreasing temperature. Copyright © 2007 John Wiley & Sons, Ltd.     

Lineshape analysis of stimulated Raman spectra of the near‐nozzle region of free jet expansions

An anomalous lineshape of stimulated Raman spectra obtained from the region very close to the nozzle of supersonic pulsed expansions of nitrogen is presented. High‐resolution Raman spectra of the Q branch of the fundamental vibration mode of N₂ have been recorded from two different nitrogen expansions at T₀ = 295 K and P₀ = 1.5–3.5 bar, the lasers crossing the jet axis in the range z/D = 0.25–1.25, where D is the effective nozzle diameter. The combination of Doppler shifts and strong gradients of density and temperature in the near‐nozzle region yield an inhomogeneous broadening and a double peak structure of the recorded Raman line profiles. The comparison of the experimental results with the simulation of the Raman spectrum from this region provides valuable information about the near‐nozzle flow field. The lineshape described here is different from another reported previously in the literature, which is based on a depletion of the density of free molecules on the axis due to condensation. Copyright © 2009 John Wiley & Sons, Ltd.     

Detailed analysis of the charge transfer complex N,N‐dimethylaniline–SO2 by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N‐dimethylaniline (DMA) and sulfur dioxide (SO₂). The formation of a deep red oil by the reaction of SO₂ with DMA is an evidence of the charge transfer (CT) nature of the DMA–SO₂ interaction. The DMA–SO₂ normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm⁻¹, which are enhanced when resonance is approached. These bands are assigned to ν_s(SO₂) and ν(ϕ N) vibrational modes, respectively, confirming the interaction between SO₂ and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO₂ with the ring π electrons, which gives rise to a π–π* low‐energy CT electronic transition, as confirmed by time‐dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA–SO₂ spectrum at the B3LYP/6‐311 + + g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopy of selected borate minerals of the pinakiolité group

The Raman spectra of a series of related minerals of the pinakiolité group have been collected and the spectra related to the mineral structure. These minerals are based upon an isolated BO₃³⁻ ion. The site symmetry is reduced from D_3h to C₁. Intense Raman bands are observed for the minerals takeuchiité, pinakiolité, fredrikssonité and azoproité at 1084, 1086, 1086 and 1086 cm⁻¹. These bands are assigned to the ν₁ BO₃³⁻ symmetric stretching mode. Low‐intensity Raman bands are observed for the minerals at 1345, 1748; 1435, 1748; 1435, 1750; and 1436, 1749 cm⁻¹, respectively. One probable assignment is to ν₃ BO₃³⁻ antisymmetric stretching mode. Intense Raman bands of the studied minerals at 712 cm⁻¹ are attributed to the ν₂ out‐of‐plane bending mode. Importantly, through the comparison of the Raman spectra, the molecular structure of borate minerals with ill‐defined structures can be obtained. Copyright © 2010 John Wiley & Sons, Ltd.     

Using Raman spectroscopy as a tool for the detection of iron in glass

Raman spectroscopy has been used to identify iron‐containing glasses. This nondestructive technique offers a fast method to obtain qualitative information about the presence of iron oxides in glass. The effect of the iron content in glass samples is reflected on the topology of the Raman spectra: A strong link between the ratio of the Q₂/Q₃ vibration units of the silica tetrahedral structure is seen. If matrix effects are taken into account, also (semi)quantitative results can be obtained from the calibration lines. The linear calibration is based on the normalized band intensity at 980 cm⁻¹ (I₉₈₀/I₁₀₉₀) and the iron oxide concentration for similar glasses. In amber and dark colored glasses, an extra peak in the spectrum indicates the presence of a FeS chromophore. Different series of glasses of various origins (ancient and modern/industrial glass) have been considered. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of supplementary manganese on the sporulation of Bacillus endospores analysed by Raman spectroscopy

It is a common practice in microbiology to induce and accelerate sporulation of spore‐forming bacteria by adding small amounts of divalent manganese to the cultivation medium. By micro‐Raman spectroscopy the effect of supplementary divalent manganese during the growth and sporulation of Bacillus spp. bacteria was studied. The spectral alterations in the Raman spectra of single endospores due to this cultivation parameter comprised slight alterations of the bands attributed to intracellular, abundantly present calcium dipicolinate (CaDPA). Those signals suffered a loss of intensity or partial band broadening because of the appearance of new weak signals next to them. Exclusively in Raman spectra of single B. sphaericuss endospores, the band at 1485 cm⁻¹ vanished. The theoretical spectra of CaDPA and manganese dipicolinate (MnDPA) were calculated and compared with the experimental spectra to prove the hypothesis that, while the overall intracellular DPA content decreased, an intracellular assembly of MnDPA in the endospores might also occur. Band shifts of the COO⁻ vibrations in the salt's spectra as well as in the endospore's spectra, and the decrease of the two CaDPA bands, confirmed this proposal. The appearance of the 1030 cm⁻¹ band in all Bacillus spectra as well as the disappearance of the 1485 cm⁻¹ band in the B. sphaericus spectra still needs to be clarified. With the help of two multivariate chemometric methods, these spectral alterations allowed discrimination between single endospores of different Bacillus strains cultivated on normal nutrient agar (NA) and those grown on NA with MnSO₄ · xH₂O addition. With these investigations, a possible strategy is shown to trace back the cultivation environment of matured single endospores. Utilizing the joint concept of micro‐Raman spectroscopy and chemometric analysis, the differentiation between natively grown endospores and those cultivated in a laboratory with the help of manganous salts as a common sporulation accelerator seems accomplishable. Copyright © 2009 John Wiley & Sons, Ltd.     

FT‐Raman and FTIR spectroscopic characterization of biogenic carbonates from Philippine venus seashell and Porites sp. coral

Some seashells of the Philippine venus species and sea coral of Porites sp. were studied by means of FT‐Raman, Fourier transform infrared spectroscopy (FTIR) and Far‐FTIR spectroscopic methods. The Raman spectra show that both Porites sp. and P. venus are of aragonite‐structured CaCO₃. Detailed spectral analysis, however, reveals some small differences, due to differences in the crystallite size or habit and to different minor element contents. IR spectra show that Porites sp. contains also some small quantities of calcite‐structured carbonates. The ν₂ band (shoulder) of calcite at 875.7 cm⁻¹ is present in the IR spectrum. The separation of the two ν₂ bands (856.4 cm⁻¹ for aragonite and 875.7 cm⁻¹ for calcite) suggests the absence of solid solution of the two polymorphic phases of CaCO₃. Spectroscopic results were confirmed also by X‐ray powder diffraction measurements. Copyright © 2008 John Wiley & Sons, Ltd.     

Single‐crystal Raman spectroscopy of brandholzite Mg[Sb(OH)6]2•6H2O and bottinoite Ni[Sb(OH)6]2• 6H2O and the polycrystalline Raman spectrum of mopungite Na[Sb(OH)6]

The single‐crystal Raman spectra of minerals brandholzite and bottinoite, formula M[Sb(OH)₆]₂•6H₂O, where M is Mg⁺² and Ni⁺², respectively, and the non‐aligned Raman spectrum of mopungite, formula Na[Sb(OH)₆], are presented for the first time. The mixed metal minerals comprise alternating layers of [Sb(OH)₆]⁻¹ octahedra and mixed [M(H₂O)₆]⁺²/[Sb(OH)₆]⁻¹ octahedra. Mopungite comprises hydrogen‐bonded layers of [Sb(OH)₆]⁻¹ octahedra linked within the layer by Na⁺ ions. The spectra of the three minerals were dominated by the Sb O symmetric stretch of the [Sb(OH)₆]⁻¹ octahedron, which occurs at approximately 620 cm⁻¹. The Raman spectrum of mopungite showed many similarities to spectra of the di‐octahedral minerals, supporting the view that the Sb octahedra give rise to most of the Raman bands observed, particularly below 1200 cm⁻¹. Assignments have been proposed on the basis of the spectral comparison between the minerals, prior literature and density functional theory (DFT) calculations of the vibrational spectra of the free [Sb(OH)₆]⁻¹ and [M(H₂O)₆]⁺² octahedra by a model chemistry of B3LYP/6‐31G(d) and lanl2dz for the Sb atom. The single‐crystal spectra showed good mode separation, allowing most of the bands to be assigned to the symmetry species A or E. Copyright © 2010 John Wiley & Sons, Ltd.     

Polarization‐sensitive CARS spectroscopy on free‐base porphyrins: coproporphyrin I tetramethyl ester

The application of polarization‐sensitive (PS) coherent anti‐Stokes Raman scattering (CARS) spectroscopy for the investigation of highly luminescent free‐base porphyrins under Q_x band resonance is discussed. For coproporphyrin I tetramethyl ester (CP‐I‐TME), PS CARS spectra involving resonances with the electronic Q_x absorption band as well as polarized spontaneous Raman spectra involving B band resonance are presented. A quantitative evaluation of the CP‐I‐TME spectra is performed and the results are compared to our previously presented data on free‐base octaethylporphine (OEP) and mesoporphyrin IX dimethyl ester (MP‐IX‐DME), which were obtained under identical excitation conditions. This comprehensive analysis reveals several spectral differences that can be attributed to the different β–substitution pattern of the porphyrin macrocycle. Additionally, the strong resonance enhancement of totally symmetric modes under Q_x band excitation is identified as a common property for OEP, CP‐I‐TME, and MP‐IX‐DME; this enhancement selectivity distinguishes the investigated substances from what is generally observed for metallo porphyrins. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman Spectroscopic Study of the Molybdate Mineral Szenicsite and Comparison with Other Paragenetically Related Molybdate Minerals

Abstract

The molybdate‐bearing mineral szenicsite, Cu₃(MoO₄)(OH)₄, has been studied by Raman and infrared spectroscopy. A comparison of the Raman spectra is made with those of the closely related molybdate‐bearing minerals, wulfenite, powellite, lindgrenite, and iriginite, which show common paragenesis. The Raman spectrum of szenicsite displays an intense, sharp band at 898 cm^?1, attributed to the ν₁ symmetric stretching vibration of the MoO₄ units. The position of this particular band may be compared with the values of 871 cm^?1 for wulfenite and scheelite and 879 cm^?1 for powellite. Two Raman bands are observed at 827 and 801 cm^?1 for szenicsite, which are assigned to the ν₃(E _g ) vibrational mode of the molybdate anion. The two MO₄ ν₂ modes are observed at 349 (B _g ) and 308 cm^?1 (A _g ). The Raman band at 408 cm^?1 for szenicsite is assigned to the ν₄(E _g ) band. The Raman spectra are assigned according to a factor group analysis and are related to the structure of the minerals. The various minerals mentioned have characteristically different Raman spectra.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.