Journal of Raman Spectroscopy

Cover image for Vol. 45 Issue 9

Early View (Online Version of Record published before inclusion in an issue)

Impact Factor: 2.519

ISI Journal Citation Reports © Ranking: 2013: 14/44 (Spectroscopy)

Online ISSN: 1097-4555

VIEW

  1. 1 - 48
  1. Research articles

    1. Stimulated Raman spectroscopy using chirped pulses

      Barbara Dunlap, Peter Richter and David W. McCamant

      Article first published online: 17 SEP 2014 | DOI: 10.1002/jrs.4578

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      Theoretical and experimental characterization of a new method using chirped pulses for stimulated Raman spectroscopy is presented. When a time delay is introduced between two chirped broadband pulses, an instantaneous frequency difference (IFD) is created at different time delays. When the IFD is resonant with a Raman-active vibration, stimulated Raman gain is generated in one pulse and inverse Raman loss is generated in the other.

    2. Origin of the variability of the mechanical properties of silk fibers: 4. Order/crystallinity along silkworm and spider fibers

      Marine Wojcieszak, Aline Percot, Sylvie Noinville, Gwénaël Gouadec, Bernard Mauchamp and Philippe Colomban

      Article first published online: 17 SEP 2014 | DOI: 10.1002/jrs.4579

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      A large variability is observed along silk fibers in the spectral window going from −200 to 200 cm−1, which corresponds to the long-range order signature of polyamide chains. This questions the validity of previous literature data considering silk as a homogeneous material. On the other hand, the ‘amide I’ band is almost independent of the targeted point, which sets a limit to this widely used structure probe. The comparison of the nanomechanics (Raman shift) and macromechanics (stress–strain curves) demonstrates that the same macromolecular chains belong to both ordered and amorphous ‘regions’.

    3. Drop coating deposition Raman spectroscopy as a potential tool for identification and determination of fructose in seminal plasma

      Zufang Huang, Jing Wang, Jinyong Lin, Xiwen Chen, Yan Sun, Gang Cao, Juqiang Lin, Jinping Lei, Hongxin Lin and Rong Chen

      Article first published online: 12 SEP 2014 | DOI: 10.1002/jrs.4572

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      The drop coating deposition Raman (DCDR) method was utilized to achieve pre-concentration and quantitative determination of seminal plasma fructose. Optimization of experimental parameters to achieve reagent-free and rapid detection of fructose was also investigated. Different fructose concentrations within physiological level demonstrate a linear relationship with the band intensity of 627 cm−1 (assigned to fructose), and the relative error of predicted seminal plasma fructose concentration is 10.23%. DCDR method has the potential of being an alternative technique for identification and determination of fructose in seminal plasma.

    4. Raman spectroscopy and chemometrics for quantitative analysis of complex flows in an industrial transesterification process

      Aurélie Filliung, David Chapron, Patrice Bourson, Gisèle Finqueneisel, Alain Riondel and Jean Guilment

      Article first published online: 11 SEP 2014 | DOI: 10.1002/jrs.4577

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      Raman spectra of the acrylate mixture from the industrial flow compared with the spectra of pure compounds. A lot of overlapping peaks lead to multivariate analysis in order to quantify each compound concentration.

    5. The influence of chemical solvents on the properties of CVD graphene

      Zhang Ting Wu, Wei Wei Zhao, Wei Yu Chen, Jie Jiang, Hai Yan Nan, Xi Tao Guo, Zheng Liang, Yu Ming Chen, Yun Fei Chen and Zhen Hua Ni

      Article first published online: 11 SEP 2014 | DOI: 10.1002/jrs.4582

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      The influence of commonly used etching solvents during the transfer process of chemical vapor deposition (CVD) graphene on its property is studied by Raman spectroscopy. Strong p-doping as well as reduction of phonon lifetime is observed for graphene transferred by ferric chloride and ferric nitrate, as compared to that transferred by ammonium persulfate. The latter would also introduce a great reduction of thermal conductivity of graphene, e.g. with 76% reduction for graphene transferred by ferric nitrate as compared to that transferred by ammonium persulfate.

    6. Analytical FT-Raman spectroscopy to chemotype Leptospermum scoparium and generate predictive models for screening for dihydroxyacetone levels in floral nectar

      Elizabeth M. Nickless, Stephen E. Holroyd, Jonathan M. Stephens, Keith C. Gordon and Jason J. Wargent

      Article first published online: 8 SEP 2014 | DOI: 10.1002/jrs.4576

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      Leptospermum scoparium (Mānuka) is the source of nectar for Unique Mānuka Factor (UMF) honey. FT-Raman spectroscopy, in combination with principal component analysis and partial least squares regression, was investigated as an analytical tool for building a screening model for DHA in the nectar of L. scoparium. Results showed that the application of multivariate analysis of FT-Raman spectra from leaf material is a useful analytical tool to screen for DHA potential in L. scoparium.

  2. Short communications

    1. Early 20th C Russian painting? Raman identification of modern pigments on a pastel supposedly Painted by the renowned artist Natalia Goncharova

      Tracey D. Chaplin, Robin J. H. Clark and Brian W. Singer

      Article first published online: 27 AUG 2014 | DOI: 10.1002/jrs.4569

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      A rayist pastel painting signed by renowned avant-garde Russian artist Natalia Goncharova and dated as 1913 has been shown by Raman microscopy of the pigments to have been painted after 1952, with the identification of a dioxazine purple pigment.

  3. Research articles

    1. Correlation of structure and spin–phonon coupling in (La, Nd) doped BiFeO3 films

      Anju Ahlawat, S. Satapathy, Satish Maan, V. G. Sathe and P. K. Gupta

      Article first published online: 25 AUG 2014 | DOI: 10.1002/jrs.4573

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      Raman spectroscopy has been used to study the effect of structural change on the spin–phonon coupling in doped BiFeO3 (BFO) films (Bi0.8La0.1Nd0.1FeO3) grown on SrTiO3 (001) substrate. The temperature-dependent Raman studies show phonon anomalies in the vicinity of magnetic ordering temperature (TN ~380 °C) owing to the spin–phonon coupling. Doped films exhibit strong anomalies in the line widths of Raman bands around TN revealing the presence of strong spin–lattice coupling. The enhanced spin–lattice coupling as a result of A-site doping in BFO films establishes a strong relation between local structure and spin–phonon interactions. The structural transformation in BFO films plays a significant role in controlling the spin–lattice coupling.

    2. Label-free optical detection of type II diabetes based on surface-enhanced Raman spectroscopy and multivariate analysis

      Jinyong Lin, Zufang Huang, Shangyuan Feng, Juqiang Lin, Nenrong Liu, Jing Wang, Ling Li, Yongyi Zeng, Buhong Li, Haishan Zeng and Rong Chen

      Article first published online: 25 AUG 2014 | DOI: 10.1002/jrs.4574

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      Silver nanoparticles-based surface-enhanced Raman scattering spectroscopy was first employed to detect oxyhemoglobin (OxyHb) variation in type II diabetic development. Specific structural changes of OxyHb molecule in diabetes, including heme transformation and globin variation, were detected. Furthermore, partial least squares and principal component analysis combined with linear discriminate analysis diagnostic algorithms are employed to classify the surface-enhanced Raman scattering spectra acquired from diabetic and healthy OxyHb, yielding the diagnostic accuracies of 90.0% and 95.5%, respectively. These results are very promising for developing a label-free tool for type II diabetes detection.

    3. Abnormal Raman spectra in Er-doped BaTiO3 ceramics

      Da-Yong Lu, Wei Cheng, Xiu-Yun Sun, Qiao-Li Liu, De-Xu Li and Zhong-Yu Li

      Article first published online: 25 AUG 2014 | DOI: 10.1002/jrs.4575

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      Greatly enhanced and abnormal Raman spectra are discovered in Er-doped BaTiO3 ceramics, and a large increase in intensity shows a hundredfold selectivity for Ba-site Er3+ ions over Ti-site Er3+ ions. The abnormal Raman spectra originate from a fluorescent effect. A strong EPR signal at g = 1.974, which originates from ionized Ba vacancy defects, was discovered in Er-doped BaTiO3 ceramic. A new broad EPR signal at g = 2.23 possibly arises from Er3+ (4f11, 4I15/2) Kramers ions.

    4. Are metabolites of Fusarium oxysporum responsible for fungal skin invasion? A morphological and Raman spectroscopy monitoring

      Kátia Cristina Sibin Melo, Terezinha Inez Estivalet Svidzinski, Mariana Cristina Vicente Umada Zapater, Thiago Honório Dutra da Silva, Gutierrez Rodrigues de Morais, Francielle Sato, Mauro Luciano Baesso and Luzmarina Hernandes

      Article first published online: 21 AUG 2014 | DOI: 10.1002/jrs.4567

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      Fourier transform Raman spectroscopy and histological techniques were used to investigate the effects of a fraction of crude metabolic extract of Fusarium oxysporum on the skin of healthy rats. The treated skin showed spectral Raman changes indicating that the fraction contains elements that contribute to the invasion of the skin by F. oxysporum, disrupting the organization of the extracellular matrix.

    5. Revealing interactions between polyaza pyridinophane compounds and DNA/RNA polynucleotides by SERS spectroscopy

      Adriana Dijanošić, Snežana Miljanić, Ivo Piantanida, Jorge González-García and Enrique García-España

      Article first published online: 20 AUG 2014 | DOI: 10.1002/jrs.4564

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      Interactions of polyaza pyridinophane molecules, containing pyridine or phenanthroline as the central unit, with DNA/RNA polynucleotides were studied by SERS spectroscopy. Distinctive bands appearing in spectra were assigned to polynucleotide moieties involved in interactions with the pyridinophane molecules. Both compounds bound within the minor groove of poly dAdT-poly dAdT, while only pyridine-based analog preferred the major groove of RNA analog. Intensity ratios suggested intercalation of the phenanthroline derivative into GC polynucleotide.

    6. Probing interlayer coupling in twisted single-crystal bilayer graphene by Raman spectroscopy

      Chao-Hui Yeh, Yung-Chang Lin, Pramoda K. Nayak, Chun-Chieh Lu, Zheng Liu, Kazu Suenaga and Po-Wen Chiu

      Article first published online: 19 AUG 2014 | DOI: 10.1002/jrs.4571

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      Twisted bilayer graphene, in which interlayer interaction plays a critical role in this coupled system, is characterized for its angle-dependent electronic and optical properties. Here, we present a systematic Raman study of single-crystal twisted bilayer graphene grains, with the spectra of each bilayer graphene precisely correlated to its twist angle using combined transmission electron microscopic technique. Van Hove singularities develop as a result of band rehybridization at the crossing Dirac cones of the two layers, giving rise to a critical twist angle that determines the energy separation between the saddle points in the band structure and the resonance Raman spectra accordingly. The 2D mode becomes sensitive to the twist angle, showing the angle-dependent position, peak width, and intensity.

  4. Rapid communications

    1. Bisignate resonance Raman optical activity: a pseudo breakdown of the single electronic state model of RROA?

      Grzegorz Zajac, Agnieszka Kaczor, Katarzyna Chruszcz-Lipska, Jan Cz. Dobrowolski and Malgorzata Baranska

      Article first published online: 14 AUG 2014 | DOI: 10.1002/jrs.4563

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      Raman optical activity spectra were calculated for a set of conformers of astaxanthin, which is a non-rigidmolecule exhibiting strong resonance enhancement in the visible range. The impact of chosen functional, basis set, and excitation line on the calculation of astaxanthin resonance Raman optical activity spectrum is discussed.

  5. Research articles

    1. Pigment analysis of Portuguese portrait miniatures of 17th and 18th centuries by Raman Microscopy and SEM-EDS

      Alfredina Veiga, José Mirão, António J. Candeias, Paulo Simões Rodrigues, Dora Martins Teixeira, Vânia S. F. Muralha and Jorge Ginja Teixeira

      Article first published online: 13 AUG 2014 | DOI: 10.1002/jrs.4570

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      Seventeen Portuguese miniature portraits on copper support from the collection of the Museum of Évora (Portugal) were analyzed in situ and nondestructively by Raman microscopy, SEM-EDS, and stereomicroscopy. μ-Raman analysis allowed the identification of 19 compounds, one of which is a pigment rarely found in oil paintings—the bluish black covellite. SEM-EDS was used as an important complementary technique to confirm the chemical identities of some pigments and to identify the pigment shell gold (gold dust) in some portraits.

    2. Combined approach of FT-Raman, SERS and IR micro-ATR spectroscopies to enlighten ancient technologies of painted and varnished works of art

      Céline Daher, Léa Drieu, Ludovic Bellot-Gurlet, Aline Percot, Céline Paris and Anne-Solenn Le Hô

      Article first published online: 12 AUG 2014 | DOI: 10.1002/jrs.4565

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      French Decorative Arts objects from 18th century museum collections were studied. These complex materials were analyzed using FT-IR, FT-Raman and SERS, and particularly organic materials such as lake pigments, binders and varnishes were identified thanks to the right choice of analytical parameters and, for some complex mixtures specific data treatments.

  6. Short communications

    1. Instantaneous shifted-excitation Raman difference spectroscopy (iSERDS)

      Johannes Kiefer

      Article first published online: 11 AUG 2014 | DOI: 10.1002/jrs.4566

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      An approach for instantaneous SERDS (iSERDS) is presented utilizing a broadband light source. The broadband radiation is spatially dispersed in the focal plane inside the object of investigation. The generated scattering signal is imaged onto the slit of an imaging spectrograph. The individual pixel lines on the detector represent Raman spectra with slightly shifted excitation wavelength and hence allow SERDS spectra to be derived.

  7. Research articles

    1. Raman microspectroscopy of gemstones from a chalice made in 1732

      Miha Jeršek and Sabina Kramar

      Article first published online: 25 JUL 2014 | DOI: 10.1002/jrs.4560

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      This study deals with the Raman microspectroscopy study of gemstones and their inclusions of the baroque chalice made in 1732, one the most richly decorated chalices in Slovenia. The origins of the diamonds, rubies, sapphires, and emeralds were assessed. At a later date, sapphire, glass, synthetic ruby, and green agate were embedded into the chalice as substitutes for lost stones.

    2. Monitoring of optimized SERS active gel substrates for painting and paper substrates by unilateral NMR profilometry

      Brenda Doherty, Federica Presciutti, Antonio Sgamellotti, Brunetto G. Brunetti and Costanza Miliani

      Article first published online: 20 JUL 2014 | DOI: 10.1002/jrs.4542

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      To reach surface enhanced Raman spectroscopy (SERS) protocols for in-situ non-invasive protocol with portable instrumentation, this contribution oversees the optimization of a removable active methylcellulose gel and the applicability of an innovative silver doped gelatin as evaluated by non-invasive portable nuclear magnetic resonance profilometry. SERS activity, gel penetration and removal from an unvarnished painted surface and commercial dyed paper substrates are herein examined.

    3. A portable versus micro-Raman equipment comparison for gemmological purposes: the case of sapphires and their imitations

      Germana Barone, Danilo Bersani, Vincenza Crupi, Francesca Longo, Ugo Longobardo, Pier Paolo Lottici, Irene Aliatis, Domenico Majolino, Paolo Mazzoleni, Simona Raneri and Valentina Venuti

      Article first published online: 20 JUL 2014 | DOI: 10.1002/jrs.4555

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      In recent years, the use of a portable Raman spectrometer for fast and in-situ gem identification has became useful in gemological and archeological fields. In this work, 13 faceted loose blue gems have been analysed both with portable and micro-Raman equipments in order to show the potentiality of a portable spectrometer in the identification of sapphire and its imitation. Micro-Raman analysis has been also carried out with the aim at deeper studying inclusions in natural sapphire. The study is improved by portable X-ray fluorescence analysis useful to identify the cromophore responsible for the blue colour.

    4. Raman study of different crystalline forms of PbCrO4 and PbCr1−xSxO4 solid solutions for the noninvasive identification of chrome yellows in paintings: a focus on works by Vincent van Gogh

      Letizia Monico, Koen Janssens, Ella Hendriks, Brunetto G. Brunetti and Costanza Miliani

      Article first published online: 17 JUL 2014 | DOI: 10.1002/jrs.4548

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      In this paper, the valuable capabilities of Raman spectroscopy as a reliable and sensitive tool for identifying and mapping different varieties of chrome yellow on works of art is described. This characterization is based on a Raman study of several oil paint model samples made up of monoclinic and/or orthorhombic crystalline forms of PbCrO4 and PbCr1−xSxO4 (0.1 ≤ × ≤ 0.8), and it is possible using both bench-top and portable devices. Because of the absence resonance Raman effect and the absence of any laser-induced photodecomposition, it is advantageous to acquire data at 785.0 nm.

    5. Characterisation of metal carboxylates by Raman and infrared spectroscopy in works of art

      Vanessa Otero, Diogo Sanches, Cristina Montagner, Márcia Vilarigues, Leslie Carlyle, João A. Lopes and Maria J. Melo

      Article first published online: 10 JUL 2014 | DOI: 10.1002/jrs.4520

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      Raman and infrared spectroscopy proved to be complementary techniques for a full identification of metal carboxylates in a complex aged paint; while Raman allows a clear identification of the chain length, infrared enables the identification of the metal cation. Using a reference database, principal component analysis models were developed, enabling a fast and reliable method to characterise metal soaps within complex aged oil paint systems. Applying this methodology, copper palmitate and copper azelate were detected in two 19th-century oil paintings.

    6. Protective ability index measurement through Raman quantification imaging to diagnose the conservation state of weathering steel structures

      Julene Aramendia, Leticia Gomez-Nubla, Ludovic Bellot-Gurlet, Kepa Castro, Céline Paris, Philippe Colomban and Juan Manuel Madariaga

      Article first published online: 9 JUL 2014 | DOI: 10.1002/jrs.4549

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      In order to assess the protective ability of different weathering steel sculptures, Raman quantification imaging was carried out over their surfaces. The protective ability is calculated by the ratio of different iron phases present in the steel surface, and they were quantified by using homemade software called CorATmos that is based on the linear combination of spectra.

    7. Spectroscopic characterisation of crusts interstratified with prehistoric paintings preserved in open-air rock art shelters

      Antonio Hernanz, Juan F. Ruiz-López, Juan Manuel Madariaga, Egor Gavrilenko, Maite Maguregui, Silvia Fdez-Ortiz de Vallejuelo, Irantzu Martínez-Arkarazo, Ramiro Alloza-Izquierdo, Vicente Baldellou-Martínez, Ramón Viñas-Vallverdú, Albert Rubio i Mora, Àfrica Pitarch and Anastasia Giakoumaki

      Article first published online: 3 JUL 2014 | DOI: 10.1002/jrs.4535

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      In situ micro-Raman spectroscopy (μ-RS) of rock paintings in open-air rock shelters entails difficulties that have been faced in five sites of the eastern Iberian Peninsula using a portable μ-Raman microscope and handheld energy dispersive X-ray fluorescence and diffuse reflectance infrared Fourier transform spectroscopy instruments. The microstratigraphic composition of crusts insterstratified with the paintings have been characterised by μ-RS and scanning electronic microscopy combined with energy dispersive X-ray spectroscopy. Whewellite, gypsum, calcite, clay, dolomite, α-quartz, anatase and haematite have been identified in the crusts and haematite and amorphous carbon in red and black pictographs, respectively.

    8. Raman spectroscopy as a non-destructive screening technique for studying white substances from archaeological and forensic burial contexts

      Eline M. J. Schotsmans, Andrew S. Wilson, Rhea Brettell, Tasnim Munshi and Howell G. M. Edwards

      Article first published online: 2 JUL 2014 | DOI: 10.1002/jrs.4526

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      Raman spectroscopy was evaluated as a non-destructive analytical tool for the characterisation of white substances in burials, and Fourier transform Raman spectroscopy was used to assess the conversion of hydrated lime into calcium carbonate. Fourteen samples of white substances from archaeological and forensic sites were analysed and characterised. The results show that not all white residues in burials are lime. Lime can easily be mistaken for other building materials (gypsum), for minerals (brushite) or degraded metal (cerussite).

    9. Raman investigation of artificial patinas on recent bronze protected by different azole type inhibitors in an outdoor environment

      Tadeja Kosec, Andraž Legat and Polonca Ropret

      Article first published online: 1 JUL 2014 | DOI: 10.1002/jrs.4532

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      Inhibitor's efficiency of benzotriazole (BTA) and 2-mercaptobenzimidazole (MBI) inhibitors on chemically patinated-bronze surface was studied. Raman analysis defines the interaction between the inhibitor and the patinated surface. Electrochemical results show that protective behavior of MBI and BTA is increased on nitrate and sulfide patina, whereas MBI showed better protective properties on green chloride patina than BTA.

    10. Characterization of emeralds by micro-Raman spectroscopy

      Danilo Bersani, Giulia Azzi, Erica Lambruschi, Germana Barone, Paolo Mazzoleni, Simona Raneri, Ugo Longobardo and Pier Paolo Lottici

      Article first published online: 27 JUN 2014 | DOI: 10.1002/jrs.4524

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      Raman analysis is able to obtain a large amount of information on gems. In this work, 14 faceted emeralds and simulants were extensively investigated allowing the identification of some fakes (garnet, glasses, and quartz).

      The OH stretching region of the spectrum was used to estimate the amount of alkali ions present in the channels of the structure. Inclusions were identified in order to identify the gems provenance. The shape and position of the luminescence of Cr3+ ions were used to better define the origin of the gems.

    11. TLC-SERS of mauve, the first synthetic dye

      M. V. Cañamares, D. A. Reagan, J. R. Lombardi and M. Leona

      Article first published online: 24 JUN 2014 | DOI: 10.1002/jrs.4508

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      Mauve was synthesized and analyzed by normal Raman, FT-Raman and surface-enhanced Raman scattering (SERS). The different components of the dye were separated by thin layer chromatography and analyzed by the Raman techniques. Good spectra could be only obtained by means of SERS spectroscopy.

    12. Gem quality and archeological green ‘jadeite jade’ versus ‘omphacite jade’

      Alessia Coccato, Stefanos Karampelas, Marie Wörle, Samuel van Willigen and Pierre Pétrequin

      Article first published online: 24 JUN 2014 | DOI: 10.1002/jrs.4512

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      Seven gem quality green ‘jade’ samples and three green ‘jade’ samples of archaeological importance were characterized using Raman spectroscopy and other nondestructive means. Five samples of gem quality and two samples of archaeological interest were found to be ‘jadeite jade’, whereas two samples of gem quality and one sample of archaeological interest were ‘omphacite jade’.

    13. Surface-enhanced Raman spectroscopy (SERS) analysis of organic colourants utilising a new UV-photoreduced substrate

      Klara Retko, Polonca Ropret and Romana Cerc Korošec

      Article first published online: 22 JUN 2014 | DOI: 10.1002/jrs.4533

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      A new UV-photoreduced surface-enhanced Raman spectroscopy (SERS) substrate consisting of silver nanoparticles is proposed for the examination of works of art. Substrate enabled a successful detection of selected organic colourants (alizarin red S, madder lake and alizarin crimson dark), through a prominent enhancement of Raman signal, and fluorescence quenching. Furthermore, a selective analysis of organic colourants also in paint layers, without sample pre-treatment, and a positive identification of an organic dye present in the glaze layer on a cross section of a sample were achieved.

    14. Estimating the concentrations of pigments and binders in lead-based paints using FT-Raman spectroscopy and principal component analysis

      Anuradha Pallipurath, Róza Villő Vőfély, Jonathan Skelton, Paola Ricciardi, Spike Bucklow and Stephen Elliott

      Article first published online: 18 JUN 2014 | DOI: 10.1002/jrs.4525

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      Fourier transform Raman and principal component analysis can be a powerful combination in analysing pigments and binders and also help to understand ageing. Here, these techniques are used to estimate the concentrations of both the pigments and the binders in paint films. This represents a tentative first step towards a semi-automated and quantitative method for analysing cultural heritage objects, which may help boost our understanding of their history, and enable conservators to make more informed decisions so as to ensure their preservation.

    15. Suitability of Ag-agar gel for the micro-extraction of organic dyes on different substrates: the case study of wool, silk, printed cotton and a panel painting mock-up

      Elena Platania, John R. Lombardi, Marco Leona, Nobuko Shibayama, Cristiana Lofrumento, Marilena Ricci, Maurizio Becucci and Emilio Castellucci

      Article first published online: 15 JUN 2014 | DOI: 10.1002/jrs.4531

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      Ag-agar gel has been adopted for the non-destructive extraction of very tiny amounts of organic dyes on silk, wool, and printed cotton and on a mock-up panel painting. After the extraction, surface-enhanced Raman spectroscopy measurements have been performed on the Ag-agar gel probe, showing very good spectra. The method has been found to be extremely suitable for the recognition of a piece of textile of unknown chemical composition.

    16. Mineral impurities in azurite pigments: artistic or natural selection?

      Mariafrancesca Aru, Lucia Burgio and Michael S. Rumsey

      Article first published online: 9 JUN 2014 | DOI: 10.1002/jrs.4469

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      This study corrects the widespread assumption that black and orange-brown impurities in azurite pigments are mainly copper oxides (cuprite and tenorite) and proves that they are iron oxides instead. It also shows that the presence of these pigment impurities in azurite is not a deliberate choice by the artist but a consequence of the natural make-up of mineral azurite specimens.

    17. Surface-enhanced Raman scattering for the analysis of red lake pigments in painting layers mounted in cross sections

      Ambra Idone, Maurizio Aceto, Eliano Diana, Lorenzo Appolonia and Monica Gulmini

      Article first published online: 9 JUN 2014 | DOI: 10.1002/jrs.4491

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      Cross sections are useful in the scientific investigation of paintings as they show the sequence of the layers and allow the detection of colorants in each layer through micro-Raman spectroscopy. The application of silver colloidal pastes has been explored here on two cross sections obtained from historical artworks to identify red lake pigments.

      The work represents a further step towards the possibility of fully exploiting the high spatial resolution of the micro-Raman spectrometer to investigate samples from painted objects.

    18. The influence of UV–Vis radiation, and oscillations of temperature and relative humidity, on malachite alteration in the presence of different organic binders and varnishes

      Tanja Špec, Klara Retko, Polonca Ropret, Anton Meden and Janez Bernard

      Article first published online: 6 JUN 2014 | DOI: 10.1002/jrs.4518

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      An extended study on the degradation of malachite colour layers was carried out, by preparation of easel (model) paintings and exposure to the different environmental parameters, such as UV–Vis, temperature and humidity oscillations. Utilizing Raman microscopy, aged and non-aged colour layers were investigated in order to obtain decomposition of the pigment and to detect degradation products. The results obtained were supported also by scanning electron microscopy/energy dispersive spectrometry and X-ray diffraction analysis.

    19. Pigment identification of an illuminated mediaeval manuscript De Civitate Dei by means of a portable Raman equipment

      Debbie Lauwers, Vincent Cattersel, Ludo Vandamme, Annabel Van Eester, Kaat De Langhe, Luc Moens and Peter Vandenabeele

      Article first published online: 2 JUN 2014 | DOI: 10.1002/jrs.4500

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      Direct identification of pigments in manuscripts was one of the first applications of Raman spectroscopy in art and archaeology. In this work, a portable, dual laser Raman spectrometer is introduced to characterise pigments used in an illuminated mediaeval manuscript, De Civitate Dei. Characteristics important for these in situ measurements are discussed. Next to this, pigment identification of De Civitate Dei was performed. Pigments typically used during the middle ages are identified. The detection of chrome yellow suggests a modern restoration.

    20. Identification of endolithic traces on stone monuments and natural outcrops: preliminary evidences

      A. Casanova Municchia, G. Caneva, M. A. Ricci and A. Sodo

      Article first published online: 30 MAY 2014 | DOI: 10.1002/jrs.4517

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      Raman spectra of rocks alterations and pigments traces produced by endoliths in Temperate and Mediterranean climates are reported. Both monument fragments and natural outcrops have been investigated. Traces of compounds, such as scytonemin, anthraquinone, carotenoid compounds (Bio-markers) and iron mobilization (geo-markers) have been identified. All these compounds are produced by endoliths as survival strategy against strong UV- radiations.

    21. Characterization of gypsum and anhydrite ground layers in 15th and 16th centuries Portuguese paintings by Raman Spectroscopy and other techniques

      Vanessa Antunes, António Candeias, Maria José Oliveira, Stéphane Longelin, Vitor Serrão, Ana Isabel Seruya, João Coroado, Luís Dias, José Mirão and Maria Luísa Carvalho

      Article first published online: 20 MAY 2014 | DOI: 10.1002/jrs.4488

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      The results of this article put in evidence, by characterizing Portuguese wood painting ground layers from the 15th and 16th centuries (1450–1600), differences between the examined groups, giving important information on the various workshop practices and also on the possible future conservative intervention on the paintings.

    22. The source of blue colour of archaeological glass and glazes: the Raman spectroscopy/SEM-EDS answers

      Maria Cristina Caggiani, Pasquale Acquafredda, Philippe Colomban and Annarosa Mangone

      Article first published online: 15 MAY 2014 | DOI: 10.1002/jrs.4492

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      Temperature-controlled Raman measurements and Raman mappings are tested on haüyne, lazurite and blue enamels. A distinction between chromophore-bearing minerals in different rocks to give blue colour to glass seems possible thanks to the detection of the associated minerals.

    23. Raman analysis of multilayer automotive paints in forensic science: measurement variability and depth profile

      Danny Lambert, Cyril Muehlethaler, Line Gueissaz and Geneviève Massonnet

      Article first published online: 14 MAY 2014 | DOI: 10.1002/jrs.4490

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      Analysis of car paint samples in a forensic context. The Raman measurement variability is explored through a design of experiments, which highlights the importance of the surface roughness of the sample. Moreover, depth profile experiment through a clearcoat is performed.

    24. Micro-Raman spectroscopy analysis of the 17th century panel painting ‘Servilius Appius’ by Isaac van den Blocke

      Ewa Pięta, Edyta Proniewicz, Bożena Szmelter-Fausek, Justyna Olszewska-Świetlik and Leonard M. Proniewicz

      Article first published online: 9 MAY 2014 | DOI: 10.1002/jrs.4489

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      Micro-Raman spectroscopy method was applied to characterize the pigments, state of conservation, and painting techniques used in the 17th century panel painting ‘Servilius Appius’, by Isaac van den Blocke, located at the Gdańsk History Museum.

    25. A systematic analysis of red lake pigments in French Impressionist and Post-Impressionist paintings by surface-enhanced Raman spectroscopy (SERS)

      Federica Pozzi, Klaas Jan van den Berg, Inge Fiedler and Francesca Casadio

      Article first published online: 2 MAY 2014 | DOI: 10.1002/jrs.4483

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      Surface-enhanced Raman spectroscopy analyses revealed an extensive use of cochineal and madder lakes, or mixtures of the two, in paintings by Manet, Pissarro, Renoir, Monet and Gauguin from the Art Institute of Chicago collection. Examination of a number of real samples and 19th century historically accurate red lake paint reconstructions demonstrated that dye identification can be successfully accomplished in any type of matrix, i.e. even when extenders, inorganic pigments, ground materials or binding media are associated with the red lake in the sample analyzed.

    26. Raman spectroscopic study of the degradation of a middle age mural painting: the role of agricultural activities

      Marco Veneranda, Mireia Irazola, Marta Díez, Ane Iturregui, Julene Aramendia, Kepa Castro and Juan Manuel Madariaga

      Article first published online: 29 APR 2014 | DOI: 10.1002/jrs.4485

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      The products used to fertilize the agricultural fields surrounding the village of Alaiza represent the primary cause of the increase of the concentration of acidic ion NH4+ in the soil. These cations ascent the walls of the Assumption's Church in the infiltration waters provoking the main deteriorations of the medieval paintings such as salt efflorescence and mortar disaggregation.

    27. Raman and structural comparison between the new gemstone pezzottaite Cs(Be2Li)Al2Si6O18 and Cs-beryl

      Erica Lambruschi, G. Diego Gatta, Ilaria Adamo, Danilo Bersani, Emma Salvioli-Mariani and Pier Paolo Lottici

      Article first published online: 27 APR 2014 | DOI: 10.1002/jrs.4479

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      The Raman spectrum over the region 100–3800 cm−1 of the new gemstone pezzottaite [Cs(Be2Li)Al2Si6O18] is compared with that of Cs-beryl. The spectrum of pezzottaite shows two main characteristic bands at 111 and 1100 cm−1 with respect to Cs-beryl. The nature of the two bands is not completely understood, but Raman spectroscopy enables a quick identification of pezzottaite in gemology.

    28. Vibrational spectroscopy and X-ray diffraction applied to the study of Cretaceous fish fossils from Araripe Basin, Northeast of Brazil

      Paulo T. C. Freire, João H. Silva, F. E. Sousa-Filho, Bruno T. O. Abagaro, Bartolomeu C. Viana, Gilberto D. Saraiva, Thatiany A. Batista, Olga A. Barros and Antonio A. F. Saraiva

      Article first published online: 10 APR 2014 | DOI: 10.1002/jrs.4471

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      Fossils of the fish coelacanth belonging to the Cretaceous Period from two different formations of Araripe Basin in Northeast of Brazil were investigated through Raman and infrared spectroscopy and X-ray diffraction. The results show the constitution of both the fossil and matrix of two different geological formations of the Araripe Basin.

    29. The detection of copper resinate pigment in works of art: contribution from Raman spectroscopy

      Claudia Conti, Jana Striova, Irene Aliatis, Elena Possenti, Geneviève Massonnet, Cyril Muehlethaler, Tommaso Poli and Matteo Positano

      Article first published online: 2 MAR 2014 | DOI: 10.1002/jrs.4455

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      Copper resinate is a green pigment widely used by the 16th century painters but its detection is up to this time an analytical challenge. This study shows how Raman spectroscopy is an effective tool able to identify this pigment in paintings. The research is focused on the exploration of the characteristic Raman signatures of commercial copper resinate in pure forms and in specimens simulating the paint layers. Six laser sources (488, 514, 532, 633, 785 and 830 nm) were used in different laboratories to highlight the drawbacks and advantages of a specific excitation source. Raman features of verdigris, a pigment commonly used for the copper resinate preparation, were also studied for comparison and the obtained results were applied in the analyses of a famous Caravaggio's painting.

    30. Gold in the Alhambra: study of materials, technologies, and decay processes on decorative gilded plasterwork

      Maria Jose de la Torre-López, Ana Dominguez-Vidal, Maria Jose Campos-Suñol, Ramon Rubio-Domene, Ulrich Schade and Maria Jose Ayora-Cañada

      Article first published online: 24 FEB 2014 | DOI: 10.1002/jrs.4454

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      The combination of elemental, microstructural, and molecular characterization allowed for the identification of ancient gilding technologies and the main decay processes. Two different types of gilding were identified: one, original, employing a thin gold leaf and redecorations with a laminated structure of gold over tin foil. Degradation of the organic materials employed as binders and tin oxidation were the main decay processes affecting the gildings.

    31. Decorated plasterwork in the Alhambra investigated by Raman spectroscopy: comparative field and laboratory study

      A. Dominguez-Vidal, M. J. de la Torre-López, M. J. Campos-Suñol, R. Rubio-Domene and M. J. Ayora-Cañada

      Article first published online: 22 JAN 2014 | DOI: 10.1002/jrs.4439

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      Almost all the pigments present in the decorations (cinnabar, minium, carbon black and natural lapis lazuli) together with several decay products of the red pigments were identified during the non-invasive field investigations. Complementary laboratory analysis revealed the presence of azurite severely degraded to clinoatacamite and other green decorations composed of copper hydroxychlorides with small amounts of lapis lazuli. The presence of re-decorations with overlaying layers of pigments was also investigated.

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