Journal of Raman Spectroscopy

Cover image for Vol. 45 Issue 7

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

Impact Factor: 2.679

ISI Journal Citation Reports © Ranking: 2012: 11/43 (Spectroscopy)

Online ISSN: 1097-4555

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  1. 1 - 55
  1. Research articles

    1. Surface-enhanced Raman scattering of N-acetylneuraminic acid on silver nanoparticle surface

      Ekaterina Vinogradova, Alfredo Tlahuice-Flores, J. Jesus Velazquez-Salazar, Eduardo Larios-Rodriguez and Miguel Jose-Yacaman

      Article first published online: 22 JUL 2014 | DOI: 10.1002/jrs.4544

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      Silver nanoparticle-based surface-enhanced Raman scattering and density functional theory analysis methods were used to characterize sialic acid (Neu5Ac), a monosaccharide that is recognized as a potential biomarker for a variety of pathophysiological processes. The Raman and surface-enhanced Raman scattering vibrational signatures, spectroscopic band assignments, and possible mechanism of adsorption of Neu5Ac on silver surface are reported.

    2. Portuguese 16th century tiles from Santo António da Charneca's kiln: a spectroscopic characterization of pigments, glazes and pastes

      L. F. Vieira Ferreira, D. S. Conceição, D. P. Ferreira, L. F. Santos, T. M. Casimiro and I. Ferreira Machado

      Article first published online: 22 JUL 2014 | DOI: 10.1002/jrs.4551

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      The first reported tiles produced in Portugal (Santo António da Charneca, 16th century) were studied with the use of surface spectroscopies techniques, namely, μ-Raman. This is the first spectroscopic study of these ceramics, and significant differences between the Portuguese and coeval Spanish samples from Seville were identified.

    3. Crocoite PbCrO4 and mimetite Pb5(AsO4)3Cl: rare minerals in highly degraded mediaeval murals in Northern Bohemia

      David Hradil, Janka Hradilová, Petr Bezdička, Silvie Švarcová, Zdeňka Čermáková, Veronika Košařová and Ivan Němec

      Article first published online: 22 JUL 2014 | DOI: 10.1002/jrs.4556

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      Natural crocoite (PbCrO4) was detected by Raman micro-spectroscopy in fragmentarily preserved wall paintings in Kuřívody, Northern Bohemia, dated to around 1300, as intentionally used yellow pigment. Even less common mimetite Pb5(AsO4)3Cl was formed through corrosion of orpiment (As2S3) in mixture with lead pigments. Micro-Raman in combination with micro-XRD was able to answer key questions in technological and art-historical contexts.

    4. 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.

    5. 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.

    6. 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.

    7. Rapid detection of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) using a portable Au-colloid SERS sensor

      Zhenli Sun, Jingjing Du, Li Yan and Chuanyong Jing

      Article first published online: 15 JUL 2014 | DOI: 10.1002/jrs.4554

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      A portable surface-enhanced Raman scattering sensor was developed for rapid 2,2′,4,4′-tetrabromodiphenyl ether detection and identification. The density function theory calculation agreed with our experimental results and demonstrated the existence of electromagnetic enhancement and charge-transfer mechanism. This in situ surface-enhanced Raman scattering platform allows easy and reliable detection of 2,2′,4,4′-tetrabromodiphenyl ether in complex matrices.

    8. The effects of contact area and applied load on the morphology of in vitro worn ultra-high molecular weight knee prostheses: a micro-Raman and gravimetric study

      Silvia Tozzi, Enrico Modena, Stefano Falcioni, Alessandra Sudanese, Saverio Affatato and Paola Taddei

      Article first published online: 13 JUL 2014 | DOI: 10.1002/jrs.4545

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      Ultra-high molecular weight polyethylene knee prostheses of two different sizes were run on a knee wear simulator in two tests differing for the applied load. Raman spectroscopy showed a more significant polymer degradation in the smaller prostheses. Micro-Raman analyses on in vivo worn knee prostheses confirmed the results obtained in vitro, showing that the conditions used in the in vitro tests well simulate the knee kinematics of the knee joint and thus the in vivo wear.

    9. On-line surface enhanced Raman spectroscopic detection in a recyclable Au@SiO2 modified glass capillary

      Weiwei Wang, Qinghua Guo, Minmin Xu, Yaxian Yuan, Renao Gu and Jianlin Yao

      Article first published online: 13 JUL 2014 | DOI: 10.1002/jrs.4553

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      A facile method was developed to fabricate a high sensitive, reproducible and recyclable surface enhanced Raman spectroscopy (SERS) active glass capillary. The adsorbed SERS probe molecules could be rapidly and completely removed away to obtain a refresh substrate for the cyclic SERS detection. The results indicated that the SERS-active substrate has potential applications on the on-line high throughput detection.

    10. Effects of laser excitation wavelength and optical mode on Raman spectra of human fresh colon, pancreas, and prostate tissues

      Ran Li, Dominique Verreault, Andrea Payne, Charles L. Hitchcock, Stephen P. Povoski, Edward W. Martin Jr. and Heather C. Allen

      Article first published online: 10 JUL 2014 | DOI: 10.1002/jrs.4540

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      Both laser excitation wavelength and optical mode affect Raman measurements in fresh human tissues. Background in Raman spectra could come from both autofluorescence and Mie scattering.

    11. 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.

    12. Polarized Raman spectroscopy of aligned insulin fibrils

      Valentin Sereda and Igor K. Lednev

      Article first published online: 9 JUL 2014 | DOI: 10.1002/jrs.4523

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      A simple ‘coffee ring’ drying method showed very efficient orientation of amyloid fibrils, which were subjected to polarized Raman spectroscopic characterization. The orientation of selected chemical groups relative to the fibril axis was probed including peptides' carbonyl groups, which were found to be oriented at 13±5°angle. The result is consistent with a previously reported cross-β core fibril structure and a qualitative description of an almost parallel orientation of the C=O groups relative to the main fibril axis.

    13. Dipole-like backscatter stimulated Raman scattering for in vivo imaging

      Robert D. Frankel

      Article first published online: 9 JUL 2014 | DOI: 10.1002/jrs.4539

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      A method called Stokes interference stimulated Raman scattering (SRS) imaging for SRS microscopy is proposed that enables dipole-like forward and backward SRS in a confocal microscopy, by reducing the emission focal spot size to subwavelength dimensions. This is accomplished with the addition of an annular beam, the donut, of a slightly different wavelength than the probe beam. The difference frequencies of the pump and probe and the pump and donut are both within the third-order resonant Raman frequency response. During periods of probe and donut destructive interference, dipole-like backscatter stimulated emission occurs, enabling high-resolution, high-speed imaging from deep within tissues.

    14. 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.

    15. In situ study of stones adorning a silver Torah shield using portable Raman spectrometers

      Kateřina Osterrothová, Laura Minaříková, Adam Culka, Jaroslav Kuntoš and Jan Jehlička

      Article first published online: 8 JUL 2014 | DOI: 10.1002/jrs.4541

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      A silver Torah shield fitted with a set of precious stones and glass imitations crafted in Poland in the first half of the 19th century was investigated using two of the currently distributed portable and relatively low-cost Raman spectrometers in situ at the Jewish Museum in Prague. Here, for the first time, three different types of materials were identified on a historic Jewish artifact: gemstones (garnets, aquamarine), common minerals forming the pearl inorganic matrix (aragonite), glass, as well as corals, where inorganic as well as carotenoid/polyenes organics have been detected.

    16. Study on new magnetization property and its micro-mechanism that occurred in anti-ferromagnetic NiO nanoflowers with nearly uniform size

      Lei Xia, Wanyu Li, Chun-Xiao Wang, Yan Zhang, Jian-Zhong Jiang and Shu-Lin Zhang

      Article first published online: 8 JUL 2014 | DOI: 10.1002/jrs.4547

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      Anti-ferromagnetic NiO nanoflowers were studied by temperature-dependent magnetization and the magnon Raman spectra. The results exhibit that the temperature dependencies of the double magnon (2M) Raman wavenumber and intensity are similar to those of magnetization. A magnetic granules model (MGM) consisted of a nano-crystalline core enclosed by a shell is proposed. Based on the MGM, the micro-mechanism of the observed magnetic behavior is interpreted. The MGM can be applicable to common magnetic nano-particles.

    17. Spectrally dispersed femtosecond CARS investigation of vibrational characteristics in ethanol

      Yang Zhao, Sheng Zhang, Boyang Zhou, Zhiwei Dong, Deying Chen, Zhonghua Zhang and Yuanqin Xia

      Article first published online: 4 JUL 2014 | DOI: 10.1002/jrs.4538

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      Spectrally dispersed femtosecond time-resolved coherent anti-Stokes Raman spectroscopy is applied to study the ultrafast vibrational dynamics in ethanol at room temperature. The Raman modes of C–H stretching vibrations from 2700 to 3500 cm −1 and the Raman modes of C–O and C–C stretching vibrations from 800 to 1100 cm −1 in ethanol were obtained. By simply changing the timing of the laser pulses, the vibrational dynamics between the excited Raman transitions in ethanol molecules can be tracked and detected.

    18. 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.

    19. 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).

    20. Raman spectroscopic characterization of CH4 density over a wide range of temperature and pressure

      Linbo Shang, I-Ming Chou, R. C. Burruss, Ruizhong Hu and Xianwu Bi

      Article first published online: 2 JUL 2014 | DOI: 10.1002/jrs.4529

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      Raman spectra of CH4 were collected over a wide range of temperature and pressure. The results show that the CH4 ν1 band shift is a function of both methane density and temperature; the band shifts to lower wavenumbers as the density increases and the temperature decreases.

    21. 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.

    22. 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.

    23. Phase equilibrium measurements of acoustically levitated squalane–CO2 mixtures by Raman spectroscopy

      Sebastian Baer, Cemal Esen and Andreas Ostendorf

      Article first published online: 27 JUN 2014 | DOI: 10.1002/jrs.4511

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      This work describes the phase equilibrium measurements of acoustically levitated binary mixtures with concentration measurements using Raman spectroscopy without sample extraction of the autoclave. The levitator design is implemented in a Single-Droplet Optical Cell for levitation processes under varying atmospheres. The advantages of acoustic levitation of small droplets under increased temperatures and pressure combined with spectroscopic applications like Raman spectroscopy enable novel experiments possibly relevant to the fields of chemical engineering.

  2. Research article

    1. The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities

      Lorenzo Maschio, Raffaella Demichelis, Roberto Orlando, Marco De La Pierre, Agnes Mahmoud and Roberto Dovesi

      Article first published online: 24 JUN 2014 | DOI: 10.1002/jrs.4527

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      We have computed the Raman spectrum of grossular – the calcium–aluminium end-member of garnets (Ca 3Al 2Si 3O12) – by using an ab initio quantum-mechanical approach. Wavenumbers of the 25 Raman active modes are in excellent agreement with the available experimental measurements. Computed Raman intensities are provided for the first time. This study can then be considered as an accurate reference data set for grossular other than a clear evidence that quantum-mechanical simulation is an actual tool to predict spectroscopic properties of minerals.

  3. Research articles

    1. 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.

    2. 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’.

    3. Evolution and defect analysis of vertical graphene nanosheets

      Subrata Ghosh, K. Ganesan, Shyamal R. Polaki, T. R. Ravindran, Nanda Gopala Krishna, M. Kamruddin and A. K. Tyagi

      Article first published online: 24 JUN 2014 | DOI: 10.1002/jrs.4530

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      Using Raman spectroscopy, we have identified the type of defects and the transformation of defects over the time-dependent growth of vertical graphene nanosheets. The growth mechanism, defect analysis, and their correlation with electrical and optical properties are investigated. This study would help to develop the vertical graphene nanosheets with desired characteristics that are needed for optoelectronic and energy applications.

    4. 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.

    5. Synthesis and Raman study on needlelike silicates in ancient Chinese Pb-Ba glass in Qin and Han dynasties

      Mo Li, Jie Wang, Julin Wang, Qinglin Ma and Zhiguo Zhang

      Article first published online: 20 JUN 2014 | DOI: 10.1002/jrs.4534

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      Two ancient green Chinese Pb-Ba glass (Qin and Han dynasties, 221 bc–8 ad) were studied with Raman microspectroscopy, scanning electron microscopy, and energy dispersive X-ray spectrometry. Some needlelike silicates was found in the samples and inferred as PbSiO3, BaSiO3, and Al2O3. Attempts are made to provide references Raman spectra of Pb-Ba glass samples by synthesizing the related compounds in the laboratory and give some ideas about the crystallization process of the world's first baric glass system.

    6. 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.

    7. Raman spectrum of NaAlSi2O6 jadeite. A quantum mechanical simulation

      Mauro Prencipe, Lorenzo Maschio, Bernard Kirtman, Simone Salustro, Alessandro Erba and Roberto Dovesi

      Article first published online: 16 JUN 2014 | DOI: 10.1002/jrs.4519

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      The Raman spectrum of NaAlSi2O6 jadeite is simulated and compared with two recent experimental data sets. Using an all-electron Gaussian-type basis set, together with the hybrid B3LYP density functional, the full set of 30 active modes and their (polycrystalline and polarized) intensities is obtained. The simulated intensities explain why 10–13 missing peaks in experimental spectra were not seen. This ultimately leads to excellent agreement between experiment and theory.

    8. 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.

    9. Disulfide linkage Raman markers: a reconsideration attempt

      Belén Hernández, Fernando Pflüger, Eduardo López-Tobar, Sergei G. Kruglik, José V. Garcia-Ramos, Santiago Sanchez-Cortes and Mahmoud Ghomi

      Article first published online: 11 JUN 2014 | DOI: 10.1002/jrs.4521

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      It has been shown that the old notations (ggg, ggt, and tgt) are insufficient for analyzing the conformational and vibrational features of disulfide linkages in peptides and proteins. This failure can be improved by considering the new topological notations based on the signs of the five torsion angles in going from one α-carbon to the other in the cystine unit.

    10. An acoustically enhanced gold film Raman sensor on a lithium niobate substrate

      Esa A. Jaatinen, Matthew P. Adams, Alison Chou, Nick McKay Parry and Peter M. Fredericks

      Article first published online: 11 JUN 2014 | DOI: 10.1002/jrs.4522

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      We demonstrate the use of surface acoustic waves to enhance the Raman signal obtained from thiophenol adsorbed on thin gold films deposited on lithium niobate substrates. It is shown that the Raman signal can be reversibly increased by simply changing the acoustic wave amplitude without change in analyte concentration on the sensor surface.

    11. Simple and sensitive detection of cyanide using pinhole shell-isolated nanoparticle-enhanced Raman spectroscopy

      Jing Gao, Lei Guo, Jianfeng Wu, Jianlin Feng, Shunmu Wang, Fulong Lai, Jianwei Xie and Zhongqun Tian

      Article first published online: 9 JUN 2014 | DOI: 10.1002/jrs.4497

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      We developed a simple and sensitive method for cyanide sensing based on pinhole shell-isolated nanoparticle-enhanced Raman spectroscopy technique. With remarkable stability provided by the pinhole Au@SiO2 nanoparticles, we achieved a direct on-site detection of cyanide in simple environmental water samples at a trace level using a portable Raman spectrometer. To address the issue towards cyanide measurement in complex matrices such as polluted water, we then coupled a self-designed online hydrogen generation device and obtained satisfying results.

    12. 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.

    13. 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.

    14. Linear quantification calibration of crystallinity at subpercent and its evaluation based on spectral and spatial information inherited in Raman chemical images

      Jianping Wu

      Article first published online: 9 JUN 2014 | DOI: 10.1002/jrs.4516

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      In this paper, the author reported two methods to extract spectral or spatial information inherited in the Raman chemical images for linear quantification calibration of crystallinity. The two approaches reported quantification results according to the spectral mean score of overall pixels or the spatial percentage of the pixels with a score greater than and equal to the threshold over the total pixels of the chemical images, respectively. From this study, it can be concluded that, first, sampling method for data collection in mapping has to be optimized to achieve linear quantification calibration through simple univariate analysis approaches.

    15. 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.

    16. 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.

    17. Multiscale electromagnetic SERS enhancement on self-assembled micropatterned gold nanoparticle films

      Cosmin Leordean, Monica Potara, Sanda Boca-Farcau, Adriana Vulpoi, Simion Astilean and Cosmin Farcau

      Article first published online: 1 JUN 2014 | DOI: 10.1002/jrs.4510

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      Surface-enhanced Raman scattering analyses on periodically micropatterned films made of colloidal gold nanoparticles reveal a multiplicative electromagnetic enhancement caused by the combination of optical interactions on two scales: surface plasmon-enhanced near-fields due to nanoscale features and far-field photonic coupling by periodic microscale features. The periodically patterned films are made of colloidal gold nanoparticles directly from colloidal suspension, without using lithography or patterned substrates, which makes the fabrication approach of interest for the development of nanoparticle-based sensors/devices.

    18. 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.

    19. Probing high-energy ion-implanted silicon by micro-Raman spectroscopy

      I. Kopsalis, V. Paneta, M. Kokkoris, E. Liarokapis, M. Erich, S. Petrović, S. Fazinić and T. Tadić

      Article first published online: 30 MAY 2014 | DOI: 10.1002/jrs.4507

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      The lattice damage of ion-implanted (random or channeling) silicon wafers was assessed by probing the side surface of cleaved wafers at submicron step. The micro-Raman results are in excellent agreement with those of other characterization techniques. By modifying the phonon confinement model, the phonon characteristics could be reproduced that indicate that at a critical doping level, the induced defects and lattice distortions relax by breaking the silicon single crystal into nanocrystallites, creating the observed zones of strongly distorted lattice.

    20. Chemical aerosol detection and identification using Raman scattering

      R. L. Aggarwal, S. Di Cecca, L. W. Farrar and T. H. Jeys

      Article first published online: 27 MAY 2014 | DOI: 10.1002/jrs.4509

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      An aerosol of isovanillin of mass concentration 1.8 ng/cm3 has been detected with a signal-to-noise ratio of ~19 in 30 s for the 1116-cm−1 mode with a Raman cross section of 3.3 × 10−28 cm2 using Raman scattering with a 532-nm continuous wave laser.

    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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