Journal of Raman Spectroscopy

Cover image for Vol. 43 Issue 9

September 2012

Volume 43, Issue 9

Pages 1177–1345

  1. Research articles

    1. Top of page
    2. Research articles
    3. Short communication
    1. Highly reproducible tip-enhanced Raman scattering using an oxidized and metallized silicon cantilever tip as a tool for everyone (pages 1177–1182)

      Norihiko Hayazawa, Taka-aki Yano and Satoshi Kawata

      Version of Record online: 7 AUG 2012 | DOI: 10.1002/jrs.4032

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      We have successfully improved the reproducibility of tip-enhancement effect on metallized silicon cantilever tips for characterization of carbon nanotubes. Plasmon resonance tuning relative to an excitation wavelength is crucial for efficient tip-enhancement, which is accomplished by thermal oxidization and subsequent metallization of commercial silicon tips. Because of the change of the refractive index, the plasmon resonance of the silver coated tip is blue-shifted showing an enormous enhancement at 532 nm excitation. Highly reproducible tips exhibit an enhancement factor of >100 with a 100% yield. This approach provides an important step of ‘tip-enhanced Raman spectroscopy for everyone’.

    2. Complex concentration dependence of SERS and UV–Vis absorption of glycine/Ag-substrates because of glycine-mediated Ag-nanostructure modifications (pages 1183–1190)

      Animesh K. Ojha, Patrice Donfack and Arnulf Materny

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.3162

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      Gly strongly interacts with AgNPs and consistently modifies their structures as a function of concentration, leading to the observation of complex concentration dependent UV-VIS, SERS and TEM behaviors.

    3. Charge-transfer contributions in surface-enhanced Raman scattering from Ag, Ag2S and Ag2Se substrates (pages 1191–1195)

      Xiaoqi Fu, Tingshun Jiang, Qian Zhao and Hengbo Yin

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.4033

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      The degree of charge-transfer in Ag–4-mercaptopyridine (4-Mpy) and Ag2S–4-Mpy systems is investigated by use of surface-enhanced Raman spectroscopy. We find ~25% of charge-transfer contribution for Ag–4-Mpy and 81 ~ 93% for that of Ag2S–4-Mpy, estimated by using a pCT equation. Energy level diagram is applied to discuss the likely charge-transfer transition between Ag, Ag2S, Ag2Se and 4-Mpy.

    4. Adsorption of neurotensin-family peptides on SERS-active Ag substrates (pages 1196–1203)

      Edyta Podstawka-Proniewicz, Andrzej Kudelski, Younkyoo Kim and Leonard M. Proniewicz

      Version of Record online: 28 AUG 2012 | DOI: 10.1002/jrs.4034

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      Kinetensin and its amino acids 1–8 fragment, neuromedin N, and xenopsin-related peptides belong to the neurotensin family of peptides and are known to stimulate the growth of human tumors. In this work, we report Fourier transform-Raman and surface-enhanced Raman scattering (SERS) studies of these peptides and discuss their structures, orientation, and mode of adsorption onto a highly specific, electrochemically roughened SERS-active Ag electrode that is characterized by the formation of a 50–150 nm Ag island on its surface.

    5. Magnetic separation and SERS observation of analyte molecules on bifunctional silver/iron oxide composite nanostructures (pages 1204–1207)

      Marina Gühlke, Sören Selve and Janina Kneipp

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.4039

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      Bifunctional, nanometer-sized, SERS-active silver–iron oxide composite structures enable separation and monitoring of analyte molecules.

    6. A novel approach to determine leucomalachite green and malachite green in fish fillets with surface-enhanced Raman spectroscopy (SERS) and multivariate analyses (pages 1208–1213)

      Yuanyuan Zhang, Keqiang Lai, Jinglie Zhou, Xichang Wang, Barbara A. Rasco and Yiqun Huang

      Version of Record online: 4 JUL 2012 | DOI: 10.1002/jrs.4050

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      The use of surface-enhanced Raman spectroscopy technology combined with multivariate analysis could detect malachite green (MG) in contaminated fish samples at single-digit part-per-billion levels ranging from 1 to 5 ng g−1, which depended upon the complexity of sample preparation methods. The simplest extraction method developed could reduce sample throughput time and provide for faster detection of MG and its derivative in fish fillets.

    7. Computing Raman and infrared wavenumbers of nanostructures: application to silicon nanowires (pages 1214–1220)

      Felix Zörgiebel, Jens Kunstmann, Daijiro Nozaki and Gianaurelio Cuniberti

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.4045

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      We introduce a method to compute Raman and infrared wavenumbers of nanostructures and present results for silicon nanowires. Our method bridges the gap between computationally intensive exact calculations of optical spectra and faster but less exact empiric models. The method is designed to work with existing simulation tools to make it applicable for a wide range of researchers.

    8. Polarization behaviors of twisted carbon nanotube fibers (pages 1221–1226)

      Jinyuan Zhou, Gengzhi Sun, Zhaoyao Zhan, Jianing An, Yongzhe Zhang, Yani Zhang and Lianxi Zheng

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.4044

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      Polarization behaviors of carbon nanotube (CNT) fibers with different twisting were studied. Twisting is found to significantly affect the polarization of a CNT fiber, and polarized Raman could be used to evaluate the alignment distribution of CNTs in a fiber.

    9. Self-assembly and structure formation in liquid crystalline phthalocyanine thin films studied by Raman spectroscopy and AFM (pages 1227–1236)

      Florian Latteyer, Sabine Savu, Heiko Peisert and Thomas Chassé

      Version of Record online: 25 JUL 2012 | DOI: 10.1002/jrs.4053

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      A liquid crystalline phthalocyanine forms different microstructures if thin films are prepared by doctor blade casting at different coating temperatures. The structures appear rod-like and island-like if coating is performed at 25 or 80 °C, respectively. Their molecular orientation and laterally different relative crystallinities are probed by Raman spectroscopy and supported by atomic force microscopy and Raman imaging.

    10. Raman spectroscopy reveals differences in collagen secondary structure which relate to the levels of mineralisation in bones that have evolved for different functions (pages 1237–1243)

      Kevin Buckley, Pavel Matousek, Anthony W. Parker and Allen E. Goodship

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.4038

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      Functionally adapted bones with varying levels of mineralisation are probed through Raman spectroscopy, and the hypothesis that bones with different levels of mineralisation have qualitatively different collagen is explored. The study demonstrates that Raman spectroscopy can provide a means to investigate the mechanisms that control the mineral to collagen ratio of bone.

    11. Cysteine-linked aromatic nitriles as UV resonance Raman probes of protein structure (pages 1244–1249)

      Colin L. Weeks, Hyunil Jo, Brandon Kier, William F. DeGrado and Thomas G. Spiro

      Version of Record online: 8 AUG 2012 | DOI: 10.1002/jrs.3167

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      A methodology for convenient attachment of aromatic nitrile probes to peptide or protein cysteine residues is presented. The spectroscopic features of these probes and their dependence on local environment are characterized by UV resonance Raman.

    12. An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia, Spain) (pages 1250–1259)

      María Teresa Doménech-Carbó, Howell G.M. Edwards, Antonio Doménech-Carbó, Julio M. del Hoyo-Meléndez and Juana de la Cruz-Cañizares

      Version of Record online: 7 JUN 2012 | DOI: 10.1002/jrs.3168

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      This paper reports an analytical study focused on the characterisation and discrimination of the palette and painting procedures used by Palomino and Guillo in the 17th century frescoes of the Sant Joan del Mercat church (Valencia, Spain). This analytical study offers a unique case study that enables an accurate comparison between the materials and painting techniques theoretically established by the artist in his treatise and the real work executed on the vaulted ceiling. A multi-technique approach, that includes Raman spectroscopy, has been employed.

    13. Evolution of past enamel technology and metal conservation issues: the case of two Byzantine style bindings (pages 1260–1264)

      A. Sodo, M. A. Ricci, S. Mangialardo, P. Postorino, M. Micheli and P. Crisostomi

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.4035

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      Raman investigation of the cloisonne’ and basse-taille enamels, from two Byzantine style bindings, is presented. Interestingly the white and yellow color of the 13th century enamels have been obtained by an ancient technique of the glass technology, based on the use of calcium antimonate and Naples yellow, and already obsolete at that time. The transparency of the 14th century enamels has allowed the comparison of metal degradation below the enamels and in regions exposed to the atmosphere.

    14. Raman and FTIR spectroscopy applied to the conservation report of paleontological collections: identification of Raman and FTIR signatures of several iron sulfate species such as ferrinatrite and sideronatrite (pages 1265–1274)

      Véronique Rouchon, Hugues Badet, Oulfa Belhadj, Olivier Bonnerot, Bertrand Lavédrine, Jean-Guy Michard and Serge Miska

      Version of Record online: 28 JUN 2012 | DOI: 10.1002/jrs.4041

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      This work presents an analytical methodology that combines Raman, infrared, and X-ray diffraction for the analysis of crystal efflorescence formed on the surface of damaged fossils. It enabled the Raman and FTIR identification of several iron sulfate species.

    15. Gemstones and noble metals adorning the sceptre of the Faculty of Science of Charles University in Prague: integrated analysis by Raman and XRF handheld instruments (pages 1275–1280)

      Z. Petrová, J. Jehlička, T. Čapoun, R. Hanus, T. Trojek and V. Goliáš

      Version of Record online: 4 JUL 2012 | DOI: 10.1002/jrs.4043

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      Gemstones and noble metals of the university sceptre have been analysed by Raman and X-ray fluorescence handheld instruments that were used to the authors' best knowledge for the first time for this purpose. Identification of the gemstones and the metals as well as suggestion concerning previous restoration treatment were made possible.

    16. Synthetic organic pigments in contemporary Balinese painting: a Raman microscopy study (pages 1281–1292)

      Maria do Rosário Marcelino and Vânia S. F. Muralha

      Version of Record online: 4 JUL 2012 | DOI: 10.1002/jrs.4047

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      The colour palette of contemporary Indonesian paintings (from the Island of Bali) was studied by Raman microscopy. In addition, samples of pigments sent by a renowned Balinese painter were also analysed. The most interesting finding of our study was the increasing substitution of traditional inorganic pigments by modern synthetic organic pigments. Raman microscopy, alongside Fourier transform infrared spectroscopy, μ-XRF and high-performance liquid chromatography, proved invaluable in identifying both the synthetic organic pigments and the traditional pigments.

    17. Absolute Raman intensity measurements and determination of the vibrational second hyperpolarizability of adamantyl endcapped polyynes (pages 1293–1298)

      A. Lucotti, M. Tommasini, D. Fazzi, M. Del Zoppo, W. A. Chalifoux, R. R. Tykwinski and G. Zerbi

      Version of Record online: 1 JUN 2012 | DOI: 10.1002/jrs.3166

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      Quantitative Raman spectroscopic analysis of a series of polyynes allows determination of the vibrational contribution to the molecular second hyperpolarizability (γvib) and shows that polyynes display significant nonlinear optical behavior.

    18. A Bayesian Whittaker–Henderson smoother for general-purpose and sample-based spectral baseline estimation and peak extraction (pages 1299–1305)

      Sok Kiang Lau, Peter Winlove, Julian Moger, Olivia L. Champion, Richard W. Titball, Zi Hua Yang and Zheng Rong Yang

      Version of Record online: 7 JUN 2012 | DOI: 10.1002/jrs.3165

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      The Bayesian Whittaker–Henderson smoother accurately removes the baseline of a Raman spectrum and generates a peak list with a minimal number of false peaks. The smoother uses a global aligner to ensure consistent extraction of peaks from multiple Raman spectra. The figure shows one application of baseline line removal of five replicates of macrophage Raman spectra.

    19. Low-resolution Raman spectroscopy over a wide spectral range with a single-diffraction order arrayed-waveguide grating (pages 1306–1311)

      A. C. Baclig, N. Ismail, R. M. de Ridder, M. Pollnau, P. J. Caspers and G. J. Puppels

      Version of Record online: 21 MAY 2012 | DOI: 10.1002/jrs.4048

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      Raman signal detection of cyclohexane using a low resolution arrayed-waveguide grating (AWG) in a single diffraction order without order overlap is demonstrated. The AWG measurement based on the integrated intensity output of the device corresponds well to the expected channel output of the AWG. Quantitative Raman information based on band positions and band intensity ratios from the AWG channel is also preserved compared with spectral integration of bands.

    20. Probing reoxidation sites by in situ Raman spectroscopy: differences between reduced CeO2 and Pt/CeO2 (pages 1312–1319)

      Marlène Daniel and Stéphane Loridant

      Version of Record online: 10 JUN 2012 | DOI: 10.1002/jrs.4030

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      The peroxo and superoxo species formed on 0.7% Pt/CeO2 compound and the CeO2 were compared after different reductions. Superoxo species were more stabilized on reduced 0.7%Pt/CeO2 after short reduction at 773 K than on reduced CeO2. Additionally, less stable peroxo species were formed on Pt/CeO2 compared to CeO2 after long reduction at 773 K in spite of similar amounts. These two features revealed that new sites were created during the preparation and reduction of Pt/CeO2 compared to its bare support.

    21. Raman tensor analysis of (K0.5Na0.5)NbO3–LiSbO3 lead-free ceramics and its application to study grain/domain orientation (pages 1320–1328)

      Wenliang Zhu, Jiliang Zhu, Mingsong Wang, Bo Zhu, Xiaohong Zhu and Giuseppe Pezzotti

      Version of Record online: 11 JUL 2012 | DOI: 10.1002/jrs.4031

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      A quantitative polarized Raman analysis of ferroelectric grain/domain orientation in LiSbO3 (LS-modified) (K0.5Na0.5)NbO3 (KNN) ceramics is presented, based on the analysis of the complex orientation dependence in space of their Raman-active modes. We demonstrate that polarized Raman spectroscopy is a valuable and efficient tool for nondestructive three-dimensional assessments of grain/domain orientation in ferroelectric materials with complex polymorphic structures.

    22. Conformational and structural studies of n-propylamine from temperature dependent Raman and far infrared spectra of xenon solutions and ab initio calculations (pages 1329–1336)

      James R. Durig, Ikhlas D. Darkhalil, Joshua J. Klaassen, Wouter A. Herrebout, Johan J. J. Dom and Benjamin J. van der Veken

      Version of Record online: 23 JUN 2012 | DOI: 10.1002/jrs.3163

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      Five possible conformers have been identified in the vibrational spectra of n-propylamine. The enthalpy difference between these five conformers has been determined using variable temperature spectra of the sample dissolved in xenon solution.

    23. Conformational energies of silacyclohexanes C5H10SiHMe, C5H10SiH(CF3) and C5H10SiCl(SiCl3) from variable temperature Raman spectra (pages 1337–1342)

      Thomas Kern, Margit Hölbling, Ana Dzambaski, Michaela Flock, Karl Hassler, Sunna Ó. Wallevik, Ingvar Arnason and Ragnar Bjornsson

      Version of Record online: 25 JUL 2012 | DOI: 10.1002/jrs.3164

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      Supported by quantum chemical calculations, the axial/equatorial conformer energy differences for the title compounds have been determined using variable temperature vibrational Raman spectroscopy.

  2. Short communication

    1. Top of page
    2. Research articles
    3. Short communication
    1. Effective methods for preparation and characterization of HNO-adducts of heme proteins (pages 1343–1345)

      Kazimierz Czarnecki and James R. Kincaid

      Version of Record online: 15 JUL 2012 | DOI: 10.1002/jrs.4046

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      The combination of γ-ray cryoradiolysis with resonance Raman spectroscopy provides an efficient approach for the preparation and structural characterization of protonated nitroxyl adducts of heme proteins.

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