Journal of Raman Spectroscopy

Cover image for Vol. 44 Issue 3

March 2013

Volume 44, Issue 3

Pages 339–507

  1. Editorial

    1. Top of page
    2. Editorial
    3. Research articles
    4. Erratum
    1. You have free access to this content
      Congratulations Larry! (page 339)

      P. Trevorrow and L. Ziegler

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/jrs.4260

  2. Research articles

    1. Top of page
    2. Editorial
    3. Research articles
    4. Erratum
    1. Possibilities for human skin characterization based on strongly reduced Raman spectroscopic information (pages 340–345)

      A. C. Baclig, T. C. Bakker Schut, G. M. O'Regan, A. D. Irvine, W. H. I. McLean, G. J. Puppels and P. J. Caspers

      Version of Record online: 17 FEB 2013 | DOI: 10.1002/jrs.4198

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      It is demonstrated that relevant clinical information about the human skin can be extracted from Raman spectra with substantially reduced spectral information. By using the integrated intensities of only four carefully selected spectral regions, discrimination of skin with low natural moisturizing factor (NMF) content from skin with normal NMF content with high accuracy is demonstrated. This simplified detection of Raman signal can be exploited to decrease the complexity and cost of Raman instrumentation for the identification of people with increased risk of developing atopic dermatitis.

    2. Structural changes induced by interactions between thyroid hormones and phospholipid membranes: a Raman Spectroscopy study (pages 346–354)

      Ariel A. Petruk and Rosa María S. Álvarez

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/jrs.4205

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      Interactions of T2, T3, and T4 with a model membrane of dilauroylphosphatidylcholine in the liquid-crystalline phase were analyzed by Raman spectroscopy. Insights into the nature of the hormone effects on the membrane properties, as well the structural adaptations of the hormones in response to the lipid environment were derived from the spectral changes. The series of progressive iodine substituents on the ring-β allowed to correlate the hormone effects according to the number of the iodine atoms.

    3. Adsorption mode of neurotensin family peptides onto a colloidal silver surface: SERS studies (pages 355–361)

      Edyta Proniewicz, Yukihiro Ozaki, Younkyoo Kim and Leonard M. Proniewicz

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/jrs.4207

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      Kinetensin (KN) and its amino acids 1–8 fragment ([des-Leu9]KN), neuromedin N (NMN), and xenopsin (XP) and its two analogs (human XP-1/xenin-8 and XP-2) belong to the neurotensin family of peptides and are known to stimulate the growth of human tumors. In this work, we report SERS studies of these peptides and discuss their structures, orientation, and mode of adsorption onto a colloidal assembly of apparently randomly adhering Ag spheres with diameters of approximately 20 – 25 nm. We show that small alternations in both the amino acid composition and tertiary structure, which induce striking biological in vitro, were responsible for the observed spectroscopic changes.

    4. Near-infrared surface-enhanced Raman spectroscopy (NIR-SERS) studies on oxyheamoglobin (OxyHb) of liver cancer based on PVA-Ag nanofilm (pages 362–369)

      Renming Liu, Yang Xiong, Weiyue Tang, Yan Guo, Xinhui Yan and Minzhen Si

      Version of Record online: 16 JAN 2013 | DOI: 10.1002/jrs.4216

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      PCA Scores of 1, 2 and 7 for the near-infrared surface-enhanced Raman spectroscopy spectra acquired from the OxyHb samples of the healthy volunteers and the liver cancer patients can separate the spectral features of the two groups into two distinct clusters with the specificity of 85.7% and the sensitivity of 95%.

    5. Raman spectroscopic investigation of frozen and deparaffinized tissue sections of pediatric tumors: neuroblastoma and ganglioneuroma (pages 370–376)

      Suneetha Devpura, Jagdish S. Thakur, Janet M. Poulik, Rajah Rabah, Vaman M. Naik and Ratna Naik

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/jrs.4223

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      We have investigated neuroblastoma and ganglioneuroma using Raman spectroscopy and compared their spectral characteristics with those of normal adrenal gland. The frozen sections of normal adrenal gland tissues show higher levels of carotenoids, lipids, and cholesterol compared with the neuroblastoma and ganglioneuroma tissues. Preservation of tissues using formalin and paraffin leads to removal of carotenoids, lipids, and cholesterol in adrenal tissues. The study shows that Raman spectroscopy in conjunction with chemometric methods can be used to distinguish neuroblastoma and ganglioneuroma.

    6. The combination of surface enhanced Raman spectroscopy and an ionic liquid as a model system to study the adhesion interface between sulfur and brass (pages 377–381)

      Kitty Baert, Tom Breugelmans, Guy Buytaert, Johan Van Brabant and Annick Hubin

      Version of Record online: 16 JAN 2013 | DOI: 10.1002/jrs.4199

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      This work highlights the potential of an ionic liquid combined with Raman/surface enhanced Raman spectroscopy to study in situ the sulfuring process of brass substrates, an important mechanism during the vulcanization process of reinforced rubber.

      The IL, used as a model system for rubber, together with spectro-electrochemical experiments offers a powerful diagnostic tool to characterize the adhesion interface between rubber (sulfur) and brass-coated steel.

    7. SERS from light localization positions (pages 382–392)

      V. V. Maksimenko, L. Yu. Kupriyanov, V. A. Zagaynov and I. E. Agranovski

      Version of Record online: 4 FEB 2013 | DOI: 10.1002/jrs.4208

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      We propose a model allowing analysis of reasons for SERS by molecules adsorbed onto surfaces of metal particles. It considers multiple inelastic scatterings of photons, which move along loop inside a system of closely packed metallic particles. The reason for the photon motion along the closed loop is related to constructive interference of amplitudes corresponding to two alternative ways of the loop passing; clockwise and counter clockwise. Peculiarities of charge density fluctuations behaviour allow explaining some features of flicker noise.

    8. Silver macro-texture substrates fabricated by plasma selective etching for surface-enhanced Raman scattering (pages 393–400)

      Fanxin Liu, Xuhong Ye, Chaojun Tang and Hongtao Ma

      Version of Record online: 8 NOV 2012 | DOI: 10.1002/jrs.4209

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      We demonstrated a novel method of plasma selective etching combining with deposition of a silver film to generate a SERS substrate. This substrate shows a spatially uniform enhancement factor of approximately 106. Finally, we combine this novel Ag marco-texture substrate with a 10 Å ta -C film and get a higher enhancement than the uncoated Ag marco-texture substrate.

    9. Quantitative surface enhanced Raman scattering measurements at the early stage of active agent release processes (pages 401–405)

      J. A. Anastasopoulos, A. Soto Beobide and G. A. Voyiatzis

      Version of Record online: 27 DEC 2012 | DOI: 10.1002/jrs.4222

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      The surface enhanced Raman scattering spectroscopy (SERS) is introduced as a new method to probe the initial release of active agents from controlled delivery systems. Surface enhanced resonance Raman scattering measurements of mitoxantrone allowed the quantitative delineation of the initial drug release profile, and the technique has proved as a highly sensitive method to quantitatively monitor the initial release of the medicine even at the very early stage of the delivery process.

    10. Steric hindrance in cationic and neutral rhodamine 6 G molecules adsorbed on Au nanoparticles (pages 406–411)

      Toru Yajima, Yingying Yu and Masayuki Futamata

      Version of Record online: 25 JAN 2013 | DOI: 10.1002/jrs.4204

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      Adsorption of R6G molecules on Au nanoparticles was elucidated by surface enhanced Raman scattering. The steric hindrance at hydroethyl amino groups in R6G was evidenced by the observation that R6G+ adsorb on as-prepared gold nanoparticles (AuNPs) only with electrostatic forces in contrast to the electrostatic and chemical adsorption of R123+. It also yielded fewer saturation coverage compared to R123+. Raman bands from phenyl and ethyl substituent are specifically enhanced under an inclined orientation of R6G0 on AuNPs chemisorbed via amino groups.

    11. Temperature-dependent Raman spectroscopy of BaTiO3 nanorods synthesized by using a template-assisted sol–gel procedure (pages 412–420)

      Andreja Gajović, Jelena Vukajlović Pleština, Kristina Žagar, Milivoj Plodinec, Sašo Šturm and Miran Čeh

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/jrs.4206

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      The aim of the work is the study of the phase transition from the tetragonal ferroelectric to the cubic paraelectric phase in polycrystalline BaTiO3 nanorods that is crucial for possible application. Nanorods consist of tetragonal nanocrystals with intergrown nanolamellas of the hexagonal phase. Raman spectroscopy showed that nanorods underwent a diffuse phase transition from tetragonal to cubic phase with respect to the temperature, whereas the final phase-transition temperature was shifted to higher values compared to that typically expected for BTO.

    12. The influence of impurity formation on electron inelastic scattering of suspended graphene (pages 421–424)

      Chang-Jiang Chen

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/jrs.4212

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      The intrinsic properties and the behavior of electron scattering of graphene have attracted enormous attention. We report here the influence of impurity formation on suspended graphene by using the transmission electron microscopy and scanning Raman spectroscopy to observe the graphene for the same area. The dramatic changes in the inelastic scattering rate of electrons and impurity formation of graphene are discussed.

    13. Theoretical investigation on surface-enhanced Raman evidence for conformation transition of dimercaptoazobenzene adsorbed on gold nanoclusters (pages 425–432)

      Xiu-Feng Lang, Peng-Gang Yin, En-Zhong Tan, Ting-Ting You and Lin Guo

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/jrs.4217

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      Based on the density functional calculations, Raman spectral features of the free or adsorbed dimercaptoazobenzene (DMAB) are demonstrated to be quite different for its trans and cis configurations. The magnitude of chemical enhancement of the trans/cis DMAB–Au19 complex can be well described by the energy difference between the HOMO of the molecule and the LUMO of the metal nanocluster.

    14. Temperature measurements in condensed phases using non-resonant femtosecond stimulated Raman scattering (pages 433–439)

      N. C. Dang, C. A. Bolme, D. S. Moore and S. D. McGrane

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/jrs.4215

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      The comparison of the theoretical sensitivity to T of the femtosecond stimulated Raman scattering (FSRS) and spontaneous Raman (Spont. RS) method shows that FSRS has significant advantages over Spont. RS; the T-sensitivity increases with the Raman gain constants (GC) and becomes more sensitive than Spont. RS for FSRS gain contant > 0.3.

    15. A-band structural dynamics of thioanisole by resonance Raman spectroscopy (pages 440–446)

      Ming-Xia Liu, Bin-Bin Xie, Ming-Juan Li, Yan-Ying Zhao, Ke-Mei Pei, Hui-Gang Wang and Xuming Zheng

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/jrs.4213

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      The A-band structural dynamics of thioanisole was studied by using resonance Raman spectroscopy and density functional theory calculations. The C1S7C8 anti-symmetric stretch mode ν23 and the C1S7C8 symmetric stretch mode ν24 are two characteristic modes that mark the key S(ππ*)/S(πσ*) conical intersectional seam towards the S7–C8 bond dissociation reaction of thioanisole.

    16. Determination of one-dimensional spherically aberrated point spread function in depth profiling by confocal Raman microscopy (pages 447–452)

      María de la Paz Miguel and J. Pablo Tomba

      Version of Record online: 16 JAN 2013 | DOI: 10.1002/jrs.4195

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      We present a simple experiment that allows full characterization of the point spread function (PSF) in refraction-aberrated depth profiling experiments with confocal Raman microscopy. We used a wedge-shaped solid polymer film to induce refraction aberrations on the response of an infinitesimally thin Raman scatterer (a silicon wafer). Via depth slicing of the specimen, we were able to directly characterize the shape of refraction-aberrated PSF as a function of the nominal focusing depth.

    17. Evaluation method for Raman depolarization measurements including geometrical effects and polarization aberrations (pages 453–462)

      M. Schlösser, T. M. James, S. Fischer, R. J. Lewis, B. Bornschein and H. H. Telle

      Version of Record online: 24 JAN 2013 | DOI: 10.1002/jrs.4201

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      A numerical model was developed to evaluate, for realistic experimental configurations, effective Raman line strength functions, Φ, and depolarization ratios, ρ. It is based on interlinked integrations over the angles in the light collection path and a finite Raman source volume along the excitation laser beam. The model can take into account polarization aberrations introduced by sample cell windows and can deal with more than one optical component in the light collection path and the associated di-attenuation and retardance effects.

    18. Trace level detection and identification of nitro-based explosives by surface-enhanced Raman spectroscopy (pages 463–468)

      S. Botti, S. Almaviva, L. Cantarini, A. Palucci, A. Puiu and A. Rufoloni

      Version of Record online: 25 JAN 2013 | DOI: 10.1002/jrs.4203

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      In this paper, SERS was applied to trace level detection of PETN, EGDN, RDX and TNT. PCA of the data showed that explosives can be clearly classified, on the basis of the SERS spectra, at quantities as low as tens of pg. Our measurements further demonstrate the potential for using SERS as fast, in situ analytical tool for safety devices, with a sensitivity which competes and, in some cases, overcomes other techniques.

    19. On the potential of Raman-spectroscopy-based carbonate mass spectrometry (pages 469–474)

      Nicholas P. McKay, David L. Dettman, Robert T. Downs and Jonathan T. Overpeck

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/jrs.4218

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      We investigated the potential of Raman spectroscopy for oxygen mass spectrometry in calcites by measuring the Raman spectra of a suite of synthesized calcite crystals. We found a 1:1 correspondence between the ratio of ν1 peak heights in the Raman spectra and the isotopic ratios measured by standard calcite mass spectrometry.

    20. Switching of hydrogen bonds of water in ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (pages 475–480)

      Yukihiro Yoshimura, Takahiro Takekiyo, Chikara Okamoto, Naohiro Hatano and Hiroshi Abe

      Version of Record online: 16 JAN 2013 | DOI: 10.1002/jrs.4197

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      We have investigated temperature-induced Raman spectral changes of deuterated water in an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), between room temperature and 77 K. The comparison of the OH and OD stretching vibrational spectra at 77 K shows that the strength of the hydrogen bonds in [bmim][BF4]–water mixtures strongly depends on the type of water, i.e. H2O and D2O. In the [bmim][BF4]–D2O system, remarkably strong hydrogen bonds form at low temperatures, but they switch to nearly free hydrogen bonds on heating.

    21. Ionic liquids based on the bis(trifluoromethylsulfonyl)imide anion for high-pressure Raman spectroscopy measurements (pages 481–484)

      Luiz F. O. Faria, Marcelo M. Nobrega, Marcia L. A. Temperini and Mauro C. C. Ribeiro

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/jrs.4220

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      Ionic liquids based on [(CF3SO2)2 N]- anion are proposed for pressure transmitting and calibrant material for using in diamond anvil cells.

    22. Physical insight of superconductivity of Nb2AlC: in situ Raman spectrometry investigation (pages 485–488)

      Huimin Xiang, Xiaohui Wang, Jingyang Wang and Yanchun Zhou

      Version of Record online: 15 JAN 2013 | DOI: 10.1002/jrs.4196

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      This work explores the electron–phonon coupling strengths in nano-laminated Nb2AlC from in situ measurements of Raman spectra. The origin of superconductivity of Nb2AlC is explained by the coupling of Nb 4d electrons with E2g (ω2) and A1g (ω4) phonon modes.

    23. Phase transformations in CaCO3/iron oxide composite induced by thermal treatment and laser irradiation (pages 489–495)

      T. Beuvier, J.-F. Bardeau, B. Calvignac, G. Corbel, F. Hindré, J.-M. Grenèche, F. Boury and A. Gibaud

      Version of Record online: 26 OCT 2012 | DOI: 10.1002/jrs.4200

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      Phase transitions of the calcium carbonate (CaCO3)/iron oxide composites synthesized by mixing iron oxide nanoparticles (maghemite and magnetite) of about 6 nm in size and CaCO3 microparticles (Φ = 2 mm−8 mm, vaterite phase) were studied as a function of the temperature of thermal treatment and the output laser power.

    24. Micro-Raman depth profiling of silicon amorphization induced by high-energy ion channeling implantation (pages 496–500)

      M. Erich, S. Petrović, M. Kokkoris, E. Liarokapis, A. Antonakos and I. Telečki

      Version of Record online: 10 JAN 2013 | DOI: 10.1002/jrs.4211

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      A novel method for obtaining silicon amorphization depth profile induced by implantation of 6-MeV Al2+ ions in silicon crystal using micro-Raman scanning measurement along transversal cross section of implanted region has been successfully implemented. The obtained silicon amorphization depth profiles were cross-checked by the scanning electron microscope image and the Rutherford backscattering method in the random and channeling orientation spectra.

    25. In situ Raman spectroscopic observation of sequential hydrolysis of stannous chloride to abhurite, hydroromarchite, and romarchite (pages 501–506)

      Xiaoyun Chen and Matthew Grandbois

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/jrs.4214

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      The pH-induced sequential conversion from tin (II) chloride, to abhurite, hydroromarchite, and romarchite was followed in situ by Raman spectroscopy.

  3. Erratum

    1. Top of page
    2. Editorial
    3. Research articles
    4. Erratum
    1. You have free access to this content
      Surface-enhanced Raman scattering spectroscopy for potential noninvasive nasopharyngeal cancer detection (page 507)

      Juqiang Lin, Rong Chen, Shangyuan Feng, Jianji Pan, Buhong Li, Guannan Chen, Shaojun Lin, Chao Li, Li-qing Sun, Zufang Huang and Haishan Zeng

      Version of Record online: 7 FEB 2013 | DOI: 10.1002/jrs.4256

      This article corrects:

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