Journal of Raman Spectroscopy

Cover image for Vol. 43 Issue 1

January 2012

Volume 43, Issue 1

Pages 1–172

  1. Research Articles

    1. Top of page
    2. Research Articles
    3. Short Communications
    1. Triple-resonant two-phonon Raman scattering in graphene (pages 1–5)

      I. Kupčić

      Article first published online: 30 JUN 2011 | DOI: 10.1002/jrs.3003

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      The triple-resonant second-order Raman scattering mechanism in graphene is re-examined. It is shown that the magnitude of the triple-resonant contribution to the photon-G′ mode coupling function in graphene is one order of magnitude larger than the widely accepted two-resonant coupling. Enhancement of the order of 100 in the Raman intensity, with respect to the usual double-resonant model, is found for the G′ band in graphene.

    2. Investigation of adhesive–dentin interfaces using Raman microspectroscopy and small angle X-ray scattering (pages 6–15)

      Sevgi Haman Bayarı, Christoph Krafft, Semra İde, Jürgen Popp, Gunseli Guven, Zafer C. Cehreli and Elif Hilal Soylu

      Article first published online: 28 JUN 2011 | DOI: 10.1002/jrs.3008

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      Dental adhesive systems are used by dentists in restoration of teeth for bonding dental resins to enamel and dentin. The bonding systems used in this study were of the etch-and-rinse type. The purpose of this study was to compare the molecular structure of the adhesive–dentin and adhesive–enamel interface using Raman microspectroscopy. Raman images were obtained from univariate and multivariate methods. The dentin–resin interface was also studied using scanning electron microscopy and small-angle X-ray scattering.

    3. Analysis of cold denaturation mechanism of β-lactoglobulin and comparison with thermal denaturation from Raman spectroscopy investigations (pages 16–23)

      Alain Hédoux, Jeong-Ah Seo, Yannick Guinet and Laurent Paccou

      Article first published online: 30 JUN 2011 | DOI: 10.1002/jrs.3009

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      Stability curve of the protein in the presence of 4 M urea was determined from the analysis of amide I band in the 260–360 K temperature range. Low wavenumber analyses have shown the important influence of solvent dynamics on cold and heat protein denaturations.

    4. The changing biochemical composition and organisation of the murine oocyte and early embryo as revealed by Raman spectroscopic mapping (pages 24–31)

      Bryony Davidson, Norah Spears, Alison Murray and Alistair Elfick

      Article first published online: 10 MAY 2011 | DOI: 10.1002/jrs.2964

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      Using Raman spectroscopic mapping, the biochemical modifications associated with murine oocyte and early embryo development have been investigated, revealing a distinct asymmetrical organisation of macromolecules in the mature oocyte.

    5. Laser-Raman and atomic force microscopy assessment of the chlorococcalean affinity of problematic microfossils (pages 32–39)

      Barbara Kremer, Michael Bauer, Robert W. Stark, Norbert Gast, Wladyslaw Altermann, Hans-Jürgen Gursky, Wolfgang M. Heckl and Józef Kazmierczak

      Article first published online: 1 JUL 2011 | DOI: 10.1002/jrs.2985

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      A combined Raman and AFM investigation was used to study in situ early Silurian enigmatic organic-walled microfossils classified traditionally to an informal taxonomic group named acritarcha. Based on the detection of internal spore-like bodies, acritarchs have been recently re-interpreted as vegetative cells of unicellular green algae (chlorococcales). To prove the identity of the internal bodies as spores, confocal Raman microscopy was applied to examine their chemical and mineral content.

    6. Synthesis of ultrathin and compact Au@MnO2 nanoparticles for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) (pages 40–45)

      Xiao-Dong Lin, Viviane Uzayisenga, Jian-Feng Li, Ping-Ping Fang, De-Yin Wu, Bin Ren and Zhong-Qun Tian

      Article first published online: 15 JUL 2011 | DOI: 10.1002/jrs.3007

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      The peak intensity from 55 nm Au@1.2 nm MnO2 NPs is about 10 times of that from 55 nm Au@4 nm SiO2 NPs. In SHINERS, the distance of the SERS-active core and the substrate is controlled by the thickness of the shell. Considering a much thinner shell thickness of MnO2 than that of SiO2, higher signal intensity obtained in the former system is reasonable. The improved signal intensity of Au@MnO2 SHINERS NPs has a strong advantage in increasing the sensitivity and decreasing the detection limit.

    7. Shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) investigation of benzotriazole film formation on Cu(100), Cu(111), and Cu(poly) (pages 46–50)

      Nicole R. Honesty and Andrew A. Gewirth

      Article first published online: 19 MAY 2011 | DOI: 10.1002/jrs.2989

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      Benzotriazole film formation was investigated on single-crystal and polycrystalline Cu surfaces with SHINERS. Potential-dependent spectra display reversible BTA film formation on polycrystalline Cu and irreversible film formation on single-crystal Cu.

    8. Structure and conformation of Arg8 vasopressin modified analogs (pages 51–60)

      Edyta Podstawka-Proniewicz, Dariusz Sobolewski, Adam Prahl, Younkyoo Kim and Leonard M. Proniewicz

      Article first published online: 27 JUN 2011 | DOI: 10.1002/jrs.2986

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      FT-Raman and IR spectra acquired for four arginine vasopressin (AVP) analogs containing L-diphenylalanine (Dpa): [Dpa2]AVP, [Cpa1,Dpa2]AVP, [Dpa3]AVP, and [Cpa1,Dpa3]AVP were compared and analyzed. In addition, the FT-Raman spectra were compared to the corresponding SERS spectra recorded in an aqueous silver colloidal dispersion. The geometry of these molecules etched on the silver surface was deduced from observed changes in the intensity enhancement, broadness, and shift in wavenumber of the Raman bands in the spectra of the bound versus free species.

    9. Surface-enhanced Raman scattering of molecules adsorbed on Co-doped ZnO nanoparticles (pages 61–64)

      Xiangxin Xue, Weidong Ruan, Libin Yang, Wei Ji, Yunfei Xie, Lei Chen, Wei Song, Bing Zhao and John R. Lombardi

      Article first published online: 18 MAY 2011 | DOI: 10.1002/jrs.2988

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      Significant enhancements in SERS signals were observed when the probing molecules of 4-mercaptobenzoic acid were adsorbed on the surface of Co-doped ZnO nanoparticles. The crystalline defects of the Co[BOND]ZnO nanoparticles caused by Co doping play an important role in the SERS activity.

    10. A thioester substrate binds to the enzyme Arthrobacter thioesterase in two ionization states: evidence from Raman difference spectroscopy (pages 65–71)

      Jian Dong, Zhihao Zhuang, Feng Song, Debra Dunaway-Mariano and Paul R. Carey

      Article first published online: 2 AUG 2011 | DOI: 10.1002/jrs.3002

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      Mixed populations of the bound substrate are identified in the active site of the Arthrobacter enzyme where the 4-hydroxy groups are present as 4-O and 4-OH.

    11. Raman spectroscopy to probe residual stress in ZnO nanowire (pages 72–75)

      Satyaprakash Sahoo, G. L. Sharma and Ram. S. Katiyar

      Article first published online: 28 JUN 2011 | DOI: 10.1002/jrs.3004

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      Raman spectroscopic studies of the zone-centre E2high optical phonon of a bent ZnO nanowire show a systematic red shift as the junction of the two arms of the nanowire is approached. The analysis of the Raman spectrum indicates the presence of tensile strain on the nanowire. Strain in the bent nanowire is also investigated using photoluminescence (PL) spectroscopy. Results of both Raman and PL study confirm that the bend nanowire is under tensile strain.

    12. Oxygen vacancy-induced microstructural changes of annealed CeO2−x nanocrystals (pages 76–81)

      S. Aškrabić, Z. Dohčević-Mitrović, A. Kremenović, N. Lazarević, V. Kahlenberg and Z. V. Popović

      Article first published online: 19 MAY 2011 | DOI: 10.1002/jrs.2987

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      Oxygen-induced microstructural changes in annealed nanocrystalline CeO2−x were investigated by X-ray diffraction and Raman spectroscopy. Analysis of structural and vibrational properties of annealed ceria demonstrated that microstrain changes, because of variable defect content, dominate over the crystallite size effect in annealed samples. A new Raman mode (S), ascribed to surface mode, originates from the defective and disordered structure.

    13. Reorientation dynamics in liquid alcohols from Raman spectroscopy (pages 82–88)

      Ke Lin, Naiyin Hu, Xiaoguo Zhou, Shilin Liu and Yi Luo

      Article first published online: 30 MAY 2011 | DOI: 10.1002/jrs.2997

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      Translational relaxations of alcohol molecules in pure and water solution have been studied with polarized Raman spectroscopy. Temperature-dependent measurements show that the hydrogen-bonding (HB) and hydrophobic interactions control the translational motion. The hydrophobic interaction reduces the relaxation time more apparently for [BOND]CH3 group than the skeleton motion. By adding water in alcohol liquids, translational motions generally slow down but show different concentration-dependent behaviors. Different mechanisms have been proposed to interpret these interesting observations, which are related to the HB networks in aqueous alcohols.

    14. Simultaneous acquisition of all four forms of circular polarization Raman optical activity: results for α-pinene and lysozyme (pages 89–94)

      Honggang Li and Laurence A. Nafie

      Article first published online: 30 MAY 2011 | DOI: 10.1002/jrs.3000

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      A design extension of the only commercial Raman optical activity (ROA) spectrometer, the ChiralRAMAN which provides only scattered circular polarization ROA, is implemented for the simultaneous acquisition of all four forms of CP ROA.

    15. Bent polyynes: ring geometry studied by Raman and IR spectroscopy (pages 95–101)

      Andrea Lucotti, Matteo Tommasini, Wesley A. Chalifoux, Daniele Fazzi, Giuseppe Zerbi and Rik R. Tykwinski

      Article first published online: 8 JUL 2011 | DOI: 10.1002/jrs.2992

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      Vibrational spectroscopy is used to evaluate molecular geometry in cyclic tetraynes via analysis of C≡C stretching bands that are activated when the center of symmetry in a polyyne structure is lost through bending of the ring.

    16. Morphine studied by vibrational spectroscopy and DFT calculations (pages 102–107)

      M. Baranska and A. Kaczor

      Article first published online: 11 JUL 2011 | DOI: 10.1002/jrs.3005

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      This article presents the application of Raman and FT-IR spectroscopy for complex investigation of morphine, its metabolite and salts as well as a pharmaceutical product. Experimental analysis is supported by quantum-chemical calculations performed at the B3LYP/6–311++G(d,p) level.

    17. Local structural order in carbonic acid polymorphs: Raman and FT-IR spectroscopy (pages 108–115)

      Christian Mitterdorfer, Jürgen Bernard, Frederik Klauser, Katrin Winkel, Ingrid Kohl, Klaus R. Liedl, Hinrich Grothe, Erwin Mayer and Thomas Loerting

      Article first published online: 30 JUN 2011 | DOI: 10.1002/jrs.3001

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      There are only a few small inorganic molecules of fundamental importance for which thecrystal structures are unknown. Carbonic acid (H2CO3) is one of them. Raman and IR spectra of the two known polymorphs of carbonic acid are reported here. Based on the data, local structural hydrogen-bonding motifs are presentedand suggested as building blocks of the crystal structures of α-H2CO3 and β-H2CO3.

    18. Conformational, vibrational, and structural studies of 2,2,3,3,3-pentafluoropropylamine from Raman and infrared spectra of gas, liquid, xenon solutions, and solid supported by ab initio calculations (pages 116–126)

      Gamil A. Guirgis,, Ikhlas D. Darkhalil,, Joshua J. Klaassen,, Arindam Ganguly,, Justin K. Wyatt, and James R. Durig

      Article first published online: 28 JUN 2011 | DOI: 10.1002/jrs.2993

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      Two of the five possible conformers have been identified in the vibrational spectra of 2,2,3,3,3-pentafluoropropylamine. The enthalpy difference between these two conformers has been determined using variable temperature spectra of the sample dissolved in liquid xenon.

    19. Micro-Raman study of orbiton–phonon coupling in YbVO3 (pages 127–130)

      B. Roberge, S. Jandl, A. A. Nugroho and T. T. M. Palstra

      Article first published online: 28 JUN 2011 | DOI: 10.1002/jrs.3006

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      First-order and multiphonon Raman active excitations are studied in YbVO3 as a function of temperature. Below T ≃ 170 K, new excitations are activated, following the G-orbital ordering and the concomitant orthorhombic to monoclinic phase transition. The observed phonon combinations around 1400 cm−1 with a dominant Jahn-Teller vibration ∼690 cm−1 are related to a possible orbiton-phonon coupling.

    20. Forensic examination of multilayer white paint by lateral scanning Raman spectroscopy (pages 131–137)

      S.P. Stewart, S.E.J. Bell, W.J. Armstrong, G. Kee and S.J. Speers

      Article first published online: 13 JUL 2011 | DOI: 10.1002/jrs.2982

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      Raman spectra obtained at points along line scans of multilayer white paints show the change in composition between each layer and thus provide a method of discriminating optically identical paint samples.

    21. Hydrogen-bonding interactions in fully deuterated α-glycine at high pressures (pages 138–145)

      Bharat Bhooshan Sharma, Chitra Murli, R. Chitra and Surinder M. Sharma

      Article first published online: 28 JUN 2011 | DOI: 10.1002/jrs.2994

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      We report the first in situ high-pressure Raman investigations of fully deuterated α-glycine up to ∼20 GPa. The spectral changes in the ND3+ and COO modes indicate subtle structural rearrangements across 3 GPa. The decrease in the intensity of ND3+ torsional mode is found to be similar to that of undeuterated α-glycine. The pressure-induced stiffening of N[BOND]D and CD2 stretching modes is discussed in the context of changes in the hydrogen-bonding interactions.

    22. Pressure-induced phase transitions in palmitic acid: C form (pages 146–152)

      F. F. de Sousa, G. D. Saraiva, P. T. C. Freire, J. A. Lima Jr, P. Alcantara Jr, F. E. A. Melo and J. Mendes Filho

      Article first published online: 28 JUN 2011 | DOI: 10.1002/jrs.2980

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      In this article, we report a high-pressure Raman spectroscopy study of the palmitic acid (PA, C form) from ambient pressure up to 21 GPa. The effects of hydrostatic pressure on the vibrational spectrum of PA are reported, and the data show that PA experiences a rich sequence of phase transformations. These changes in the crystal structure occur gradually as the pressure increases and they are related with the highly flexible crystalline structure.

    23. Structural modifications of LixV2O5 in a composite cathode (0≤x < 2) investigated by Raman microspectrometry (pages 153–160)

      R. Baddour-Hadjean, A. Marzouk and J. P. Pereira-Ramos

      Article first published online: 27 JUN 2011 | DOI: 10.1002/jrs.2984

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      A detailed description of phase transitions occurring in the LixV2O5 active material in a composite electrode (0≤x < 2) is provided here for the first time using Raman spectroscopy. The successive emergence of the various phases governing the electrochemical properties of this cathode material is spectroscopically observed. This work demontrates that Raman spectroscopy constitutes a powerful tool to explore the structural changes induced by electrochemical Li insertion-extraction reactions in electrode materials for lithium batteries.

  2. Short Communications

    1. Top of page
    2. Research Articles
    3. Short Communications
    1. Polyenic pigments from the Brazilian octocoral Phyllogorgia dilatata Esper, 1806 characterized by Raman spectroscopy (pages 161–164)

      Lenize F. Maia, Vanessa E. de Oliveira, Maria Edwiges R. de Oliveira, Beatriz G. Fleury and Luiz Fernando C. de Oliveira

      Article first published online: 14 JUL 2011 | DOI: 10.1002/jrs.3025

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      Differentiation of healthy and diseased tissues from the Brazilian octocoral Phyllogorgia dilatata was performed by in situ Raman Spectroscopy analysis. Spectral data of the healthy portion showed major vibrational bands at ca. 1520, 1160, and 1000 cm−1 due to ν(C[DOUBLE BOND]C), ν(C[BOND]C), and ρ(C[BOND]CH3) respectively, corresponding to carotenoids. However, the diseased tissue, which has a purple pigmentation, showed bands at ca. 1500 and 1120 cm−1 attributed to polyenals belonging to psittacofulvin class.

    2. Two-dimensional standoff Raman measurements of distant samples (pages 165–167)

      John N. Porter, Charles E. Helsley, Shiv K. Sharma, Anupam K. Misra, David E. Bates and Barry R. Lienert

      Article first published online: 28 JUN 2011 | DOI: 10.1002/jrs.2998

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      Point-by-point standoff Raman measurements are made of distant samples using a precise pan-tilt system and then combined into a molecular species image of the distant target area.

    3. First-order Raman scattering of the MAX phases: Ti2AlN, Ti2AlC0.5N0.5, Ti2AlC, (Ti0.5V0.5)2AlC, V2AlC, Ti3AlC2, and Ti3GeC2 (pages 168–172)

      Volker Presser, Michael Naguib, Laurent Chaput, Atsushi Togo, Gilles Hug and Michel W. Barsoum

      Article first published online: 2 AUG 2011 | DOI: 10.1002/jrs.3036

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      The Raman spectra of a number of MAX phases (Ti2AlN, Ti2AlC0.5N0.5, [Ti0.5,V0.5]2AlC, Ti2AlC, V2AlC, Ti3AlC2 and Ti3GeC2), mostly not spectroscopically investigated before, are measured and compared to the calculated mode wavenumbers via density functional theory. The 211 phases only show modes associated to atomic displacements of the ‘M’ and ‘A’ atomic planes, while the Ti3AlC2 and Ti3GeC2 also show modes that correspond with vibrations of the ‘X’ sublattice relative to itself.