Journal of Raman Spectroscopy

Cover image for Vol. 43 Issue 2

February 2012

Volume 43, Issue 2

Pages 173–350

  1. Research Articles

    1. Top of page
    2. Research Articles
    1. Exploring the origin of tip-enhanced Raman scattering; preparation of efficient TERS probes with high yield (pages 173–180)

      Mehdi Asghari-Khiavi, Bayden R. Wood, Pejman Hojati-Talemi, Andrew Downes, Don McNaughton and Adam Mechler

      Version of Record online: 2 AUG 2011 | DOI: 10.1002/jrs.3021

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      The aspect ratio of the tip can play a significant role in the efficiency of TERS probes with the electrostatic field arising from the lightning rod effect having a substantial role in the observed TERS effect.

    2. Comparison of SERS effectiveness of copper substrates prepared by different methods: what are the values of enhancement factors? (pages 181–186)

      Marcela Dendisová-Vyškovská, Vadym Prokopec, Martin Člupek and Pavel Matějka

      Version of Record online: 8 JUL 2011 | DOI: 10.1002/jrs.3022

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      Surface enhancement factors (EFs) of copper surface/substrates formed by different preparation procedures (electrochemically prepared large substrates and colloidal systems) in FT-SERS spectroscopy were studied. Surface morphology of the large substrates was studied using atomic force microscopy. The size distribution of colloidal nanoparticles was monitored by dynamic light scattering. The EF values are in both cases more than 105 for FT-SERS spectra, demonstrating the fundamental role of nanostructured copper as a substrate material at the excitation wavelength (1064 nm) used.

    3. SERS study of methylated and nonmethylated ribonucleosides and the effect of aggregating agents (pages 187–195)

      Alison J. Hobro, Salim Abdali and Ewan W. Blanch

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/jrs.3029

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      We report SERS marker bands for methylated and nonmethylated ribonucleosides, using a variety of Ag-colloidal systems, that distinguish between each of these species. The roles of aggregating agents on these SERS spectra, and in regulating the interactions between the nucleosides and the colloid surfaces, are shown to be important.

    4. A hybrid substrate for surface-enhanced Raman scattering spectroscopy: coupling metal nanoparticles to strong localised fields on a micro-structured surface (pages 196–201)

      F. H. Scholes, T. J. Davis, K. C. Vernon, D. Lau, S. A. Furman and A. M. Glenn

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/jrs.3034

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      Electromagnetic coupling between localised plasmons on metal nanoparticles and the strong localised fields on a micro-structured surface is demonstrated as a means to increase the enhancement factor in surface-enhanced Raman scattering (SERS).

    5. SERS activity and stability of the most frequently used silver colloids (pages 202–206)

      I. A. Larmour, K. Faulds and D. Graham

      Version of Record online: 19 OCT 2011 | DOI: 10.1002/jrs.3038

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      We have investigated the suitability of five standard silver colloids for future ultra-sensitive SERS experiments. Stability, surface chemistry, presence of spurious spectral features and SERS activity were studied.

    6. How to obtain a reliable structural characterization of polished graphitized carbons by Raman microspectroscopy (pages 207–211)

      M. R. Ammar and J.-N. Rouzaud

      Version of Record online: 11 JUL 2011 | DOI: 10.1002/jrs.3014

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      We report here the applicability of Raman microspectroscopy to the particular case of polished carbon materials, and show that meaningful Raman structural characterization of such materials is still possible by using an appropriate parameter.

    7. A planetary environment and analysis chamber (PEACh) for coordinated Raman–LIBS–IR measurements under planetary surface environmental conditions (pages 212–227)

      Pablo Sobron and Alian Wang

      Version of Record online: 12 JUL 2011 | DOI: 10.1002/jrs.3017

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      We have developed a planetary environment and analysis chamber to perform in situ multiple spectroscopic measurements on geological samples under planetary-relevant environmental conditions, and to support future planetary missions, with particular interest on Mars. Coordinated spectroscopic sensing on the same geological samples under well-controlled atmospheric conditions establishes a way to link the results from the laboratory experiments to the spectral data obtained by landed and orbital planetary exploration missions.

    8. Surface characteristics of Ag-doped Au nanoparticles probed by Raman scattering spectroscopy (pages 228–236)

      Kwan Kim, Kyung Lock Kim and Kuan Soo Shin

      Version of Record online: 14 JUL 2011 | DOI: 10.1002/jrs.3027

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      We have examined the surface characteristics of Ag-doped Au nanoparticles by means of the surface-enhanced Raman scattering of 2, 6-dimethylphenylisocyanide and 4-nitrobenzenethiol. It clearly indicates that the surface content of Ag increases almost linearly as a function of overall mole fraction of Ag and, once the Au/Ag nanoparticles reach 5 mol% of Ag, their surfaces are fully covered with Ag and show the same surface characteristics of pure Ag nanoparticles.

    9. Raman scattering by folded acoustic phonons in InGaN/GaN superlattices (pages 237–240)

      J. Ibáñez, A. Rapaport, C. Boney, R. Oliva, R. Cuscó, A. Bensaoula and L. Artús

      Version of Record online: 14 JUL 2011 | DOI: 10.1002/jrs.3028

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      A novel ultralow wavenumber filtering module, which provides access to ultralow wavenumber Raman modes on single-grating spectrometers, is employed to study the folded longitudinal acoustic (LA) phonon modes of InxGa1−xN/GaN superlattices (SLs) grown by molecular beam epitaxy. The wavenumber behavior of the folded LA modes is well reproduced by elastic continuum theory. The wavenumber of the doublets is used to evaluate the period of the SLs.

    10. Interference spectroscopy with coherent anti-Stokes Raman scattering of noisy broadband pulses (pages 241–247)

      Evgeny A. Shapiro, Stanislav O. Konorov and Valery Milner

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/jrs.3023

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      We propose and investigate a new technique for comparing two Raman active samples. The method employs optical interference of the signals generated via coherent anti-Stokes Raman scattering of broadband laser pulses with noisy spectra. It does not require spectrally resolved detection, and no prior knowledge about either the Raman spectrum of the samples or the spectrum of the incident light is needed.

    11. Raman and surface-enhanced Raman scattering in the study of human rotator cuff tissues after shock wave treatment (pages 248–254)

      J. J. Cárcamo, A. E. Aliaga, E. Clavijo, M. Brañes and M. M. Campos-Vallette

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/jrs.3019

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      Neo-angiogenesis stimulation and hypercellularization are the result of shock wave treatment. The present work provides a first approach of structural aspects resulting of collagens type I and III by the shock wave treatment.

    12. Characterizing variability in in vivo Raman spectroscopic properties of different anatomical sites of normal tissue in the oral cavity (pages 255–262)

      Mads Sylvest Bergholt, Wei Zheng and Zhiwei Huang

      Version of Record online: 12 AUG 2011 | DOI: 10.1002/jrs.3026

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      This study demonstrates for the first time in vivo Raman spectroscopy in the fingerprint region (800–1800 cm−1) of the oral cavity. High-quality in vivo Raman spectra could be acquired in real time (<0.5 s) from 20 patients. Difference spectra and semiquantitative non-negative constrained least squares minimization of reference biochemicals disclose that inter-anatomical variability is significant and should be considered as an important parameter in the interpretation and rendering of Raman diagnostic algorithms for oral tissue diagnosis.

    13. Conformational polymorphism of the antidiabetic drug chlorpropamide (pages 263–272)

      A. P. Ayala, M. W. C. Caetano, S. B. Honorato, J. Mendes Filho, H. W. Siesler, S. N. Faudone, S. L. Cuffini, F. T. Martins, C. C. P. da Silva and J. Ellena

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/jrs.3012

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      The conformational polymorphism of chlorpropamide was investigated applying Raman spectroscopy combined with a detailed analysis of the crystal structure and quantum mechanical calculations. The temperature dependence of the Raman spectra of form I confirmed the existence of a low-temperature polymorph.

    14. Reversible and irreversible denaturation processes in globular proteins: from collective to molecular spectroscopic analysis (pages 273–279)

      Paola Sassi, Stefania Perticaroli, Lucia Comez, Laura Lupi, Marco Paolantoni, Daniele Fioretto and Assunta Morresi

      Version of Record online: 30 JUN 2011 | DOI: 10.1002/jrs.3013

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      Thermally induced reversible and irreversible denaturation of lysozyme in salt-free aqueous solution were followed by Brillouin and Raman scattering and FTIR absorption spectroscopy. The characterization of the protein system, from the conformation of the polypeptide chain to the exposure of side chains to the solvent and the arrangement of the solution network, was achieved in the 25–85 °C range.

    15. Pharmaceutical polymorphs quantified with transmission Raman spectroscopy (pages 280–285)

      Cushla M. McGoverin, Michael D. Hargreaves, Pavel Matousek and Keith C. Gordon

      Version of Record online: 12 JUL 2011 | DOI: 10.1002/jrs.3020

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      The ranitidine hydrochloride polymorph profile of tablets and capsules was quantified using transmission and Fourier transform Raman spectroscopy. More accurate predictions of ranitidine hydrochloride form I content in both tablets and capsules were obtained when using transmission Raman spectroscopy.

    16. In situ analysis of chiral components of pichtae essential oil by means of ROA spectroscopy: experimental and theoretical Raman and ROA spectra of bornyl acetate (pages 286–293)

      Katarzyna Chruszcz-Lipska and Ewan W. Blanch

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/jrs.3033

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      Raman and Raman optical activity (ROA) spectra of (+)- and (−)-bornyl acetate (BA) have been measured and calculated by the DFT/B3LYP/6-311 + + G** method. ROA spectra were found to be in good agreement with the experimental data and their detailed vibrational assignment is reported for the first time. Further, the combination of Raman and ROA spectroscopy as well as DFT calculations was successfully applied not only to detect BA, the main constituent of pichtae essential oil, but also to determine its specific enantiomer present in the investigated oil samples.

    17. Testing of Raman spectroscopy as a non-invasive tool for the investigation of glass-protected miniature portraits (pages 294–302)

      Diana Mancini, Aurélie Tournié, Maria-Cristina Caggiani and Philippe Colomban

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/jrs.3010

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      Raman spectroscopy is used to investigate six French miniatures on ivory or paper dating back to the 18th and 19th century. Different operative conditions and parameters were tried in order to assess the optimal procedure of analysis for this fragile kind of work of art through their protective glass. The results obtained for the different pigments and the relative criteria of dating are presented.

    18. The use of chromium minerals in the 4th–3rd century BC China? A preliminary study of a bronze Pan unearthed from Jiuliandun Graves, Hubei Province, central southern China (pages 303–306)

      Wugan Luo and Tao Li

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/jrs.3015

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      The combined use of micro-Raman, WDXRF, and XRD has enabled us to investigate and determine the chemical and physical compositions of the brown-black film covered on a bronze Pan (water vessel) that was excavated from the Jiuliandun tombs (∼300 BC), Hubei Province, central southern China. Based on the analytical results and with reference to the records in Chinese historical literature, we deduce that, as early as in the 3rd century BC, people in central southern China might have discovered and intentionally used chromium minerals for bronze treatment (casting, decoration, etc.). The source(s) of chromium minerals used in this period might be Cr-spinel minerals from meteorites.

    19. Raman spectroscopy applied to early (ca. 1746–1754) English steatitic porcelains: a tentative study of compositions (pages 307–316)

      W. H. Jay and J. O. Orwa

      Version of Record online: 1 JUL 2011 | DOI: 10.1002/jrs.3016

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      The mineralogy of the body and glaze compositions of unmarked early English stetitic porcelain wares has indicated the presence of both enstatite and forsterite in one and enstatite and diopside in the other. Different lead-based glazes and pigment compositions were used. The vase has now been attributed to Worcester (ca. 1753–1754) manufacture and the coffee cup to Bow (ca. 1746).

    20. Raman Microspectroscopic study of Iberian pottery from the La Vispesa archaeological site, Spain (pages 317–322)

      M. J. Ayora-Cañada, A. Domínguez-Arranz and A. Dominguez-Vidal

      Version of Record online: 2 AUG 2011 | DOI: 10.1002/jrs.3030

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      This is the first attempt to characterize Iberian pottery from the La Vispesa Spanish archeological site using Raman microspectroscopy. Pigments and crystalline inclusions of different minerals in the ceramic pastes have been identified. Firing conditions and provenance markers for the clays are discussed.

    21. Development of oxidative sample preparation for the analysis of forensic soil samples with near-IR Raman spectroscopy (pages 323–325)

      Howell Edwards, Tasnim Munshi, Ian Scowen, Alexander Surtees and Graeme T. Swindles

      Version of Record online: 2 AUG 2011 | DOI: 10.1002/jrs.3031

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      Soil samples were collected from both urban and rural environments. This study demonstrates how, with the use of oxidative preparation methods, Raman spectroscopy can be used to successfully discriminate between soil types using mineralogy as well as the organic and water-soluble fractions of soils.

    22. Inelastic light scattering studies of diffuse phase transition in ferroelectric Sr1.9Ca0.1NaNb5O15 thin films (pages 326–330)

      W. C. Liu, W. Zhou, R. Sooryakumar and C. L. Mak

      Version of Record online: 13 JUL 2011 | DOI: 10.1002/jrs.3018

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      The dynamic behavior of highly oriented ferroelectric Sr1.9Ca0.1NaNb5O15 thin films has been investigated by Brillouin light scattering over a wide temperature range between 25 and 450°C. The width of the central peak decreases steadily upon cooling from ∼400°C to Tc and shows little subsequent change within the ferroelectric state, indicating an increase of the number of polar nanoregions (PNRs) and a slowing down of their dynamics. The evidence for this diffuse phase transition provided by Brillouin scattering is in agreement with results obtained from the temperature-dependent dielectric permittivity, refractive index, and Raman spectra.

    23. Precise determination of Mg/Fe ratios applicable to terrestrial olivine samples using Raman spectroscopy (pages 331–337)

      Hidemi Ishibashi, Masashi Arakawa, Junji Yamamoto and Hiroyuki Kagi

      Version of Record online: 14 JUL 2011 | DOI: 10.1002/jrs.3024

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      Relations between Mg# [ = 100 Mg/(Mg + Fe)] and Raman wavenumbers of olivine samples are analyzed for five bands in the 800–1000 cm−1 spectral range for the Mg# range of 100–62. The wavenumber of each peak shifts linearly with Mg#. An equation describing these relations enables us to determine Mg# with geologically satisfactory precision of ± 1 Mg# (1σ).

    24. The structural independence of Raman scattering cross sections of ν1(NO3) and ν(H2O) (pages 338–343)

      Kai-Kai Li, Shu-Feng Pang, Guang Zeng, Feng Wang and Yun-Hong Zhang

      Version of Record online: 15 JUL 2011 | DOI: 10.1002/jrs.3035

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      A linear relationship is observed between the integrated intensity ratio of the O[BOND]H stretching envelope of water to the symmetric stretching band of the nitrate ion and the molar water-to-solute ratio. It indicates that the Raman scattering cross sections of NO3 and H2O are insensitive to the structures of both ion pairs and hydrogen bonding, which is important for quantitative analysis with Raman intensity.

    25. Effect of high-energy light-ion irradiation on SI-GaAs and GaAs:Cr as observed by Raman spectroscopy (pages 344–350)

      Shramana Mishra, D. Kabiraj, Anushree Roy and Subhasis Ghosh

      Version of Record online: 12 AUG 2011 | DOI: 10.1002/jrs.3039

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      The structural evolution of high-energy (50 MeV) lithium ion (Li3+) irradiated undoped semi-insulating GaAs (SI-GaAs) and chromium doped SI-GaAs (GaAs:Cr) have been investigated by Raman measurements. We have observed that high-energy Li3+ irradiation causes amorphization beyond a fluence of 3 × 1013 ions/cm2 in undoped SI-GaAs, but the same fluence of irradiation does not affect the crystallinity in GaAs:Cr appreciably.