Journal of Raman Spectroscopy

Cover image for Vol. 43 Issue 8

August 2012

Volume 43, Issue 8

Pages 965–1176

  1. Research Articles

    1. Top of page
    2. Research Articles
    1. Plasmon-enhanced Raman scattering of coaxial hybrid nanowires made with light-emitting polymer and gold (pages 965–970)

      Se Hee Park, Dong Hyuk Park, Young Ki Hong, Seok Ho Lee, Dae-Chul Kim, Krishna Prasad Dhakal, Jinsoo Joo and Jeongyong Kim

      Article first published online: 27 MAR 2012 | DOI: 10.1002/jrs.3121

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      Coaxial hybrid nanowires (NWs) made with light emitting poly(3-methylthiophene) (P3MT) and Au showed a great enhancement of Raman scattering by up to 15 times over plain P3MT NWs. Raman spectra by three different excitation wavelengths showed that the observed Raman enhancement was due to the surface plasmon resonance in hybrid coaxial NWs.

    2. Quantification of purine basis in their mixtures at femto-molar concentration levels using FT-SERS (pages 971–976)

      Vaclav Ranc, Jana Hruzikova, Kamil Maitner, Robert Prucek, David Milde and Libor Kvítek

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3124

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      By the means of surface-enhanced Raman scattering with Fourier transformation, we have developed a method for the quantification of adenine, xanthine, and hypoxanthine bases at their femtomolar concentrations.

    3. Enhancement in SERS intensity with hierarchical nanostructures by bimetallic deposition approach (pages 977–985)

      Chit Yaw Fu, Kiang Wei Kho, U. S. Dinish, Zhen Yu Koh and Olivo Malini

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3128

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      Additional SERS enhancement induced on bimetallic (Ag/Au) hierarchical structure is investigated using nanosphere arrays with Ag underlayer and Au overlayer. The significant dependency of SERS enhancement on the Ag/Au thickness ratio is confirmed. Importantly, compared with Au-array, the optimized bimetallic structures exhibit quasi-particles on the nanospheres with surpassing SERS (2.5×), approaching to that of Ag-array. The elevated SERS is attributed to the formation of effective hot-spots associated with enhanced roughness of the outer Au layer given by bimetallic deposition approach.

    4. Ag-nanoparticle-modified single Ag nanowire for detection of melamine by surface-enhanced Raman spectroscopy (pages 986–991)

      Li-Miao Chen and You-Nian Liu

      Article first published online: 26 JUN 2012 | DOI: 10.1002/jrs.3137

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      Silver-nanoparticle-decorated silver (AgNP/Ag) nanowires were prepared and used as surface-enhanced Raman scattering (SERS) substrates. Single AgNP/Ag nanowire exhibited strong SERS effect. Their application in detection of melamine in raw milk demonstrated the potential of single AgNP/Ag nanowire as a SERS substrate for convenient and sensitive detection of melamine in a complex mixture.

    5. Quantitative and multicomponent analysis of prevalent urinary calculi using Raman spectroscopy (pages 992–997)

      Yichun Chiu, Yi-Yu Huang, Po-An Chen, Shing-Hwa Lu, Allen W. Chiu and Huihua Kenny Chiang

      Article first published online: 23 JUN 2012 | DOI: 10.1002/jrs.3138

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      This study established a quantitative micro-Raman spectroscopic (MRS) method for measuring multicomponents (binary and ternary compositions) of prevalent urine calculi extracted from the ureter after the ureteroscopic lithotripsy procedure. The novelty of this paper lies in the analytic approach to determine the concentration of components in urine stone powders having ternary composition. This research successfully applied the quantitative MRS-based analysis technique from bench to bedside.

    6. Quantification of DNT isomers by capillary liquid chromatography using at-line SERS detection or multivariate analysis of SERS spectra of DNT isomer mixtures (pages 998–1002)

      Bernhard Zachhuber, Carolina Carrillo-Carrión, Bartolomé M. Simonet Suau and Bernhard Lendl

      Article first published online: 3 AUG 2012 | DOI: 10.1002/jrs.3149

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      Silver quantum dot surface-enhanced Raman scattering quantification was performed on 2,4-dinitrotoluene (DNT) and 2,6-DNT mixtures at the ppm level (A) after capillary high-performance liquid chromatography separation and (B) on unseparated DNT isomer mixtures via surface-enhanced Raman scattering and multivariate partial least squares quantification, avoiding the chromatographic separation step.

    7. Application of calixarene to high active surface-enhanced Raman scattering (SERS) substrates suitable for in situ detection of polycyclic aromatic hydrocarbons (PAHs) in seawater (pages 1003–1009)

      Yong-Hyok Kwon, Kay Sowoidnich, Heinar Schmidt and Heinz-Detlef Kronfeldt

      Article first published online: 7 JUN 2012 | DOI: 10.1002/jrs.3157

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      Sol-gel matrix embedding Ag nanoparticles with calix[4]arene was introduced for the detection of polycyclic aromatic hydrocarbons in seawater at very low concentrations using a 671-nm diode laser excitation. A calibration procedure reveals that the surface-enhanced Raman scattering substrates have a limit of detection that is less than 1 nmol/l for pyrene and 13 nmol/l for naphthalene in artificial seawater.

    8. Adsorption of 1,2,4-triazole on a silver electrode: surface-enhanced Raman spectroscopy and density functional theory studies (pages 1010–1017)

      B. Wrzosek, J. Cukras and J. Bukowska

      Article first published online: 7 JUN 2012 | DOI: 10.1002/jrs.3161

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      The pH-dependent surface-enhanced Raman scattering spectra of 1,2,4-triazole adsorbed on silver electrode, supported by density functional theory calculations of model complexes of silver with various molecular forms of triazole provided information about the structure of studied adlayers. In alkaline and neutral environment, triazole adsorbs in deprotonated form in almost flat orientation with respect to the surface. In moderately acidic medium a neutral, native form is preserved in the adlayer, with the ring plane tilted to the metal surface.

    9. On the determination of diameter distribution in multi-wall carbon nanotubes by Raman spectroscopy: issues related to excitation laser energy (pages 1018–1023)

      S. Scalese, V. Scuderi, S. Bagiante, I. Deretzis, A. La Magna, C. Bongiorno, G. Compagnini, S. Gibilisco, N. Piluso and V. Privitera

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3139

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      Multi-wall carbon nanotubes (MWCNT) produced by the arc discharge between two graphite rods in liquid nitrogen have been investigated with the use of Raman spectroscopy and transmission electron microscopy (TEM). The effect of the applied voltage on the MWCNTs has been observed, in particular, as it concerns the size of the innermost and outermost diameters. The apparent discrepancies between the Raman and TEM results and the observation of a selective response of the MWCNTs to the excitation laser energy, similar to the case of single-wall CNTs, are explained by electronic structure calculation.

    10. Selective reduction of nitroaromatic compounds on silver nanoparticles by visible light (pages 1024–1028)

      Lixin Xia, Xinhu Hu, Mengtao Sun, Jushi Li, Donghui Yang, Xiaofang Wang and Hongxing Xu

      Article first published online: 5 JUN 2012 | DOI: 10.1002/jrs.3143

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      Nitroaromatic compounds, 2,4-dinitrobenzenethiol and 4-chloro-2-nitrobenzenethiol, on silver sols can be selectively reduced to 2-amino-4-nitrobenzenethiol and 2-amino-4-chlorobenzenethiol simply by irradiating with a visible light in ambient conditions, and the selective photoreduction is a very facile process. The results of quantum chemical calculations are in good agreement with our experimental data.

    11. Carbon nanostructures produced by pyrolysis under high pressure inside a nanosize silica matrix (pages 1029–1034)

      Antonio E. L. Villanueva, Naira M. Balzaretti and Joao A. H. da Jornada

      Article first published online: 9 JUL 2012 | DOI: 10.1002/jrs.3150

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      The pyrolysis of carbon precursors under high pressure is a promising new route to produce graphene-like structures of very small dimensions (below 10 nm) in a controlled and confined way. Hydrophobic Aerosil samples are very suitable for creating these carbon structures, which can be probed by Raman and transmission electron microscopy analysis.

    12. Origin of the variability of the mechanical properties of silk fibres: 2 The nanomechanics of single silkworm and spider fibres (pages 1035–1041)

      Philippe Colomban and Hung Manh Dinh

      Article first published online: 23 MAY 2012 | DOI: 10.1002/jrs.3123

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      A perfect relationship between the tensile macroscopic and the nanometric bond behaviour of Bombyx mori and Nephila madagascarensis fibres (elastic Hookean regime, the yield α−β transition regime…) is observed as in other polyamide fibres (keratin; PA66,…) using the vN–H mode as a local probe.

    13. Origin of the variability of the mechanical properties of silk fibres: 3. Order and macromolecule orientation in Bombyx mori bave, hand-stretched strings and Nephila madagascarensis spider fibres (pages 1042–1048)

      Philippe Colomban, Hung Manh Dinh, Aurélie Tournié and Vincent Jauzein

      Article first published online: 2 MAR 2012 | DOI: 10.1002/jrs.3122

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      The comparison of the low wavenumber polarized Raman spectra (60–350 cm–1) of Bombyx mori (fresh cocoons fibres, hand-stretched strings or bundles of fibres from the gland content, dried gland, regenerated silk films, etc.) and Nephila madagascarensis silks points out the higher (long range) order/orientation in the case of spider fibre. The differences in order degree are discussed.

    14. On the quantification of ciprofloxacin in proprietary Ciproxin tablets and generic ciprofloxacin tablets using handheld Raman spectroscopy (pages 1049–1057)

      Sulaf Assi, Robert A. Watt and Anthony C. Moffat

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3125

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      The quantification of ciprofloxacin in proprietary and generic tablets was investigated using a handheld Raman spectroscopic instrument. The potential of inbuilt and off-line algorithms for quantification were investigated. For off-line quantification, univariate regression and partial least squares regression methods were compared.

    15. Raman spectroscopic detection of Nickel impact on single Streptomyces cells – possible bioindicators for heavy metal contamination (pages 1058–1064)

      Angela Walter, Susanne Kuhri, Martin Reinicke, Thomas Bocklitz, Wilm Schumacher, Petra Rösch, Dirk Merten, Georg Büchel, Erika Kothe and Jürgen Popp

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3126

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      Soil bacteria of the genus Streptomyces are used as bioindicators for heavy metal contamination investigated via micro-Raman spectroscopy. Single cell Raman spectra are differentiated according to the varying Ni2+ concentration of the culture medium. The application of a support vector machine enables the classification spectra recorded from cells exposed to unknown Ni2+ concentration.

    16. Tobacco alkaloids analyzed by Raman spectroscopy and DFT calculations (pages 1065–1073)

      M. Baranska, J. Cz. Dobrowolski, A. Kaczor, K. Chruszcz-Lipska, K. Gorz and A. Rygula

      Article first published online: 28 FEB 2012 | DOI: 10.1002/jrs.3127

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      The tobacco alkaloids, including nicotine, were analyzed by means of Raman spectroscopy supported by the B3LYP/aug-cc-pVDZ calculations. The form and distribution of nicotine directly in plant and pharmaceutical products were investigated by in situ Raman mapping. Additionally, for the first time, the Raman optical activity spectrum of (–)-nicotine in aqueous solution was measured and interpreted.

    17. Using surface-enhanced Raman scattering (SERS) and fluorescence spectroscopy for screening yeast extracts, a complex component of cell culture media (pages 1074–1082)

      Boyan Li, Narayana M. S. Sirimuthu, Bryan H. Ray and Alan G. Ryder

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3141

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      Yeastolate or yeast extract, which are hydrolysates produced by autolysis of yeast, are often employed as a raw material in the media used for industrial mammalian cell culture. Here, we demonstrate how surface-enhanced Raman scattering (SERS) can be used for the analysis of these materials.

    18. Detection of polymorphism in the methlyenetetrahydrofolate reductase gene by Raman spectroscopy (pages 1083–1088)

      Alexandra Chapsky, Osnat Melamed, Dalia Galron, Hava M. Golan and Ilana Bar

      Article first published online: 7 JUN 2012 | DOI: 10.1002/jrs.3146

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      This study aimed to develop a new approach for characterizing changes associated with DNA methylation levels, playing important roles in regulation of gene expression. By monitoring the ‘fingerprints’ of genomic DNA strands with Raman spectroscopy, the extent of DNA methylation was determined and correlated with polymorphisms in the methlyenetetrahydrofolate reductase gene. This approach has the potential to contribute to disease diagnosis and to a better understanding of the physical and biomolecular processes related to epigenetic regulation of the genome.

    19. Identification of oxygen in dental enamel following tooth bleaching using confocal micro Raman spectroscopy (pages 1089–1093)

      João Miguel Silveira, Stephane Longelin, António Duarte Mata and Maria Luísa Carvalho

      Article first published online: 22 JUN 2012 | DOI: 10.1002/jrs.3153

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      A confocal micro Raman spectroscopy technique was used to identify the presence of oxygen in dental enamel following tooth bleaching. A decrease of fluorescence was also observed. Accordingly, to previously undemonstrated theories, the presence of residual oxygen in dental enamel may be responsible for a reduced efficacy of several dental treatments following this esthetic treatment.

    20. Resonant Raman spectroscopy and spectroelectrochemistry characterization of carbon nanotubes/polyaniline thin film obtained through interfacial polymerization (pages 1094–1100)

      Rodrigo V. Salvatierra, Luciano G. Moura, Marcela M. Oliveira, Marcos A. Pimenta and Aldo J. G. Zarbin

      Article first published online: 29 MAY 2012 | DOI: 10.1002/jrs.3144

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      The effect of the presence of carbon nanotubes on the structure and conformation of polyaniline chains in nanocomposite thin films have been studied by resonant Raman spectroscopy and UV–Vis and Raman spectroelectrochemistry.

    21. Micro-Raman and infrared analysis of medieval pottery findings from Braničevo, Serbia (pages 1101–1110)

      Ivanka Holclajtner-Antunović, Danica Bajuk-Bogdanović, Vesna Bikić and Milica Marić-Stojanović

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3129

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      Medieval Byzantine table pottery findings from Serbia have been analyzed by Fourier transform infrared, micro-Raman and scanning electron microscopy with energy dispersive spectroscopy. The vessels were made of noncalcareous clays and fired at temperatures between 700 and 900°C. The main type of transparent glaze was identified as lead-rich, while two samples were covered by an alkali–lime type of glaze.

    22. Portable Raman study on the conservation state of four CorTen steel-based sculptures by Eduardo Chillida impacted by urban atmospheres (pages 1111–1117)

      J. Aramendia, L. Gomez-Nubla, K. Castro, I. Martinez-Arkarazo, D. Vega, A. Sanz López de Heredia, A. García Ibáñez de Opakua and J. M. Madariaga

      Article first published online: 28 JUN 2012 | DOI: 10.1002/jrs.3158

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      The evolution of the rust layer present on the weathering steels is different, depending both on the exposure and the particular type of the steel. The evolution of four CorTen sculptures has been analyzed with portable Raman spectroscopy demonstrating that different factors could decrease the protective function of the rust layer.

    23. Raman light scattering, infrared absorption and DSC studies of the phase transition and vibrational and reorientational dynamics of H2O ligands and ClO4 anions in [Ba(H2O)3](ClO4)2 (pages 1118–1125)

      Joanna Hetmańczyk, Łukasz Hetmańczyk, Anna Migdał-Mikuli, Edward Mikuli and Aleksandra Wesełucha-Birczyńska

      Article first published online: 29 MAY 2012 | DOI: 10.1002/jrs.3130

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      One phase transition in [Ba(H2O)3](ClO4)2 was detected. It is mainly connected with the small change of the crystal structure. The analysis of the full-width at half-maximum of the particular bands in infrared and Raman spectra performed in the wide temperature range showed that ligands and anions perform fast picosecond stochastic reorientations in high temperature phase, which are slowed at ~120 K. In the case of ClO4 this motion is slightly disturbed in the vicinity of phase transition.

    24. Conformity and precision of CO2 densimetry in CO2 inclusions: microthermometry versus Raman microspectroscopic densimetry (pages 1126–1133)

      Tomoyuki Kobayashi, Junji Yamamoto, Takao Hirajima, Hidemi Ishibashi, Naoto Hirano, Yong Lai, Vladimir S. Prikhod'ko and Shoji Arai

      Article first published online: 30 MAY 2012 | DOI: 10.1002/jrs.3134

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      We compare two methods, microthermometry and Raman microspectroscopic densimetry, for CO2. Regarding the applicability of the densimetries, Raman microspectroscopic densimetry enables determination of CO2 density in very small inclusions (~1 µm diameter) having widely varied densities even in a semi-opaque mineral. The selection of densimetry for CO2 as appropriate according to the type of CO2 inclusion in mantle minerals will enhance the resolution of the mantle structure.

    25. Raman spectra of osmotic solutes of halophiles (pages 1134–1140)

      Jan Jehlička, Aharon Oren and Howell G. M. Edwards

      Article first published online: 22 DEC 2011 | DOI: 10.1002/jrs.3136

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      A great diversity of organic osmotic solutes is found in nature. Thanks to the high concentrations in which these compounds are often present, Raman spectroscopy may be a useful technique for rapid analysis of such solutes both in individual organisms and in natural microbial communities in high-salt environments. In this paper, a database of Raman spectra of the most commonly encountered compatible solutes, as well as some less common ones, is presented.

    26. Ferroelectric Q and antiferroelectric P phases' coexistence and local phase transitions in oxygen-deficient NaNbO3 single crystal: micro-Raman, dielectric and dilatometric studies (pages 1141–1145)

      R. A. Shakhovoy, S. I. Raevskaya, L. A. Shakhovaya, D. V. Suzdalev, I. P. Raevski, Yu. I. Yuzyuk, A. F. Semenchev and M. El Marssi

      Article first published online: 21 MAY 2012 | DOI: 10.1002/jrs.3140

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      Micro-Raman studies of oxygen-deficient gray-colored NaNbO3 single crystals have shown that at room temperature both antiferroelectric P and ferroelectric Q phases are present simultaneously as separate regions tens of micrometers in size. For the first time, the sequence of phase transitions between antiferroelectric phase P and ferroelectric Q and N phases has been revealed.

    27. Amorphous to crystalline transformation in Ta2O5 studied by Raman spectroscopy (pages 1146–1150)

      C. Joseph, P. Bourson and M. D. Fontana

      Article first published online: 7 JUN 2012 | DOI: 10.1002/jrs.3142

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      Many of the interesting properties that make Ta2O5 a strategic material in microelectronics, chemistry and optics depend on its structural characteristics. Here, we use Raman spectroscopy to probe structural modifications in amorphous Ta2O5 submitted to thermal annealing. Experimental spectra are explained by simulating disorder-induced breaking of Raman selection rules over a phonon density of states. Our original approach allows assignment of the vibrational features in the amorphous case, and provides quantitative indicators to analyse phase transformations.

    28. Quantitative analysis of essential oils from rosemary in virgin olive oil using Raman spectroscopy and chemometrics (pages 1151–1156)

      Jone Omar, Alfredo Sarmiento, Maitane Olivares, Ibone Alonso and Nestor Etxebarria

      Article first published online: 30 DEC 2011 | DOI: 10.1002/jrs.3152

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      Rosemary essential oils have been quantified in a complex matrix (olive oil) by means of multivariate calibration in Raman Spectroscopy. Experimental design has been carried out in order to optimize the Raman measurements. Different spectra pre-processing algorithms were evaluated and predicted concentrations were compared with Comprehensive Two-Dimensional Gas Chromatography.

    29. Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure-dependent and temperature-dependent Raman study (pages 1157–1165)

      Surajit Saha, Pallavi Ghalsasi, D. V. S. Muthu, Surjeet Singh, R. Suryanarayanan, A. Revcolevschi and A. K. Sood

      Article first published online: 24 MAY 2012 | DOI: 10.1002/jrs.3154

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      A new phonon mode appears below 110 K in pyrochlore spin ice Dy2Ti2O7 at atmospheric pressure because of a subtle structural transition, which shifts to higher temperatures as the applied pressure increases.

    30. The use of hot-stage microscopy and thermal micro-Raman spectroscopy in the study of phase transformation of metoclopramide HCl monohydrate (pages 1166–1170)

      Shan-Yang Lin and Wen-Ting Cheng

      Article first published online: 30 DEC 2011 | DOI: 10.1002/jrs.3155

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      DSC, TG, hot-stage microscopy and thermal Raman microspectroscopy are used to characterize the phase transformation of metoclopramide HCl monohydrate.

    31. A novel method for quantification of ethanol and methanol in distilled alcoholic beverages using Raman spectroscopy (pages 1171–1176)

      Ismail Hakki Boyaci, Hüseyin Efe Genis, Burcu Guven, Ugur Tamer and Neslihan Alper

      Article first published online: 28 JUN 2012 | DOI: 10.1002/jrs.3159

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      A new method for quantification of ethanol and methanol in distilled alcoholic beverages was developed using Raman spectroscopy. The method was validated based on linearity, sensitivity, intraday and interday repeatability, and recovery tests. The developed method gives an opportunity to determine ethanol and methanol concentrations simultaneously, sensitively, and rapidly (total analyze time for quantification of two alcohols is less than 30 s).

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