Journal of Raman Spectroscopy

Cover image for Vol. 43 Issue 6

June 2012

Volume 43, Issue 6

Pages 689–816

  1. Rapid Communications

    1. Top of page
    2. Rapid Communications
    3. Research Articles
    1. Spacer-free SERRS spectra of unperturbed porphyrin detected at 100 fM concentration in Ag hydrosols prepared by modified Tollens method (pages 689–691)

      Karolína Šišková, Ondřej Bečička, Vlastimil Mašek, Klára Šafářová and Radek Zbořil

      Article first published online: 11 NOV 2011 | DOI: 10.1002/jrs.3098

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      A repeatable detection of unperturbed water-soluble cationic porphyrin 5,10,15,20-tetrakis(1-methyl-4-pyridyl)21H,23H-porphine (TMPyP) at a very low concentration using surface-enhanced resonance Raman scattering spectroscopy is reported. No post-modification of Ag nanoparticles prepared by modified Tollens method is necessary to observe the surface-enhanced resonance Raman scattering signal of free-base TMPyP. Possible reasons of hindered metalation and detection of a very low TMPyP concentration are discussed.

  2. Research Articles

    1. Top of page
    2. Rapid Communications
    3. Research Articles
    1. Raman analysis of insulin denaturation induced by high-pressure and thermal treatments (pages 692–700)

      S. Mangialardo, F. Piccirilli, A. Perucchi, P. Dore and P. Postorino

      Article first published online: 11 NOV 2011 | DOI: 10.1002/jrs.3097

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      Raman spectroscopy has been used to investigate different conformational states of insulin: the native form and several structurally modified states with different extent of denaturation induced by thermo-chemical treatment and by applying very high pressure (up to 8 GPa) using a diamond anvil cell. High-pressure results confirm the peculiar strength to volume compression of insulin and largely extend the pressure range of its structural stability. Above 4.2 Gpa, insulin undergoes an irreversible transition to a new conformational state.

    2. Surface-enhanced Raman spectra of melamine and other chemicals using a 1550 nm (retina-safe) laser (pages 701–705)

      Hermes Huang, Chetan Shende, Atanu Sengupta, Frank Inscore, Carl Brouillette, Wayne Smith and Stuart Farquharson

      Article first published online: 24 NOV 2011 | DOI: 10.1002/jrs.3079

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      Surface-enhanced Raman spectra were measured for melamine and other chemicals at 1550 nm laser excitation. The results are compared with spectra at 785 and 1064 nm using similar Raman optical systems and the same surface-enhanced Raman scattering substrate

    3. Label-free detection of binary mixtures of proteins using surface-enhanced Raman scattering (pages 706–711)

      Zhen Zhou, Xiaoxia Han, Genin Gary Huang and Yukihiro Ozaki

      Article first published online: 11 NOV 2011 | DOI: 10.1002/jrs.3085

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      For the binary mixture in which both proteins do not contain chromophores, variations in the intensities of surface-enhanced Raman scattering signals with changes in relative concentration of the two kinds of proteins is largely proportional to the relative concentration of the protein mixture. However, when another binary mixture is investigated, in which one protein contains chromophore while the other protein does not, the surface-enhanced Raman scattering intensities of the protein mixture displays a bell-shaped variation versus the changes in the mixture composites.

    4. Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering (pages 712–717)

      Leandro M. S. Takata, Augusto C. Gonçalves, Rômulo A. Ando, Alcindo A. Dos Santos and Pedro H. C. Camargo

      Article first published online: 7 DEC 2011 | DOI: 10.1002/jrs.3081

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      This paper describes a surface-enhanced Raman scattering study regarding the functionalization of Au and Ag NPs with the diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Functionalization took place with the cleavage of the chalcogen–chalcogen bond, and the detected differences in the spectra were assigned to the distinct stretching frequencies of the carbon–chalcogen bond and its relative contribution to the ring vibrational modes

    5. Surface-enhanced Raman measurements and DFT calculations for l-tryptophan of varying pH in silver sol (pages 718–723)

      Susmita Bhattacharya, Nidhi Vyas, Animesh K. Ojha, Swagata Dasgupta and Anushree Roy

      Article first published online: 24 FEB 2012 | DOI: 10.1002/jrs.3083

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      The interaction of l-tryptophan with silver colloids was investigated at between pH values of 6.11 and 10.6 of the sol. Density functional theory calculations were used to calculate the electric charge at different atoms. The nonmonotonous variation in the ratio of the spectral intensities of Fermi resonance bands with pH reflects the effect of the colloidal environment on l-tryptophan.

    6. Improved performance of surface-enhanced Raman scattering on silver substrates prepared in nitric acid solutions (pages 724–729)

      Fu-Der Mai, Ting-Chu Hsu, Yu-Chuan Liu and Kuang-Hsuan Yang

      Article first published online: 27 OCT 2011 | DOI: 10.1002/jrs.3084

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      The SERS of R6G adsorbed on the roughened Ag substrate developed in this work exhibits a higher intensity by ca. 4-fold of magnitude, as compared with that of R6G adsorbed on a roughened Ag substrate prepared in a chloride-containing solution, which were generally shown in the literature.

    7. SERS active Ag nanoparticles in mesoporous silicon: detection of organic molecules and peptide–antibody assays (pages 730–736)

      Alessandro Virga, Paola Rivolo, Emiliano Descrovi, Alessandro Chiolerio, Gabriella Digregorio, Francesca Frascella, Marco Soster, Federico Bussolino, Serena Marchiò, Francesco Geobaldo and Fabrizio Giorgis

      Article first published online: 24 NOV 2011 | DOI: 10.1002/jrs.3086

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      Ag nanoparticles synthesized on porous silicon samples were studied and applied as surface-enhanced Raman scattering (SERS) substrates. SERS activity was tested using Cy5 dye verifying an enhancement factor up to 107. CGIYRLRS peptides were chemisorbed on the Ag nanoparticles with the plasmonic resonance tuned at the excitation energy. Such oligopeptides were used as baits for a specific polyclonal antibody. The overall Raman enhancement allowed to evidence a good selectivity to the target analyte as required by most of the SERS applications on biological assays.

    8. In situ Raman and photoluminescence study on pressure-induced phase transition in C60 nanotubes (pages 737–740)

      Dedi Liu, Mingguang Yao, Quanjun Li, Wen Cui, Lin Wang, Zepeng Li, Bo Liu, Hang Lv, Bo Zou, Tian Cui, Bingbing Liu and Bertil Sundqvist

      Article first published online: 16 JAN 2012 | DOI: 10.1002/jrs.3087

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      The molecule structure stabilities of C60 under high pressure is enhanced in nanotubes than in bulk crystals.

    9. Enhancement of Raman scattering of light by ultramarine microcrystals in presence of silver nanoparticles (pages 741–744)

      E. V. Klyachkovskaya, D. V. Guzatov, N. D. Strekal, S. V. Vaschenko, A. N. Harbachova, M. V. Belkov and S. V. Gaponenko

      Article first published online: 16 MAR 2012 | DOI: 10.1002/jrs.3088

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      Approximately 102-fold enhancement of Raman scattering by ultramarine microcrystals is reported by means of interaction with silver nanoparticles in films and powders. Theoretical modeling predicts the maximal 1010-fold enhancement in close vicinity of a silver spherical nanoparticle (0.24 nm) with rapid decay of enhancement factor to 1 in the range of approximately 50 nm. Experimental enhancement factor is treated as overall effect within the small portion of every microcrystal in the close vicinity of silver nanoparticle(s).

    10. Synthesis and attachment of silver nanowires on atomic force microscopy cantilevers for tip-enhanced Raman spectroscopy (pages 745–749)

      Pierre Brodard, Mikhael Bechelany, Laetitia Philippe and Johann Michler

      Article first published online: 27 OCT 2011 | DOI: 10.1002/jrs.3091

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      Silver nanowires (diameter = 200 nm) are synthesized by electrochemical deposition in the pores of an alumina mask. After dissolution of the alumina template, a single silver nanowire is nanomanipulated and attached to an atomic force microscopy (AFM) cantilever by focused electron beam induced deposition. These nanowire-functionalized AFM-tips present a strong and reliable tip-enhanced Raman spectroscopy effect and very good AFM imaging capabilities. This method is capable of producing nanowires of different metals with diameters down to 50 nm and with various shapes.

    11. Proline and hydroxyproline deposited on silver nanoparticles. A Raman, SERS and theoretical study (pages 750–755)

      J. J. Cárcamo, A. E. Aliaga, E. Clavijo, C. Garrido, J. S. Gómez-Jeria and M. M. Campos-Vallette

      Article first published online: 11 NOV 2011 | DOI: 10.1002/jrs.3092

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      The Raman and surface-enhanced Raman scattering (SERS) spectra of l-proline (Pro) and trans-4-hydroxy- l-proline (Hyp) were registered. SERS spectra were recorded by using Ag colloidal obtained from hydroxylamine reduction agent. The accommodation time of Pro and Hyp in the colloidal solution resulted fundamentally in obtaining SERS spectrum. The spectroscopic results are supported by quantum chemical calculations, performed by using extended Hückel theory of the title compounds interacting with an Ag cluster model.

    12. Raman investigation of silicon nanocrystals: quantum confinement and laser-induced thermal effects (pages 756–760)

      Y. Duan, J. F. Kong and W. Z. Shen

      Article first published online: 27 OCT 2011 | DOI: 10.1002/jrs.3094

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      Detailed experimental and theoretical Raman investigations of quantum confinement and laser-induced local thermal effects have been performed on hydrogenated nanocrystalline silicon with different nanocrystal sizes. We have shown that the phonon dynamic behavior correlates well with the phonon density of states in Si nanocrystals.

    13. Micro-Raman and photoluminescence analysis of composite vanadium oxide/poly-vinyl acetate fibres synthesised by electro-spinning (pages 761–768)

      G. Faggio, V. Modafferi, G. Panzera, D. Alfieri and S. Santangelo

      Article first published online: 3 NOV 2011 | DOI: 10.1002/jrs.3089

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      Composite fibres based on vanadium oxide are synthesised by the combined sol–gel/electro-spinning method. The effect of calcination at different temperatures (300–500 °C) on their microstructure and composition is investigated in view of the possible use of the fibres in gas sensor fabrication.

    14. The determination of percentage dissociation of zircon (ZrSiO4) to plasma-dissociated zircon (ZrO2.SiO2) by Raman spectroscopy (pages 769–773)

      L. D. Kock, M. D. S. Lekgoathi, E. Snyders, J. B. Wagener, J. T. Nel and J. L. Havenga

      Article first published online: 7 DEC 2011 | DOI: 10.1002/jrs.3090

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      A quick and reliable method, using Fourier transform–Raman and partial least squares analysis is used to determine percentage dissociation of mineral zircon to plasma-dissociated zircon. The Raman band at 477 cm–1 (Ag) proved to be consistent and reliable for implementation in industrial situations. The ease of implementation is a vast improvement on previous wet chemical methods that are wasteful, time consuming, and use highly corrosive acids such as hydrofluoric acid.

    15. Influence of the chloro substituent position on the triplet reactivity of benzophenone derivatives: a time-resolved resonance Raman and density functional theory study (pages 774–780)

      Wen Li, Jiadan Xue, Shun Cheung Cheng, Yong Du and David Lee Phillips

      Article first published online: 27 OCT 2011 | DOI: 10.1002/jrs.3078

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      Time-resolved resonance Raman results show that the 2-chloro substituent reduces the hydrogen abstraction ability of the substituted benzophenone triplet while the 3-chloro, 4-chloro and 4,4′-dichloro ones have little influences on their triplet properties and reactivities. The experimental spectra were indentified and analysed with the aid of density functional theory calculations.

    16. Discrimination of aged mixtures of lipidic paint binders by Raman spectroscopy and chemometrics (pages 781–786)

      Eloisa Manzano, José García-Atero, Ana Dominguez-Vidal, Maria José Ayora-Cañada, Luis Fermín Capitán-Vallvey and Natalia Navas

      Article first published online: 11 NOV 2011 | DOI: 10.1002/jrs.3082

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      The application of chemometric techniques to Raman spectra to study natural aged lipidic paint binders has been evaluated. Model samples of the pure binders (linseed, poppy-seed and walnut oils and egg yolk) and of binary mixtures were used. These model samples were left to age naturally for six years and further characterized by Raman spectroscopy. A comparative study of the Raman spectral features before and after ageing process was carried out. This showed changes mainly in the bands located at 1267, 1655 and 3011 cm–1, which correspond to vibrations in cis double bonds. Multivariate analysis was performed by applying principal component analysis and partial least-squares discriminant analysis on the corresponding Raman spectra to test whether spectral differences allowed samples to be distinguished on the basis of their composition.

    17. Raman studies of Japanese art objects by a portable Raman spectrometer using liquid crystal tunable filters (pages 787–791)

      Akira Sakamoto, Shukichi Ochiai, Hisamitsu Higashiyama, Koji Masutani, Jun-ichi Kimura, Emi Koseto-Horyu and Mitsuo Tasumi

      Article first published online: 27 OCT 2011 | DOI: 10.1002/jrs.3080

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      Raman spectroscopic studies of a few Japanese art objects have been performed by using a portable Raman spectrometer constructed with liquid crystal tunable filters as dispersive elements. Interesting information has been obtained from Raman spectra observed from ukiyo-e's (Japanese woodblock prints) and their woodblocks

    18. Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro-Raman mapping and X-ray diffraction (pages 792–798)

      Biljana Minčeva-Šukarova, Ali İssi, Aleksandra Raškovska, Orhideja Grupče, Vinka Tanevska, Merve Yaygıngöl, Alpagut Kara and Philippe Colomban

      Article first published online: 27 OCT 2011 | DOI: 10.1002/jrs.3077

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      Point-to-point micro-Raman spectroscopy and X-ray diffraction (XRD) technique were employed to characterize mineralogical content of 27 pottery artifacts. Twenty-six different minerals were identified by their Raman spectra and 13 minerals were identified by XRD. The results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well, while the identification of the less abundant minerals in the clay matrixes, from the XRD data, was very difficult, if at all possible.

    19. On-site Raman and XRF analysis of Japanese/Chinese bronze/brass patina – the search for specific Raman signatures (pages 799–808)

      Philippe Colomban, Aurélie Tournié, Michel Maucuer and Philippe Meynard

      Article first published online: 11 NOV 2011 | DOI: 10.1002/jrs.3095

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      Discrimination of ancient Asian bronzes and brasses is complex because the copies have been made since ancient times. A selection of 30 Japanese and/or Chinese Bronzes are studied on-site in the storage and exhibition rooms of the Cernuschi Museum in Paris. Attempts are made to identify specific Raman signatures of the patina to detect similarity in a nondestructive procedure and to discuss the relationship between the patina phases and the bronze composition.

    20. The first spectroscopic analysis of Ethiopian prehistoric rock painting (pages 809–816)

      Cristiana Lofrumento, Marilena Ricci, Luca Bachechi, Denise De Feo and Emilio Mario Castellucci

      Article first published online: 16 NOV 2011 | DOI: 10.1002/jrs.3096

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      An extensive micro-Raman study of prehistoric rock paintings found in Hararghe region, Ethiopia, was conducted to evaluate the production skill of the local artists and the period of production of the discovered paintings. The pigments used were hematite, calcite or gypsum, and carbonaceous material. A green earth pigment was also investigated. Raman mapping evidenced that Ca-oxalate, found on red and white samples, is ascribed to the use of an organic stuff to spread properly the pigments on the substrate.