Journal of Raman Spectroscopy

Cover image for Vol. 43 Issue 12

December 2012

Volume 43, Issue 12

Pages 1845–2034

  1. Review

    1. Top of page
    2. Review
    3. Rapid communication
    4. Research articles
    1. Recent advances in linear and nonlinear Raman spectroscopy. Part VI (pages 1845–1863)

      Laurence A. Nafie

      Article first published online: 4 DEC 2012 | DOI: 10.1002/jrs.4221

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      A review of the current status of Raman spectroscopy is presented based on a survey of published papers by category of Raman spectroscopy over the past decade, highlights of the 2012 International Conference on Raman Spectroscopy (ICORS 2012) and SCIX (FACSS) 2012, and papers published in the Journal of Raman Spectroscopy during the year 2011. This is Part VI in this ongoing annual review of Raman spectroscopy.

  2. Rapid communication

    1. Top of page
    2. Review
    3. Rapid communication
    4. Research articles
    1. Raman imaging on high-quality graphene grown by hot-filament chemical vapor deposition (pages 1864–1867)

      S. Kataria, Avinash Patsha, S. Dhara, A. K. Tyagi and Harish C. Barshilia

      Article first published online: 1 AUG 2012 | DOI: 10.1002/jrs.4113

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      High-quality graphene on Cu foils and its subsequent in-situ hydrogenation by hot-filament chemical vapor deposition technique using CH4 and H2 gas mixture are reported. Micro-Raman spectroscopic along with area mapping studies confirm growth of monolayer graphene as inferred from the intensity ratio of 2D to G peak which is nearly four in unhydrogenated samples. The grown layer is also transferred onto a Si substrate over ~10 × 10 mm sq. area.

  3. Research articles

    1. Top of page
    2. Review
    3. Rapid communication
    4. Research articles
    1. Raman and fluorescence investigations on retrieved Biolox® delta femoral heads (pages 1868–1876)

      Paola Taddei, Enrico Modena, Francesco Traina and Saverio Affatato

      Article first published online: 15 JUL 2012 | DOI: 10.1002/jrs.4105

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      Biolox® delta retrievals were here characterised for the first time at the molecular level. Fluorescence and Raman data showed a progressive improvement of the material properties between 1999 and 2009. Wear was found as the main cause of the in vivo tetragonal-to-monoclinic zirconia transformation, which involved a region much more extended than as reported in the literature. The in vitro accelerated ageing protocols proposed in the literature to simulate the effects of the in vivo wear were validated.

    2. Aggregation processes in micellar solutions: a Raman study (pages 1877–1883)

      G. Cazzolli, S. Caponi, A. Defant, C. M. C. Gambi, S. Marchetti, M. Mattarelli, M. Montagna, B. Rossi, F. Rossi and G. Viliani

      Article first published online: 12 JUL 2012 | DOI: 10.1002/jrs.4120

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      Raman spectroscopy has been used in order to study the aggregation processes, that involve SDS above the critical micellar concentration and as a consequence of the addition of macrocyclic molecules such as 18C6 and K222. The aggregation of micelles produces changes of the wavenumbers and intensities of the Raman bands of the micelle, the ligand and the hydration layer.

    3. Range-independent background subtraction algorithm for recovery of Raman spectra of biological tissue (pages 1884–1894)

      Hemant Krishna, Shovan K. Majumder and Pradeep K. Gupta

      Article first published online: 27 AUG 2012 | DOI: 10.1002/jrs.4127

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      We report a range-independent background subtraction algorithm based on modified iterative moving point average smoothing of the measured raw Raman spectra for rapid and automated retrieval of Raman signatures of biological tissues. The algorithm fulfils all the requirements of an effective background subtraction method that is desired for successful use of Raman spectroscopy for real-time, non-invasive, automated diagnosis of various cancers in a clinical situation.

    4. Understanding tip-enhanced Raman spectra of biological molecules: a combined Raman, SERS and TERS study (pages 1895–1904)

      Carolin Blum, Thomas Schmid, Lothar Opilik, Simon Weidmann, Stephan R. Fagerer and Renato Zenobi

      Article first published online: 22 JUN 2012 | DOI: 10.1002/jrs.4099

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      Confocal Raman, surface-enhanced Raman and tip-enhanced Raman spectra of peptides and a protein are compared to learn from their differences and similarities. We show that (1) the widely used assumption that spectral bands do not shift when comparing these methods is valid, (2) the band intensities can vary dramatically and (3) marker bands can be assigned, which should allow one to localize proteins in a complex environment. General guidelines for the interpretation of tip-enhanced Raman spectra of biological molecules are presented.

    5. Distinguishable behavior of multiple and individual rhodamine-6G molecules on spherical Ag nanoparticles examined via time dependence of the SERS spectra (pages 1905–1912)

      Zhixun Luo, W. Hunter Woodward and A. W. Castleman Jr.

      Article first published online: 16 JUL 2012 | DOI: 10.1002/jrs.4107

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      By analysis of the different time dependence of SERS spectra from multiple and individual Rh6G molecules adsorbed on spherical Ag nanoparticles, we show an evidence for the molecular moving and trapping in the ‘hot-spots’ under laser excitation.

    6. Adsorption and catalysis of flavonoid quercetin on different plasmonic metal nanoparticles monitored by SERS (pages 1913–1919)

      Z. Jurasekova, C. Domingo, J. V. Garcia-Ramos and S. Sanchez-Cortes

      Article first published online: 10 SEP 2012 | DOI: 10.1002/jrs.4114

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      Quercetin (QUC), one of the most common flavonols widely distributed in the plant kingdom, is of interest both as a dye and biologically active molecule. The surface-enhanced Raman scattering spectrum of QUC has been already reported in a number of previous papers. However, a deeper interpretation of the chemical processes developed by QUC on metal nanoparticles is discussed here for the first time. In addition, characteristic spectral assignment for the species recognized under different experimental conditions has been conducted.

    7. Effects of trap density on the surface-enhanced Raman scattering of molecules adsorbed on TiO2 (Degussa P25) (pages 1920–1923)

      Z. L. Zhang, D. N. Li and Y. L. Mao

      Article first published online: 15 JUL 2012 | DOI: 10.1002/jrs.4128

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      The variation of SERS intensity with the calcination temperature rising was observed with TiO2 (Degussa P25). The trap density of TiO2 was directly measured. The increase of trap density is favorable for the increase of SERS intensity.

    8. Effect of shape and interstice on surface enhanced Raman scattering (SERS) of molecules adsorbed on gold nanoparticles in the near-dipole and quadrupole regions (pages 1924–1930)

      T. Abdallah, T.A. El-Brolosy, M. B. Mohamed, K. Easawi, S. Negm and H. Talaat

      Article first published online: 15 JUL 2012 | DOI: 10.1002/jrs.4131

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      Surface enhanced Raman scattering (SERS) of adsorbed molecule on colloidal gold nanospheres (NSs), nanorods, and nanoprisms (NPs) in the near-dipole and near-quadrpole regions of the nanoparticles, show that the SERS enhancement is the largest for the sharp tip NPs and least for the NSs. These enhancements are due to the binding energies of the nanocrystal facets, but a larger contribution from the plasmon electromagnetic fields. FDTD show agreement with SERS enhancement for the different shapes.

    9. Ultraviolet tip-enhanced nanoscale Raman imaging (pages 1931–1934)

      Kyoung-Duck Park, Yong Hwan Kim, Jin-Ho Park, Jung Su Park, Hong Seok Lee, Sang-Youp Yim, Young Hee Lee and Mun Seok Jeong

      Article first published online: 11 SEP 2012 | DOI: 10.1002/jrs.4158

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      We have constructed an ultraviolet (UV)-apertureless near-field scanning optical microscope-Raman spectroscopy system by using an aluminum tip for the simultaneous measurement of topography and Raman scattering of nano materials with high spatial resolution. The topography, Rayleigh scattering image, and tip-enhanced Raman scattering image of the carbon nanotube film showed that a spatial resolution of around 19 nm was achieved. This spatial resolution of UV-Raman mapping image exceeds that of previous approaches which have several hundred nanometers of spatial resolution.

    10. Increase of the stimulated Raman scattering threshold at droplets by spectral broadening of nanosecond laser pulses (pages 1935–1940)

      R. F. Hankel, A. Braeuer and A. Leipertz

      Article first published online: 11 AUG 2012 | DOI: 10.1002/jrs.4106

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      The SRS threshold for droplets in the micro scale is determined experimentally in dependency of the spectral broadness of the excitation source. The possibility of stimulated effect inside the droplet is reduced due to the lower spectral power density of the broadband laser pulse.

    11. The vibrations of vitreous silica observed in hyper-Raman scattering (pages 1941–1950)

      B. Hehlen and G. Simon

      Article first published online: 15 JUL 2012 | DOI: 10.1002/jrs.4110

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      Hyper-Raman scattering (HRS) is performed in vitreous silica and compared to Raman and infrared data. The specificity of the HRS selection rules allows to easily separate transverse and longitudinal components of the polar modes and provides new information on the vibrations, as for example their spatial extension. The nature of the modes underlying the boson peak at low frequency is also discussed.

    12. Single-wall carbon nanotube interactions with copper-oxamato building block of molecule-based magnets probed by resonance Raman spectroscopy (pages 1951–1956)

      Gustavo M. do Nascimento, Wdeson P. Barros, Yoong Ahm Kim, Hiroyuki Muramatsu, Takuya Hayashi, Morinobu Endo, Noriberto A. Pradie, Cristiano Fantini, Marcos A. Pimenta, Mildred S. Dresselhaus and Humberto O. Stumpf

      Article first published online: 4 JUL 2012 | DOI: 10.1002/jrs.4111

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      The electronic interactions between the [Cu(opba)]2− anions and the single-wall carbon nanotubes (SWCNTs) were investigated, and some charge transfer is observed from SWCNTs to the [Cu(opba)]2− anions. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes.

    13. Raman tensor analysis of hexagonal polyoxymethylene and its application to study the molecular arrangement in highly crystalline electrospun nanofibers (pages 1957–1963)

      Leonardo Puppulin, Masaya Kotaki, Morimasa Nakamura, Daisuke Iba, Ichiro Moriwaki and Giuseppe Pezzotti

      Article first published online: 15 JUL 2012 | DOI: 10.1002/jrs.4116

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      The orientation dependence in space of Raman-active A1 and E1 vibrational modes of the hexagonal structure of polyoxymethylene is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. An approach based on the introduction of orientation distribution functions is applied to quantitatively assess and compare on a statistical base the molecular orientation of two different types of polyoxymethylene nanofibers.

    14. Competition between strain and confinement effects on the crystalline quality of InAs/GaAs (001) quantum dots probed by Raman spectroscopy (pages 1964–1968)

      K. Rezgui, S. Aloulou, J. Rihani and M. Oueslati

      Article first published online: 1 OCT 2012 | DOI: 10.1002/jrs.4122

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      Nanometer-sized self-assembled quantum dots (QDs) (Fig.1) have emerged as a new exciting research field due to their unique electronic properties. These structures are formed following a strained coherent islanding in heteroepitaxial systems under substantial strain. Quantum dot phonons play an important role in the carrier relaxation and emission properties of QDs. Many issues related to the effects on QD phonon shifts of phonon confinement in the QD, the presence of inhomogeneous strain fields, alloy formation at the interfaces, and the wetting layer role are far from trivial. Raman scattering provides a direct measurement of QD phonon frequencies (Fig.2) and a valuable insight into these unresolved questions.

    15. Resonance Raman spectroscopy and theoretical study on the photodissociation dynamics of diuron in S2 state (pages 1969–1974)

      Kemei Pei, Mingyang Su, Lin Chen, Fanglong Li and Xuming Zheng

      Article first published online: 16 JUL 2012 | DOI: 10.1002/jrs.4117

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      To diuron, dissociation by Ph-Cl (para) cleavage at S2 state directly or relaxation to T2 state by internal conversion (S2[RIGHTWARDS ARROW] S1) and intersystem crossing (S1/T2) is expected by ~250nm irradiation based on the RRS, complete active space self-consisted field, configuration interaction singles and time-dependent density functionaltheory calculations.

    16. Pigments and enamelling/gilding technology of Mamluk mosque lamps and bottle (pages 1975–1984)

      Philippe Colomban, Aurélie Tournié, Maria Cristina Caggiani and Céline Paris

      Article first published online: 17 JUL 2012 | DOI: 10.1002/jrs.4101

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      On-site Raman spectroscopy is used to investigate four mosque lamps and a bottle dating back to the 13–14th centuries (Mamluk). The pigments and the enamelled glass matrix are identified in order to discuss their technology. A comparison is made with a 19th-century Brocard masterpiece.

    17. Rapid screening of sildenafil and tadalafil adulterated in healthcare products by Micro-Raman spectroscopy (pages 1985–1990)

      Dan-Zhuo Mao, Xin-Xin Weng and Yong-Jian Yang

      Article first published online: 12 JUL 2012 | DOI: 10.1002/jrs.4102

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      This research provided a quick and convenient method for screening sildenafil and tadalafil adulterated in healthcare products.

    18. The autooxidation process in linoleic acid screened by Raman spectroscopy (pages 1991–2000)

      N. F. L. Machado, L. A. E. Batista de Carvalho, J. C. Otero and M. P. M. Marques

      Article first published online: 8 NOV 2012 | DOI: 10.1002/jrs.4121

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      The chemical changes associated to the autooxidation process of LA were detected by Raman spectroscopy and interpreted in the light of DFT calculations. The success of Raman spectroscopy in probing the oxidation state of a fatty acid, coupled to a simpler setup and virtually no sample preparation, renders this technique a very useful and promising tool, namely for assessing the quality of edible oils and other lipid-containing food products in situ.

    19. Systematic investigations of anthocyanin–metal interactions by Raman spectroscopy (pages 2001–2007)

      Maria Buchweitz, Gennadi Gudi, Reinhold Carle, Dietmar R. Kammerer and Hartwig Schulz

      Article first published online: 18 SEP 2012 | DOI: 10.1002/jrs.4123

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      Raman spectra of the chloride salts of various anthocyanidin-3-glucosides, their structures at pH 5.0 and interaction with aluminium and ferric ions are presented and discussed for the first time. Formation of metal chelates is verified for anthocyanins in the presence of sugar beet pectin solutions, and the impact of pectin on chelate formation is investigated. Our results demonstrate that Raman spectroscopy is a very useful tool in studying anthocyanin – ferric and aluminium chelate formation.

    20. Semiclassical line broadening calculations, using an ab initio potential energy surface, in Q-branch and S-branch of N2 perturbed by H2 (pages 2008–2014)

      M. Dhyne, M. Lepère and P. Joubert

      Article first published online: 16 JUL 2012 | DOI: 10.1002/jrs.4126

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      H2 broadening coefficients of Raman lines belonging to Q-branch and S-branch of N2 have been calculated using a numerical procedure based on the semiclassical Robert–Bonamy model. With the ab initio potential energy surface used, results are obtained for a large range of temperatures and J quantum numbers and compared with a satisfactory agreement with previous experimental data.

    21. Study on solid structure of pentacene thin films using Raman imaging (pages 2015–2019)

      Keisuke Seto and Yukio Furukawa

      Article first published online: 16 OCT 2012 | DOI: 10.1002/jrs.4090

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      The solid-state phases of pentacene thin films have been investigated by images and histograms of the ratio (R) of intensity of the 1596-cm−1 band (b3g) to that of the 1533-cm−1 band (ag). Raman images showed that 1.44-nm phase domains are grown on the 1.54-nm phase layer from 50 nm and cover its entire surface from 100 nm. Structural disorders have been discussed on the basis of the distribution of R values in the histograms.

    22. Raman scattering studies of spin-waves in hexagonal BaFe12O19 (pages 2020–2024)

      Nguyen Thi Minh Hien, Kiok Han, Xiang-Bai Chen, Jung Chul Sur and In-Sang Yang

      Article first published online: 10 SEP 2012 | DOI: 10.1002/jrs.4100

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      We present the results of polarized Raman spectroscopy of hexagonal BaFe12O19 single crystal. The spectra, recorded from 200 to 800 cm–1 and 1100 to 1700 cm–1 in the 20–250 K temperature range, are analyzed on the basis of both crystal vibrations and spin-waves. In the low wavenumber range, the Γ-point phonons are observed. In the high wavenumber range, phonon mixings are observed; more interestingly, four modes of spin-waves are identified in hexagonal BaFe12O19. Both have not been studied previously. Our analyses of the spin-waves provide an optical method for quantitatively estimating the spin exchange interactions in hexagonal BaFe12O19. The four strong exchange integrals are found to have the values of Jce = 1.31 meV, Jae = 1.36 meV, Jcd = 1.46 meV, and Jbd = 1.71 meV. Our results also indicate that at ~200 and ~80 K, there would be additional spin-ordering transitions in hexagonal BaFe12O19.

    23. Raman analyses of co-phasing and hysteresis behaviors in V2O3 thin film (pages 2025–2028)

      Xiang-Bai Chen, Jun-Hwan Shin, Hyun-Tak Kim and Yong-Sik Lim

      Article first published online: 12 JUL 2012 | DOI: 10.1002/jrs.4112

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      We present the studies of the phase transition behaviors of V2O3 thin film using temperature-dependent Raman scattering spectroscopy. Our results show that in both the cooling and heating processes of V2O3 thin film, the phase transition occurs gradually but not suddenly, contrary to that in single crystal. The coexistence of both the metal and insulator phases with co-phasing ΔTc larger than 30 K is observed in both the cooling and heating processes. We discuss that this large co-phasing ΔTc should be distinguished with the large hysteresis ΔTh reported in nanostructures. In addition, our discussions indicate that co-phasing ΔTc and hysteresis ΔTh would be mainly correlated with stress and defect states in sample, respectively. Furthermore, we suggest that stress would induce phase transitions in V2O3, and the stress (pressure)-induced phase transitions would behave differently comparing with the temperature-induced transitions under normal pressure.

    24. Molecular orientation analysis of organic thin films by z-polarization Raman microscope (pages 2029–2034)

      Toshihiro Mino, Yuika Saito, Hiroyuki Yoshida, Satoshi Kawata and Prabhat Verma

      Article first published online: 11 AUG 2012 | DOI: 10.1002/jrs.4118

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      We have demonstrated orientation analysis of pentacene thin films by the z-polarization Raman microscope with spatial resolution of 300 nm. This results indicate that the lamellar grains show the lower tilt angles compared to the neighboring islands. Our technique can be ideally applied to the characterization of molecular thin films, which is essential for organic transistor research.

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