Journal of Raman Spectroscopy

Cover image for Vol. 44 Issue 10

Special Issue: Joint special issue on the European Conference on Nonlinear Optical Spectroscopy (ECONOS 2012) and the II Italian Conference of the National Group of Raman Spectroscopy and Non-Linear Effects (GISR 2012)

October 2013

Volume 44, Issue 10

Pages 1317–1477

Issue edited by: Johannes Kiefer, Peter Radi, Maria Grazia Giorgini

  1. Editorials

    1. Top of page
    2. Editorials
    3. Research articles
    4. Review
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    2. You have free access to this content
  2. Research articles

    1. Top of page
    2. Editorials
    3. Research articles
    4. Review
    1. Pure rotational Coherent anti-Stokes Raman spectroscopy of water vapor and its relevance for combustion diagnostics (pages 1322–1325)

      Emil Nordström, Alexis Bohlin and Per-Erik Bengtsson

      Article first published online: 25 FEB 2013 | DOI: 10.1002/jrs.4275

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      The rotational coherent anti-Stokes Raman spectroscopy (CARS) spectrum of water vapor, recorded through experiments at 400 K and 670 K, is reported for the first time, along with a brief discussion on the influence of the presence of water on rotational CARS spectra recorded in product gases of combustion.

    2. Effect of vibration–rotation coupling on simultaneous extraction of temperature and species concentration from vibrational CARS spectra of hot gases (pages 1326–1329)

      Michele Marrocco

      Article first published online: 7 AUG 2013 | DOI: 10.1002/jrs.4357

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      The coupling between vibration and rotation in light molecules changes the strength of the coherent anti-Stokes Raman scattering in comparison to the conventional rigid-rotor approximation. The results show that small changes of the fitted temperature correspond to larger deviations for the determination of concentrations and non-resonant background. An example is the figure where the plot of the sum of squared differences indicates significant deviations for the physical parameters when the reference temperature is 2300 K.

    3. Single-shot thermometry using fiber-based picosecond coherent anti-stokes Raman scattering (CARS) spectroscopy (pages 1330–1335)

      Paul S. Hsu, Waruna D. Kulatilaka, James R. Gord and Sukesh Roy

      Article first published online: 1 MAR 2013 | DOI: 10.1002/jrs.4280

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      We have developed a fiber-based picosecond-coherent anti-Stokes Raman scattering (CARS) system for gas phase thermometry in harsh combustion environments. Proof-of-principle, single-laser-shot temperature measurements using 1-m-long and 3-m-long fiber systems are demonstrated in atmospheric pressure, near-adiabatic, laboratory H2–air flames. Limitations that are imposed by long-length multimode-fiber beam delivery for CARS thermometry are investigated and potential system improvements are suggested.

    4. Hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering for high-speed CH4/N2 measurements in binary gas mixtures (pages 1336–1343)

      Sascha R. Engel, Joseph D. Miller, Chloe E. Dedic, Thomas Seeger, Alfred Leipertz and Terrence R. Meyer

      Article first published online: 27 FEB 2013 | DOI: 10.1002/jrs.4261

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      Hybrid femtosecond/picosecond vibrational coherent anti-Stokes Raman scattering was demonstrated for high-speed, in situ measurements of CH4/N2 mole fractions in binary gas mixtures with temporal nonresonant suppression. A typical accuracy of ~95% was achieved for CH4 mole fractions from 0.02-0.70, and a precision of ~4% was achieved by maximizing relative excitation energy through induced chirp in the pump and Stokes pulses. Furthermore, mole fraction measurements were not affected by variations in bi-molecular broadened linewidths over a wide range of mixture fractions.

    5. Time-resolved femtosecond CARS from 10 to 50 Bar: collisional sensitivity (pages 1344–1348)

      Paul J. Wrzesinski, Hans U. Stauffer, Waruna D. Kulatilaka, James R. Gord and Sukesh Roy

      Article first published online: 26 MAR 2013 | DOI: 10.1002/jrs.4287

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      Time-resolved fs-coherent anti-Stokes Raman scattering (CARS) measurements on neat gases and gas mixtures at pressures up to 50 bar exhibit no dependence on the system pressure during the first 1–3 picoseconds. This is significant in that most CARS diagnostic approaches require accurate modeling of pressure-dependent effects, which proves to be challenging over large pressure ranges using traditional scaling-law treatment of rotational energy transfer.

    6. Polarization- and time-resolved DFWM spectroscopy of the A 2Σ+– X 2Π (0,0) band transitions of nascent OH radicals generated by 266 nm laser photolysis of H2O2 (pages 1349–1355)

      P. Maksyutenko, P. P. Radi, D. N. Kozlov and A. P. Kouzov

      Article first published online: 15 MAY 2013 | DOI: 10.1002/jrs.4299

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      Degenerate four-wave mixing is used to measure the line shapes of specific rovibrational transitions in the A2Σ+ - X2Π (0,0) band of nascent OH radicals upon pulsed photo-dissociation of H2O2. Isotropic and anisotropic components of the non-linear susceptibility tensor are separately accessible by using appropriate polarization geometries. In particular, four-wave mixing signals can be generated that are exclusively due to the occurrence of the transient anisotropy of the recoil velocity and angular momentum vector distributions of the fragments emerging from the dissociation reaction.

    7. Simultaneous measurements of fuel vapor concentration and temperature in a flash-boiling propane jet using laser-induced gratings (pages 1356–1362)

      B. Roshani, A. Flügel, I. Schmitz, D. N. Kozlov, T. Seeger, L. Zigan, J. Kiefer and A. Leipertz

      Article first published online: 22 MAY 2013 | DOI: 10.1002/jrs.4315

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      The laser-induced grating technique was further developed to measure two key parameter, vapor fuel concentration and gas phase temperature, during a direct injection process of liquid propane as the main component of liquefied petroleum gas.

    8. CARS diagnostics of fluid phase behavior in small mesopores at near-critical temperatures (pages 1363–1368)

      V. G. Arakcheev and V. B. Morozov

      Article first published online: 9 APR 2013 | DOI: 10.1002/jrs.4289

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      Coherent anti-Stokes Raman scattering spectroscopy is applied to investigate the fluid phase behavior in small mesopores with radii of 2 and 3 nm at bulk sub- and supercritical temperatures. The spectral transformations with pressure indicate the formation of a condensed phase inside pores at both temperatures pointing out the shift of critical point of the fluid. The spectrum of carbon dioxide condensed in the wider pores corresponds approximately to the critical density in bulk. In narrower pores, the spectrum is red-shifted that corresponds to higher density of condensed fluid.

    9. Non-Markovian nature of the fluctuation of the polarizability in molecular liquids by time-domain and frequency-domain measurements (pages 1369–1372)

      Yuji Sakai, Junji Watanabe and Shuichi Kinoshita

      Article first published online: 29 APR 2013 | DOI: 10.1002/jrs.4306

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      It is well known that spectra of molecular liquids in a low-wavenumber region show Lorentzian-like shape. However, we have found that the spectra are Lorentzian like in a limited wavenumber region, which is comparable with the half width ωd of the spectra. This is observed over three orders of magnitude of ωd ranging from ~0.005 to ~2 cm−1.

    10. Multimodal, label-free nonlinear optical imaging for applications in biology and biomedical science (pages 1373–1378)

      R. Mouras, P. Bagnaninchi, A. Downes and A. Elfick

      Article first published online: 11 JUN 2013 | DOI: 10.1002/jrs.4305

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      Multimodal image of adipose-derived stem cells induced towards adipocytes (a) and osteoblasts (b) at day 14 post-induction showing changes in cell morphology and the appearance of functional markers such as lipid droplets (red), fibrous collagen (blue), flavoproteins and lipofuscin (green).

    11. Elimination of two-photon excited fluorescence using a single-beam coherent anti-Stokes Raman scattering setup (pages 1379–1384)

      Alexander Wipfler, Jean Rehbinder, Tiago Buckup and Marcus Motzkus

      Article first published online: 25 FEB 2013 | DOI: 10.1002/jrs.4243

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      Coherent quantum control is used to detect single-beam CARS spectra in the presence of strong two-photon excited fluorescence. The corresponding schemes are theoretically evaluated and demonstrated experimentally on a model system.

    12. Raman-induced Kerr effect microscopy with balanced detection (pages 1385–1392)

      Egle Molotokaite, Vikas Kumar, Cristian Manzoni, Dario Polli, Giulio Cerullo and Marco Marangoni

      Article first published online: 18 MAR 2013 | DOI: 10.1002/jrs.4250

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      We present a new coherent Raman scattering technique, which we call balanced-detection Raman-induced Kerr effect. The technique relies on a balanced detection architecture which allows one to sensitively measure the Raman-induced Kerr effect-induced polarization rotation of the Stokes field. Balanced detection provides an intrinsic rejection of laser noise and, by properly changing the detection conditions, it allows the reconstruction of the full complex vibrational response, both in amplitude and phase, greatly increasing chemical selectivity in single-color excitation.

    13. Spectroscopic characterization of graphene films grown on Pt(111) surface by chemical vapor deposition of ethylene (pages 1393–1397)

      Enzo Cazzanelli, T. Caruso, M. Castriota, A. R. Marino, A. Politano, G. Chiarello, M. Giarola and G. Mariotto

      Article first published online: 2 APR 2013 | DOI: 10.1002/jrs.4285

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      In-situ and ex-situ characterization techniques (low-energy electron diffraction, high-resolution electron energy loss spectroscopy, scanning electron microscopy and Raman micro-spectroscopy) here used indicate the prevalence of single-layer regions and the presence of two different orientations of the graphene sheets, tilted of 0° and 30°, with respect to the Pt(111) substrate. Both these domain orientations generate a comparable Raman signal. Data from micro-Raman sampling indicates a better film quality than in previous deposition experiments on the same metal substrate.

    14. Structure and chain polarization of long polyynes investigated with infrared and Raman spectroscopy (pages 1398–1410)

      N. R. Agarwal, A. Lucotti, D. Fazzi, M. Tommasini, C. Castiglioni, W.A. Chalifoux and R. R. Tykwinski

      Article first published online: 27 MAY 2013 | DOI: 10.1002/jrs.4300

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      Using vibrational spectroscopy and density functional theory calculations, long symmetrically capped polyynes have been studied as a function of increasing chain length for phonon dispersions. Unsymmetrically capped polyynes have been also studied as a comparison. Raman and infrared data demonstrate polarization and structural effects for these series of long polyyne chains.

    15. Polarized micro-Raman spectroscopy and ab initio phonon modes calculations of LuPO4 (pages 1411–1415)

      A. Sanson, M. Giarola, M. Bettinelli, A. Speghini and G. Mariotto

      Article first published online: 31 MAR 2013 | DOI: 10.1002/jrs.4257

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      The vibrational dynamics of lutetium orthophosphate single crystals has been investigated by means of polarized micro-Raman spectroscopy and ab initio calculations. Eleven of the twelve independent components of its polarizability tensor were observed in turn and assigned in symmetry. The only B1g(2) Raman mode was not observed, likewise due to either its very small intensity or its nearness in energy with forbidden Raman modes, which spill and could hide it. Density-functional theory calculations, using effective core pseudo-potential, were adopted to evaluate both its Raman and infrared vibrational modes, with an excellent agreement with the experimental frequencies. On the basis of our ab initio results and of reduced-mass ratio considerations, the expected wavenumber of the missing B1g (2) mode falls close to that of Eg(3) mode peaked at about 306 cm−1, and therefore we can definitively conclude that the observation of the missing B1g (2) mode is masked by the spill-over of this Eg mode.

    16. SERS investigation on the adsorption and photoreaction of 4-nitroanisole in Ag hydrosols (pages 1416–1421)

      Maurizio Muniz-Miranda

      Article first published online: 6 MAR 2013 | DOI: 10.1002/jrs.4236

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      A surface-enhanced Raman spectroscopy signal could be detected only in chloride-activated silver colloids, but the spectrum was not related to 4-nitroanisole, but to its azoderivative, formed by the reduction of the nitrogroup.

    17. Vibrational characterization and surface-enhanced Raman scattering detection of probenecid doping drug (pages 1422–1427)

      Irene Izquierdo-Lorenzo, José Vicente García-Ramos and Santiago Sanchez-Cortes

      Article first published online: 5 APR 2013 | DOI: 10.1002/jrs.4284

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      We report the detection by SERS of Probenecid, a drug employed to reduce the excretion of other drugs in urine and also employed as masking agent in sport doping. A previous vibrational study was done by FTIR, FT-Raman and DFT calculations. The experimental conditions of SERS measurement were optimized by varying parameters like the metal, its reduction protocol to fabricate the nanoparticles and the pH. The adsorption isotherms of PB on the metal nanoparticles were obtained and the adsorption mechanism of this drug on Ag nanoparticles was deduced from the analysis of SERS spectra. Finally, a quantitative SERS study was carried out on the basis of the calibration curve deduced from the adsorption isotherms.

    18. SERS detection of benzophenones on viologen functionalized Ag nanoparticles: application to breakfast cereals (pages 1428–1434)

      Enrica Droghetti, Francesco P. Nicoletti, Luca Guandalini, Gianluca Bartolucci and Giulietta Smulevich

      Article first published online: 18 MAR 2013 | DOI: 10.1002/jrs.4273

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      Surface-enhanced Raman scattering (SERS) spectroscopy using lucigenin as a molecular assembler in the functionalization of silver nanoparticles allowed us to reveal the presence of benzophenone and 4-methyl benzophenone in spiked breakfast cereal samples. The detection limit was at trace level, 25 ppm. The samples were analyzed with both SERS spectroscopy and gas chromatography-tandem mass spectrometry. For concentration above 70 μM (25 ppm), there was a very good agreement between the two techniques.

    19. Raman characterization of the interactions between gliadins and anthocyanins (pages 1435–1439)

      Paola Taddei, Nicola Zanna and Silvia Tozzi

      Article first published online: 22 MAR 2013 | DOI: 10.1002/jrs.4288

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      Raman spectroscopy demonstrated that the anthocyanins induce in gliadins conformational changes of different extents. The treatment with any of the considered anthocyanins altered the distribution of the disulphide conformations; in addition, malvin and pelargonin provoked a significant decrease of the β-turns content. Since both these structural elements have been related to gluten allergenicity, anthocyanins appeared interesting molecules, potentially able to decrease allergen immunoreactivity.

    20. Micro-Raman spectroscopy identifies crocidolite and erionite fibers in tissue sections (pages 1440–1445)

      Alessandro Croce, Maya Musa, Mario Allegrina, Caterina Rinaudo, Y. Izzettin Baris, A. Umran Dogan, Amy Powers, Zeyana Rivera, Pietro Bertino, Haining Yang, Giovanni Gaudino and Michele Carbone

      Article first published online: 28 APR 2013 | DOI: 10.1002/jrs.4286

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      Micro-Raman Spectroscopy and Scanning Electron Microscopy were applied to identify fibers on histological sections from different tissues of mice injected with crocidolite asbestos or erionite. Also, sections prepared for medical diagnosis from lung biopsies of patients affected by malignant mesothelioma from Cappadocia were analyzed. Micro-Raman spectroscopy is proved as technique allowing an easy and sure identification of crocidolite and erionite, both in mice tissues and in human biopsies.

    21. Spectroscopic investigation on the structural modifications induced by radical stress on oligopeptides for tissue engineering (pages 1446–1450)

      M. Di Foggia, A. Torreggiani, P. Taddei, M. Dettin and A. Tinti

      Article first published online: 27 FEB 2013 | DOI: 10.1002/jrs.4271

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      Eight oligopeptides derived from EAK16, useful as biomimetic materials, were undergone to oxidative radical stress to test their resistance to free radical attack, and examined by vibrational spectroscopy. This study may contribute to gain insight into the different biological performances of the EAK16 derived peptides and to identify the most adequate materials usable for bone regeneration.

    22. Study of Raman scattering and luminescence properties of orchil dye for its nondestructive identification on artworks (pages 1451–1456)

      F. Rosi, C. Clementi, M. Paolantoni, A. Romani, R. Pellegrino, B. G. Brunetti, W. Nowik and C. Miliani

      Article first published online: 25 FEB 2013 | DOI: 10.1002/jrs.4254

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      Ultraviolet and visible fluorescence combined with resonance Raman spectroscopy allowed for the nondestructive identification of orchil dye in two ancient fragments. Subtracted shifted Raman spectroscopy has been exploited for removing the strong fluorescence background. The electronic and vibrational characterization highlighted spectral differences with respect to orcein and analogies with both photoaged orcein and litmus.

    23. Connection between the vibrational dynamics and the cross-linking properties in cyclodextrins-based polymers (pages 1457–1462)

      Vincenza Crupi, Aldo Fontana, Marco Giarola, Domenico Majolino, Gino Mariotto, Andrea Mele, Lucio Melone, Carlo Punta, Barbara Rossi, Francesco Trotta and Valentina Venuti

      Article first published online: 31 MAR 2013 | DOI: 10.1002/jrs.4255

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      The vibrational dynamics of a new class of cyclodextrin-based cross-linked polymers is here investigated. The simultaneous analysis of intermolecular vibrational bands and of the so-called boson peak allowed us to deeply explore the cross-linking degree and the elastic properties of these innovative materials.

    24. Vibrational spectroscopy investigation of swelling phenomena in cyclodextrin nanosponges (pages 1463–1469)

      Franca Castiglione, Vincenza Crupi, Domenico Majolino, Andrea Mele, Barbara Rossi, Francesco Trotta and Valentina Venuti

      Article first published online: 15 APR 2013 | DOI: 10.1002/jrs.4282

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      The swelling behaviour of β-cyclodextrin nanosponges has been investigated versus different hydration levels and temperatures by the analysis of the vibrational dynamics through Fourier-transform infrared spectroscopy in Attenuated Total Reflectance geometry and Raman scattering. The spectral components of the O–H stretching and HOH bending regions have been discussed in terms of water molecules engaged in different hydrogen bonding networks, ascribed to three different ‘types’ of water, namely ‘bonded’, ‘intermediate’ and ‘free’.

  3. Review

    1. Top of page
    2. Editorials
    3. Research articles
    4. Review
    1. 2D-IR spectroscopy: an additional dimension to investigate ultrafast structural dynamics (pages 1470–1477)

      Manuela Lima, Marco Candelaresi and Paolo Foggi

      Article first published online: 15 MAY 2013 | DOI: 10.1002/jrs.4311

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      The theory, the experimental details, and the data analysis of two-dimensional infrared (2D-IR) spectroscopy are discussed. An application of the technique to the study of a dipeptide in solution and the effects of solvent dynamics on Glycine-Alanine-Methylamide by 2D-IR are also discussed.

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