Journal of Raman Spectroscopy

Cover image for Vol. 41 Issue 12

December 2010

Volume 41, Issue 12

Pages 1563–1802

  1. Errata

    1. Top of page
    2. Errata
    3. Rapid Communications
    4. Reviews
    5. Research Articles
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  2. Rapid Communications

    1. Top of page
    2. Errata
    3. Rapid Communications
    4. Reviews
    5. Research Articles
    1. Observation of resonance electronic and non-resonance-enhanced vibrational natural Raman optical activity (pages 1563–1565)

      Christian Merten, Honggang Li, Xuefang Lu, Andreas Hartwig and Laurence A. Nafie

      Article first published online: 15 JUL 2010 | DOI: 10.1002/jrs.2750

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      Both the natural resonance electronic Raman optical activity (ROA), observed for the first time, and also the first example of vibrational ROA enhanced by low-lying electronic transition are reported for the complex (+)-Eu(tfc)3.

  3. Reviews

    1. Top of page
    2. Errata
    3. Rapid Communications
    4. Reviews
    5. Research Articles
    1. Recent advances in linear and nonlinear Raman spectroscopy. Part IV (pages 1566–1586)

      Laurence A. Nafie

      Article first published online: 17 DEC 2010 | DOI: 10.1002/jrs.2859

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      A review is presented on important developments published within the Journal of Raman Spectroscopy during 2009. This fourth overview again highlights advances in the field of research, provides readers of JRS with introductions to developments within the various sub-fields of Raman spectroscopy and reflects the trends of research of the Raman community.

  4. Research Articles

    1. Top of page
    2. Errata
    3. Rapid Communications
    4. Reviews
    5. Research Articles
    1. Charge-transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy (pages 1587–1593)

      Gustavo M. do Nascimento, Tilana B. Silva, Paola Corio and Mildred S. Dresselhaus

      Article first published online: 18 JAN 2010 | DOI: 10.1002/jrs.2598

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      PANI/SWNTs composites were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was investigated. The results indicate that a charge-transfer process occurs between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized.

    2. Cesium doped and undoped ZnO nanocrystalline thin films: a comparative study of structural and micro-Raman investigation of optical phonons (pages 1594–1600)

      R. Thangavel, Rakesh Singh Moirangthem, Wei-Shan Lee, Yia-Chung Chang, Pei-Kuen Wei and J. Kumar

      Article first published online: 18 JAN 2010 | DOI: 10.1002/jrs.2599

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      The integrated intensity ratio of each Gaussian line n LO to 1 LO as a function of n (number of LO phonons) for different concentrations of cesium and different annealing temperatures for a duration of 1 h. For undoped ZnO, the first LO mode was observed at around 573 cm−1, in good agreement with the literature value.

    3. A Raman spectroscopic study on the allocation of ammonium adsorbing sites on H2Ti3O7 nanofibre and its structural derivation during calcination (pages 1601–1605)

      Hongwei Liu, Zhanfeng Zheng, Dongjiang Yang, Eric Waclawik, Xuebin Ke, Huaiyong Zhu, Sara Palmer and Ray L. Frost

      Article first published online: 9 MAR 2010 | DOI: 10.1002/jrs.2632

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      The adsorption behaviour of ammonia and the structural derivation of the layered proton trititanate were characterized by Raman spectroscopy. The intensity of the Raman band at 309 cm−1 corresponding to very long Ti[BOND]O bonds (2.2 Å) became weak during the adsorption of the ammonium ions.

    4. Structural, thermal and optical study of nanocrystalline silicon produced by ball milling (pages 1606–1609)

      Claudio M. Poffo, João C. de Lima, Sergio M. Souza, Daniela M. Trichês, Tarciso A. Grandi and Ronaldo S. de Biasi

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2623

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      The ball milling process was used to obtain nanocrystalline cubic silicon. According to Raman spectroscopy and X-ray diffraction results, the volume fractions of the crystalline, interfacial and amorphous silicon phases were about 30, 39 and 31%, respectively.

    5. Surface-enhanced Raman spectroscopy for quantitative measurement of lactic acid at physiological concentration in human serum (pages 1610–1614)

      Po-Hsiang Hsu and Huihua Kenny Chiang

      Article first published online: 25 FEB 2010 | DOI: 10.1002/jrs.2609

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      The silver colloidal nanoparticles were employed to enhance the Raman signal of lactic acid at physiological concentration range (10−3 M). The SERS characteristic bands of lactic acid were defined in this study. The 1395 cm−1 band of lactic acid were concentration sensitive (10−4–10−3 M) and used for the quantitative study.

    6. Multifunctional human serum albumin in the surface-enhanced Raman spectroscopy of porphyrin: demetalation promoter, molecular spacer and stabilizer (pages 1615–1620)

      Guoqing Jia, Zhaochi Feng, Chunying Wei and Can Li

      Article first published online: 3 FEB 2010 | DOI: 10.1002/jrs.2611

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      A multifunctional human serum albumin (HSA) has been observed in the SERS investigation of H2TMPyP4. HSA, as a stabilizer, makes an SERS active system, which shows high stability and good S/N SERS spectra. For the (H2TMPyP4-Ag colloid)/HSA system, HSA can also function as a critical promoter in the photoinduced demetalation of Ag(II)TMPyP4. However, in the case of (HSA-H2TMPyP4)/Ag colloid system, HSA is an effective molecular spacer to obtain an SERS spectrum of free base H2TMPyP4.

    7. Surface-enhanced resonance Raman spectroscopic characterization of cytochrome c immobilized on 2-mercaptoethanesulfonate monolayers on silver (pages 1621–1631)

      Agata Królikowska and Jolanta Bukowska

      Article first published online: 27 JAN 2010 | DOI: 10.1002/jrs.2618

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      SERRS studies demonstrated that mercaptoethanesulfonate (MES) SAMs on Ag (see on the right for schematic SAM representation) successfully bind electrostatically cytochrome c (cyt c). Cyt c redox activity at pH 7 was confirmed with spectroelectrochemical experiment. The protein dynamics is expected to be the electron transfer rate-limiting factor, mostly due to the relatively high electric field provided by MES coating.

    8. Bacterial mixture identification using Raman and surface-enhanced Raman chemical imaging (pages 1632–1637)

      Jason Guicheteau, Steven Christesen, Darren Emge and Ashish Tripathi

      Article first published online: 26 JAN 2010 | DOI: 10.1002/jrs.2601

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      Surface-enhanced Raman chemical imaging is explored and compared with normal Raman chemical imaging of complex mixtures of bacteria. In the presented results, a 60-fold reduction in image acquisition time and a factor of 10 increase in the signal-to-noise ratio are observed.

    9. Chemical imaging of glucose by CARS microscopy (pages 1638–1644)

      Madeleine Åkeson, Christian Brackmann, Lena Gustafsson and Annika Enejder

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2619

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      A microscopy technique based on coherent anti-Stokes Raman scattering (CARS) for specific, quantitative imaging of glucose with submicrometer resolution is presented. No additional reporter molecules are required, so the metabolite is studied under natural conditions. The method is demonstrated by mapping glucose in a microfluidic bioreactor and in lipid-bilayer vesicles. Furthermore, the metabolic response to a glucose pulse has been monitored in living yeast cells. This study introduces monitoring of carbohydrates as a new application of CARS microscopy.

    10. The effects of L- to D-isomerization and C-terminus deamidation on the secondary structure of antimicrobial peptide Anoplin in aqueous and membrane mimicking environment (pages 1645–1649)

      Stahs Pripotnev, Amy Won and Anatoli Ianoul

      Article first published online: 3 FEB 2010 | DOI: 10.1002/jrs.2608

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      UV resonance Raman spectra of the antimicrobial peptide Anoplin (L-Ano-NH2) and two of its derivatives (enantiomer D-Ano-NH2 and C-terminus deamidated L-Ano-OH) were measured. All three peptides were found to adopt predominantly β turn-like conformation in aqueous solution and become more α-helical in membrane-mimetic environment.

    11. Effect of the structural order of all-trans-β-carotene on the Raman scattering cross section at low concentrations (pages 1650–1654)

      Shun-Li OuYang, Cheng-Lin Sun, Mi Zhou, Zhan-Long Li, Zhi-Wei Men, Dong-Fei Li, Zuo-Wei Li, Shu-Qin Gao and Guo-Hui Lu

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2602

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      We measured the Raman scattering cross sections (RSCS) of all-trans-β-carotene in carbon disulfide (CS2) at concentrations ranging from 10−6 to 10−11M. It was found that the RSCSs were extremely high in all-trans-β-carotene with decreasing concentration. In addition, a theoretical interpretation of the anomalous experimental results is given, which introduces a qualitative nonlinear model of coherent weakly damped electron-lattice vibrations in the structural order of all-trans-β-carotene.

    12. Detection of melamine in liquid milk using surface-enhanced Raman scattering spectroscopy (pages 1655–1660)

      Xiao-Fang Zhang, Ming-Qiang Zou, Xiao-Hua Qi, Feng Liu, Xin-Hua Zhu and Bin-Han Zhao

      Article first published online: 25 FEB 2010 | DOI: 10.1002/jrs.2629

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      Surface-enhanced Raman scattering spectroscopy was used to detect melamine in liquid milk on silver colloids. The detection limit of melamine was 0.01 µg ml−1 for standard samples and 0.5 µg ml−1 in liquid milk, which may gear up the application of rapid, on-line, and field detection of melamine in liquid milk.

    13. Influence of fluorescent dye on the linear polarization direction of stimulated Raman Stokes scattering in liquid-core optical fibers (pages 1661–1663)

      Zhiwei Men, Wenhui Fang, Zuowei Li, Guannan Qu, Chenglin Sun, Shuqin Gao and Guohui Lu

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2617

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      A simple analytical model to describe the stimulated Raman Stokes scattering linear polarization spectroscopy of fluorescence dye solutions in liquid core optical fiber(LCOFs) is presented. We demonstrate the stimulated Raman Stokes scattering of all-trans-β-carotene or fluorescein in Carbon bisulfide(CS2) solutions, due to the optical field-induced reorientation effect, which makes the first-order Stokes polarization direction rotate an angle 88° or 61°, respectively.

    14. Incident circularly polarized Raman optical activity spectrometer based on circularity conversion method (pages 1664–1669)

      Shigeki Yamamoto and Hitoshi Watarai

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2616

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      A simple instrument for the measurement of incident circularly polarized Raman optical activity (ICP ROA) was constructed by applying the circularity conversion method based on the concept of virtual enantiomers. The new instrument successfully attained photon shot-noise-limited condition for all bands except for the very strongly polarized Raman band.

    15. Surface-sensitive Raman microscopy with total internal reflection illumination (pages 1670–1677)

      Chris A. Michaels

      Article first published online: 27 JAN 2010 | DOI: 10.1002/jrs.2610

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      A Raman microscope using a total internal reflection (TIR) annular illumination geometry through a ZnSe solid immersion lens is described. Spectra acquired in this configuration demonstrate a high degree of surface selectivity, as the decay length of the evanescent excitation field limits the probe depth. TIR Raman images of a micropatterned polymer film are also reported.

    16. Heterodyne interferometric polarization coherent anti-Stokes Raman scattering (HIP-CARS) spectroscopy (pages 1678–1681)

      K. Orsel, E. T. Garbacik, M. Jurna, J. P. Korterik, C. Otto, J. L. Herek and H. L. Offerhaus

      Article first published online: 25 FEB 2010 | DOI: 10.1002/jrs.2621

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      We demonstrate heterodyne interferometric polarization coherent anti-Stokes Raman scattering (HIP-CARS) in toluene in the relatively unexplored fingerprint region (600–1650 cm−1). HIP-CARS combines the advantages of interferometric detection (strong amplification) and polarization CARS (background rejection) to generate background-free spectra.

    17. Characterization of archeological glasses by micro-Raman spectroscopy (pages 1682–1687)

      A. Cesaratto, P. Sichel, D. Bersani, P. P. Lottici, A. Montenero, E. Salvioli-Mariani and M. Catarsi

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2613

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      Mosaic tesserae of Roman ages from Massa Lubrense, Napoli, Italy, and medieval glassy rosary grains from San Martino di Rivosecco, Parma, Italy, were investigated by micro-Raman spectroscopy. From the observed spectra, it was possible to obtain the polymerization index, suggesting firing temperatures between 1000 and 1100 °C both for Roman and medieval glasses, and an estimation of the lead content.

    18. Metal-assisted regioselectivity in nucleophilic substitutions: a study by Raman spectroscopy and density functional theory calculations (pages 1688–1693)

      Andrea Defant, Barbara Rossi, Gabriele Viliani, Graziano Guella and Ines Mancini

      Article first published online: 9 MAR 2010 | DOI: 10.1002/jrs.2631

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      Experimental Raman signals, assigned by DFT calculations for the Fe(II), Cu(II) and Ni(II) complexes of 6,7-dichloroquinoline-5,8-dione, were influenced by the type of metal ion and resulted in agreement with the regioselective formation of the products when these chelated systems were involved in the reaction with piperidine.

    19. Metal–metal bonding and structures of trinickel and tricobalt dipyridylamido complexes from surface-enhanced Raman spectra (pages 1694–1699)

      Szu-Hsueh Lai, Chung-Jen Hsiao, Yu-Min Huang, I-Chia Chen, Wen-Zhen Wang and Shie-Ming Peng

      Article first published online: 26 JAN 2010 | DOI: 10.1002/jrs.2604

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      SERS spectra of Ni3(dpa)4Cl2 on silver nanoparticles in CH2Cl2 solution. The upper trace is with AgPF6 added to obtain the oxidized form [Ni3(dpa)4]3+. The SERS line at 242 cm−1 is assigned to Ni3 symmetric-stretching mode. The same motion for [Ni3(dpa)4]3+ is at wavenumber 274 cm−1, greater than that for neutral Ni3(dpa)4Cl2, in agreement with a prediction of delocalized molecular-orbital theory that an electron is removed from an antibonding orbital after oxidation.

    20. Raman and infrared spectra of doped La8+xSr2−y(SiO4)6O2+δ compounds compared to the ab initio-obtained spectroscopic characteristics of fully stoichiometric La8Sr2(SiO4)6O2 (pages 1700–1707)

      M. Smirnov, S. Sukhomlinov, A. Mirgorodsky, O. Masson, E. Béchade, M. Colas, T. Merle-Méjean, I. Julien and P. Thomas

      Article first published online: 25 FEB 2010 | DOI: 10.1002/jrs.2626

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      Spectral features in infrared and Raman spectra of La8Sr2(SiO4)6O2 and related oxygen-excess compounds are discussed on the basis of the results of density functional calculations. Spectral manifestations of oxygen ion modes localized within La-formed channels are established. They indicate that the excess oxygen ions are localized primarily inside the channels, thus providing valuable information on mechanism of the oxide ion conductivity.

    21. Effects of conformation and hydrogen bonding on the C[DOUBLE BOND]C and NCN stretching Raman bands of N-deuterated histidinium (pages 1708–1713)

      Hirotsugu Hiramatsu, Noriko Miki and Hideo Takeuchi

      Article first published online: 26 JAN 2010 | DOI: 10.1002/jrs.2606

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      Raman spectra of N-deuterated histidinium in 12 crystals with known structures were examined to find empirical correlations of the Raman wavenumbers of the C[DOUBLE BOND]C and NCN stretching vibrations with the conformation and hydrogen bonding states of the imidazole side chain. The revealed correlations may be useful in structural analysis of histidine residues in proteins.

    22. Hydrogen bonding in the pyrimidine/ formamide system: a concentration-dependent Raman and DFT study (pages 1714–1719)

      Sunil K. Srivastava, Sebastian Schlücker and Wagner A. Alves

      Article first published online: 27 JAN 2010 | DOI: 10.1002/jrs.2607

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      High-resolution Raman spectra of pyrimidine (PD) and formamide (FA) mixtures with different compositions recorded in the ring breathing region of PD (ν1 ∼ 991 cm−1) are presented. The dilution of PD with FA leads to the appearance of a new band at ν1′ ∼ 994 cm−1, which is assigned to hydrogen-bonded PD:FA species. From a quantitative analysis, the average number of FA molecules in the first solvation sphere of PD is determined as being equal to 2 and this value is supported by DFT calculations, where a symmetric 1:2 complex is the most stable species.

    23. Raman spectra of acetonitrile in imidazolium ionic liquids (pages 1720–1724)

      Humberto C. Garcia, Luiz F. C. de Oliveira, Bruno G. Nicolau and Mauro C. C. Ribeiro

      Article first published online: 25 FEB 2010 | DOI: 10.1002/jrs.2628

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      Raman bandshapes of the CN stretching mode of CH3CN, ν(CN) and the symmetric ν1 CD3 stretching mode of CD3CN, reveal characteristic features of ionic liquids' polarity.

    24. Raman spectroscopy of n-pentyl methyl ether and deuterium labelled analogues (pages 1725–1734)

      Richard D. Bowen, Howell G. M. Edwards, Dennis W. Farwell and Sara E Morgan

      Article first published online: 3 FEB 2010 | DOI: 10.1002/jrs.2595

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      The Raman spectra of n-pentyl methyl ether and six selectively deuteriated analogues are reported and correlations between the observed ν(sp3CH) stretching and bending bands and the position of the deuterium atoms in the alkyl chain are developed and refined.

    25. Polarized Raman mapping study of the microheterogeneity in 0.67PbMg1/3 Nb2/3O3-0.33PbTiO3 single crystal (pages 1735–1742)

      Y. Yang, Y. L. Liu, L. Y. Zhang, K. Zhu, S. Y. Ma, G. G. Siu, Z. K. Xu and H. S. Luo

      Article first published online: 18 JAN 2010 | DOI: 10.1002/jrs.2600

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      According to the Raman selection rules, the angular dependences of the Raman modes indicate that a PMN-33%PT single crystal is in the monoclinic phase. The color patterns in the Raman images reveal that the microheterogeneity in a PMN-33%PT single crystal originates from the coexistence of the MA-type and MC-type monoclinic phases.

    26. Raman microspectrometric investigationof urea in calcite and gypsum powder matrices (pages 1743–1747)

      Adam Culka and Jan Jehlička

      Article first published online: 17 MAR 2010 | DOI: 10.1002/jrs.2643

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      Raman microspectrometry was used for the detection of urea in artificially prepared mineral matrices. Various concentrations of urea mixed with calcite and gypsum powders were analyzed. Measurements of powders and analysis through the natural crystals of calcite and gypsum were carried out. The detection limit for urea was 1 wt% for both minerals, and in the measurements through crystals the detection limit lay between 1 and 5 wt% for calcite and above 5 wt% in the case of gypsum.

    27. Raman study of pressure-induced phase transitions in crystals of orthorhombic and monoclinic polymorphs of L-cysteine: dynamics of the side chain (pages 1748–1758)

      Vasily S. Minkov, Sergei V. Goryainov, Elena V. Boldyreva and Carl Henrik Görbitz

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2624

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      Cysteine is an amino acid with a very labile side-chain residue—CH2SH. This lability accounts for numerous phase transitions on cooling and with increasing pressure. The effect of pressure on different polymorphs of the same amino acid is shown to be different, giving different high-pressure phases at the same P, T conditions depending on the starting form.

    28. Raman study of Fano interference in p-type doped silicon (pages 1759–1764)

      Brian G. Burke, Jack Chan, Keith A. Williams, Zili Wu, Alexander A. Puretzky and David B. Geohegan

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2614

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      The effect of inter-valence band transitions on the zone center optical phonon in heavily p-type doped silicon is studied by Raman spectroscopy for a wide range of excitation wavelengths extending from the red (632.8 nm) into the ultra-violet (325 nm). The asymmetry in the one-phonon Raman lineshape is attributed to a Fano interference involving the overlap of a continuum of electronic excitations with a discrete phonon state.

    29. Temperature-dependent low wavenumber Raman scattering studies in LiCsSO4 crystal (pages 1765–1768)

      M. Kaczmarski and M. Wiesner

      Article first published online: 27 JAN 2010 | DOI: 10.1002/jrs.2603

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      New phase transitions at 100 and 180 K have been discovered. They result in critical changes in the lattice dynamics. The phase transitions are accompanied by anomalies in temperature dependence of the wavenumbers, the full widths at half-maxima and intensities of the peaks related to several lattice vibrations.

    30. Raman spectroscopic study of the hydroxy-arsenate-sulfate mineral chalcophyllite Cu18Al2(AsO4)4(SO4)3(OH)24·36H2O (pages 1769–1774)

      Ray L. Frost, Sara J. Palmer and Elle C. Keeffe

      Article first published online: 25 FEB 2010 | DOI: 10.1002/jrs.2625

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      The mixed anion mineral chalco-phyllite Cu18Al2(AsO4)4(SO4)3(OH)24·36H2O has been studied by using Raman spectroscopy. Characteristic bands associated with arsenate, sulfate and hydroxyl units are identified. Hydrogen bond distances are estimated from the band positions of the OH stretching vibrations.

    31. Anomalous Raman phenomenon of CuCrS2 (pages 1775–1778)

      G. M. Abramova, G. A. Petrakovskiy, A. N. Vtyurin, J. C. E. Rasch, A. S. Krylov, J. V. Gerasimova, D. A. Velikanov, V. M. Boehm and V. Sokolov

      Article first published online: 17 MAR 2010 | DOI: 10.1002/jrs.2630

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      Structural dynamics of the layered CuCrS2 compounds synthesized by different methods are investigated by using Raman spectroscopy. The Raman scattering and infrared absorption spectra were simulated within the valence force field model with the LADY program.

    32. Raman spectroscopic study of the mineral gerstleyite Na2(Sb,As)8S13·2H2O and comparison with some heavy-metal sulfides (pages 1779–1783)

      Ray L. Frost, Silmarilly Bahfenne and Eloise C. Keeffe

      Article first published online: 9 MAR 2010 | DOI: 10.1002/jrs.2627

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      The mineral gerstleyite is described as a sulphosalt as opposed to a sulphide. This study focuses on the Raman spectrum of gerstleyite Na2(Sb,As)8S13: 2H2O and makes a comparison with the Raman spectra of other common sulphides including stibnite, cinnabar and realgar. The spectra are related to the mineral structures.

    33. Vibrational spectroscopy of alkaline tungsten oxyfluoride crystals: structure, lattice dynamics, ordering processes, and phase transitions (pages 1784–1791)

      A. N. Vtyurin, Ju. V. Gerasimova, A. S. Krylov, A. A. Ivanenko, N. P. Shestakov, N. M. Laptash and E. I. Voyt

      Article first published online: 4 MAR 2010 | DOI: 10.1002/jrs.2637

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      Raman scattering (RS) and IR spectra of (NH4)3WO3F3, (NH4)2KWO3F3, and Cs2(NH4)WO3F3 were compared for the first time within the temperature range 92–303 K. Conspicuous matching of most spectral lines in the IR and RS spectra, i.e. polar vibrations active in both spectra, is indicative of the breaking of the exclusion rule. It is shown that cations in the structures of these crystals have the fac configuration.

    34. A Raman spectroscopic study on the active site of sodium cations in the structure of Na2Ti3O7 during the adsorption of Sr2+ and Ba2+ cations (pages 1792–1796)

      Hongwei Liu, Dongjiang Yang, Eric R. Waclawik, Xuebin Ke, Zhanfeng Zheng, Huaiyong Zhu and Ray L. Frost

      Article first published online: 4 MAR 2010 | DOI: 10.1002/jrs.2634

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      The adsorption behavior of divalent radioactive cations by sodium trititanate and the structural deformation of trititanate were characterized by Raman spectroscopy.

    35. Synthesis and Raman spectroscopy of indium-based hydrotalcites of formula Mg6In2(CO3)(OH)16· 4H2O (pages 1797–1802)

      Ray L. Frost, Sara J. Palmer and Laure-Marie Grand

      Article first published online: 18 JAN 2010 | DOI: 10.1002/jrs.2571

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      Indium-containing hydrotalcites of formula Mg4In2(CO3)(OH)12·4H2O (2:1 In-LDH) through to Mg8In2 (CO3)(OH)18·4H2O (4:1 In-LDH) with variation in the Mg : In ratio have been successfully synthesized and characterized by Raman spectroscopy.

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