Journal of Raman Spectroscopy

Cover image for Vol. 44 Issue 2

February 2013

Volume 44, Issue 2

Pages 167–338

  1. Rapid communication

    1. Top of page
    2. Rapid communication
    3. Research articles
    1. Investigation of organelle-specific intracellular water structures with Raman microspectroscopy (pages 167–169)

      Shraeddha Tiwari, Masahiro Ando and Hiro-o Hamaguchi

      Article first published online: 8 NOV 2012 | DOI: 10.1002/jrs.4165

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      The intracellular state of water molecules determines physiological responses in living cells but has proved to be a challenging system to study so far. Raman microspectroscopic imaging coupled with multivariate analysis unveils the existence of different organelle-specific water structures inside a living yeast cell.

  2. Research articles

    1. Top of page
    2. Rapid communication
    3. Research articles
    1. Reusable plasmonic substrates fabricated by interference lithography: a platform for systematic sensing studies (pages 170–175)

      Thomas Siegfried, Martin Kind, Andreas Terfort, Olivier J. F. Martin, Michael Zharnikov, Nirmalya Ballav and Hans Sigg

      Article first published online: 31 AUG 2012 | DOI: 10.1002/jrs.4163

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      Periodic, nanoslit-based gold substrates fabricated by EUV interference lithography provide excellent reproducibility in the SERS enhancement and, additionally, reusability of the substrate. The outstanding capabilities were demonstrated using monomolecular films of thiols and open a powerful platform for an analytical tool or for advanced SERS studies for the investigation of chemical enhancement effects, surface selection rules and molecular alignment.

    2. Exploring the possible interlinked structures in single-wall carbon nanotubes under pressure by Raman spectroscopy (pages 176–182)

      Shuangchen Lu, Mingguang Yao, Quanjun Li, Hang lv, Dedi Liu, Bo Liu, Ran Liu, Linhai Jiang, Zhen Yao, Zhaodong Liu, Bo Zou, Tian Cui and Bingbing Liu

      Article first published online: 5 SEP 2012 | DOI: 10.1002/jrs.4166

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      High-pressure Raman measurements on single-wall carbon nanotubes have been carried out in a diamond anvil cell. With pressure increasing up to 15–17 GPa, we observed that anomalous changes take place in both the Raman wavenumber and the linewidth of G-band. We propose that the interlinked configuration with sp3 bonds forms in the SWNT bundles under pressure, which was the cause for the occurrence of the Raman anomalies.

    3. Influence of oligonucleotide interaction on electronic properties of single walled carbon nanotubes (pages 183–189)

      Sevcan Ayaksız Ozturk, Seda Kelestemur and Mustafa Culha

      Article first published online: 26 SEP 2012 | DOI: 10.1002/jrs.4185

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      The influence of the non-covalent interactions and chemical attachment of oligonucleotides (10 and 25 bases), composed of polyA, polyT, polyG and polyC, on the electronic structure of single wall carbon nanotubes (SWCNTs) is investigated by means of Raman spectroscopy. While interactions of SWCNTs with short length polyA, polyT and polyG increase with increasing incubation time, it decreases for longer polyA, polyT and polyG except for polyC, which interacts with SWCNT regardless of incubation time and base length.

    4. Affinity of protein fibres towards sulfation (pages 190–197)

      Paola Taddei, Masuhiro Tsukada and Giuliano Freddi

      Article first published online: 21 SEP 2012 | DOI: 10.1002/jrs.4168

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      Wool, B. mori and Tussah silk fibres were treated with chlorosulfonic acid in pyridine and investigated by IR and Raman spectroscopies as well as mechanical measurements. The reactivity towards sulfation decreased along the series: wool > B. mori silk > Tussah silk. Weight gain, spectroscopic and mechanical data are discussed in relation to the difference in fibre morphology, structure and crystallinity. The results obtained appeared promising in view of widening the biomedical utility of natural polymers as biomaterials.

    5. Biomolecular component analysis of cultured cell nucleoli by Raman microspectrometry (pages 198–204)

      Andrey N. Kuzmin, Artem Pliss and Aliaksandr V. Kachynski

      Article first published online: 18 SEP 2012 | DOI: 10.1002/jrs.4173

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      Confocal Raman spectroscopy technique and biomolecular component analysis were employed for characterization of the complex molecular organization of major structure–function compartment of the cell nucleus, the nucleolus.

    6. B2 bradykinin receptor antagonists: adsorption mechanism on electrochemically roughened Ag substrate (pages 205–211)

      Edyta Proniewicz, Dominika Skołuba, Andrzej Kudelski, Dariusz Sobolewski, Adam Prahl, Younkyoo Kim and Leonard M. Proniewicz

      Article first published online: 22 NOV 2012 | DOI: 10.1002/jrs.4182

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      In this paper, the surface-enhanced Raman scattering (SERS) spectra of the potent B2 bradykinin receptor antagonists, [D-Arg0,Hyp3,Thi5,8,L-Pip7]BK, Aaa[D-Arg0,Hyp3,Thi5,8, L-Pip7]BK, [D-Arg0,Hyp3,Thi5,D-Phe7,L-Pip8]BK, and Aaa[D-Arg0,Hyp3,Thi5,D-Phe7,L-Pip8]BK, were measured when immobilized onto a highly specific electrochemically roughened SERS-active Ag substrate characterized by the formation of a 50 – 150 nm Ag islands on its surface. The observed SERS bands corresponding to different vibrational modes of the molecule, attached to or near Ag, and the variations in these bands resulting from competitive interactions of the functional groups of the peptides with the SERS-active Ag surfaces and reorientation occurring over time of adsorption were analyzed in this study.

    7. Characterization of adsorption mode of new B2 bradykinin receptor antagonists onto colloidal Ag substrate (pages 212–218)

      Dariusz Sobolewski, Edyta Proniewicz, Dominika Skołuba, Adam Prahl, Yukihiro Ozaki, Younkyoo Kim and Leonard M. Proniewicz

      Article first published online: 10 JAN 2013 | DOI: 10.1002/jrs.4193

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      In this study, we discussed the orientation and mode of adsorption of [D-Arg0, Hyp3,Thi5,8,L-Pip7]BK, Aaa[D-Arg0,Hyp3,Thi5,8,L-Pip7] BK, [D-Arg0,Hyp3,Thi5,D-Phe7,L-Pip8]BK, and Aaa[D-Arg0,Hyp3, Thi5,D-Phe7,L-Pip8]BK, potent B2 bradykinin receptor antagonists, adsorbed on a colloidal Ag surface, using SERS. To reveal the adsorption mechanism of these species from their SERS spectra, Fourier-transform-Raman spectra of the non-adsorbed molecules were measured and then compared with corresponding SERS spectra.

    8. Raman spectroscopic investigations on intermolecular interactions in aggregates and crystalline forms of trans-astaxanthin (pages 219–226)

      Balaji Subramanian, Nadéjda Tchoukanova, Yahia Djaoued, Claude Pelletier and Mathieu Ferron

      Article first published online: 26 OCT 2012 | DOI: 10.1002/jrs.4194

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      Raman spectroscopic studies evidenced the presence of π-stacking interaction in card-packed aggregates and hydrogen bonding leading to the formation of head-to-tail aggregates of trans-astaxanthin.

    9. Characterizing unusual metal substrates for gap-mode tip-enhanced Raman spectroscopy (pages 227–233)

      Johannes Stadler, Benedikt Oswald, Thomas Schmid and Renato Zenobi

      Article first published online: 21 NOV 2012 | DOI: 10.1002/jrs.4169

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      The efficiency of wide range of rarely or previously unused metal substrates for tip-enhanced Raman spectroscopy is examined experimentally as well as theoretically using 3D full-wave electromagnetic techniques. Far more metals than initially expected show strong electromagnetic field enhancement and promise good performance when used for tip-enhanced Raman spectroscopy experiments.

    10. Spectral characterization and intracellular detection of Surface-Enhanced Raman Scattering (SERS)-encoded plasmonic gold nanostars (pages 234–239)

      Hsiangkuo Yuan, Andrew M. Fales, Christopher G. Khoury, Jesse Liu and Tuan Vo-Dinh

      Article first published online: 5 OCT 2012 | DOI: 10.1002/jrs.4172

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      SERS-ensemble comparison of gold nanostars, silver nanospheres and gold nanospheres of similar sizes and concentrations. Gold nanostars, with plasmon in the near infrared and multiple sharp braches, produce SERS enhancement similar to that of silver nanospheres without the need of aggregation.

    11. Large-area Ag nanorod array substrates for SERS: AAO template-assisted fabrication, functionalization, and application in detection PCBs (pages 240–246)

      Zhulin Huang, Guowen Meng, Qing Huang, Bin Chen, Chuhong Zhu and Zhuo Zhang

      Article first published online: 14 OCT 2012 | DOI: 10.1002/jrs.4184

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      Large-area arrays of highly ordered HS-β-CD decorated Ag nanorods with 10-nm gaps between the neighboring rods stably supported on Cu base were achieved and demonstrated remarkable surface-enhanced Raman scattering sensitivity and ability to capture PCB molecules, which have potential in effective detection PCBs.

    12. Adsorption of dicarboxylic acids onto nano-structured silver surfaces – surface-enhanced Raman scattering studies of pH-dependent adsorption geometries (pages 247–254)

      J. P. Schulte, S. Grass and L. Treuel

      Article first published online: 27 OCT 2012 | DOI: 10.1002/jrs.4190

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      Surface-enhanced Raman spectroscopy was used to study pH-dependent adsorption orientations of dicarboxylic acids (maleic acid and fumaric acid) on nano-structured silver surfaces. Results revealed how the influence of pH on the observed adsorption geometries correlates with the dissociation states of the two acidic groups.

    13. Quadruplex CARS micro-spectroscopy (pages 255–261)

      Israel Rocha-Mendoza, Paola Borri and Wolfgang Langbein

      Article first published online: 20 SEP 2012 | DOI: 10.1002/jrs.4181

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      A coherent anti-Stokes Raman scattering spectroscopy technique, based on femtosecond laser sources and spectral focusing with glass dispersion, is extended to detect four different vibrational frequencies simultaneously by simply adding dispersive optical elements to the optical beam paths. This technique allows fast acquisition speed using single-photomultiplier detection being limited only by the available laser power, the sample heating, and the high-frequency cut-off of the photomultiplier.

    14. Triply resonant Raman scattering in perovskite semiconductor CsSnI3 (pages 262–265)

      Chonglong Yu, Zhuo Chen and Kai Shum

      Article first published online: 2 OCT 2012 | DOI: 10.1002/jrs.4180

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      We report on the first-order and second-order Raman scattering (SORS) by longitudinal optical (LO) phonons in perovskite semiconductor CsSnI3. The intensity of SORS is stronger than that of the first order. The spectral line shape of SORS is asymmetric and much broader than that of the first order. It is identified that the strong SORS intensity is attributable to the triply enhanced resonant process, which is naturally implemented through the peculiar band structure of this semiconductor compound having two adjacent parallel conduction bands with a separation close to the energy of two LO phonons.

    15. Deep UV resonance Raman spectroscopic study of CnF2n+2 molecules: the excitation of C–C σ bond (pages 266–269)

      Shaoqing Jin, Meiling Guo, Fengtao Fan, Jingxiu Yang, Ying Zhang, Baokun Huang, Zhaochi Feng and Can Li

      Article first published online: 26 OCT 2012 | DOI: 10.1002/jrs.4188

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      The σ–σ* transition of C–C bond in CnF2n+2 molecules was studied by deep UV resonance Raman spectroscopy. The C–C σ bond is selectively excited by the deep UV laser at 177.3 nm, and the resonance Raman spectra of CnF2n+2 molecules were obtained on our home-assembled deep UV Raman spectrograph. The Raman bands at 1298, 1380 and 2584 cm−1 due to the C–C skeletal stretching modes are evidently enhanced owing to the resonance Raman effect. Based on the resonance Raman spectra and theoretical calculation results, the electronic geometry of CnF2n+2 molecules at the σσ* excited state was proposed.

    16. Effect of chlorine substitution on triplet state structure of thioxanthone: A time-resolved resonance Raman study (pages 270–276)

      Rishikesh Pandey, Nagappan Rajkumar and Siva Umapathy

      Article first published online: 21 JAN 2013 | DOI: 10.1002/jrs.4189

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      This paper reports a vibrational spectroscopic investigation of 2-chlorothioxanthone (CTX) in its ground and lowest excited triplet states. The coexistence of two triplets has been observed, and the T1 state has been identified as π-π* whereas, n-π* configuration has been ascribed to the T2 state. The population ratio of 3n-π* and 3π-π* states has been found to be more in CTX as compared to the parent compound, thioxanthone suggesting increased photoreduction activity after chlorine substitution.

    17. Surface-enhanced Raman scattering (SERS) and complementary techniques applied for the investigation of an Italian cultural heritage canvas (pages 277–282)

      O. M. Gui, A. Fălămaş, L. Barbu-Tudoran, M. Aluaş, B. Giambra and S. Cîntă Pînzaru

      Article first published online: 16 OCT 2012 | DOI: 10.1002/jrs.4186

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      The paper presents the first report on the SERS investigation of flax used in linen from a 19th century cultural heritage canvas. Vibrational data in conjunction with scanning electron microscopy and solid-state 13C-NMR were able to offer valuable insight into the painting technique, unknown prior to this study.

    18. The use of Raman spectroscopy to characterize the carbon materials found in Amazonian anthrosoils (pages 283–289)

      J. Ribeiro-Soares, L. G. Cançado, N. P. S. Falcão, E. H. Martins Ferreira, C. A. Achete and A. Jorio

      Article first published online: 16 OCT 2012 | DOI: 10.1002/jrs.4191

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      Raman spectroscopy is used to characterize the carbon materials found in an extremely fertile soil found in the Amazon region – the Indian Dark Earth (or Terra Preta do Índio – TPI). The results are compared with charcoal produced in laboratory for the generation of artificial Indian Dark Earth.

    19. DFT-assisted interpretation of the Raman spectra of hydrogen-ordered ice XV (pages 290–298)

      Thomas F. Whale, Stewart J. Clark, John L. Finney and Christoph G. Salzmann

      Article first published online: 26 SEP 2012 | DOI: 10.1002/jrs.4170

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      The Raman spectra of the recently discovered ice XV are reported, and the spectra are fully interpreted in terms of assigning normal modes to the various spectral features by using DFT calculations. The calculated spectra of the experimental antiferroelectric crystal structure are in good agreement with the experimental Raman spectra whereas the calculated spectrum of a ferroelectric structure, which computational studies have suggested as the crystal structure of ice XV, differs substantially.

    20. Micro-Raman analysis and finite-element modeling of 3 C-SiC microstructures (pages 299–306)

      N. Piluso, R. Anzalone, M. Camarda, A. Severino, A. La Magna, G. D'Arrigo and F. La Via

      Article first published online: 1 SEP 2012 | DOI: 10.1002/jrs.4171

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      Micro Raman spectroscopy and finite-element modeling (FEM) are used to determine the stress gradient acting on free standing microstructures. The anchorage points show an intense stress field described via an overlap of the diagonal and non-diagonal components of the Raman stress tensor. The results reveal an abrupt change of the Raman transverse optical mode (up to 2.5 cm−1) close to the anchorage point. FEM confirms such result highlighting the role of the shear component. The results lead to a complete determination of the local stress field in the epitaxial thin film released.

    21. Raman spectroscopic investigation on femtosecond laser induced residual stress and element distribution in bismuth germanate glasses (pages 307–311)

      Zhanfeng Tu, Yu Teng, Jiajia Zhou, Shifeng Zhou, Heping Zeng and Jianrong Qiu

      Article first published online: 16 OCT 2012 | DOI: 10.1002/jrs.4175

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      Localized microstructure and elemental redistribution were induced in bismuth germanate glasses by irradiation with high repetition rate 800 nm femtosecond laser pulses. The microscopic Raman spectra indicated that the residual thermal stress increases from the unmodified region to the center of the laser modified region, while Bi is enriched at the boundary area of the inner structure of the laser modified region relative to Ge. Electron microprobe analysis further confirmed the elemental redistribution of Bi and Ge, which agrees well with the Raman spectral analysis.

    22. Aqua oxyhydroxycarbonate second phases at the surface of Ba/Sr-based proton conducting perovskites: a source of confusion in the understanding of proton conduction (pages 312–320)

      Ph. Colomban, C. Tran, O. Zaafrani and A. Slodczyk

      Article first published online: 26 SEP 2012 | DOI: 10.1002/jrs.4179

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      Ba/Sr-based zirconates and cerates appear as potential proton conducting electrolytes for water electrolysers, hydrogen fuel cells and CO2/syngas converters. Their complex vibrational signatures assigned by some authors to the bulk protonic species actually arose from the surface species - a mixture of Ba/SrO, Ba/Sr(OH)2 and Ba/SrCO3. Since these second phases exhibit high proton conductivity, their presence is very detrimental in the determination of intrinsic electrolyte bulk properties and interpretation of the conduction mechanisms.

    23. Depth-resolved micro-Raman spectroscopy of tri-layer PFSA membrane for PEM fuel cells: how to obtain reliable inner water contents (pages 321–328)

      Z. Peng, P. Huguet, S. Deabate, A. Morin and A. K. Sutor

      Article first published online: 23 OCT 2012 | DOI: 10.1002/jrs.4192

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      Raman depth-profiling microspectroscopy is currently emerging as a fast and non-invasive method for the local content measurement of water diffusing across the perfluorosulfonic acid polymer used as electrolyte in low-temperature fuel cells. However, water depth profiles obtained thereby can be affected by artificial gradients due to the gradual degradation of the Raman signal as the probed volume is moved further into the sample. The appropriate way to rectify raw data, in order to measure reliable inner water contents, is discussed for the case of membranes soaked in water. The method is tested on a tri-layer membrane composed by stacked perfluorosulfonic acid ionomers with different chemical composition, ionic exchange capacity and swelling.

    24. Estimation of signal backgrounds on multivariate loadings improves model generation in face of complex variation in backgrounds and constituents (pages 329–338)

      J. Renwick Beattie and John J. McGarvey

      Article first published online: 26 SEP 2012 | DOI: 10.1002/jrs.4178

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      Background estimation using the traditional per-signal paradigm is compared with estimation on the loadings obtained from SVD of a whole dataset. Estimating baseline correction on SVD loadings rather than on individual signals significantly improves the model quality from subsequent data analysis. This is due to the ability of using the SVD-based approach to handle multiple complex background sources and multiple chemical contributors with inconsistent baseline points.