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Journal of Raman Spectroscopy

Cover image for Vol. 45 Issue 1

January 2014

Volume 45, Issue 1

Pages 1–147

  1. Research articles

    1. Top of page
    2. Research articles
    1. You have free access to this content
      Graphene sensing an inhomogeneous strain due to the surface relief in FeNiCoTi shape memory alloy (pages 1–6)

      Liqiang Zhang, Yang Shao, Zhiqiang Tu, Rui Liu, Fan Yang, Daqiang Jiang, Yunpeng Guo, Zhizhen Ye, Ting Liu, Junsong Zhang, Zhenfei Gao, Yongfeng Li and Lishan Cui

      Article first published online: 21 NOV 2013 | DOI: 10.1002/jrs.4410

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      A large sheet of graphene was fabricated by a chemical vapor deposition method and transferred onto the FeNiCoTi shape memory alloy substrate. The flat surface of the substrate becomes winkle due to the surface relief after phase transformation. After loading a tensile strain on the surface graphene, the two-dimensional Raman peak of graphene is found to demonstrate a significant red shift due to the strain. The different colors in the Raman mapping image for graphene can directly display the strain distribution information due to the surface relief.

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      Direct observation of p,p′-dimercaptoazobenzene produced from p-aminothiophenol and p-nitrothiophenol on Cu2O nanoparticles by surface-enhanced Raman spectroscopy (pages 7–14)

      Tingting You, Li Jiang, Penggang Yin, Yang Shang, Dongfeng Zhang, Lin Guo and Shihe Yang

      Article first published online: 21 NOV 2013 | DOI: 10.1002/jrs.4411

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      p,p′-Dimercaptoazo-benzene was produced from p-nitrothiopheno or p-aminothiophenol by surface photocatalyzed reaction on the surface of cuprous oxide nanoparticles, which was monitored by surface-enhanced Raman spectroscopy and investigated via a combined surface-enhanced Raman scattering and density functional theory study.

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      Enhancement of lattice defect signatures in graphene and ultrathin graphite using tip-enhanced Raman spectroscopy (pages 15–21)

      R. H. Rickman and P. R. Dunstan

      Article first published online: 22 NOV 2013 | DOI: 10.1002/jrs.4416

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      Using tip-enhanced Raman spectroscopy, this study observed preferential enhancement of the D band on multilayered graphene and graphite. Heightened defect sensitivity was demonstrated on graphene edges, folds, and overlapping regions.

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      Tip-enhanced Raman spectroscopy – an interlaboratory reproducibility and comparison study (pages 22–31)

      Carolin Blum, Lothar Opilik, Joanna M. Atkin, Kai Braun, Stefan B. Kämmer, Vasily Kravtsov, Naresh Kumar, Sergey Lemeshko, Jian-Feng Li, Karol Luszcz, Teimour Maleki, Alfred J. Meixner, Steve Minne, Markus B. Raschke, Bin Ren, Jan Rogalski, Debdulal Roy, Bruno Stephanidis, Xiang Wang, Dai Zhang, Jin-Hui Zhong and Renato Zenobi

      Article first published online: 9 JAN 2014 | DOI: 10.1002/jrs.4423

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      Different groups around the world participated in an interlaboratory reproducibility and comparison study for tip-enhanced Raman spectroscopy. Different experimental configurations of tip, sample, and illumination/detection geometry were used by the participating groups. It was found that all research groups obtained similar spectral patterns, even though the relative peak position varied, most probably due to different spectrometer calibrations.

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      Preparation and characterisation of a stable silver colloid for SER(R)S spectroscopy (pages 32–40)

      P. White and J. Hjortkjaer

      Article first published online: 25 NOV 2013 | DOI: 10.1002/jrs.4412

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      A highly reproducible method for the preparation of a silver colloid for surface-enhanced Raman scattering spectroscopy is described. The colloid, obtained by reduction of silver nitrate with hydroxylamine phosphate, is shown to have a particle size of ~20 nm with a narrow size distribution of 10–30 nm and a shelf life that exceeds 8 months. Ultraviolet–visible and surface-enhanced Raman scattering spectra together with zeta potential, transmission electron microscopy and energy dispersive X-ray data have been used to characterise this colloid.

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      Ultrasensitive RDX detection with commercial SERS substrates (pages 41–46)

      S. Almaviva, S. Botti, L. Cantarini, R. Fantoni, S. Lecci, A. Palucci, A. Puiu and A. Rufoloni

      Article first published online: 21 NOV 2013 | DOI: 10.1002/jrs.4413

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      The main Raman features of 1,3,5-trinitroperhydro-1,3,5-triazine were identified, and a careful optimization of acquisition parameters was performed in order to increase the overall sensitivity of the apparatus. The analyte film was deposited on Klarite® substrates and the amount of the sampled substance resulted to be of the order of few tens of picograms, as requested for infield applications.

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      Fabrication of uniform substrate based on silver nanoparticles decorated glycidyl methacrylate-ethylene dimethacrylate porous material for ultrasensitive surface-enhanced Raman scattering detection (pages 47–53)

      Xuan Wang, Yiping Du, Qingqing Li, Ting Wu, Huilian Hu, Ying Xu, Han Zhang and Yingcheng Pan

      Article first published online: 15 DEC 2013 | DOI: 10.1002/jrs.4418

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      Ag nanoparticles (AgNPs) are inverted self-assembled on glycidyl methacrylate-ethylene dimethacrylate porous material to fabricate a NOVEL surface-enhanced Raman scattering (SERS) substrate. With this method, the AgNPs are immobilized on the material steadily and uniformly. The fabricating SERS substrate has ultra sensitivity and good signal reproducibility in detection of the probe molecule R6G, paraquat and thymine.

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      Theoretical elucidation of the origin of surface-enhanced Raman spectra of PCB52 adsorbed on silver substrates (pages 54–61)

      Wen-Xiao Pan, Yong-Chao Lai, Ruo-Xi Wang, Dong-Ju Zhang and Jin-Hua Zhan

      Article first published online: 2 JAN 2014 | DOI: 10.1002/jrs.4421

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      The normal Raman and surface enhanced Raman spectra (SERS) of 2,2′,5,5′-tetrachlorobiphenyl (PCB52) adsorbed on small silver clusters Agn (n = 2, 4, 6, and 10) were calculated. The normal Raman spectra intensity of PCB52–Agn are only slightly enhanced, while the corresponding SERS spectra calculated at adopted incident light are strongly enhanced, which is consistent with the experimentally observed results. The dominant enhancement in SERS intensities origins from the charge transfer resonance enhancement between the molecule and cluster.

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      DFT study on the influence of electric field on surface-enhanced Raman scattering from pyridine–metal complex (pages 62–67)

      Xiuming Zhao and Maodu Chen

      Article first published online: 21 DEC 2013 | DOI: 10.1002/jrs.4422

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      The influence of a static external electric field on surface-enhanced Raman scattering is investigated by employing density functional theory method. The changes in bonding, frequency shifts, charge transfer states, especially Raman intensities due to the external electric field are analyzed in details. Raman spectra could be modulated by tuning the strength and direction of the electric field.

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      Individual SERS substrate with core–satellite structure decorated in shrinkable hydrogel template for pesticide detection (pages 68–74)

      Yiping Wu, Pan Li, Liangbao Yang and Jinhuai Liu

      Article first published online: 2 JAN 2014 | DOI: 10.1002/jrs.4429

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      Individual Au@PNIPAM/Ag composite can be seen directly through Raman optical microscope, and the gaps between the Au and Ag nanoparticles can decrease because the PNIPAM shrinks from swollen to collapse state, so high repeatable surface-enhanced Raman scattering signals are given out.

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      A SERS-active enzymatic product used for the quantification of disease-related molecules (pages 75–81)

      Zhi Yu, Lei Chen, Yue Wang, Xu Wang, Wei Song, Weidong Ruan, Bing Zhao and Qian Cong

      Article first published online: 26 DEC 2013 | DOI: 10.1002/jrs.4425

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      The Enzyme catalysis products (TMB2+) exhibits perfect surface-enhanced Raman scattering activities. And by analyzing the concentration-based surface-enhanced Raman scattering spectra of TMB2+, the quantitative analysis of diseased-related molecule (cTnT) was realized.

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      Accessing Raman spectral variability in human stratum corneum for quantitative in vitro depth profiling (pages 82–88)

      Lutz Franzen and Maike Windbergs

      Article first published online: 19 DEC 2013 | DOI: 10.1002/jrs.4428

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      This study represents a systematic evaluation of the intensity variability of Raman spectra obtained from excised human skin. We acquired Raman depth profiles from skin samples and spectral dissimilarity between different measurements on the same sample as well as between different skin donors was calculated with reference to spectral acquisition depth. This study clarifies the necessity of comprehensive spectral analysis of the endogenous Raman spectra and accomplishes a further crucial step towards direct quantification by CRM in human skin.

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      Theoretical investigation and computational evaluation of overtone and combination features in resonance Raman spectra of polyenes and carotenoids (pages 89–96)

      Matteo Tommasini, Giovanna Longhi, Sergio Abbate and Giuseppe Zerbi

      Article first published online: 2 JAN 2014 | DOI: 10.1002/jrs.4415

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      We review the theory for overtones and combinations in resonant Raman spectroscopy introduced by Nafie et al. in 1971, and we apply it to β-carotene with the support of density functional theory calculations. Comparison with experimental results obtained by Tasumi's group in 1994 is provided. The theory here presented allows a prompt evaluation of resonant Raman intensities with presently available quantum chemistry tools.

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      Resonance Raman determination of vinyl group disposition in different derivatives of native myoglobin and its heme-disoriented form (pages 97–104)

      Freeborn Rwere, Piotr J. Mak and James R. Kincaid

      Article first published online: 2 JAN 2014 | DOI: 10.1002/jrs.4419

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      Resonance Raman spectroscopy is used to interrogate the relative orientations of the two peripheral vinyl groups of the heme in the met-, deoxy-, and ferrous CO adducts of horse heart myoglobin in the native form and that bearing a reversed heme conformation. Specifically, a protoheme that is deuterated only at the 4-vinyl group provides a spectral editing mechanism for selectively tracking the disposition of the individual vinyl groups. This is important because vinyl group orientation can impact protein function.

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      Structural dynamics of 4-cyanobenzaldehyde in S2(ππ*) state (pages 105–113)

      Yi Yang, Sheng Pan, Jia-Dan Xue, Xuming Zheng, Wei-Hai Fang and David Lee Phillips

      Article first published online: 18 DEC 2013 | DOI: 10.1002/jrs.4420

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      The structural dynamics of 4-cyanobenzaldehyde was studied by using resonance Raman spectroscopy and quantum mechanical calculations. The conical intersection between S1(nOπ3) and S22π3) states of p-CNB was determined. The ν16 Raman band is the signature for the existence of the [S1(nOπ3)/S21π2π3π4)] conical intersection.

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      An integrated Raman and petrographic characterization of Italian mediaeval artifacts in pietra ollare (soapstone) (pages 114–122)

      Chiara Baita, Pier Paolo Lottici, Emma Salvioli-Mariani, Peter Vandenabeele, Mauro Librenti, Fabrizio Antonelli and Danilo Bersani

      Article first published online: 18 DEC 2013 | DOI: 10.1002/jrs.4414

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      Ten fragments of pots made by ‘pietra ollare’ (9th–10th century AD) found in archeological site of Crocetta di Sant'Agata Bolognese (Italy) have been characterized and their provenance defined. The extensive use of a non-destructive technique, Raman spectroscopy, in both laboratory and portable forms, coupled with more traditional techniques (petrological studies, XRD, SEM-EDX) allowed to identify Valchiavenna (Italy) as the provenance of the raw material.

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      In situ microanalysis of organic colorants by inkjet colloid deposition surface-enhanced Raman scattering (pages 123–127)

      Dario P. Benedetti, Jie Zhang, Thomas J. Tague Jr, John R. Lombardi and Marco Leona

      Article first published online: 20 DEC 2013 | DOI: 10.1002/jrs.4424

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      A compact piezoelectric inkjet head integrated with the optical system of a large-stage Raman microscope was used to accurately and precisely deliver colloid nanodroplets onto a target for surface-enhanced Raman spectroscopy analysis. The approach is functionally nondestructive as the amount of silver delivered and the area affected are too small to be detected by visual observation. The method was successfully applied to the analysis of gel pen ink on paper and of a 19th century Japanese woodblock print.

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      Raman spectroscopic characterization of novel carbon-bonded filter compositions for steel melt filtration (pages 128–132)

      Christian Röder, Torsten Weißbach, Cameliu Himcinschi, Jens Kortus, Steffen Dudczig and Christos G. Aneziris

      Article first published online: 19 DEC 2013 | DOI: 10.1002/jrs.4426

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      Raman scattering results on novel carbon-bonded filter compositions are reported for the first time. The recorded Raman spectra in the figure indicate thermally induced structural changes. Analyzing the position, intensity, and full width at half maximum of G and D peaks, it could be determined that the carbon appears in graphitic form and its lateral cluster size increases with increasing coking temperature.

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      Optimising image quality in 2D and 3D confocal Raman mapping (pages 133–138)

      Neil Everall

      Article first published online: 18 DEC 2013 | DOI: 10.1002/jrs.4430

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      The use of oil immersion and metallurgical objectives is compared for 2D and 3D Raman imaging of complex structures including laminates, heterofilament fibres and dissolving particles. The oil immersion objective yields Raman images with far superior spatial resolution, contrast and brightness, and it eliminates some confusing artefacts that are not observed with simple planar structures.

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      Raman analysis of perrhenate and pertechnetate in alkali salts and borosilicate glasses (pages 139–147)

      Paul L. Gassman, John S. McCloy, Chuck Z. Soderquist and Michael J. Schweiger

      Article first published online: 3 JAN 2014 | DOI: 10.1002/jrs.4427

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      Raman spectra of alkali perrhenates and pertechnetates were used to better understand the incorporation of these salts in sodium borosilicate glasses. Ion exchange by Na+ from the base glass caused crystalline NaReO4 and NaTcO4 to form, indicating the importance of segregation effects by network-modifying alkali cations on long-term performance of radioactive waste glasses containing 99Tc.

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