Sample records for raman excitation profiles

  1. Resonance Raman excitation profiles of lycopene

    Hoskins, L. C.


    The resonance Raman spectrum of lycopene has been examined in acetone solvent and excitation profiles of the three fundamentals ν1, ν2, and ν3 have been determined. The excitation data and the visible spectrum have been analyzed using two-mode and three-mode vibrational models, with the two-mode model involving virtual states of ν1 and ν2 giving the best fit to the data. This mode mixing or Duskinsky effect was not observed for β-carotene. The single-mode and three-mode theories which have been used to explain the corresponding data for β-carotene are shown to be inconsistent with the experimental data of lycopene. Equations for calculating excitation profiles and visible spectra are given.

  2. Transform analysis of the resonance Raman excitation profile of lycopene

    Hoskins, L. C.


    The resonance Raman excitation profiles (RREPs) of the ν 1, ν 2 and ν 3 vibrations of lycopene in acetone, ethyl alcohol, toluene and carbon disulphide solvents have been analyzed using the transform method for calculating resonance Raman excitation profiles. The tests show excellent agreement between the calculated and observed profiles for the ν 2 and ν 3 RREPs, but greater difference between experiment and theory occurs for the ν 1 RREP, especially in carbon disulphide solvent.

  3. Effects of inhomogeneous broadening on the resonance Raman excitation profile of lycopene

    Cotting, J. E.; Hoskins, L. C.; Levan, M. E.


    The resonance Raman excitation profiles for the ν1, ν2, and ν3 vibrations of lycopene in ethyl alcohol, toluene, and carbon disulfide solvents have been measured. The results are interpreted in terms of a three-mode vibrational theory which includes both homogeneous and inhomogeneous broadening effects. Excellent agreement between calculated and observed excitation profiles and visible spectra was found, thus emphasizing the need to interpret resonance Raman data using a multimode vibrational model. The results indicate that the major broadening mechanism is homogeneous broadening, with about a 25% contribution from inhomogeneous broadening. The excitation profiles in carbon disulfide gave the largest inhomogeneous broadening.

  4. Time Dependent Coupled Cluster Approach to Resonance Raman Excitation Profiles from General Anharmonic Surfaces

    M. Durga Prasad


    Full Text Available Abstract: A time dependent coupled cluster approach to the calculation of Resonance Raman excitation profiles on general anharmonic surfaces is presented. The vibrational wave functions on the ground electronic surface are obtained by the coupled cluster method (CCM. It is shown that the propagation of the vibrational ground state on the upper surface is equivalent to propagation of the vacuum state by an effective hamiltonian generated by the similarity transformation of the vibrational hamiltonian of that surface by the CCM wave operator of the lower surface up to a normalization constant. This time propagation is carried out by the time-dependent coupled cluster method in a time dependent frame. Numerical studies are presented to asses the validity of the approach.

  5. Analysis of the excitation profiles of Raman bands of linear-chain mixed-valence complexes. The geometry of [Pt(en) 2][Pt(en) 2Br 2]Br 4 in the intervalence state

    Clark, Robin J. H.; Dines, Trevor J.


    Calculations of the resonance Raman excitation profiles for the ν 1 band and its overtones have been performed for the linear- chain mixed-valence platinum complex [Pt(en) 2Br 2]Br 4. It is found that the Pt IV length increases by 0.075 Å in the intervalence state. A satisfactory fit to the excitation profiles requires the inclusion of a second excited state at 16500 cm -1, which we have assigned to Br→Pt IV charge transfer.

  6. Raman active high energy excitations in URu2Si2

    Buhot, Jonathan; Gallais, Yann; Cazayous, Maximilien; Sacuto, Alain; Piekarz, Przemysław; Lapertot, Gérard; Aoki, Dai; Méasson, Marie-Aude


    We have performed Raman scattering measurements on URu2Si2 single crystals on a large energy range up to ∼1300 cm-1 and in all the Raman active symmetries as a function of temperature down to 15 K. A large excitation, active only in the Eg symmetry, is reported. It has been assigned to a crystal electric field excitation on the Uranium site. We discuss how this constrains the crystal electric field scheme of the Uranium ions. Furthermore, three excitations in the A1g symmetry are observed. They have been associated to double Raman phonon processes consistently with ab initio calculations of the phonons dispersion.

  7. Complementary analysis of tissue homogenates composition obtained by Vis and NIR laser excitations and Raman spectroscopy

    Staniszewska-Slezak, Emilia; Malek, Kamilla; Baranska, Malgorzata


    Raman spectroscopy and four excitation lines in the visible (Vis: 488, 532, 633 nm) and near infrared (NIR: 785 nm) were used for biochemical analysis of rat tissue homogenates, i.e. myocardium, brain, liver, lung, intestine, and kidney. The Vis Raman spectra are very similar for some organs (brain/intestines and kidney/liver) and dominated by heme signals when tissues of lung and myocardium were investigated (especially with 532 nm excitation). On the other hand, the NIR Raman spectra are specific for each tissue and more informative than the corresponding ones collected with the Vis excitations. The spectra analyzed without any special pre-processing clearly illustrate different chemical composition of each tissue and give information about main components e.g. lipids or proteins, but also about the content of some specific compounds such as amino acid residues, nucleotides and nucleobases. However, in order to obtain the whole spectral information about tissues complex composition the spectra of Vis and NIR excitations should be collected and analyzed together. A good agreement of data gathered from Raman spectra of the homogenates and those obtained previously from Raman imaging of the tissue cross-sections indicates that the presented here approach can be a method of choice for an investigation of biochemical variation in animal tissues. Moreover, the Raman spectral profile of tissue homogenates is specific enough to be used for an investigation of potential pathological changes the organism undergoes, in particular when supported by the complementary FTIR spectroscopy.

  8. Laser Raman Spectroscopy with Different Excitation Sources and Extension to Surface Enhanced Raman Spectroscopy

    Md. Wahadoszamen


    Full Text Available A dispersive Raman spectrometer was used with three different excitation sources (Argon-ion, He-Ne, and Diode lasers operating at 514.5 nm, 633 nm, and 782 nm, resp.. The system was employed to a variety of Raman active compounds. Many of the compounds exhibit very strong fluorescence while being excited with a laser emitting at UV-VIS region, hereby imposing severe limitation to the detection efficiency of the particular Raman system. The Raman system with variable excitation laser sources provided us with a desired flexibility toward the suppression of unwanted fluorescence signal. With this Raman system, we could detect and specify the different vibrational modes of various hazardous organic compounds and some typical dyes (both fluorescent and nonfluorescent. We then compared those results with the ones reported in literature and found the deviation within the range of ±2 cm−1, which indicates reasonable accuracy and usability of the Raman system. Then, the surface enhancement technique of Raman spectrum was employed to the present system. To this end, we used chemically prepared colloidal suspension of silver nanoparticles as substrate and Rhodamine 6G as probe. We could observe significant enhancement of Raman signal from Rhodamine 6G using the colloidal solution of silver nanoparticles the average magnitude of which is estimated to be 103.

  9. Raman scattering excitation spectroscopy of monolayer WS2.

    Molas, Maciej R; Nogajewski, Karol; Potemski, Marek; Babiński, Adam


    Resonant Raman scattering is investigated in monolayer WS2 at low temperature with the aid of an unconventional technique, i.e., Raman scattering excitation (RSE) spectroscopy. The RSE spectrum is made up by sweeping the excitation energy, when the detection energy is fixed in resonance with excitonic transitions related to either neutral or charged excitons. We demonstrate that the shape of the RSE spectrum strongly depends on the selected detection energy. The resonance of outgoing light with the neutral exciton leads to an extremely rich RSE spectrum, which displays several Raman scattering features not reported so far, while no clear effect on the associated background photoluminescence is observed. Instead, when the outgoing photons resonate with the negatively charged exciton, a strong enhancement of the related emission occurs. Presented results show that the RSE spectroscopy can be a useful technique to study electron-phonon interactions in thin layers of transition metal dichalcogenides.

  10. A Fourier transform Raman spectrometer with visible laser excitation

    Dzsaber, S; Bernáth, B; Gyüre, B; Fehér, T; Kramberger, C; Pichler, T; Simon, F


    We present the development and performance of a Fourier transformation (FT) based Raman spectrometer working with visible laser (532 nm) excitation. It is generally thought that FT-Raman spectrometers are not viable in the visible range where shot-noise limits the detector performance and therein they are outperformed by grating based, dispersive ones. We show that contrary to this common belief, the recent advances of high-performance interference filters makes the FT-Raman design a valid alternative to dispersive Raman spectrometers for samples which do not luminesce. We critically compare the performance of our spectrometer to two dispersive ones: a home-built single channel and a state-of-the-art CCD based instruments. We demonstrate a similar or even better sensitivity than the CCD based dispersive spectrometer particularly when the laser power density is considered. The instrument possesses all the known advantages of the FT principle of spectral accuracy, high throughput, and economic design. We also d...

  11. Impulsive X-ray Raman excitation of NO$_2$

    Haxton, Daniel J


    We investigate impulsive X-ray Raman excitation of the NO$_2$ molecule. We seek to optimize population transfer to valence states of the NO$_2$ molecule using using 1fs pulses tuned below the Oxygen K-edge, and detect subsequent coherent electron motion among valence excited states by using a second, weak X-ray pulse with variable time delay that ionizes a Nitrogen 1$s$ electron. Toward these ends, impulsive X-ray Raman excitations were calculated in the fixed-nuclei approximation using the multiconfiguration time-dependent Hartree-Fock (MCTDHF) method. Fixing the duration but varying the central frequency and intensity of the pulse, not considering chirp, we find optimum population transfer at intensity approximately 3$\\times$10$^{17}$ W cm$^{-2}$, an intensity for which 2nd order pertubation theory is no longer applicable, with the central frequency substantially 8eV red-detuned from the 2nd order optimum.

  12. UV Raman imaging--a promising tool for astrobiology: comparative Raman studies with different excitation wavelengths on SNC Martian meteorites.

    Frosch, Torsten; Tarcea, Nicolae; Schmitt, Michael; Thiele, Hans; Langenhorst, Falko; Popp, Jürgen


    The great capabilities of UV Raman imaging have been demonstrated on the three Martian meteorites: Sayh al Uhaymir, Dar al Gani, and Zagami. Raman spectra without disturbing fluorescence and with high signal-to-noise-ratios and full of spectral features were derived. This result is of utmost importance for the development of powerful instruments for space missions. By point scanning the surfaces of the meteorite samples, it was possible for the first time to construct UV-Raman images out of the array of Raman spectra. Deep-UV Raman images are to the best of our knowledge presented for the first time. The images were used for a discussion of the chemical-mineralogical composition and texture of the meteorite surfaces. Comparative Raman studies applying visible and NIR Raman excitation wavelengths demonstrate a much better performance for UV Raman excitation. This comparative study of different Raman excitation wavelengths at the same sample spots was done by constructing a versatile, robust sample holder with a fixed micro-raster. The overall advantages of UV resonance Raman spectroscopy in terms of sensitivity and selectivity are demonstrated and discussed. Finally the application of this new technique for a UV Raman instrument for envisaged astrobiological focused space missions is suggested.

  13. Surface-enhanced Raman scattering on aluminum using near infrared and visible excitation

    Mogensen, Klaus Bo; Gühlke, Marina; Kneipp, Janina;


    We observed strong surface-enhanced Raman scattering on discontinuous nanostructured aluminum films using 785 nm excitation even though dielectric constants of this metal suggest plasmon supported spectroscopy in the ultraviolet range. The excitation of SERS correlates with plasmon resonances...

  14. Geometrical constraint experimental determination of Raman lidar overlap profile.

    Li, Jian; Li, Chengcai; Zhao, Yiming; Li, Jing; Chu, Yiqi


    A simple experimental method to determine the overlap profile of Raman lidar is presented in this paper. Based on Mie and Raman backscattering signals and a geometrically constrained condition, the overlap profile of a Raman lidar system can be determined. Our approach simultaneously retrieves the lidar ratio of aerosols, which is one of the most important sources of uncertainty in the overlap profile determination. The results indicate that the overlap factor is significantly influenced by the lidar ratio in experimental methods. A representative case study indicates that the correction of the overlap profile obtained by this method is practical and feasible.

  15. Formation of infrared solitons in graphene ensemble under Raman excitation

    Ding, Chunling; Yu, Rong; Yang, Xiaoxue; Zhang, Duo; Huang, Mingju


    The formation of infrared solitons in graphene under Raman excitation is investigated using density-matrix approach. We find that the unique band structure and selection rules for the optical transitions near the Dirac point can result in extremely strong optical nonlinearity. Theoretical investigations with the aid of slowly varying envelope approximation and perturbation theory clearly indicate the existence of bright and dark solitons in Landau-quantized graphene. Actually, the formation of spatial soliton in such a material is the consequence of the balance between nonlinear effects and the dispersion properties. Also, the corresponding carrier frequency is tunable in the infrared range. These results can make us know better the crossover between optical solitons and graphene metamaterials. The predicted nonlinear optical effect in graphene may provide a new possibility for designing high-fidelity graphene-based information processing device.

  16. Phenotypic Profiling of Antibiotic Response Signatures in Escherichia coli Using Raman Spectroscopy

    Athamneh, A. I. M.; Alajlouni, R. A.; Wallace, R. S.; Seleem, M. N.


    Identifying the mechanism of action of new potential antibiotics is a necessary but time-consuming and costly process. Phenotypic profiling has been utilized effectively to facilitate the discovery of the mechanism of action and molecular targets of uncharacterized drugs. In this research, Raman spectroscopy was used to profile the phenotypic response of Escherichia coli to applied antibiotics. The use of Raman spectroscopy is advantageous because it is noninvasive, label free, and prone to automation, and its results can be obtained in real time. In this research, E. coli cultures were subjected to three times the MICs of 15 different antibiotics (representing five functional antibiotic classes) with known mechanisms of action for 30 min before being analyzed by Raman spectroscopy (using a 532-nm excitation wavelength). The resulting Raman spectra contained sufficient biochemical information to distinguish between profiles induced by individual antibiotics belonging to the same class. The collected spectral data were used to build a discriminant analysis model that identified the effects of unknown antibiotic compounds on the phenotype of E. coli cultures. Chemometric analysis showed the ability of Raman spectroscopy to predict the functional class of an unknown antibiotic and to identify individual antibiotics that elicit similar phenotypic responses. Results of this research demonstrate the power of Raman spectroscopy as a cellular phenotypic profiling methodology and its potential impact on antibiotic drug development research. PMID:24295982

  17. "Parallel factor analysis of multi-excitation ultraviolet resonance Raman spectra for protein secondary structure determination".

    Oshokoya, Olayinka O; JiJi, Renee D


    Protein secondary structural analysis is important for understanding the relationship between protein structure and function, or more importantly how changes in structure relate to loss of function. The structurally sensitive protein vibrational modes (amide I, II, III and S) in deep-ultraviolet resonance Raman (DUVRR) spectra resulting from the backbone C-O and N-H vibrations make DUVRR a potentially powerful tool for studying secondary structure changes. Experimental studies reveal that the position and intensity of the four amide modes in DUVRR spectra of proteins are largely correlated with the varying fractions of α-helix, β-sheet and disordered structural content of proteins. Employing multivariate calibration methods and DUVRR spectra of globular proteins with varying structural compositions, the secondary structure of a protein with unknown structure can be predicted. A disadvantage of multivariate calibration methods is the requirement of known concentration or spectral profiles. Second-order curve resolution methods, such as parallel factor analysis (PARAFAC), do not have such a requirement due to the "second-order advantage." An exceptional feature of DUVRR spectroscopy is that DUVRR spectra are linearly dependent on both excitation wavelength and secondary structure composition. Thus, higher order data can be created by combining protein DUVRR spectra of several proteins collected at multiple excitation wavelengths to give multi-excitation ultraviolet resonance Raman data (ME-UVRR). PARAFAC has been used to analyze ME-UVRR data of nine proteins to resolve the pure spectral, excitation and compositional profiles. A three factor model with non-negativity constraints produced three unique factors that were correlated with the relative abundance of helical, β-sheet and poly-proline II dihedral angles. This is the first empirical evidence that the typically resolved "disordered" spectrum represents the better defined poly-proline II type structure.

  18. The evaluation of temporal electronic structures of nonresonant Raman excited virtual state of thiourea

    Fang Chao; Sun Li-Feng


    An algorithm has been introduced to calculate molecular bond polarizabilities of thiourea, which supply essential electronic information about the nonresonant Raman excited virtual states.The main dynamical behaviour of the excited virtual states of thiourea is that the Raman excited electrons tend to flow to the N-H bonds and C-N bonds from the S-C bonds because of the electronic repulsion effect. The difference in Raman excited electron relaxation time of thiourea under 514.5-nm and 325-nm excitations has been observed, which quantitatively shows that the Raman scattering process is dependent on the wavelength of the pumping laser. Finally, the distribution of the electrons at the final stage of relaxation is given out through the comparison between the bond electronic densities of the ground states and the bond polarizabilities after deexcitation.

  19. Raman signal enhancement by multiple beam excitation and its application for the detection of chemicals

    Gupta, Sakshi [Laser Science and Technology Centre, Metcalfe House, Delhi 110054 (India); Instrument Design and Development Centre, Indian Institute of Technology, Hauz Khas, New Delhi 110016 (India); Ahmad, Azeem; Mehta, Dalip S., E-mail: [Department of Physics, Indian Institute of Technology, Hauz Khas, New Delhi 110016 (India); Gambhir, Vijayeta; Reddy, Martha N. [Laser Science and Technology Centre, Metcalfe House, Delhi 110054 (India)


    In a typical Raman based sensor, a single laser beam is used for exciting the sample and the backscattered or forward scattered light is collected using collection optics and is analyzed by a spectrometer. We have investigated that by means of exciting the sample with multiple beams, i.e., by dividing the same input power of the single beam into two or three or more beams and exciting the sample from different angles, the Raman signal enhances significantly. Due to the presence of multiple beams passing through the same volume of the sample, an interference pattern is formed and the volume of interaction of excitation beams with the sample increases. By means of this geometry, the enhancement in the Raman signal is observed and it was found that the signal strength increases linearly with the increase in number of excitation beams. Experimental results of this scheme for excitation of the samples are reported for explosive detection at a standoff distance.

  20. Detection of munitions grade g-series nerve agents using Raman excitation at 1064 nm

    Roy, Eric; Wilcox, Phillip G.; Hoffland, Soren; Pardoe, Ian


    Raman spectroscopy is a powerful tool for obtaining molecular structure information of a sample. While Raman spectroscopy is a common laboratory based analytical tool, miniaturization of opto-electronic components has allowed handheld Raman analyzers to become commercially available. These handheld systems are utilized by Military and First Responder operators tasked with rapidly identifying potentially hazardous chemicals in the field. However, one limitation of many handheld Raman detection systems is strong interference caused by fluorescence of the sample or underlying surface which obscures the characteristic Raman signature of the target analyte. Munitions grade chemical warfare agents (CWAs) are produced and stored in large batches and typically have more impurities from the storage container, degradation, or unreacted precursors. In this work, Raman spectra of munitions grade CWAs were collected using a handheld Raman spectrometer with a 1064 nm excitation laser. While Raman scattering generated by a 1064 nm laser is inherently less efficient than excitation at shorter wavelengths, high quality spectra were easily obtained due to significantly reduced fluorescence of the munitions grade CWAs. The spectra of these less pure, but more operationally relevant, munitions grade CWAs were then compared to spectra of CASARM grade CWAs, as well as Raman spectra collected using the more common 785 nm excitation laser.

  1. Shifted Excitation Raman Difference Spectroscopy applied to extraterrestrial particles returned from the asteroid Itokawa

    Böttger, U.; Maiwald, M.; Hanke, F.; Braune, M.; Pavlov, S. G.; Schröder, S.; Weber, I.; Busemann, H.; Sumpf, B.; Tränkle, G.; Hübers, H.-W.


    Two extraterrestrial particles from the asteroid Itokawa are investigated applying Shifted Excitation Raman Difference Spectroscopy (SERDS). These particles were returned by the Hayabusa mission of the Japanese Space Agency JAXA. For SERDS a diode laser based microsystem light source at 488 nm is used for excitation. It has been found that fluorescence signals masking the Raman spectral features of interest can be substantially separated by applying SERDS. Therefore, SERDS improves the information obtained from the Raman spectra and enables a reliable analysis for investigations on extraterrestrial samples.

  2. The attosecond regime of impulsive stimulated electronic Raman excitation

    Ware, Matthew R; Cryan, James P; Haxton, Daniel J


    We have calculated the resonant and nonresonant contributions to attosecond impulsive stimulated electronic Raman scattering (SERS) in regions of autoionizing transitions. Comparison with Multiconfiguration Time-Dependent Hartree-Fock (MCTDHF) calculations find that attosecond SERS is dominated by continuum transitions and not autoionizing resonances. These results agree quantitatively with a rate equation that includes second-order Raman and first-and second-order photoionization rates. Such rate models can be extended to larger molecular systems. Our results indicate that attosecond SERS transition probabilities may be understood in terms of two-photon generalized cross sections even in the high-intensity limit for extreme ultraviolet wavelengths.

  3. Reversible quantum optical data storage based on resonant Raman optical field excited spin coherence.

    Ham, Byoung S


    A method of reversible quantum optical data storage is presented using resonant Raman field excited spin coherence, where the spin coherence is stored in an inhomogeneously broadened spin ensemble. Unlike the photon echo method, in the present technique, a 2pi Raman optical rephasing pulse area is used and multimode (parallel) optical channels are available in which the multimode access gives a great benefit to quantum information processors such as quantum repeaters.

  4. Raman active high energy excitations in URu{sub 2}Si{sub 2}

    Buhot, Jonathan [Laboratoire Matériaux et Phénomènes Quantiques, UMR 7162 CNRS, Université Paris Diderot - Paris 7, Bât. Condorcet, 75205 Paris Cedex 13 (France); High Field Magnet Laboratory (HFML - EMFL), Institute for Molecules and Materials, Radboud University, Toernooiveld 7, 6525 ED Nijmegen (Netherlands); Gallais, Yann; Cazayous, Maximilien; Sacuto, Alain [Laboratoire Matériaux et Phénomènes Quantiques, UMR 7162 CNRS, Université Paris Diderot - Paris 7, Bât. Condorcet, 75205 Paris Cedex 13 (France); Piekarz, Przemysław [Institute of Nuclear Physics, Polish Academy of Sciences, 31-342 Krakòw (Poland); Lapertot, Gérard [Université Grenoble Alpes, INAC-SPSMS, F-38000 Grenoble (France); CEA, INAC-SPSMS, F-38000 Grenoble (France); Aoki, Dai [Université Grenoble Alpes, INAC-SPSMS, F-38000 Grenoble (France); CEA, INAC-SPSMS, F-38000 Grenoble (France); Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan); Méasson, Marie-Aude, E-mail: [Laboratoire Matériaux et Phénomènes Quantiques, UMR 7162 CNRS, Université Paris Diderot - Paris 7, Bât. Condorcet, 75205 Paris Cedex 13 (France)


    We have performed Raman scattering measurements on URu{sub 2}Si{sub 2} single crystals on a large energy range up to ∼1300 cm{sup −1} and in all the Raman active symmetries as a function of temperature down to 15 K. A large excitation, active only in the E{sub g} symmetry, is reported. It has been assigned to a crystal electric field excitation on the Uranium site. We discuss how this constrains the crystal electric field scheme of the Uranium ions. Furthermore, three excitations in the A{sub 1g} symmetry are observed. They have been associated to double Raman phonon processes consistently with ab initio calculations of the phonons dispersion.

  5. Experimental Investigation on Selective Excitation of Two-Pulse Coherent Anti-Stokes Raman Scattering

    LI Xia; ZHANG Hui; ZHANG Xiang-Yun; ZHANG Shi-An; WANG Zu-Geng; SUN Zhen-Rong


    Selective excitation of coherent anti-Stokes Raman scattering from the benzene solution is achieved by adaptive pulse shaping based on genetic algorithm, and second harmonic generation frequency-resolved optical gating (SHG-FROG) technique is adopted to characterize the original and optimal laser pulses. The mechanism for two-pulse coherent mode-selective excitation of Raman scattering is experimentally investigated by modulating the pump pulse in the frequency domain, and it is indicated that two-pulse coherent mode-selective excitation of Raman scattering mainly depends on the effective frequency components of the pump pulse related to specific vibrational mode. The experimental results suggest that two-pulse CARS has good signal-to-background ratio and high sensitivity, and it has attractive potential applications in the complicated molecular system.

  6. Monitoring the cementitious materials subjected to sulfate attack with optical fiber excitation Raman spectroscopy

    Yue, Yanfei; Bai, Yun; Muhammed Basheer, P. A.; Boland, John J.; Wang, Jing Jing


    Formation of ettringite and gypsum from sulfate attack together with carbonation and chloride ingress have been considered as the most serious deterioration mechanisms of concrete structures. Although electrical resistance sensors and fiber optic chemical sensors could be used to monitor the latter two mechanisms on site, currently there is no system for monitoring the deterioration mechanisms of sulfate attack. In this paper, a preliminary study was carried out to investigate the feasibility of monitoring sulfate attack with optical fiber excitation Raman spectroscopy through characterizing the ettringite and gypsum formed in deteriorated cementitious materials under an optical fiber excitation + objective collection configuration. Bench-mounted Raman spectroscopy analysis was also conducted to validate the spectrum obtained from the fiber-objective configuration. The results showed that the expected Raman bands of ettringite and gypsum in the sulfate-attacked cement paste can be clearly identified by the optical fiber excitation Raman spectrometer and are in good agreement with those identified from bench-mounted Raman spectrometer. Therefore, based on these preliminary results, it is considered that there is a good potential for developing an optical fiber-based Raman system to monitor the deterioration mechanisms of concrete subjected to sulfate attack in the future.

  7. Raman lidar water vapor profiling over Warsaw, Poland

    Stachlewska, Iwona S.; Costa-Surós, Montserrat; Althausen, Dietrich


    Water vapor mixing ratio and relative humidity profiles were derived from the multi-wavelength Raman PollyXT lidar at the EARLINET site in Warsaw, using the Rayleigh molecular extinction calculation based on atmospheric temperature and pressure from three different sources: i) the standard atmosphere US 62, ii) the Global Data Assimilation System (GDAS) model output, and iii) the WMO 12374 radiosoundings launched at Legionowo. With each method, 136 midnight relative humidity profiles were obtained for lidar observations from July 2013 to August 2015. Comparisons of these profiles showed in favor of the latter method (iii), but it also indicated that the other two data sources could replace it, if necessary. Such use was demonstrated for an automated retrieval of water vapor mixing ratio from dusk until dawn on 19/20 March 2015; a case study related to an advection of biomass burning aerosol from forest fires over Ukraine. Additionally, an algorithm that applies thresholds to the radiosounding relative humidity profiles to estimate macro-physical cloud vertical structure was used for the first time on the Raman lidar relative humidity profiles. The results, based on a subset of 66 profiles, indicate that below 6 km cloud bases/tops can be successfully obtained in 53% and 76% cases from lidar and radiosounding profiles, respectively. Finally, a contribution of the lidar derived mean relative humidity to cloudy conditions within the range of 0.8 to 6.2 km, in comparison to clear-sky conditions, was estimated.

  8. Raman study on single-walled carbon nanotubes with different laser excitation energies

    S S Islam; Khurshed Ahmad Shah; H S Mavi; A K Shaukla; S Rath; Harsh


    The industrial use of carbon nanotubes is increasing day by day; therefore, it is very important to identify the nature of carbon nanotubes in a bundle. In this study, we have used the Raman spectroscopic analysis on vertically aligned single-walled carbon nanotubes (SWCNTs) grown by the chemical vapour deposition (CVD) technique. The grown sample is excited with two laser excitation wavelengths, 633 nm from He–Ne laser and 514.5 nm from Ar+ laser. Raman spectrum in the backscattering geometry provides the characteristic spectra of SWCNTs with its radial breathing mode (RBM), defect-induced disorder mode (D band), and highenergy modes (G and M bands). The Raman signal positions of the spectra in RBM, G and M bands confirm the grown sample to be of semiconducting type in nature.

  9. Excitation-emission fluorescence spectroscopy and time-gated Raman microscopy analysis of dental tissues

    Mukhin, M.; Sen, S.; Kouklin, Nikolai A.; Skliarov, A.; Dhuru, D. B.; Iacopino, A. M.; Yakovlev, Vladislav V.


    We applied two new spectroscopic techniques (time-gated Raman microscopy and excitation-emission fluorescence microspectroscopy) to characterize healthy and carious dental tissues. These methods were used together with visual inspection, DIAGNOdent, optical polarization microscopy, scanning electron microscopy, and chemical microanalysis to get a more detailed picture of chemical and structural transformations in dental tissues as a result of caries development.

  10. Mode specific excited state dynamics study of bis(phenylethynyl)benzene from ultrafast Raman loss spectroscopy

    Roy, Khokan; Kayal, Surajit; Ariese, Freek; Beeby, Andrew; Umapathy, Siva


    Femtosecond transient absorption (fs-TA) and Ultrafast Raman Loss Spectroscopy (URLS) have been applied to reveal the excited state dynamics of bis(phenylethynyl)benzene (BPEB), a model system for one-dimensional molecular wires that have numerous applications in opto-electronics. It is known from the literature that in the ground state BPEB has a low torsional barrier, resulting in a mixed population of rotamers in solution at room temperature. For the excited state this torsional barrier had been calculated to be much higher. Our femtosecond TA measurements show a multi-exponential behaviour, related to the complex structural dynamics in the excited electronic state. Time-resolved, excited state URLS studies in different solvents reveal mode-dependent kinetics and picosecond vibrational relaxation dynamics of high frequency vibrations. After excitation, a gradual increase in intensity is observed for all Raman bands, which reflects the structural reorganization of Franck-Condon excited, non-planar rotamers to a planar conformation. It is argued that this excited state planarization is also responsible for its high fluorescence quantum yield. The time dependent peak positions of high frequency vibrations provide additional information: a rapid, sub-picosecond decrease in peak frequency, followed by a slower increase, indicates the extent of conjugation during different phases of excited state relaxation. The CC triple (-C≡C-) bond responds somewhat faster to structural reorganization than the CC double (>C=Cwires."

  11. Red emitting monolithic dual wavelength DBR diode lasers for shifted excitation Raman difference spectroscopy

    Sumpf, B.; Maiwald, M.; Müller, A.; Bugge, F.; Fricke, J.; Ressel, P.; Pohl, J.; Erbert, G.; Tränkle, G.


    Raman lines are often obscured by background light or fluorescence especially when investigating biological samples or samples containing impurities. Shifted excitation Raman difference spectroscopy (SERDS) is a technique to overcome this. By exciting the sample with two slightly shifted wavelengths, it is possible to separate the Raman lines and distortions. In this paper, monolithic dual wavelength DBR diode lasers meeting the demands of Raman spectroscopy and SERDS will be presented. The wavelengths are stabilized and selected by using deeply-etched 10th order surface gratings with different periods manufactured using i-line wafer stepper lithography. Two possible resonator concepts, i.e. a mini-array of two parallel DBR RW-lasers and a Y-branch DBR laser, will be compared. Established excitation wavelengths for Raman spectroscopy at 671 nm and 785 nm are chosen. The total laser length is 3 mm; the ridge width is 2.2 μm for the 785 nm devices and 5 μm for the 671 nm lasers. The length of the DBR gratings is 500 μm. The devices at 671 nm reach output powers up to 100 mW having an emission width smaller than 12 pm (FWHM). The 785 nm lasers show output powers up to 200 mW and a narrow emission below 22 pm. For the dual wavelength lasers the spectral distance between the two excitation lines is about 0.5 nm as targeted. The power consumption at both wavelengths is below 1 W. These data proof that the devices are well suited for their application in portable Raman measurement systems such as handheld devices using SERDS.

  12. Excitation energy-dependent nature of Raman scattering spectrum in GaInNAs/GaAs quantum well structures.

    Erol, Ayse; Akalin, Elif; Sarcan, Fahrettin; Donmez, Omer; Akyuz, Sevim; Arikan, Cetin M; Puustinen, Janne; Guina, Mircea


    The excitation energy-dependent nature of Raman scattering spectrum, vibration, electronic or both, has been studied using different excitation sources on as-grown and annealed n- and p-type modulation-doped Ga1 - xInxNyAs1 - y/GaAs quantum well structures. The samples were grown by molecular beam technique with different N concentrations (y = 0%, 0.9%, 1.2%, 1.7%) at the same In concentration of 32%. Micro-Raman measurements have been carried out using 532 and 758 nm lines of diode lasers, and the 1064 nm line of the Nd-YAG laser has been used for Fourier transform-Raman scattering measurements. Raman scattering measurements with different excitation sources have revealed that the excitation energy is the decisive mechanism on the nature of the Raman scattering spectrum. When the excitation energy is close to the electronic band gap energy of any constituent semiconductor materials in the sample, electronic transition dominates the spectrum, leading to a very broad peak. In the condition that the excitation energy is much higher than the band gap energy, only vibrational modes contribute to the Raman scattering spectrum of the samples. Line shapes of the Raman scattering spectrum with the 785 and 1064 nm lines of lasers have been observed to be very broad peaks, whose absolute peak energy values are in good agreement with the ones obtained from photoluminescence measurements. On the other hand, Raman scattering spectrum with the 532 nm line has exhibited only vibrational modes. As a complementary tool of Raman scattering measurements with the excitation source of 532 nm, which shows weak vibrational transitions, attenuated total reflectance infrared spectroscopy has been also carried out. The results exhibited that the nature of the Raman scattering spectrum is strongly excitation energy-dependent, and with suitable excitation energy, electronic and/or vibrational transitions can be investigated.

  13. Shifted excitation resonance Raman difference spectroscopy using a microsystem light source at 488 nm

    Maiwald, M.; Sowoidnich, K.; Schmidt, H.; Sumpf, B.; Erbert, G.; Kronfeldt, H.-D.


    Experimental results in shifted excitation resonance Raman difference spectroscopy (SERRDS) at 488 nm will be presented. A novel compact diode laser system was used as excitation light source. The device is based on a distributed feedback (DFB) diode laser as a pump light source and a nonlinear frequency doubling using a periodically poled lithium niobate (PPLN) waveguide crystal. All elements including micro-optics are fixed on a micro-optical bench with a footprint of 25 mm × 5 mm. An easy temperature management of the DFB laser and the crystal was used for wavelength tuning. The second harmonic generation (SHG) provides an additional suppression of the spontaneous emission. Raman spectra of polystyrene demonstrate that no laser bandpass filter is needed for the Raman experiments. Resonance-Raman spectra of the restricted food colorant Tartrazine (FD&C Yellow 5, E 102) in distilled water excited at 488 nm demonstrate the suitability of this light source for SERRDS. A limit of detection (LOD) of 0.4 μmol.l-1 of E102 enables SERRDS at 488 nm for trace detection in e.g. food safety control as an appropriate contactless spectroscopic technique.

  14. [Rapid identification of potato cultivars using NIR-excited fluorescence and Raman spectroscopy].

    Dai, Fen; Bergholt, Mads Sylvest; Benjamin, Arnold Julian Vinoj; Hong, Tian-Sheng; Zhiwei, Huang


    Potato is one of the most important food in the world. Rapid and noninvasive identification of potato cultivars plays a important role in the better use of varieties. In this study, The identification ability of optical spectroscopy techniques, including near-infrared (NIR) Raman spectroscopy and NIR fluorescence spectroscopy, for invasive detection of potato cultivars was evaluated. A rapid NIR Raman spectroscopy system was applied to measure the composite Raman and NIR fluorescence spectroscopy of 3 different species of potatoes (98 samples in total) under 785 nm laser light excitation. Then pure Raman and NIR fluorescence spectroscopy were abstracted from the composite spectroscopy, respectively. At last, the partial least squares-discriminant analysis (PLS-DA) was utilized to analyze and classify Raman spectra of 3 different types of potatoes. All the samples were divided into two sets at random: the calibration set (74samples) and prediction set (24 samples), the model was validated using a leave-one-out, cross-validation method. The results showed that both the NIR-excited fluorescence spectra and pure Raman spectra could be used to identify three cultivars of potatoes. The fluorescence spectrum could distinguish the Favorita variety well (sensitivity: 1, specificity: 0.86 and accuracy: 0.92), but the result for Diamant (sensitivity: 0.75, specificity: 0.75 and accuracy: 0. 75) and Granola (sensitivity: 0.16, specificity: 0.89 and accuracy: 0.71) cultivars identification were a bit poorer. We demonstrated that Raman spectroscopy uncovered the main biochemical compositions contained in potato species, and provided a better classification sensitivity, specificity and accuracy (sensitivity: 1, specificity: 1 and accuracy: 1 for all 3 potato cultivars identification) among the three types of potatoes as compared to fluorescence spectroscopy.

  15. Confocal volume in laser Raman microscopy depth profiling

    Maruyama, Yutaka; Kanematsu, Wataru [National Institute of Advanced Industrial Science and Technology, 2266-98 Anagahora, Shimo-Shidami, Moryama-ku, Nagoya 463-8560 (Japan)


    To clarify the degradation of confocality in laser Raman microscopy depth profiling (optical sectioning) and the influence of pinhole filtering on it, we investigate the confocal volume in detail based on Gaussian beam optics and scalar wave optics. Theoretical depth profiles of a homogeneous transparent sample for four different pinhole sizes, which are computed using the measured incident beam waist radius w{sub 0} and only a few optical system specific parameters such as a numerical aperture (NA) and a focal length, show a good agreement with the corresponding measured depth profiles. The computed confocal volume demonstrates that the pinhole size affects the actual probe depth as well as the axial resolution and the total intensity loss.

  16. Vacuum ultraviolet resonance Raman studies of the excited electronic states of ethylene

    Sension, Roseanne J.; Hudson, Bruce S.


    A resonance Raman study of ethylene has been performed with the use of excitation wavelengths ranging from 200 to 141 nm. Excitation resonant with the V(pi pi -asterisk) state results in Raman spectra exhibiting intensity in the C = C stretching vibration, the CH2 symmetric scissors vibration, the CH2 torsional vibration and the CH2 out-of-plane wagging vibrations. These spectra confirm that the V state is strongly twisted about the C-C bond. They also indicate that the C = CH2 groups are no longer planar in the V state. The spectrum obtained in resonance with the (pi 3d) Rydberg transitions once again exhibits activity in the CH2 symmetric scissors mode.

  17. Resonance Raman enhancement optimization in the visible range by selecting different excitation wavelengths.

    Wang, Zhong; Li, Yuee


    Resonance enhancement of Raman spectroscopy (RS) has been used to significantly improve the sensitivity and selectivity of detection for specific components in complicated environments. Resonance RS gives more insight into the biochemical structure and reactivity. In this field, selecting a proper excitation wavelength to achieve optimal resonance enhancement is vital for the study of an individual chemical/biological ingredient with a particular absorption characteristic. Raman spectra of three azo derivatives with absorption spectra in the visible range are studied under the same experimental conditions at 488, 532, and 633 nm excitations. Universal laws in the visible range have been concluded by analyzing resonance Raman (RR) spectra of samples. The long wavelength edge of the absorption spectrum is a better choice for intense enhancement and the integrity of a Raman signal. The obtained results are valuable for applying RR for the selective detection of biochemical constituents whose electronic transitions take place at energies corresponding to the visible spectra, which is much friendlier to biologial samples compared to ultraviolet.

  18. Dark excited states of carotenoid in light harvesting complex probing with femtosecond stimulated Raman spectroscopy

    Sakai S.


    Full Text Available Vibrational dynamics of dark excited states in carotenoids have been investigated using tunable Raman pump pulses. The S1 state has same vibrational dynamics in light-harvesting complex (LH1 and solution. The S* state in LH1 has similar vibrational modes with the triplet state of carotenoid. However, the so-called S* state in solution does not have the modes and is concluded to be different from the S* state in LH1.

  19. Portable Raman spectroscopy using retina-safe (1550 nm) laser excitation

    Brouillette, Carl; Smith, Wayne; Donahue, Michael; Huang, Hermes; Shende, Chetan; Sengupta, Atanu; Inscore, Frank; Patient, Michael; Farquharson, Stuart


    The use of portable Raman analyzers to identify unknown substances in the field has grown dramatically during the past decade. Measurements often require the laser beam to exit the confines of the sample compartment, which increases the potential of eye or skin damage. This is especially true for most commercial analyzers, which use 785 nm laser excitation. To overcome this safety concern, we have built a portable FT-Raman analyzer using a 1550 nm retina-safe excitation laser. Excitation at 1550 nm falls within the 1400 to 2000 nm retina-safe range, so called because the least amount of damage to the eye occurs in this spectral region. In contrast to wavelengths below 1400 nm, the retina-safe wavelengths are not focused by the eye, but are absorbed by the cornea, aqueous and vitreous humor. Here we compare the performance of this system to measurements of explosives at shorter wavelengths, as well as its ability to measure surface-enhanced Raman spectra of several chemicals, including the food contaminant melamine.

  20. Generation of unipolar pulses in a circular Raman-active medium excited by few-cycle optical pulses

    Arkhipov, R M; Babushkin, I; Pakhomov, A V; Tolmachev, Yu A; Rosanov, N N


    We study theoretically a new possibility of unipolar pulses generation in Raman-active medium excited by a series of few-cycle optical pulses. We consider the case when the Raman-active particles are uniformly distributed along the circle, and demonstrate a possibility to obtain a unipolar rectangular video pulses with an arbitrarily long duration, ranging from a minimum value equal to the natural period of the low frequency vibrations in the Raman-active medium.

  1. In-situ identification of meat from different animal species by shifted excitation Raman difference spectroscopy

    Sowoidnich, Kay; Kronfeldt, Heinz-Detlef


    The identification of food products and the detection of adulteration are of global interest for food safety and quality control. We present a non-invasive in-situ approach for the differentiation of meat from selected animal species using microsystem diode laser based shifted excitation Raman difference spectroscopy (SERDS) at 671 nm and 785 nm. In that way, the fingerprint Raman spectra can be used for identification without a disturbing fluorescence background masking Raman signals often occurring in the investigation of biological samples. Two miniaturized SERDS measurement heads including the diode laser and all optical elements are fiber-optically coupled to compact laboratory spectrometers. To realize two slightly shifted excitation wavelengths necessary for SERDS the 671 nm laser (spectral shift: 0.7 nm, optical power: 50 mW) comprises two separate laser cavities each with a volume Bragg grating for frequency selection whereas the 785 nm light source (spectral shift: 0.5 nm, optical power: 110 mW) is a distributed feedback laser. For our investigations we chose the most consumed meat types in the US and Europe, i.e. chicken and turkey as white meat as well as pork and beef as red meat species. The applied optical powers were sufficient to detect meat Raman spectra with integration times of 10 seconds pointing out the ability for a rapid discrimination of meat samples. Principal components analysis was applied to the SERDS spectra to reveal spectral differences between the animals suitable for their identification. The results will be discussed with respect to specific characteristics of the analyzed meat species.

  2. Resonance Raman Intensities Demonstrate that C5 Substituents Affect the Initial Excited-State Structural Dynamics of Uracil More than C6 Substituents.

    Teimoory, Faranak; Loppnow, Glen R


    Resonance Raman derived initial excited-state structural dynamics provide insight into the photochemical mechanisms of pyrimidine nucleobases, in which the photochemistry appears to be dictated by the C5 and C6 substituents. The absorption and resonance Raman spectra and excitation profiles of 5,6-dideuterouracil were measured to further test this photochemical dependence on the C5 and C6 substituents. The resulting set of excited-state reorganization energies of the observed internal coordinates were calculated and compared to those of other 5- and 6-substituted uracils. The results show that the initial excited-state dynamics along the C5C6 stretch responds to changes in mass at C5 and C6 in the same manner but that the in-plane bends at C5 and C6 are more sensitive to substituents at the C5 position than at the C6 position. In addition, the presence of two deuterium substituents at C5 and C6 decreases the initial excited-state structural dynamics along these in-plane bends, in contrast to what is observed in the presence of two CH3 groups on C5 and C6. The results are discussed in the context of DNA nucleobase photochemistry.

  3. Expressions of excited states by triplet dimers in heisenberg antiferromagnetic ladders. Analysis of magnetic Raman spectra

    Natsume, Yuhei; Tada, Shinichiro; Suzuki, Toshihiko [Chiba Univ., Graduate School of Science and Technology, Chiba (Japan)


    Characteristic properties of excited states in antiferromagnetic ladder systems with spin-1/2 are investigated in relation with the theoretical analysis of the quite asymmetric shape of the peak for twice the spin gap {delta}{sub g} in magnetic Raman spectra. Here, the structure of exchange-scattering spectra are reproduced by the numerical calculation for the finite Heisenberg ladder, in which legs with antiferromagnetic bond J{sub c} is connected by rungs with antiferromagnetic bond J{sub r}. The singlet ground state in this system can be expressed as the ordering of singlet dimers on rungs in the ladder for J{sub c}/J{sub r} {yields} +0. In fact, the value of 0.1 is adopted to be the ratio of J{sub c}/J{sub r} in order to discuss the experimental work of the magnetic Raman spectra for the ladder of V{sup 4+} ions in the oxide compound CaV{sub 2}O{sub 5} reported in Konstantinovic et al., Phys. Rev. B61 (2000), 15185. As for this peak of 2{delta}{sub g}, quite an asymmetric observed shape is explained by the present calculation. According to the analysis of spectra, we discuss the expression of excited states by triplet dimers on rungs: The dominant contribution of the pair of triplet dimers on adjacent rungs to the corresponding state for 2{delta}{sub g} peak is pointed out. (author)

  4. Shifted excitation Raman difference spectroscopy for authentication of cheese and cheese analogues

    Sowoidnich, Kay; Kronfeldt, Heinz-Detlef


    Food authentication and the detection of adulterated products are recent major issues in the food industry as these topics are of global importance for quality control and food safety. To effectively address this challenge requires fast, reliable and non-destructive analytical techniques. Shifted Excitation Raman Difference Spectroscopy (SERDS) is well suited for identification purposes as it combines the chemically specific information obtained by Raman spectroscopy with the ability for efficient fluorescence rejection. The two slightly shifted excitation wavelengths necessary for SERDS are realized by specially designed microsystem diode lasers. At 671 nm the laser (optical power: 50 mW, spectral shift: 0.7 nm) is based on an external cavity configuration whereas an emission at 783 nm (optical power: 110 mW, spectral shift: 0.5 nm) is achieved by a distributed feedback laser. To investigate the feasibility of SERDS for rapid and nondestructive authentication purposes four types of cheese and three different cheese analogues were selected. Each sample was probed at 8 different positions using integration times of 3-10 seconds and 10 spectra were recorded at each spot. Principal components analysis was applied to the SERDS spectra revealing variations in fat and protein signals as primary distinction criterion between cheese and cheese analogues for both excitation wavelengths. Furthermore, to some extent, minor compositional differences could be identified to discriminate between individual species of cheese and cheese analogues. These findings highlight the potential of SERDS for rapid food authentication potentially paving the way for future applications of portable SERDS systems for non-invasive in situ analysis.

  5. Continuous Time Series of Water Vapor Profiles from a Combination of Raman Lidar and Microwave Radiometer

    Foth Andreas


    Full Text Available In this paper, we present a method to retrieve continuous water vapor profiles from a combination of a Raman lidar and a microwave radiometer. The integrated water vapor from the microwave radiometer is used to calibrate the Raman lidar operationally resulting in small biases compared to radiosondes. The height limitations for Raman lidars (cloud base and daylight contamination can be well compensated by the application of a two–step algorithm combining the Raman lidars mass mixing ratio and the microwave radiometers brightness temperatures.




    We have developed and implemented automated algorithms to retrieve profiles of water vapor mixing ratio, aerosol backscattering, and aerosol extinction from Southern Great Plains (SGP) Cloud and Radiation Testbed (CART) Raman Lidar data acquired during both daytime and nighttime operations. This Raman lidar system is unique in that it is turnkey, automated system designed for unattended, around-the-clock profiling of water vapor and aerosols (Goldsmith et al., 1998). These Raman lidar profiles are important for determining the clear-sky radiative flux, as well as for validating the retrieval algorithms associated with satellite sensors. Accurate, high spatial and temporal resolution profiles of water vapor are also required for assimilation into mesoscale models to improve weather forecasts. We have also developed and implemented routines to simultaneously retrieve profiles of relative humidity. These routines utilize the water vapor mixing ratio profiles derived from the Raman lidar measurements together with temperature profiles derived from a physical retrieval algorithm that uses data from a collocated Atmospheric Emitted Radiance Interferometer (AERI) and the Geostationary Operational Environmental Satellite (GOES) (Feltz et al., 1998; Turner et al., 1999). These aerosol and water vapor profiles (Raman lidar) and temperature profiles (AERI+GOES) have been combined into a single product that takes advantage of both active and passive remote sensors to characterize the clear sky atmospheric state above the CART site.

  7. Raman lidar profiling of water vapor and aerosols over the ARM SGP Site

    Ferrare, R.A.


    The authors have developed and implemented automated algorithms to retrieve profiles of water vapor mixing ratio, aerosol backscattering, and aerosol extinction from Southern Great Plains (SGP) Cloud and Radiation Testbed (CART) Raman Lidar data acquired during both daytime and nighttime operations. The Raman lidar sytem is unique in that it is turnkey, automated system designed for unattended, around-the-clock profiling of water vapor and aerosols. These Raman lidar profiles are important for determining the clear-sky radiative flux, as well as for validating the retrieval algorithms associated with satellite sensors. Accurate, high spatial and temporal resolution profiles of water vapor are also required for assimilation into mesoscale models to improve weather forecasts. The authors have also developed and implemented routines to simultaneously retrieve profiles of relative humidity. These routines utilize the water vapor mixing ratio profiles derived from the Raman lidar measurements together with temperature profiles derived from a physical retrieval algorithm that uses data from a collocated Atmospheric Emitted Radiance Interferometer (AERI) and the Geostationary Operational Environmental Satellite (GOES). These aerosol and water vapor profiles (Raman lidar) and temperature profiles (AERI+GOES) have been combined into a single product that takes advantage of both active and passive remote sensors to characterize the clear sky atmospheric state above the CART site.

  8. Inelastic electron and Raman scattering from the collective excitations in quantum wires: Zero magnetic field

    Kushwaha, Manvir S.


    intersubband single-particle as well as collective excitations], the loss functions for the IES and the Raman intensity for the ILS. We observe that it is the collective (plasmon) excitations that largely contribute to the predominant peaks in the energy-loss and the Raman spectra. The inductive reasoning is that the IES can be a potential alternative of the overused ILS for investigating collective excitations in quantum wires. We trust that this research work shall be useful to all - from novice to expert and from theorist to experimentalist - who believe in the power of traditional science.

  9. Inelastic electron and Raman scattering from the collective excitations in quantum wires: Zero magnetic field

    Manvir S. Kushwaha


    intrasubband and intersubband single-particle as well as collective excitations], the loss functions for the IES and the Raman intensity for the ILS. We observe that it is the collective (plasmon excitations that largely contribute to the predominant peaks in the energy-loss and the Raman spectra. The inductive reasoning is that the IES can be a potential alternative of the overused ILS for investigating collective excitations in quantum wires. We trust that this research work shall be useful to all – from novice to expert and from theorist to experimentalist – who believe in the power of traditional science.

  10. Ultraviolet Raman lidar for high-accuracy profiling of aerosol extinction coefficient

    Fei Gao; Xiaoquan Song; Yufeng Wang; Yi Zhou; Dengxin Hua


    An ultraviolet (UV) Raman lidar system at 354.7 nm has been developed for accurately measuring the aerosol extinction profiles. A spectroscopic filter combining a high-spectral-resolution grating with two narrowband mirrors is used to separate the vibrational Raman scattering signal of N2 at a central wave-length of 386.7 nm and the elastic scattering signal at 354.7 nm. The aerosol extinction is derived from the Raman scattering of N2 and the elastic scattering by the use of Raman method and Klett method, respectively. The derived results of aerosol extinction are used to compare the difference of two retrieval methods, and the preliminary experiment shows that the Raman lidar system operated in analog detection mode has the capability of measuring aerosol profiles up to a height of 3 km with a laser energy of 250 mJ and an integration time of 8 min.

  11. Portable Sequentially Shifted Excitation Raman spectroscopy as an innovative tool for in situ chemical interrogation of painted surfaces.

    Conti, Claudia; Botteon, Alessandra; Bertasa, Moira; Colombo, Chiara; Realini, Marco; Sali, Diego


    We present the first validation and application of portable Sequentially Shifted Excitation (SSE) Raman spectroscopy for the survey of painted layers in art. The method enables the acquisition of shifted Raman spectra and the recovery of the spectral data through the application of a suitable reconstruction algorithm. The technique has a great potentiality in art where commonly a strong fluorescence obscures the Raman signal of the target, especially when conventional portable Raman spectrometers are used for in situ analyses. Firstly, the analytical capability of portable SSE Raman spectroscopy is critically discussed using reference materials and laboratory specimens, comparing its results with other conventional high performance laboratory instruments (benchtop FT-Raman and dispersive Raman spectrometers with an external fiber optic probe); secondly, it is applied directly in situ to study the complex polychromy of Italian prestigious terracotta sculptures of the 16(th) century. Portable SSE Raman spectroscopy represents a new investigation modality in art, expanding the portfolio of non-invasive, chemically specific analytical tools.

  12. Excited states 4

    Lim, Edward C


    Excited States, Volume 4 is a collection of papers that deals with the excited states of molecular activity. One paper investigates the resonance Raman spectroscopy as the key to vibrational-electronic coupling. This paper reviews the basic theory of Raman scattering; it also explains the derivation of the Raman spectra, excitation profiles, and depolarization ratios for simple resonance systems. Another paper reviews the magnetic properties of triplet states, including the zero-field resonance techniques, the high-field experiments, and the spin Hamiltonian. This paper focuses on the magnetic

  13. Blueberry juices: a rapid multi-analysis of quality indicators by means of dispersive Raman spectroscopy excited at 1064 nm

    Ciaccheri, L.; Yuan, T.; Zhang, S.; Mencaglia, A. A.; Trono, C.; Yuan, L.; Mignani, A. G.


    Blueberry juices produced in China and in Italy were analyzed by means of Raman spectroscopy. The reference data of important nutraceutical indicators such as degrees Brix and carbohydrates were available. Some juices were produced from fresh organic fruits, while others were industrial grade, differing in qualities and prices. Raman spectra obtained with excitation at 1064 nm were acquired using a dispersive fiber-optic spectrometer. Degrees Brix were measured by means of a commercial refractometer, while carbohydrate contents were available from the producers. Multivariate processing was used for predicting Brix and carbohydrates from Raman spectra and from the reference data. Determination coefficients equal to 0.88 and 0.84, respectively, were obtained. This experiment further confirms the excellent potentials of Raman spectroscopy for both non-destructive and rapid assessments of food quality.

  14. Excited-state proton transfer of photoexcited pyranine in water observed by femtosecond stimulated Raman spectroscopy

    Han, Fangyuan; Liu, Weimin; Fang, Chong


    We use femtosecond stimulated Raman spectroscopy (FSRS) to illuminate the choreography of intermolecular excited-state proton transfer (ESPT) of photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in water. The multidimensional reaction coordinate responsible for photoacidity is revealed to involve sequential activation of characteristic skeletal motions during the ca. 1 ps preparation stage preceding ESPT. The initial ring-coplanarity breaking follows in-plane ring breathing (191 cm-1), and is facilitated by HPTS ring wagging (108 cm-1) and ring-H out-of-plane motions (321, 362, 952 cm-1), which largely decay within ∼1 ps. ESPT then occurs with intrinsic inhomogeneity via various number of intervening water molecules over relatively larger distances than those in acetate-water system. The intricate relationship between the time-resolved excited-state vibrational modes of HPTS reveals the essential role of coherent low-frequency skeletal motions gating ESPT, and the multi-staged proton-transfer process having the kinetic isotope effect (KIE) value of 3-4 in aqueous solution on the 5-200 ps timescale.

  15. Dual-wavelength Y-branch distributed Bragg reflector diode laser at 785 nanometers for shifted excitation Raman difference spectroscopy.

    Maiwald, Martin; Eppich, Bernd; Fricke, Jörg; Ginolas, Arnim; Bugge, Frank; Sumpf, Bernd; Erbert, Götz; Tränkle, Günther


    A dual-wavelength Y-branch distributed Bragg reflector (DBR) diode laser at 785 nm is presented as an excitation light source for shifted excitation Raman difference spectroscopy (SERDS). The monolithic device was realized with deeply etched surface DBR gratings using one-step epitaxy. An optical output power of 140 mW was obtained in continuous-wave (CW) operation for each laser cavity, with emission wavelengths of the device at 784.50 and 785.12 nm. A spectral width of the laser emission of 30 pm (0.5 cm(-1)), including 95% of optical power, was measured. The mean spectral distance of both excitation lines is 0.63 nm (10.2 cm(-1)) over the whole operating range. Raman experiments using polystyrene as the test sample and ambient light as the interference source were carried out and demonstrate the suitability of the dual-wavelength diode laser for SERDS.

  16. Resonance raman spectroscopic study of alumina-supported vanadium oxide catalysts with 220 and 287 nm excitation.

    Kim, H. S.; Stair, P. C.; Chemical Sciences and Engineering Division; Northwestern Univ.


    We present detailed resonance Raman spectroscopic results excited at 220 and 287 nm for alumina-supported VO{sub x} catalysts. The anharmonic constant, harmonic wavenumber, anharmonic force constant, bond dissociation energy, and bond length change in the excited state for double bonded V{double_bond}O and single bonded V-O were obtained from fundamental and overtone frequencies. Totally symmetric and nontotally symmetric modes could be discerned and assigned on the basis of the overtone and combination progressions found in the resonance Raman spectra. Selective resonance enhancement of two different vibrational modes with two different excitation wavelengths was observed. This allowed us to establish a linear relationship between charge transfer energy and VO bond length and, consequently, to assign the higher-energy charge transfer band centered around 210?250 nm in the UV?vis spectra to the V{double_bond}O transition.

  17. Red-detuned, high-intensity, short-duration sweet spot for impulsive X-ray Raman excitation in atoms

    Ware, Matthew R; Haxton, Daniel J


    Impulsive X-ray Raman excitations of Lithium, Neon, and Sodium are calculated using the Multiconfiguration Time-Dependent Hartree-Fock method. Using linearly polarized laser pulses without chirp, we determine the optimum central frequency, intensity, and duration for maximum population transfer to valence excited states. We demonstrate the existence of two "sweet spots" for optimum population transfer, either of which, depending on the system, may be superior. The "red-detuned hypothesis" is the proposition that population transfer can be maximized by nonresonant Raman transitions, red-detuned below K-edge, because such detuning minimizes core-excited populations and ionization loss. We find that this hypothesis is verified in the case of Neon -- for Neon, the global optimum for population transfer occurs at high intensity (8 $\\times$ 10$^{19}$ W cm$^{-2}$), short duration (82as full-width-at-half-maximum), and 24eV red-detuned from the K-edge.

  18. Excited-state proton transfer of photoexcited pyranine in water observed by femtosecond stimulated Raman spectroscopy

    Han, Fangyuan; Liu, Weimin; Fang, Chong, E-mail:


    Highlights: • A number of low – frequency modes are sequentially observed in photoexcited HPTS. • Evidence of coherent quantum beat in several low – frequency modes with anharmonic coupling. • The most transient low – frequency mode is the symmetric ring breathing of HPTS. • Excited – state proton transfer occurs nonadiabatically on the 5–200 ps timescale. • Kinetic isotope effect is 3–4 for the two-stage ESPT components in water. - Abstract: We use femtosecond stimulated Raman spectroscopy (FSRS) to illuminate the choreography of intermolecular excited-state proton transfer (ESPT) of photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in water. The multidimensional reaction coordinate responsible for photoacidity is revealed to involve sequential activation of characteristic skeletal motions during the ca. 1 ps preparation stage preceding ESPT. The initial ring-coplanarity breaking follows in-plane ring breathing (191 cm{sup −1}), and is facilitated by HPTS ring wagging (108 cm{sup −1}) and ring-H out-of-plane motions (321, 362, 952 cm{sup −1}), which largely decay within ∼1 ps. ESPT then occurs with intrinsic inhomogeneity via various number of intervening water molecules over relatively larger distances than those in acetate–water system. The intricate relationship between the time-resolved excited-state vibrational modes of HPTS reveals the essential role of coherent low-frequency skeletal motions gating ESPT, and the multi-staged proton-transfer process having the kinetic isotope effect (KIE) value of 3–4 in aqueous solution on the 5–200 ps timescale.

  19. Measurement of tropospheric CO2 and aerosol extinction profiles with Raman lidar

    Peitao Zhao; Yinchao Zhang; Lian Wang; Kaifa Cao; Jia Su; Shunxing Hu; Huanling Hu


    A prototype Raman lidar was designed for monitoring tropospheric CO2 profile and other scientific investigatious.The third harmonic of Nd:YAG laser (354.7-nm wavelength) was used as stimulated light source to provide nighttime measurements.Filter with high rejection ratio performance was used to extract CO2 Raman signals from Rayleigh-Mie scattering signals effectively.To improve the real time monitoring function,a two-channel signal collection system was designed to collect CO2 and N2 Raman scattering signals simultaneously. The N2 Raman scattering signals were used to retrieve aerosol extinction coefficient.Typical features of CO2 concentration profile and aerosol extinction coefficient in Herei were presented.The mixing ratio of atmospheric CO2 in Hefei can reach about 360-400 ppmv.

  20. Monolithic Y-branch dual wavelength DBR diode laser at 671nm for shifted excitation Raman difference spectroscopy

    Maiwald, M.; Fricke, J.; Ginolas, A.; Pohl, J.; Sumpf, B.; Erbert, G.; Tränkle, G.


    A dual-wavelength laser diode source suitable for shifted excitation Raman difference spectroscopy (SERDS) is presented. This monolithic device contains two ridge waveguide (RW) sections with wavelengths adjusted distributed Bragg reflection (DBR) gratings as rear side mirrors. An integrated Y-branch coupler guides the emission into a common output aperture. The two wavelengths are centered at 671 nm with a well-defined spectral spacing of about 0.5 nm, i.e. 10 cm-1. Separate RW sections can be individually addressed by injection current. An output power up to 110 mW was achieved. Raman experiments demonstrate the suitability of these devices for SERDS.

  1. Evidence of orbital excitations in CaCu3Ti4O12 probed by Raman spectroscopy.

    Mishra, Dileep K; Sathe, V G


    Raman scattering studies on CaCu(3)Ti(4)O(12) and SrCu(3)Ti(4)O(12) compounds provide evidence of the physics underlying the giant dielectric effect in the CaCu(3)Ti(4)O(12) compound. The temperature, polarization, and photon energy dependence of a broad Raman mode observed at high wavenumbers below ∼130 K indicates its origin from orbital excitations. The orbital order disorder transition observed around 100 K may be responsible for the conductivity changes required in the internal barrier layer capacitance model, hitherto used to explain the huge dielectric constant above 100 K in these compounds. © 2011 IOP Publishing Ltd

  2. Chemical Profiling of the Plant Cell Wall through Raman Microspectroscopy

    Han, Ju; Singh, Seema; Sun, Lan; Simmons, Blake; Auer, Manfred; Parvin, Bahram


    This paper presents a computational framework for chemical pro.ling of the plant cell wall through the Raman spectroscopy. The system enables query of known spectral signatures and clustering of spectral data based on intrinsic properties. As a result, presence and relative concentration of speci.c chemical bonds can be quanti.ed. The primary contribution of this paper is in representation of raman pro.le in terms of .uorescence background and multiscale peak detection at each grid point (voxel). Such a representation allows ef.cient spatial segmentation based on the coupling between high-level salient properties and low-level symbolic representation at each voxel. The high-level salient properties refer to preferred peaks and their attributes for the entire image. The low-level symbolic representations are based on .uorescence background, spectral peak locations, and their attributes. We present results on a corn stover tissue section that is imaged through Raman microscopy, and the results are consistent with the literature. In addition, automatic clustering indicates several distinct layers of the cell walls with different spectral signatures.

  3. Realization of electromagnetically induced phase grating and Kerr nonlinearity in a graphene ensemble under Raman excitation

    Naseri, Tayebeh; Moradi, Ronak


    Some optical properties including the linear and nonlinear susceptibility and electromagnetically induced phase grating (EIG) in graphene under Raman excitation is studied. A single-layer graphene nanostructure driven by coherent and incoherent fields is investigated theoretically. It is revealed that by adjusting the amplitude of control and incoherent fields, the linear and nonlinear absorption as well as Kerr nonlinearity of the medium can be optimized. It is realized that the enhanced Kerr nonlinearity can occur with zero linear absorption and nonlinear amplification. Furthermore, it should be noted that EIG in graphene is studied for the first time. The results indicate that the diffraction efficiency of the phase grating is dramatically enhanced by controlling the amplitude of coherent and incoherent fields, and an efficient electromagnetically induced phase grating can be obtained. A novel result shows a considerable improvement of the intensity of higher-order diffractions and switching between different orders of grating via incoherent pumping field. Therefore, this model can be used in real experiments for the development of new types of nanoelectronic devices used for the realization of all-optical switching processes.

  4. Optimized pulses for Raman excitation through the continuum: verification using multi-configurational time-dependent Hartree-Fock

    Greenman, Loren; Haxton, Daniel J; McCurdy, C William


    We have verified a mechanism for Raman excitation of atoms through continuum levels previously obtained by quantum optimal control using the multi-configurational time-dependent Hartree-Fock (MCTDHF) method. This mechanism, which was obtained at the time-dependent configuration interaction singles (TDCIS) level of theory, involves sequentially exciting an atom from the ground state to an intermediate core-hole state using a long pump pulse, and then transferring this population to the target Raman state with a shorter Stokes pulse. This process represents the first step in a multidimensional x-ray spectroscopy scheme that will provide a local probe of valence electronic correlations. Although at the optimal pulse intensities at the TDCIS level of theory the MCTDHF method predicts multiple ionization of the atom, at slightly lower intensities (reduced by a factor of about 4) the TDCIS mechanism is shown to hold qualitatively. Quantitatively, the MCTDHF populations are reduced from the TDCIS calculations by a f...

  5. Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

    Dallinger, R.F.; Farquharson, S.; Woodruff, W.H.; Rodgers, M.A.J.


    Resonance Raman and electronic absorption spectra are reported for the S/sub 0/ and T/sub 1/ states of the carotenoids ..beta..-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C/sub 50/)-..beta..-carotene, ..beta..-apo-8'-carotenal, and ethyl ..beta..-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S/sub 0/ and T/sub 1/, regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S/sub 0/ and T/sub 1/ reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited state which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T/sub 1/ states of carotenoids and in the S/sub 1/ states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S/sub 1/ lifetime (of the /sup 1/B/sub u/ and/or the /sup 1/A/sub g/* states) of ..beta..-carotene in benzene is less than 1 ps.

  6. Excited state structures and decay dynamics of 1,3-dimethyluracils in solutions: resonance Raman and quantum mechanical calculation study.

    Li, Ming-Juan; Liu, Ming-Xia; Zhao, Yan-Ying; Pei, Ke-Mei; Wang, Hui-Gang; Zheng, Xuming; Fang, Wei Hai


    The resonance Raman spectroscopic study of the excited state structural dynamics of 1,3-dimethyluracil (DMU), 5-bromo-1,3-dimethyluracil (5BrDMU), uracil, and thymine in water and acetonitrile were reported. Density functional theory calculations were carried out to help elucidate the ultraviolet electronic transitions associated with the A-, and B-band absorptions and the vibrational assignments of the resonance Raman spectra. The effect of the methylation at N1, N3 and C5 sites of pyrimidine ring on the structural dynamics of uracils in different solvents were explored on the basis of the resonance Raman intensity patterns. The relative resonance Raman intensities of DMU and 5BrDMU are computed at the B3LYP-TD level. Huge discrepancies between the experimental resonance Raman intensities and the B3LYP-TD predicted ones were observed. The underlying mechanism was briefly discussed. The decay channel through the S1((1)nπ*)/S2((1)ππ*) conical intersection and the S1((1)nπ*)/T1((3)ππ*) intersystem crossing were revealed by using the CASSCF(8,7)/6-31G(d) level of theory calculations.

  7. In vivo confocal Raman microspectroscopy of the skin: Noninvasive determination of molecular concentration profiles

    P.J. Caspers (Peter); G.W. Lucassen (Gerald); E.A. Carter (Elizabeth); H.A. Bruining (Hajo); G.J. Puppels (Gerwin)


    textabstractConfocal Raman spectroscopy is introduced as a noninvasive in vivo optical method to measure molecular concentration profiles in the skin. It is shown how it can be applied to determine the water concentration in the stratum corneum as a function of distance to the skin surface, with a

  8. Raman Laser Spectrometer internal Optical Head current status: opto-mechanical redesign to minimize the excitation laser trace

    Sanz, Miguel; Ramos, Gonzalo; Moral, Andoni; Pérez, Carlos; Belenguer, Tomás; del Rosario Canchal, María; Zuluaga, Pablo; Rodriguez, Jose Antonio; Santiago, Amaia; Rull, Fernando; Instituto Nacional de Técnica Aeroespacial (INTA), Universidad de Valladolid (UVa), Ingeniería de Sistemas para la Defesa de España S.A. (ISDEFE)


    Raman Laser Spectrometer (RLS) is the Pasteur Payload instruments of the ExoMars mission, within the ESA's Aurora Exploration Programme, that will perform for the first time in an out planetary mission Raman spectroscopy. RLS is composed by SPU (Spectrometer Unit), iOH (Internal Optical Head), and ICEU (Instrument Control and Excitation Unit). iOH focuses the excitation laser on the samples (excitation path), and collects the Raman emission from the sample (collection path, composed on collimation system and filtering system). The original design presented a high laser trace reaching to the detector, and although a certain level of laser trace was required for calibration purposes, the high level degrades the Signal to Noise Ratio confounding some Raman peaks.The investigation revealing that the laser trace was not properly filtered as well as the iOH opto-mechanical redesign are reported on. After the study of the Long Pass Filters Optical Density (OD) as a function of the filtering stage to the detector distance, a new set of filters (Notch filters) was decided to be evaluated. Finally, and in order to minimize the laser trace, a new collection path design (mainly consisting on that the collimation and filtering stages are now separated in two barrels, and on the kind of filters to be used) was required. Distance between filters and collimation stage first lens was increased, increasing the OD. With this new design and using two Notch filters, the laser trace was reduced to assumable values, as can be observed in the functional test comparison also reported on this paper.

  9. Near-infrared-excited confocal Raman spectroscopy advances in vivo diagnosis of cervical precancer.

    Duraipandian, Shiyamala; Zheng, Wei; Ng, Joseph; Low, Jeffrey J H; Ilancheran, Arunachalam; Huang, Zhiwei


    Raman spectroscopy is a unique optical technique that can probe the changes of vibrational modes of biomolecules associated with tissue premalignant transformation. This study evaluates the clinical utility of confocal Raman spectroscopy over near-infrared (NIR) autofluorescence (AF) spectroscopy and composite NIR AF/Raman spectroscopy for improving early diagnosis of cervical precancer in vivo at colposcopy. A rapid NIR Raman system coupled with a ball-lens fiber-optic confocal Raman probe was utilized for in vivo NIR AF/Raman spectral measurements of the cervix. A total of 1240 in vivo Raman spectra [normal (n=993), dysplasia (n=247)] were acquired from 84 cervical patients. Principal components analysis (PCA) and linear discriminant analysis (LDA) together with a leave-one-patient-out, cross-validation method were used to extract the diagnostic information associated with distinctive spectroscopic modalities. The diagnostic ability of confocal Raman spectroscopy was evaluated using the PCA-LDA model developed from the significant principal components (PCs) [i.e., PC4, 0.0023%; PC5, 0.00095%; PC8, 0.00022%, (pspectroscopy coupled with PCA-LDA modeling yielded the diagnostic accuracy of 84.1% (a sensitivity of 81.0% and a specificity of 87.1%) for in vivo discrimination of dysplastic cervix. The receiver operating characteristic curves further confirmed that the best classification was achieved using confocal Raman spectroscopy compared to the composite NIR AF/Raman spectroscopy or NIR AF spectroscopy alone. This study illustrates that confocal Raman spectroscopy has great potential to improve early diagnosis of cervical precancer in vivo during clinical colposcopy.

  10. Direct imaging Raman microscope based on tunable wavelength excitation and narrow band emission detection

    Puppels, G.J.; Grond, M.; Greve, J.


    A new type of imaging Raman microscope is described. First the advantages and disadvantages of the two possible approaches to Raman microscopy based on signal detection by means of a charge-coupled-device camera (i.e., direct imaging and image reconstruction) are discussed. Arguments are given to sh

  11. Using water Raman intensities to determine the effective excitation and emission path lengths of fluorophotometers for correcting fluorescence inner filter effect.

    Nettles, Charles B; Hu, Juan; Zhang, Dongmao


    Fluorescence and Raman inner filter effects (IFE) cause spectral distortion and nonlinearity between spectral signal intensity with increasing analyte concentration. Convenient and effective correction of fluorescence IFE has been an active research goal for decades. Presented herein is the finding that fluorescence and Raman IFE can be reliably corrected using the equation I(corr)/I(obsd) = 10(dxAx + dmAm) when the effective excitation and emission path lengths, dx and dm, of a fluorophotometer are determined by simple linear curve-fitting of Raman intensities of a series of water Raman reference samples that have known degrees of Raman IFEs. The path lengths derived with one set of Raman measurements at one specific excitation wavelength are effective for correcting fluorescence and Raman IFEs induced by any chromophore or fluorophore, regardless of the excitation and emission wavelengths. The IFE-corrected fluorescence intensities are linearly correlated to fluorophore concentration over 5 orders of magnitude (from 5.9 nM to 0.59 mM) for 2-aminopurine in a 1 cm × 0.17 cm fluorescence cuvette. This water Raman-based method is easy to implement. It does not involve complicated instrument geometry determination or difficult data manipulation. This work should be of broad significance to physical and biological sciences given the popularity of fluorescence techniques in analytical applications.

  12. Analysis of influence of atmosphere extinction to Raman lidar monitoring CO2 concentration profile

    Zhao Pei-Tao; Zhang Yin-Chao; Wang Lian; Zhao Yue-Feng; Su Jia; Fang Xin; Cao Kai-Fa; Xie Jun; Du Xiao-Yong


    Lidar (Light detection and ranging) system monitoring of the atmosphere is a novel and powerful technique tool. The Raman lidar is well established today as a leading research tool in the study of numerous important areas in the atmospheric sciences. In this paper, the principle of Raman lidar technique measurement CO2 concentration profile is presented and the errors caused by molecular and aerosol extinction for CO2 concentration profile measurement with Raman lidar are also presented. The standard atmosphere extinction profile and 'real-time' Hefei area extinction profile are used to conduct correction and the corresponding results are yielded. Simulation results with standard atmosphere mode correction indicate that the errors caused by molecule and aerosol extinction should be counted for the reason that they could reach about 8 ppm and 5 ppm respectively. The relative error caused by Hefei area extinction correction could reach about 6%. The errors caused by the two components extinction influence could produce significant changes for CO2 concentration profile and need to be counted in data processing which could improve the measurement accuracies.

  13. Raman-based noninvasive metabolic profile evaluation of in vitro bovine embryos

    dos Santos, Érika Cristina; Martinho, Herculano; Annes, Kelly; da Silva, Thais; Soares, Carlos Alexandre; Leite, Roberta Ferreira; Milazzotto, Marcella Pecora


    The timing of the first embryonic cell divisions may predict the ability of an embryo to establish pregnancy. Similarly, metabolic profiles may be markers of embryonic viability. However, in bovine, data about the metabolomics profile of these embryos are still not available. In the present work, we describe Raman-based metabolomic profiles of culture media of bovine embryos with different developmental kinetics (fast x slow) throughout the in vitro culture. The principal component analysis enabled us to classify embryos with different developmental kinetics since they presented specific spectroscopic profiles for each evaluated time point. We noticed that bands at 1076 cm-1 (lipids), 1300 cm-1 (Amide III), and 2719 cm-1 (DNA nitrogen bases) gave the most relevant spectral features, enabling the separation between fast and slow groups. Bands at 1001 cm-1 (phenylalanine) and 2892 cm-1 (methylene group of the polymethylene chain) presented specific patterns related to embryonic stage and can be considered as biomarkers of embryonic development by Raman spectroscopy. The culture media analysis by Raman spectroscopy proved to be a simple and sensitive technique that can be applied with high efficiency to characterize the profiles of in vitro produced bovine embryos with different development kinetics and different stages of development.

  14. Measuring depth profiles of residual stress with Raman spectroscopy

    Enloe, W.S.; Sparks, R.G.; Paesler, M.A.


    Knowledge of the variation of residual stress is a very important factor in understanding the properties of machined surfaces. The nature of the residual stress can determine a part`s susceptibility to wear deformation, and cracking. Raman spectroscopy is known to be a very useful technique for measuring residual stress in many materials. These measurements are routinely made with a lateral resolution of 1{mu}m and an accuracy of 0.1 kbar. The variation of stress with depth; however, has not received much attention in the past. A novel technique has been developed that allows quantitative measurement of the variation of the residual stress with depth with an accuracy of 10nm in the z direction. Qualitative techniques for determining whether the stress is varying with depth are presented. It is also demonstrated that when the stress is changing over the volume sampled, errors can be introduced if the variation of the stress with depth is ignored. Computer aided data analysis is used to determine the depth dependence of the residual stress.

  15. Adaptive super-twisting observer for estimation of random road excitation profile in automotive suspension systems.

    Rath, J J; Veluvolu, K C; Defoort, M


    The estimation of road excitation profile is important for evaluation of vehicle stability and vehicle suspension performance for autonomous vehicle control systems. In this work, the nonlinear dynamics of the active automotive system that is excited by the unknown road excitation profile are considered for modeling. To address the issue of estimation of road profile, we develop an adaptive supertwisting observer for state and unknown road profile estimation. Under Lipschitz conditions for the nonlinear functions, the convergence of the estimation error is proven. Simulation results with Ford Fiesta MK2 demonstrate the effectiveness of the proposed observer for state and unknown input estimation for nonlinear active suspension system.

  16. Adaptive Super-Twisting Observer for Estimation of Random Road Excitation Profile in Automotive Suspension Systems

    J. J. Rath


    Full Text Available The estimation of road excitation profile is important for evaluation of vehicle stability and vehicle suspension performance for autonomous vehicle control systems. In this work, the nonlinear dynamics of the active automotive system that is excited by the unknown road excitation profile are considered for modeling. To address the issue of estimation of road profile, we develop an adaptive supertwisting observer for state and unknown road profile estimation. Under Lipschitz conditions for the nonlinear functions, the convergence of the estimation error is proven. Simulation results with Ford Fiesta MK2 demonstrate the effectiveness of the proposed observer for state and unknown input estimation for nonlinear active suspension system.

  17. Raman scattering of 4-aminobenzenethiol sandwiched between Ag nanoparticle and macroscopically smooth Au substrate: effects of size of Ag nanoparticles and the excitation wavelength.

    Kim, Kwan; Choi, Jeong-Yong; Lee, Hyang Bong; Shin, Kuan Soo


    A nanogap formed by a metal nanoparticle and a flat metal substrate is one kind of "hot site" for surface-enhanced Raman scattering (SERS). Accordingly, although no Raman signal is observable when 4-aminobenzenethiol (4-ABT), for instance, is self-assembled on a flat Au substrate, a distinct spectrum is obtained when Ag or Au nanoparticles are adsorbed on the pendent amine groups of 4-ABT. This is definitely due to the electromagnetic coupling between the localized surface plasmon of Ag or Au nanoparticle with the surface plasmon polariton of the planar Au substrate, allowing an intense electric field to be induced in the gap even by visible light. To appreciate the Raman scattering enhancement and also to seek the optimal condition for SERS at the nanogap, we have thoroughly examined the size effect of Ag nanoparticles, along with the excitation wavelength dependence, by assembling 4-ABT between planar Au and a variable-size Ag nanoparticle (from 20- to 80-nm in diameter). Regarding the size dependence, a higher Raman signal was observed when larger Ag nanoparticles were attached onto 4-ABT, irrespective of the excitation wavelength. Regarding the excitation wavelength, the highest Raman signal was measured at 568 nm excitation, slightly larger than that at 632.8 nm excitation. The Raman signal measured at 514.5 and 488 nm excitation was an order of magnitude weaker than that at 568 nm excitation, in agreement with the finite-difference time domain simulation. It is noteworthy that placing an Au nanoparticle on 4-ABT, instead of an Ag nanoparticle, the enhancement at the 568 nm excitation was several tens of times weaker than that at the 632.8 nm excitation, suggesting the importance of the localized surface plasmon resonance of the Ag nanoparticles for an effective coupling with the surface plasmon polariton of the planar Au substrate to induce a very intense electric field at the nanogap.

  18. Raman spectra of normal and cancerous mouse mammary gland tissue using near infrared excitation energy

    Naik, Vaman; Serhatkulu, G. K.; Dai, H.; Shukla, N.; Weber, R.; Thakur, J. S.; Freeman, D. C.; Pandya, A. K.; Auner, G. W.; Naik, R.; Miller, R. F.; Cao, A.; Klein, M. D.; Rabah, R.


    Raman spectra of normal mammary gland tissues, malignant mammary gland tumors, and lymph nodes have been recorded using fresh tissue from mice. Tumors were induced in mice by subcutaneously injecting 4T1 BALB/c mammary tumor (a highly malignant) cell line. The Raman spectra were collected using the same tissues that were examined by histopathology for determining the cancerous/normal state of the tissue. Differences in various peak intensities, peak shifts and peak ratios were analyzed to determine the Raman spectral features that differentiate mammary gland tumors from non-tumorous tissue. Tissues that were confirmed by pathology as cancerous (tumors) show several distinctive features in the Raman spectra compared to the spectra of the normal tissues. For example, the cancerous tissues show Raman peaks at 621, 642, 1004, 1032, 1175 and 1208 cm-1 that are assignable to amino acids containing aromatic side-chains such as phenylalanine, tryptophan and tyrosine. Further, the cancerous tissues show a greatly reduced level of phospholipids compared to the normal tissues. The Raman spectral regions that are sensitive to pathologic alteration in the tissue will be discussed.

  19. Raman Investigation of Temperature Profiles of Phospholipid Dispersions in the Biochemistry Laboratory

    Craig, Norman C.


    The temperature dependence of self-assembled, cell-like dispersions of phospholipids is investigated with Raman spectroscopy in the biochemistry laboratory. Vibrational modes in the hydrocarbon interiors of phospholipid bilayers are strongly Raman active, whereas the vibrations of the polar head groups and the water matrix have little Raman activity. From Raman spectra increases in fluidity of the hydrocarbon chains can be monitored with intensity changes as a function of temperature in the CH-stretching region. The experiment uses detection of scattered 1064-nm laser light (Nicolet NXR module) by a Fourier transform infrared spectrometer (Nicolet 6700). A thermoelectric heater-cooler device (Melcor) gives convenient temperature control from 5 to 95°C for samples in melting point capillaries. Use of deuterium oxide instead of water as the matrix avoids some absorption of the exciting laser light and interference with intensity observations in the CH-stretching region. Phospholipids studied range from dimyristoylphosphotidyl choline (C14, transition T = 24°C) to dibehenoylphosphotidyl choline (C22, transition T = 74°C).

  20. Raman study of crystal-field excitations in Pr{sub 2}CuO{sub 4}

    Jandl, S. [Centre de Recherche en Physique du Solide, Departement de Physique, Universite de Sherbrooke, Sherbrooke, Quebec, J1K2R1 (CANADA); Strach, T.; Ruf, T.; Cardona, M. [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstrasse 1, D-70569 Stuttgart (Germany); Nekvasil, V. [Institute of Physics, Czech Academy of Sciences, Cukrovarnicka 10, 162 00 Prague 6 (Czech Republic); Iliev, M. [Faculty of Physics, University of Sofia, BG-1126 Sofia (Bulgaria); Zhigunov, D.I.; Barilo, S.N.; Shiryaev, S.V. [Institute of Physics of Solids and Semiconductors, Academy Science Belarus, Tolstoi street 4, 220072 Minsk (Belarus)


    Raman measurements in a Pr{sub 2}CuO{sub 4} single crystal show structures related to nine crystal-field (CF) excitations. They correspond to transitions within the {sup 3}H{sub 4}, {sup 3}H{sub 5}, and {sup 3}H{sub 6} multiplets of Pr{sup 3+} ions in C{sub 4v} site symmetry. Satellites to these CF excitations are also observed and associated with the presence of an inequivalent Pr{sup 3+} site of lower symmetry. A set of CF parameters which describes the observed energy spectra is derived and compared to previous calculations. {copyright} {ital 1997} {ital The American Physical Society}

  1. Selective excitation of molecular mode in a mixture by femtosecond resonance-enhanced coherent anti-Stokes Raman scattering spectroscopy

    He Ping; Li Si-Ning; Fan Rong-Wei; Li Xiao-Hui; Xia Yuan-Qin; Yu Xin; Chen De-Ying


    Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to investigate gaseous molecular dynamics.Due to the spectrally broad laser pulses,usually poorly resolved spectra result from this broad spectroscopy.However,it can be demonstrated that by the electronic resonance enhancement optimization control a selective excitation of specific vibrational mode is possible.Using an electronically resonance-enhanced effect,iodine molecule specific CARS spectroscopy can be obtained from a mixture of iodine-air at room temperature and a pressure of 1 atm (corresponding to a saturation iodine vapour as low as about 35 Pa).The dynamics on either the electronically excited state or the ground state of iodine molecules obtained is consistent with previous studies (vacuum,heated and pure iodine) in the femtosecond time resolved CARS spectroscopy,showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.

  2. Laser-induced gratings in the gas phase excited via Raman-active transitions

    Kozlov, D.N. [General Physics Inst., Russian Academy of Sciences, Moscow (Russian Federation); Bombach, R.; Hemmerling, B.; Hubschmid, W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    We report on a new time resolved coherent Raman technique that is based on the generation of thermal gratings following a population change among molecular levels induced by stimulated Raman pumping. This is achieved by spatially and temporally overlapping intensity interference patterns generated independently by two lasers. When this technique is used in carbon dioxide, employing transitions which belong to the Q-branches of the {nu}{sub 1}/2{nu}{sub 2} Fermi dyad, it is possible to investigate molecular energy transfer processes. (author) 2 figs., 10 refs.

  3. Stimulated Raman scattering of light absorbing media excited by ultrashort laser pulses

    Marchevskiy, F. N.; Strizhevskiy, V. L.; Feshchenko, V. P.


    The fluctuation-dissipation theory of spontaneous and stimulated vibration Raman scattering is worked out taking into account the dissipation losses at frequencies of laser pump and scattering radiation. General expressions are found, which describe the absolute intensities and shape, energy and duration of scattered pulses in terms of the parameters of the medium and the the input laser pulses. The general regularities are analyzed in detail. Conditions are found for the realization of spontaneous or stimulated Raman scattering and its dependence on absorption, pulse duration and other parameters of the problem.

  4. Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics

    Kunnus, Kristjan; Josefsson, Ida; Rajkovic, Ivan; Schreck, Simon; Quevedo, Wilson; Beye, Martin; Grübel, Sebastian; Scholz, Mirko; Nordlund, Dennis; Zhang, Wenkai; Hartsock, Robert W.; Gaffney, Kelly J.; Schlotter, William F.; Turner, Joshua J.; Kennedy, Brian; Hennies, Franz; Techert, Simone; Wernet, Philippe; Odelius, Michael; Föhlisch, Alexander


    Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)5 in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given—which will be covered experimentally by upcoming transform-limited x-ray sources.

  5. Resonance raman and absorption spectra of isomeric retinals in their lowest excited triplet states

    Wilbrandt, Robert Walter; Jensen, N.-H.; Houee-Levin, C.


    implications about the size of the energy barriers separating the various triplet species are discussed. The resonance Raman spectra obtained by using either anthracene (ET = 177.7 kJ mol-1) or naphthalene (ET = 254.8 kJ mol-1) as sensitizers were virtually identical for the corresponding triplet states from...

  6. Effects of Quantum Interference on the Profile of Excitation Spectra in the Atomic Sodium D1

    LI Yongfang; ZHANG Xiangyang; SUN Jianfeng; ZHAO Yongmei; WANG Yongchang; ZHANG Yanliang; DING Liang’en; WANG Zugeng


    In this paper, an experiment in a sodium vapor cell with cw laser pumping is reported. Two dips in the excitation spectrum profile of the sodium \\$D1\\$ line are observed. Theoretically excitation spectra in the three-level system are calculated in detail and results are identical with experiments. It is demonstrated that the appearance of the two dips in the excitation spectrum is close connected with quantum interference effect.

  7. Resonance Raman spectra of TNT and RDX using vibronic theory, excited-state gradient, and complex polarizability approximations.

    Al-Saidi, W A; Asher, Sanford A; Norman, Patrick


    Geometries, UV absorption bands, and resonance Raman (RR) cross sections of TNT and RDX are investigated using density functional theory (DFT) in conjunction with the Coulomb attenuated B3LYP exchange-correlation functional. The absorption and RR spectra are determined with use of vibronic (VB) theory, excited-state gradient, and complex polarizability (CPP) approximations. We examined low-energy isomers (two for TNT and four for RDX) whose energies differ by less than 1 kcal/mol, such that they would appreciably be populated at room temperature. The two TNT isomers differ by an internal rotation of the methyl group, while the four conformers of RDX differ by the arrangements of the nitro group relative to the ring. Our theoretical optical properties of the TNT and RDX isomers are in excellent agreement with experimental and recent CCSD-EOM results, respectively. For the two TNT isomers, the ultraviolet RR (UVRR) spectra are similar and in good agreement with recently measured experimental results. Additionally, the UVRR spectra computed using the excited-state and CPP approaches compare favorably with the VB theory results. On the other hand, the RR spectra of the RDX conformers differ from one another, reflecting the importance of the positioning of the NO2 groups with respect to the ring. In the gas phase or in solution, RDX would give a spectrum associated with a conformationally averaged structure. It is encouraging that the computed spectra of the conformers show similarities to recent measured RDX spectra in acetonitrile solution, and reproduce the 10-fold decrease in the absolute Raman cross sections of RDX compared to TNT for the observed 229 nm excitation. We show that in TNT and RDX vibrational bands that couple to NO2 or the ring are particularly resonance enhanced. Finally, the computed RDX spectra of the conformers present a benchmark for understanding the RR spectra of the solid-phase polymorphs of RDX.

  8. Experimental demonstration of mode-selective phonon excitation of 6H-SiC by a mid-infrared laser with anti-Stokes Raman scattering spectroscopy

    Yoshida, Kyohei; Hachiya, Kan; Okumura, Kensuke; Mishima, Kenta; Inukai, Motoharu; Torgasin, Konstantin; Omer, Mohamed [Graduate School of Energy Science, Kyoto University, Yoshida-honmachi, Sakyo-ku, Kyoto 606-8501 (Japan); Sonobe, Taro [Kyoto University Research Administration Office, Kyoto University, Yoshida-honmachi, Sakyo-ku, Kyoto 606-8501 (Japan); Zen, Heishun; Negm, Hani; Kii, Toshiteru; Masuda, Kai; Ohgaki, Hideaki [Institute of Advanced Energy, Kyoto University, Gokasyo, Uji, Kyoto 611-0011 (Japan)


    Mode-selective phonon excitation by a mid-infrared laser (MIR-FEL) is demonstrated via anti-Stokes Raman scattering measurements of 6H-silicon carbide (SiC). Irradiation of SiC with MIR-FEL and a Nd-YAG laser at 14 K produced a peak where the Raman shift corresponds to a photon energy of 119 meV (10.4 μm). This phenomenon is induced by mode-selective phonon excitation through the irradiation of MIR-FEL, whose photon energy corresponds to the photon-absorption of a particular phonon mode.

  9. Magnetoplasma excitations and the effect of electron and hole velocity renormalization in free-hanging graphene studied by Raman scattering

    Kukushkin, V. I.; Kirpichev, V. E.; Kukushkin, I. V.


    The properties of plasma and magnetoplasma excitations in free-hanging graphene have been studied for the first time by Raman scattering. In addition to single-particle excitations associated with transitions between empty Landau levels of electrons and holes, collective plasma and magnetoplasma excitations in the system of electrons (and holes) of various densities have been discovered for the first time. Hybridization of plasma and cyclotron modes corresponding to the Kohn law has been shown to occur in the limit of high filling factors, which allows measuring directly the plasma and cyclotron energies. The dependence of the electron and hole velocities on their density has been investigated via the magnetic-field dependence of the cyclotron energy in free-hanging graphene. The effect of strong renormalization of the electron and hole dispersion relations seen as an increase in the velocity (by 40-50%) with a decrease in the charge-carrier density to 1011 cm-2 has been discovered. The charge-carrier density dependences of the widths of magnetoplasma resonances in free-hanging graphene and graphene lying on a silicon dioxide surface have been measured and shown to be at least 3.5 and 14.8 meV, respectively.

  10. Nonlinear development of stimulated Raman scattering from electrostatic modes excited by self-consistent non-Maxwellian velocity distributions.

    Yin, L; Daughton, W; Albright, B J; Bezzerides, B; DuBois, D F; Kindel, J M; Vu, H X


    The parametric coupling involving backward stimulated scattering of a laser and electron beam acoustic modes (BAM) is described as observed in particle-in-cell (PIC) simulations. The BAM modes evolve from Langmuir waves (LW) as the electron velocity distribution is nonlinearly modified to be non-Maxwellian by backward stimulated Raman scattering (BSRS). With a marginal damping rate, BAM can be easily excited and allow an extended chirping in frequency to occur as later SRS pulses encounter modified distributions. Coincident with the emergence of this non-Maxwellian distribution is a rapid increase in BSRS reflectivities with laser intensities. Both the reflectivity scaling with laser intensity and the observed spectral features from PIC simulations are consistent with recent Trident experiments.

  11. Ceilometer Aerosol Profiling versus Raman Lidar in the Frame of Interact Campaign of Actris

    Madonna F.


    Full Text Available In this paper, multi-wavelength Raman lidar measurements are used to investigate the capability of ceilometers to provide reliable information about atmospheric aerosol properties through the INTERACT (INTERcomparison of Aerosol and Cloud Tracking campaign carried out at the CNR-IMAA Atmospheric Observatory (760 m a.s.l., 40.60 N, 15.72 E, in the framework of ACTRIS (Aerosol Clouds Trace gases Research InfraStructure FP7 project. This work is the first time that three different commercial ceilometers with an advanced Raman lidar are compared over a period of six month. The comparison of the attenuated backscatter coefficient profiles from a multi-wavelength Raman lidar and three ceilometers (CHM15k, CS135s, CT25K reveals differences due to the expected discrepancy in the SNR but also due to effect of changes in the ambient temperature on the stability of ceilometer calibration over short and mid-term. Technological improvements of ceilometers towards their operational use in the monitoring of the atmospheric aerosol in the low and free troposphere are likely needed.

  12. Raman Lidar Profiles Best Estimate Value-Added Product Technical Report

    Newson, R


    The ARM Raman lidars are semi-autonomous ground-based systems that transmit at a wavelength of 355 nm with 300 mJ, {approx}5 ns pulses, and a pulse repetition frequency of 30Hz. Signals from the various detection channels are processed to produce time- and height-resolved estimates of several geophysical quantities, such as water vapor mixing ratio, relative humidity, aerosol scattering ratio, backscatter, optical depth, extinction, and depolarization ratio. Data processing is currently handled by a suite of six value-added product (VAP) processes. Collectively, these processes are known as the Raman Lidar Profiles VAP (RLPROF). The top-level best-estimate (BE) VAP process was introduced in order to bring together the most relevant information from the intermediate-level VAPs. As such, the BE process represents the final stage in data processing for the Raman lidar. Its principal function is to extract the primary variables from each of the intermediate-level VAPs, perform additional quality control, and combine all of this information into a single output file for the end-user. The focus of this document is to describe the processing performed by the BE VAP process.

  13. The Raman effect and its application to electronic spectroscopies in metal-centered species : Techniques and investigations in ground and excited states

    Browne, W.R.; J. McGarvey, J.


    In the decades since its discovery and somewhat limited early applications, Raman scattering has become the basis for the development of a variety of methods for probing molecular structure both in ground and electronically excited states. In this review, following a brief look at the underlying pri

  14. The Raman effect and its application to electronic spectroscopies in metal-centered species : Techniques and investigations in ground and excited states

    Browne, W.R.; J. McGarvey, J.

    In the decades since its discovery and somewhat limited early applications, Raman scattering has become the basis for the development of a variety of methods for probing molecular structure both in ground and electronically excited states. In this review, following a brief look at the underlying

  15. Structural dynamics of phenylisothiocyanate in the light-absorbing excited states: Resonance Raman and complete active space self-consistent field calculation study

    Ouyang, Bing, E-mail:; Xue, Jia-Dan, E-mail:; Zheng, Xuming, E-mail:, E-mail:, E-mail: [Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Fang, Wei-Hai, E-mail:, E-mail:, E-mail: [Department of Chemistry, Beijing Normal University, Beijing 100875 (China)


    The excited state structural dynamics of phenyl isothiocyanate (PITC) after excitation to the light absorbing S{sub 2}(A′), S{sub 6}(A′), and S{sub 7}(A′) excited states were studied by using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The UV absorption bands of PITC were assigned. The vibrational assignments were done on the basis of the Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 299.1, 282.4, 266.0, 252.7, 228.7, 217.8, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PITC. The results indicated that the structural dynamics in the S{sub 2}(A′), S{sub 6}(A′), and S{sub 7}(A′) excited states were very different. The conical intersection point CI(S{sub 2}/S{sub 1}) were predicted to play important role in the low-lying excited state decay dynamics. Two major decay channels were predicted for PITC upon excitation to the S{sub 2}(A′) state: the radiative S{sub 2,min} → S{sub 0} transition and the nonradiative S{sub 2} → S{sub 1} internal conversion via CI(S{sub 2}/S{sub 1}). The differences in the decay dynamics between methyl isothiocyanate and PITC in the first light absorbing excited state were discussed. The role of the intersystem crossing point ISC(S{sub 1}/T{sub 1}) in the excited state decay dynamics of PITC is evaluated.

  16. Structural dynamics of phenylisothiocyanate in the light-absorbing excited states: resonance Raman and complete active space self-consistent field calculation study.

    Ouyang, Bing; Xue, Jia-Dan; Zheng, Xuming; Fang, Wei-Hai


    The excited state structural dynamics of phenyl isothiocyanate (PITC) after excitation to the light absorbing S2(A'), S6(A'), and S7(A') excited states were studied by using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The UV absorption bands of PITC were assigned. The vibrational assignments were done on the basis of the Fourier transform (FT)-Raman and FT-infrared measurements, the density-functional theory computations, and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohexane, acetonitrile, and methanol solvents were, respectively, obtained at 299.1, 282.4, 266.0, 252.7, 228.7, 217.8, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PITC. The results indicated that the structural dynamics in the S2(A'), S6(A'), and S7(A') excited states were very different. The conical intersection point CI(S2/S1) were predicted to play important role in the low-lying excited state decay dynamics. Two major decay channels were predicted for PITC upon excitation to the S2(A') state: the radiative S(2,min) → S0 transition and the nonradiative S2 → S1 internal conversion via CI(S2/S1). The differences in the decay dynamics between methyl isothiocyanate and PITC in the first light absorbing excited state were discussed. The role of the intersystem crossing point ISC(S1/T1) in the excited state decay dynamics of PITC is evaluated.

  17. Tip-enhanced near-field optical microscope with side-on and ATR-mode sample excitation for super-resolution Raman imaging of surfaces

    Heilman, A. L.; Gordon, M. J.


    A tip-enhanced near-field optical microscope with side-on and attenuated total reflectance (ATR) excitation and collection is described and used to demonstrate sub-diffraction-limited (super-resolution) optical and chemical characterization of surfaces. ATR illumination is combined with an Au optical antenna tip to show that (i) the tip can quantitatively transduce the optical near-field (evanescent waves) above the surface by scattering photons into the far-field, (ii) the ATR geometry enables excitation and characterization of surface plasmon polaritons (SPPs), whose associated optical fields are shown to enhance Raman scattering from a thin layer of copper phthalocyanine (CuPc), and (iii) SPPs can be used to plasmonically excite the tip for super-resolution chemical imaging of patterned CuPc via tip-enhanced Raman spectroscopy (TERS). ATR-illumination TERS is also quantitatively compared with the more conventional side-on illumination scheme. In both cases, spatial resolution was better than 40 nm and tip on/tip off Raman enhancement factors were >6500. Furthermore, ATR illumination was shown to provide similar Raman signal levels at lower "effective" pump powers due to additional optical energy delivered by SPPs to the active region in the tip-surface gap.

  18. Ceilometer aerosol profiling vs. Raman lidar in the frame of INTERACT campaign of ACTRIS

    Madonna, F.; Amato, F.; Vande Hey, J.; Pappalardo, G.


    Despite their differences from more advanced and more powerful lidars, the low construction and operation cost of ceilometers, originally designed for cloud base height monitoring, has fostered their use for the quantitative study of aerosol properties. The large number of ceilometers available worldwide represents a strong motivation to investigate both the extent to which they can be used to fill in the geographical gaps between advanced lidar stations and also how their continuous data flow can be linked to existing networks of the more advanced lidars, like EARLINET (European Aerosol Research LIdar NETwork). In this paper, multi-wavelength Raman lidar measurements are used to investigate the capability of ceilometers to provide reliable information about atmospheric aerosol content through the INTERACT (INTERcomparison of Aerosol and Cloud Tracking) campaign carried out at the CNR-IMAA Atmospheric Observatory (760 m a.s.l., 40.60° N, 15.72° E), in the framework of ACTRIS (Aerosol Clouds Trace gases Research InfraStructure) FP7 project. This work is the first time that three different commercial ceilometers with an advanced Raman lidar are compared over a period of six months. The comparison of the attenuated backscatter profiles from a multi-wavelength Raman lidar and three ceilometers (CHM15k, CS135s, CT25K) reveals differences due to the expected discrepancy in the SNR but also due to effect of changes in the ambient temperature on the short and mid-term stability of ceilometer calibration. A large instability of ceilometers in the incomplete overlap region has also been observed, making the use of a single overlap correction function for the whole duration of the campaign critical. Therefore, technological improvements of ceilometers towards their operational use in the monitoring of the atmospheric aerosol in the low and free troposphere are needed.

  19. Profiling the Near field of Nanoshells Using Surface Enhanced Raman Spectroscopy

    Lal, Surbhi


    There is tremendous interest in the enhancement of electromagnetic fields near metal surfaces. The spatial extent of the near field as a function of distance from the metal surface is of particular interest for applications such as surface enhanced Raman spectroscopy. By using specially designed molecular scaffolds with Raman-active constituents, we measure the profile of this fringing field at a nanoshell surface. Nanoshells are colloidal particles composed of a silica core covered by a gold shell, which exhibit a tunable plasmon resonance; close to this resonance there is a strong enhancement of the electromagnetic near field. The molecular scaffolds consist of polyadenine DNA strands as tethers with a terminal fluorescein molecule. By varying the length of the DNA strand, the fluorescein molecule is placed at controlled distances from the nanoshell surface. Both the DNA scaffold and the terminal fluorescein molecule provide us with independent SERS Stokes modes whose relative intensities permit us to map the average spatial decay length of the near field of the nanoparticle at its plasmon resonance.

  20. An innovative rotational Raman lidar to measure the temperature profile from the surface to 30 km altitude

    Hauchecorne, Alain; Keckhut, Philippe; Mariscal, Jean-François; d'Almeida, Eric; Dahoo, Pierre-Richard; Porteneuve, Jacques


    A concept of innovative rotational Raman lidar with daylight measurement capability is proposed to measure the vertical profile of temperature from the ground to the middle stratosphere. The optical filtering is made using a Fabry-Pérot Interferometer with line spacing equal to the line spacing of the Raman spectrum. The detection is made using a linear PMT array operated in photon counting mode. We plan to build a prototype and to test it at the Haute-Provence Observatory lidar facility. to achieve a time resolution permitting the observation of small-scale atmospheric processes playing a role in the troposphere-stratosphere interaction as gravity waves. If successful, this project will open the possibility to consider a Raman space lidar for the global observation of atmospheric temperature profiles.

  1. Remote measurement of atmospheric temperature profiles in clouds with rotational Raman lidar; Fernmessung atmosphaerischer Temperaturprofile in Wolken mit Rotations-Raman-Lidar

    Behrendt, A. [GKSS-Forschungszentrum Geesthacht GmbH (Germany). Inst. fuer Physikalische und Chemische Analytik


    The development of a lidar receiver for remote measurements of atmospheric temperature profiles with the rotational Raman method is described. By a new receiver concept, this instrument allowed for the first time remote temperature measurements without any perturbation by the presence of clouds up to a backscatter ratio of 45. In addition, high efficiency of the spectral separation of atmospheric backscatter signals leads to improved measurement resolution: the minimum integration time needed for a statistical uncertainty < {+-}1 K at, e.g., 10 km height and 960 m height resolution is only 5 minutes. The measurement range extends to over 45 km altitude. Results of field campaigns obtained with the instrument are presented and discussed. In winter 1997/98, the instrument was transferred with the GKSS Raman lidar to Esrange (67.9 N, 21.1 E) in northern Sweden, where pioneering remote measurements of local temperatures in orographically induced polar stratospheric clouds could be carried out. (orig.)

  2. Comparing Water Vapor Mixing Ratio Profiles and Cloud Vertical Structure from Multiwavelength Raman Lidar Retrievals and Radiosounding Measurements

    Costa-Surós Montserrat; Stachlewska Iwona S.; Markowicz Krzysztof


    A study of comparison of water vapor mixing ratio profiles, relative humidity profiles, and cloud vertical structures using two different instruments, a multiwavelength Aerosol-Depolarization-Raman lidar and radiosoundings, is presented. The observations were taken by the lidar located in Warsaw center and the radiosoundings located about 30km to the North in Legionowo (Poland). We compared the ground-based remote sensing technology with in-situ method in order to improve knowledge about wate...

  3. PollyNET: a global network of automated Raman-polarization lidars for continuous aerosol profiling

    Baars, H.; Kanitz, T.; Engelmann, R.; Althausen, D.; Heese, B.; Komppula, M.; Preißler, J.; Tesche, M.; Ansmann, A.; Wandinger, U.; Lim, J.-H.; Ahn, J. Y.; Stachlewska, I. S.; Amiridis, V.; Marinou, E.; Seifert, P.; Hofer, J.; Skupin, A.; Schneider, F.; Bohlmann, S.; Foth, A.; Bley, S.; Pfüller, A.; Giannakaki, E.; Lihavainen, H.; Viisanen, Y.; Hooda, R. K.; Pereira, S.; Bortoli, D.; Wagner, F.; Mattis, I.; Janicka, L.; Markowicz, K. M.; Achtert, P.; Artaxo, P.; Pauliquevis, T.; Souza, R. A. F.; Sharma, V. P.; van Zyl, P. G.; Beukes, J. P.; Sun, J. Y.; Rohwer, E. G.; Deng, R.; Mamouri, R. E.; Zamorano, F.


    A global vertically resolved aerosol data set covering more than 10 years of observations at more than 20 measurement sites distributed from 63° N to 52° S and 72° W to 124° E has been achieved within the Raman and polarization lidar network PollyNET. This network consists of portable, remote-controlled multiwavelength-polarization-Raman lidars (Polly) for automated and continuous 24/7 observations of clouds and aerosols. PollyNET is an independent, voluntary, and scientific network. All Polly lidars feature a standardized instrument design and apply unified calibration, quality control, and data analysis. The observations are processed in near-real time without manual intervention, and are presented online at"target="_blank"> The paper gives an overview of the observations on four continents and two research vessels obtained with eight Polly systems. The specific aerosol types at these locations (mineral dust, smoke, dust-smoke and other dusty mixtures, urban haze, and volcanic ash) are identified by their Ångström exponent, lidar ratio, and depolarization ratio. The vertical aerosol distribution at the PollyNET locations is discussed on the basis of more than 55 000 automatically retrieved 30 min particle backscatter coefficient profiles at 532 nm. A seasonal analysis of measurements at selected sites revealed typical and extraordinary aerosol conditions as well as seasonal differences. These studies show the potential of PollyNET to support the establishment of a global aerosol climatology that covers the entire troposphere.

  4. PollyNET: a global network of automated Raman-polarization lidars for continuous aerosol profiling

    H. Baars


    Full Text Available A global vertically resolved aerosol data set covering more than 10 years of observations at more than 20 measurement sites distributed from 63° N to 52° S and 72° W to 124° E has been achieved within the Raman and polarization lidar network PollyNET. This network consists of portable, remote-controlled multiwavelength-polarization-Raman lidars (Polly for automated and continuous 24/7 observations of clouds and aerosols. PollyNET is an independent, voluntary, and scientific network. All Polly lidars feature a standardized instrument design and apply unified calibration, quality control, and data analysis. The observations are processed in near-real time without manual intervention, and are presented online at The paper gives an overview of the observations on four continents and two research vessels obtained with eight Polly systems. The specific aerosol types at these locations (mineral dust, smoke, dust-smoke and other dusty mixtures, urban haze, and volcanic ash are identified by their Ångström exponent, lidar ratio, and depolarization ratio. The vertical aerosol distribution at the PollyNET locations is discussed on the basis of more than 55 000 automatically retrieved 30 min particle backscatter coefficient profiles at 532 nm. A seasonal analysis of measurements at selected sites revealed typical and extraordinary aerosol conditions as well as seasonal differences. These studies show the potential of PollyNET to support the establishment of a global aerosol climatology that covers the entire troposphere.

  5. Plasmonic Nanoparticle-based Hybrid Photosensitizers with Broadened Excitation Profile for Photodynamic Therapy of Cancer Cells

    Wang, Peng; Tang, Hong; Zhang, Peng


    Photodynamic therapy combining nanotechnology has shown great potential with improved therapeutic efficacy and fewer side effects. Ideal photosensitizers for cancer treatment should both have good singlet oxygen production capability and be excitable by light illuminations with deep tissue penetration. Here we report a type of hybrid photosensitizers consisting of plasmonic silver nanoparticles and photosensitizing molecules, where strong resonance coupling between the two leads to a broadened excitation profile and exceptionally high singlet oxygen production under both visible light and infrared light excitations. Our results indicate that the hybrid photosensitizers display low cytotoxicity without light illumination yet highly enhanced photodynamic inhibition efficacy against Hela cells under a broad spectrum of light illuminations including the near-infrared light, which has great implication in photodynamic therapy of deep-tissue cancers.

  6. Depth-profiling by confocal Raman microscopy (CRM): data correction by numerical techniques.

    Tomba, J Pablo; Eliçabe, Guillermo E; Miguel, María de la Paz; Perez, Claudio J


    The data obtained in confocal Raman microscopy (CRM) depth profiling experiments with dry optics are subjected to significant distortions, including an artificial compression of the depth scale, due to the combined influence of diffraction, refraction, and instrumental effects that operate on the measurement. This work explores the use of (1) regularized deconvolution and (2) the application of simple rescaling of the depth scale as methodologies to obtain an improved, more precise, confocal response. The deconvolution scheme is based on a simple predictive model for depth resolution and the use of regularization techniques to minimize the dramatic oscillations in the recovered response typical of problem inversion. That scheme is first evaluated using computer simulations on situations that reproduce smooth and sharp sample transitions between two materials and finally it is applied to correct genuine experimental data, obtained in this case from a sharp transition (planar interface) between two polymeric materials. It is shown that the methodology recovers very well most of the lost profile features in all the analyzed situations. The use of simple rescaling appears to be only useful for correcting smooth transitions, particularly those extended over distances larger than those spanned by the operative depth resolution, which limits the strategy to the study of profiles near the sample surface. However, through computer simulations, it is shown that the use of water immersion objectives may help to reduce optical distortions and to expand the application window of this simple methodology, which could be useful, for instance, to safely monitor Fickean sorption/desorption of penetrants in polymer films/coatings in a nearly noninvasive way.

  7. Excited state proton transfer dynamics of thioacetamide in S2(ππ*) state: resonance Raman spectroscopic and quantum mechanical calculations study.

    Chen, Xiao; Zhao, Yanying; Zhang, Haibo; Xue, Jiadan; Zheng, Xuming


    The photophysics and photochemistry of thioacetamide (CH3CSNH2) after excitation to the S2 electronic state were investigated by using resonance Raman spectroscopy in conjunction with the complete active space self-consistent field (CASSCF) method and density functional theory (DFT) calculations. The A-band resonance Raman spectra in acetonitrile, methanol, and water were obtained at 299.1, 282.4, 266.0, 252.7, and 245.9 nm excitation wavelengths to probe the structural dynamics of thioacetamide in the S2 state. CASSCF calculations were done to determine the transition energies and structures of the lower-lying excited states, the conical intersection points CI(S2/S1) and CI(S1/S0), and intersystem crossing points. The structural dynamics of thioacetamide in the S2 state was revealed to be along eight Franck-Condon active vibrational modes ν15, ν11, ν14, ν10, ν8, ν12, ν18, and ν19, mostly in the CC/CS/CN stretches and the CNH8,9/CCH5,6,7/CCN/CCS in-plane bends as indicated by the corresponding normal mode descriptions. The S2 → S1 decay process via the S2/S1 conical intersection point as the major channel were excluded. The thione-thiol photoisomerization reaction mechanism of thioacetamide via the S2,FC → S'1,min excited state proton transfer (ESPT) reaction channel was proposed.

  8. Depth profile study on Raman spectra of high-energy-electron-irradiated hydrogenated amorphous silicon films


    According to the different penetration depths for the incident lights of 472 nm and 532 nm in hydrogenated amorphous silicon (a-Si:H) thin films, the depth profile study on Raman spectra of a-Si:H films was carried out. The network ordering evolution in the near surface and interior region of the unirradiated and irradiated a-Si:H films was investigated. The results show that there is a structural improvement in the shortand intermediate-range order towards the surface of the unirradiated a-Si:H films. The amorphous silicon network in the near and interior region becomes more disordered on the shortand intermediate-range scales after being irradiated with high energy electrons. However, the surface of the irradiated films becomes more disordered in comparison with their interior region, indicating that the created defects caused by electron irradiation are concentrated in the near surface of the irradiated films. Annealing eliminates the irradiation effects on a-Si:H thin films and the structural order of the irradiated films is similar to that of the unirradiated ones after being annealed. There exists a structural improvement in the shortand intermediate-range order towards the surface of the irradiated a-Si:H films after being annealed.

  9. Implementation of Raman lidar for profiling of atmospheric water vapor and aerosols at the SGP CART site

    Goldsmith, J. E. M.; Blair, Forest H.; Bisson, Scott E.

    There are clearly identified scientific requirements for continuous profiling of atmospheric water vapor at the SGP CART (southern great plains cloud and radiation testbed) site. Research conducted at several laboratories, including our work in a previous ARM instrument development project, has demonstrated the suitability of Raman lidar for providing measurements that are an excellent match to those requirements. We are in the final stages of building a ruggedized Raman lidar system that will reside permanently at the CART site, and that is computer automated to reduce the requirements for operator interaction. In addition to the design goal of profiling water vapor through most of the troposphere during nighttime and through the boundary layer during daytime, the lidar will provide quantitative characterization of aerosols and clouds, including depolarization measurements for particle phase studies.

  10. CART and GSFC raman lidar measurements of atmospheric aerosol backscattering and extinction profiles for EOS validation and ARM radiation studies

    Ferrare, R. A.; Turner, D. D.; Melfi, S. H.; Whiteman, D. N.; Schwenner, G.; Evans, K. D.; Goldsmith, J. E. M.; Tooman, T.


    The aerosol retrieval algorithms used by the Moderate-Resolution Imaging Spectroradiometer (MODIS) and Multi-Angle Imaging SpectroRadiometer (MISR) sensors on the Earth Observing Satellite (EOS) AM-1 platform operate by comparing measured radiances with tabulated radiances that have been computed for specific aerosol models. These aerosol models are based almost entirely on surface and/or column averaged measurements and so may not accurately represent the ambient aerosol properties. Therefore, to validate these EOS algorithms and to determine the effects of aerosols on the clear-sky radiative flux, we have begun to evaluate the vertical variability of ambient aerosol properties using the aerosol backscattering and extinction profiles measured by the Cloud and Radiation Testbed (CART) and NASA Goddard Space Flight Center (GSFC) Raman Lidars. Using the procedures developed for the GSFC Scanning Raman Lidar (SRL), we have developed and have begun to implement algorithms for the CART Raman Lidar to routinely provide profiles of aerosol extinction and backscattering during both nighttime and ,daytime operations. Aerosol backscattering and extinction profiles are computed for both lidar systems using data acquired during the 1996 and 1997 Water Vapor Intensive Operating Periods (IOPs). By integrating these aerosol extinction profiles, we derive measurements of aerosol optical thickness and compare these with coincident sun photometer measurements. We also use these measurements to measure the aerosol extinction/backscatter ratio S(sub a) (i.e. 'lidar ratio'). Furthermore, we use the simultaneous water vapor measurements acquired by these Raman lidars to investigate the effects of water vapor on aerosol optical properties.

  11. Application of Finite Difference Technique to Raman Lidar Signals to Derive the Altitude Profiles of Atmospheric Aerosol Extinction



    Full Text Available Lidars (Laser radars are the best suitable instruments to derive the range resolved parameters of atmosphere. Single wavelength and simple backscatter lidars have been widely used to study the height profiles of particle scattering and extinction in the atmosphere. However, atmospheric extinction derived using these lidars data undergo several assumptions and hence involve a significant amount of error in estimation of extinction. The Raman lidar methodology of deriving particle extinction in the atmosphere is a simplified straight-forward method that does not involve any assumptions. The Raman lidar method of atmospheric extinction computation employs derivative of logarithm of normalized range corrected Raman backscattered signal. Usually this causes gaps in the height profiles wherever there is a gradient in the signal under examination. In the present study, a new method is proposed to derive the particle extinction in the atmospheric boundary layer. In this new method, a scheme of alternative solution methodology has been proposed using “Finite Difference Technique”. The method has an advantage that, it does not involve the gradient as compared to conventional technique and hence reduces the error. Using this method, the height profiles of particle extinction has been derived. A code in MATLAB is developed to derive the altitude distribution of aerosol extinction. In this connection, the NOAA-REDY site data has been used as the reference data for calculating the molecular extinction in the lower atmosphere.

  12. A Profile Analysis of Raman-scattered O VI Bands at 6825 \\AA\\ and 7082 \\AA\\ in Sanduleak's Star

    Heo, Jeong-Eun; Di Mille, Francesco; Palma, Tali; Lee, Hee-Won


    We present a detailed modeling of the two broad bands observed at 6825 \\AA\\ and 7082 \\AA\\ in Sanduleak's star, a controversial object in the Large Magellanic Cloud. These bands are known to originate from Raman-scattering of O VI $\\lambda\\lambda$ 1032 and 1038 photons with atomic hydrogen and are only observed in bona fide symbiotic stars. Our high-resolution spectrum obtained with the Magellan Inamori Kyocera Echelle (MIKE) spectrograph at the Magellan-Clay Telescope reveals, quite surprisingly, that the profiles of the two bands look very different: while the Raman 6825 \\AA\\ band shows a single broad profile with a redward extended bump, the Raman 7082 \\AA\\ band exhibits a distinct triple-peak profile. Our model suggests that the O VI emission nebula can be decomposed into a red, blue and central emission regions from an accretion disk, a bipolar outflow and a further compact, optically thick region. We also perform Monte Carlo simulations with the aim of fitting the observed flux ratio $F(6825)/F(7082) \\si...

  13. Profiling of liquid crystal displays with Raman spectroscopy: Preprocessing of spectra.

    O. Stanimirovic; H.F.M. Boelens; A.J.G. Mank; H.C.J. Hoefsloot; A.K. Smilde


    Raman spectroscopy is applied for characterizing paintable displays. Few other options than Raman spectroscopy exist for doing so because of the liquid nature of functional materials. The challenge is to develop a method that can be used for estimating the composition of a single display cell on the

  14. Non-invasive depth profile imaging of the stratum corneum using confocal Raman microscopy: first insights into the method.

    Ashtikar, Mukul; Matthäus, Christian; Schmitt, Michael; Krafft, Christoph; Fahr, Alfred; Popp, Jürgen


    The stratum corneum is a strong barrier that must be overcome to achieve successful transdermal delivery of a pharmaceutical agent. Many strategies have been developed to enhance the permeation through this barrier. Traditionally, drug penetration through the stratum corneum is evaluated by employing tape-stripping protocols and measuring the content of the analyte. Although effective, this method cannot provide a detailed information regarding the penetration pathways. To address this issue various microscopic techniques have been employed. Raman microscopy offers the advantage of label free imaging and provides spectral information regarding the chemical integrity of the drug as well as the tissue. In this paper we present a relatively simple method to obtain XZ-Raman profiles of human stratum corneum using confocal Raman microscopy on intact full thickness skin biopsies. The spectral datasets were analysed using a spectral unmixing algorithm. The spectral information obtained, highlights the different components of the tissue and the presence of drug. We present Raman images of untreated skin and diffusion patterns for deuterated water and beta-carotene after Franz-cell diffusion experiment.

  15. Infrared, Raman, and Ultraviolet Absorption Spectra and Theoretical Calculations and Structure of 2,6-Difluoropyridine in its Ground and Excited Electronic States

    Sheu, Hong-Li; Kim, Sunghwan; Laane, Jaan


    The infrared and Raman spectra of 2,6-difluoropyridine (26DFPy) along with ab initio and DFT computations have been used to assign the vibrations of the molecule in its S0 electronic ground state and to calculate its structure. The ultraviolet absorption spectrum showed the electronic transition to the S1(π,π*) state to be at 37,820.2 cm−1. With the aid of ab initio computations the vibrational frequencies for this excited state were also determined. TD-B3LYP and CASSCF computations for the excited states were carried out to calculate the structures for the S1(π,π*) and S2(n,π*) excited states. The CASSCF results predict that the S1(π,π*) state is planar and the S2(n,π*) state has a barrier to planarity of 256 cm−1. The TD-B3LYP computations predict a barrier of 124 cm−1 for the S1(π,π*) states, but the experimental results support the planar structure. Hypothetical models for the ring-puckering potential energy function were calculated for both electronic excited states to show the predicted quantum states. The changes in the vibrational frequencies in the two excited states reflect the weaker π bonding within the pyridine ring. PMID:24070189

  16. Electronic Raman scattering with excitation between localized states observed in the zinc M{sub 2,3} soft x-ray spectra of ZnS

    Zhou, L.; Callcott, T.A.; Jia, J.J. [Univ. of Tennessee, Knoxville, TN (United States)] [and others


    Zn M{sub 2,3} soft x-ray fluorescence (SXF) spectra of ZnS and ZnS{sub .5}Se{sub .5} excited near threshold show strong inelastic scattering effects that can be explained using a simple model and an inelastic scattering theory based on second order perturbation theory. This scattering is often called electronic resonance Raman scattering. Tulkki and Aberg have developed this theory in detail for atomic systems, but their treatment can be applied to solid systems by utilizing electronic states characteristic of solids rather than of atomic systems.

  17. Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

    Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J.; Jensen, Lasse


    A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host–guest complex (TTFcCBPQT4+). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host–guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. Finally, however, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.

  18. Raman scattering of magnetic excitations in Y1-x Prx Ba2Cu3-yAlyO7-δ single crystals

    Rübhausen, M.; Dieckmann, N.; Bock, A.; Merkt, U.; Widder, W.; Braun, H. F.


    Magnetic excitations and their role for the superconductivity in cuprate superconductors have been widely discussed in the literature. Here, we present a study of Y1-x Prx Ba2Cu3-yAlyO7-δ single crystals using Raman spectroscopy in an energy range of 50 10000 cm-1 Raman shift. The high energy range is dominated by a two-magnon scattering process at 3J, where J is the superexchange energy. In the Pr-123 single crystal, we find J = 720 cm-1, a damping of the one-magnon states Γ = 200 cm-1, and a resonance energy of 2.79eV for the two-magnon excitation. The two-magnon peak shows a continuous increase of the one-magnon damping with decreasing x and a nearly constant J across the phase transition to the superconductor. Especially, we find a weak two-magnon peak for a superconductor with a Tc = 86 K.

  19. 35Cl profiling using centric scan SPRITE with variable flip angle excitation

    Romanenko, Konstantin V.; Cano-Barrita, P. F. de J.; Balcom, Bruce J.


    An efficient MRI technique for quantitative density profiling of samples with fast spin-lattice relaxation ( T1 technique. Strong excitation of the sample at the k-space origin improves the sensitivity with respect to the original centric scan SPRITE technique. Radio frequency pulse durations are defined so as to provide uniform excitation of the sample at every k-space point. For a particular k-space point the pulse duration is required to be less than the inverse sample bandwidth. Simulations permit one to examine distortions from ideal profile geometry due to flip angle and spin-lattice relaxation effects. The proposed technique is especially suitable for the observation of low sensitivity samples, in particular, low-γ nuclei like 35Cl. In some cases, this strategy permits one to reduce the number of scans, i.e. the experiment time, by a factor of 100, depending on hardware, sample length and tolerable resolution loss. The designed pulse scheme is tested on cylindrical agar gel and type 1 Portland cement paste phantoms prepared to provide 1H and 35Cl signals, respectively.

  20. Raman scattering or fluorescence emission? Raman spectroscopy study on lime-based building and conservation materials.

    Kaszowska, Zofia; Malek, Kamilla; Staniszewska-Slezak, Emilia; Niedzielska, Karina


    This work presents an in-depth study on Raman spectra excited with 1064 and 532nm lasers of lime binders employed in the past as building materials and revealed today as valuable conservation materials. We focus our interest on the bands of strong intensity, which are present in the spectra of all binders acquired with laser excitation at 1064nm, but absent in the corresponding spectra acquired with laser excitation at 532nm. We suggest, that the first group of spectra represents fluorescence phenomena of unknown origin and the second true Raman scattering. In our studies, we also include two other phases of lime cycle, i.e. calcium carbonate (a few samples of calcite of various origins) and calcium oxide (quicklime) to assess how structural and chemical transformations of lime phases affect the NIR-Raman spectral profile. Furthermore, we analyse a set of carbonated limewashes and lime binders derived from old plasters to give an insight into their spectral characteristics after excitation with the 1064nm laser line. NIR-Raman micro-mapping results are also presented to reveal the spatial distribution of building materials and fluorescent species in the cross-section of plaster samples taken from a 15th century chapel. Our study shows that the Raman analysis can help identify lime-based building and conservation materials, however, a caution is advised in the interpretation of the spectra acquired using 1064nm excitation.

  1. Confocal Raman depth-profile analysis of the electrical and structural properties in III-nitride structures

    Strelchuk, V.V.; Bryksa, V.P.; Avramenko, K.A.; Valakh, M.Ya.; Belyaev, A.E. [V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, 45 Nauky pr., 03028 Kyiv (Ukraine); Mazur, Yu.I.; Ware, M.E.; DeCuir, E.A. Jr.; Salamo, G.J. [Department of Physics, University of Arkansas, Fayetteville, Arkansas 72701 (United States)


    Scanning confocal Raman spectroscopy was used to non-destructively evaluate the structural and electronic properties of n{sup +}/n{sub 0}/n{sup +}-GaN Gunn-diode structures. The depth profiles of the free carrier concentration and mobility were obtained from a line shape analysis of the {omega}{sup -}, {omega}{sup +} coupled phonon-plasmon modes. It was found that the intensity profiles of the Raman polar A{sub 1}(LO) phonon mode depend on the thickness of the undoped n{sub 0} layer, while the intensity profiles of the nonpolar E{sub 2}{sup high} mode were unaffected by the doping. The change in frequency and linewidth of E{sub 2}{sup high} mode throughout the thickness of the GaN layers, however reveal structural inhomogeneity in the diode structures. The carrier concentration and mobility exhibit only slight variations with thickness with the largest variation being at the free surface of the device. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Capability of Raman lidar for monitoring the variation of atmospheric CO2 profile

    Zhao Pei-Tao; Zhang Yin-Chao; Wang Lian; Hu Shun-Xing; Su Jia; Cao Kai-Fa; Zhao Yue-Feng; Hu Huan-Ling


    Lidar (Light detection and ranging) has special capabilities for remote sensing of many different behaviours of the atmosphere.One of the techniques which show a great deal of promise for several applications is Raman scattering.The detecting capability,including maximum operation range and minimum detectable gas concentration is one of the most significant parameters for lidar remote sensing of pollutants.In this paper,based on the new method for evaluating the capabilities of a Raman lidar system,we present an evaluation of detecting capability of Raman lidar for monitoring atmospheric CO2 in Hefei.Numerical simulations about the influence of atmospheric conditions on lidar detecting capability were carried out,and a conclusion can be drawn that the maximum difference of the operation ranges caused by the weather conditions alone can reach about 0.4 to 0.5kin with a measuring precision within 30ppmv.The range of minimum detectable concentration caused by the weather conditions alone can reach about 20 to 35 ppmv in vertical direction for 20000 shots at a distance of 1 km on the assumption that other parameters are kept constant.The other corresponding parameters under different conditions are also given.The capability of Raman lidar operated in vertical direction was found to be superior to that operated in horizontal direction.During practical measurement with the Raman lidar whose hardware components were fixed,aerosol scattering extinction effect would be a significant factor that influenced the capability of Raman lidar.This work may be a valuable reference for lidar system designing,measurement accuracy improving and data processing.

  3. Influence of the ac Stark effect on stimulated hyper-Raman profiles in sodium vapor

    Moore, M.A.; Garrett, W.R.; Payne, M.G.


    When pumping near the two-photon 3d resonance in pure sodium vapor and observing the backward hyper-Raman emission to the 3p substates, an asymmetry in ratios of 3p/sub 1/2/, 3p/sub 3/2/ associated emissions was observed dependent upon the direction of the initial laser detuning from the resonance. It has been determined that this asymmetry can be attributed to the ac Stark effect induced by the hyper-Raman emission itself. 3 refs., 3 figs.

  4. Classification of bladder cancer cell lines using Raman spectroscopy: a comparison of excitation wavelength, sample substrate and statistical algorithms

    Kerr, Laura T.; Adams, Aine; O'Dea, Shirley; Domijan, Katarina; Cullen, Ivor; Hennelly, Bryan M.


    Raman microspectroscopy can be applied to the urinary bladder for highly accurate classification and diagnosis of bladder cancer. This technique can be applied in vitro to bladder epithelial cells obtained from urine cytology or in vivo as an optical biopsy" to provide results in real-time with higher sensitivity and specificity than current clinical methods. However, there exists a high degree of variability across experimental parameters which need to be standardised before this technique can be utilized in an everyday clinical environment. In this study, we investigate different laser wavelengths (473 nm and 532 nm), sample substrates (glass, fused silica and calcium fluoride) and multivariate statistical methods in order to gain insight into how these various experimental parameters impact on the sensitivity and specificity of Raman cytology.

  5. One-Dimensional, Time-Resolved Raman Measurements in a Sooting Flame made with 355-nm Excitation

    Rabenstein, Friedrich; Leipertz, Alfred


    Single-shot vibrational Raman measurements were performed along an 11-mm-long line crossing the reaction zone in a premixed, fuel-rich ( 10), laminar methane air flame by use of a frequency-tripled Nd:YAG laser with a 355-nm emission wavelength. This laser source seems to have advantages relative to KrF excimer lasers as well as to Nd:YAG lasers at 532 nm for hydrocarbon combustion diagnostics. The Raman emissions of all major species (N 2 , O 2 , CH 4 , H 2 , CO 2 , H 2 O) were detected simultaneously with a spatial resolution of 0.4 mm. By integration over selected spectral intervals, the mole fractions of all species and subsequently the local gas temperatures have been obtained. A comparison of the temperatures that were found with results from filtered Rayleigh experiments showed good agreement, indicating the success of what are to the best of our knowledge the first one-dimensional single-shot Raman measurements in a sooting hydrocarbon flame.

  6. Infrared, Raman, and ultraviolet absorption spectra and theoretical calculations and structure of 2,3,5,6-tetrafluoropyridine in its ground and excited electronic states

    Sheu, Hong-Li; Boopalachandran, Praveenkumar [Department of Chemistry, Texas A& M University, College Station, TX 77843-3255 (United States); Kim, Sunghwan [National Center for Biotechnology Information, National Library of Medicine, National Institutes of Health, Department of Health and Human Services, 8600 Rockville Pike, Bethesda, MD 20894 (United States); Laane, Jaan, E-mail: [Department of Chemistry, Texas A& M University, College Station, TX 77843-3255 (United States)


    Highlights: • The structures of 2,3,5,6-tetrafluoropyridine for its S{sub 0} and S{sub 1}(π, π{sup ∗}) states have been calculated. • TFPy is rigidly planar in its ground electronic state, but is quasi-planar and floppy in S{sub 1}. • The barrier to planarity is 30 cm{sup −1} in the excited state. • The observed vibrational frequencies for both states agree well with the computations. • A ring-bending potential energy function for the S{sub 1}(π, π{sup ∗}) state was proposed. - Abstract: Infrared and Raman spectra of 2,3,5,6-tetrafluoropyridine (TFPy) were recorded and vibrational frequencies were assigned for its S{sub 0} electronic ground states. Ab initio and density functional theory (DFT) calculations were used to complement the experimental work. The lowest electronic excited state of this molecule was investigated with ultraviolet absorption spectroscopy and theoretical CASSCF calculations. The band origin was found to be at 35,704.6 cm{sup −1} in the ultraviolet absorption spectrum. A slightly puckered structure with a barrier to planarity of 30 cm{sup −1} was predicted by CASSCF calculations for the S{sub 1}(π, π{sup ∗}) state. Lower frequencies for the out-of-plane ring bending vibrations for the electronic excited state result from the weaker π bonding within the pyridine ring.

  7. Label-free detection of proteins in ternary mixtures using surface-enhanced Raman scattering and protein melting profiles

    Keskin, Sercan; Efeoğlu, Esen; Keçeci, Kaan; Çulha, Mustafa


    The multiplex detection of biologically important molecules such as proteins in complex mixtures has critical importance not only in disease diagnosis but also in other fields such as proteomics and biotechnology. Surface-enhanced Raman scattering (SERS) is a powerful technique for multiplex identification of molecular components in a mixture. We combined the multiplexing power of SERS and heat denaturation of proteins to identify proteins in ternary protein mixtures. The heat denaturation profiles of four model blood proteins, transferrin, human serum albumin, fibrinogen, and hemoglobin, were studied with SERS. Then, two ternary mixtures of these four proteins were used to test the feasibility of the approach. It was demonstrated that unique denaturation profiles of each protein could be used for their identification in the mixture.

  8. Abnormal Raman spectral phenomenon of silicon nanowires


    The Raman spectra of two one-dimensional silicon nanowire samples with different excitation wavelengths were measured and an abnormal phenomenon was discovered that the Raman spectral features change with the wavelengths of excitation. Closer analysis of the crystalline structure of samples and the changes in Raman spectral features showed that the abnormal behavior is the result of resonance Raman scattering selection effect.

  9. Transient resonance Raman spectroscopy and density functional theory investigation of iso-CHBr 2Cl and iso-CCl 3Br photoproducts produced following ultraviolet excitation of CHBr 2Cl and CCl 3Br

    Zheng, X; Lee, CW; Li, YL; Fang, WH; Phillips, DL


    Two polyhalomethanes that contain bromine and chlorine atoms (CHBr 2Cl and CCl 2Br) were studied. Transient resonance Raman spectra were obtained for the photoproducts produced after ultraviolet excitation of CHBr 2Cl and CCl 3Br in room temperature solutions and density functional theory calculations for species proposed to be products of the photodissociation reactions in the solution phase. It was found that the iso-CHBrCl-Br and iso-CHClBr-Br species are formed following ultraviolet excit...

  10. Inner-shell excitation spectroscopy of fused-ring aromatic molecules by electron energy loss and X-ray Raman techniques

    Gordon, M.L.; Tulumello, D.; Cooper, G.; Hitchcock, A.P.; Glatzel, P.; Mullins, O.C.; Cramer, S.P.; Bergmann, U. [McMaster University, Hamilton, ON (Canada). Dept. of Chemistry


    Oscillator strengths for C 1s excitation spectra of gaseous benzene, naphthalene, anthracene, phenanthracene, triphenylene, pyrene, and 1,2-benzanthracene have been derived from inner-shell electron energy loss spectroscopy recorded under scattering conditions where electric dipole transitions dominate (2.5 keV residual energy, theta {>=} 2{sup o} corresponding to a product of momentum transfer and C 1s orbital size (qr) of 0.08). These spectra are interpreted with the aid of ab initio calculations on selected species. They are compared to the C 1s spectra of solid samples of benzene, naphththalene, anthracene, triphenylene, and 1,2-benzanthracene, recorded with inelastic X-ray Raman scattering in the dipole limit (qr < 0.5). When differences in resolution are taken into account, good agreement is found between the inelastic electron scattering spectra of the gases and the inelastic photon scattering spectra of the corresponding solid. Small differences are attributed to quenching of transitions to Rydberg states in the solids. Characteristic differences related to the degree of symmetry or spatial arrangement of the fused ring aromatic hydrocarbons (e.g., linear versus bent structures) indicate that C 1s X-ray Raman spectroscopy should be useful for characterizing aromatics in bulk samples that are opaque to soft X-rays, such as coals and heavy hydrocarbon deposits.

  11. Role of ribose in the initial excited state structural dynamics of thymidine in water solution: a resonance Raman and density functional theory investigation.

    Zhu, Xin-Ming; Wang, Hui-gang; Zheng, Xuming; Phillips, David Lee


    Resonance Raman spectra were obtained for thymidine and thymine with excitation wavelengths in resonance with the approximately 260 nm band absorption spectrum. The spectra indicate that the Franck-Condon (FC) region photodissociation dynamics of thymidine have multidimensional character with motion predominantly along the nominal C5=C6 stretch + C6-H bend nu17 (delta = 0.75, lambda = 468 cm(-1)), the nominal thymine ring stretch + C6-H bend + N1-C1, stretch nu29 (delta = 0.73, lambda = 363 cm(-1)), the nominal thymine ring stretch + C5-CH3/ N1-C1, stretch nu37 (delta = 0.69, lambda = 292 cm(-1)), and accompanied by the moderate and minor changes in the nu40, nu20 and nu23, nu55, nu60, nu61, nu63 modes. A preliminary resonance Raman intensity analysis was done, and these results for thymidine and thymine were compared to each other. The roles of ribose in the FC structure dynamics of thymidine were explored and the results were used to correlate to its lifetime constants tau1 and tau2 for two nonradiative decay channels. Spi/Sn conical intersection versus a distorted structure of Spi,min in the FC region was briefly discussed.

  12. Depth profiling of APTES self-assembled monolayers using surface-enhanced confocal Raman microspectroscopy

    Sun, Yingying; Yanagisawa, Masahiro; Kunimoto, Masahiro; Nakamura, Masatoshi; Homma, Takayuki


    The internal structure of self-assembled monolayers (SAMs) such as 3-aminopropyltriethoxysilane (APTES) fabricated on a glass substrate is difficult to characterize and analyze at nanometer level. In this study, we employed surface-enhanced Raman spectroscopy (SERS) to study the internal molecular structure of APTES SAMs. The sample APTES SAMs were deposited with Ag nanoparticles to enhance the Raman signal and to obtain subtler structure information, which were supported by density functional theory calculations. In addition, in order to carry out high-resolution analysis, especially for vertical direction, a fine piezo electric positioner was used to control the depth scanning with a step of 0.1 nm. We measured and distinguished the vertical Raman intensity variations of specific groups in APTES, such as Ag/NH2, CH2, and Sisbnd O, with high resolution. The interfacial bond at the two interfaces of Ag-APTES and APTES-SiO2 was identified. Moreover, APTES molecule orientation was demonstrated to be inhomogeneous from frequency shift.

  13. Ultraviolet resonant Raman spectroscopy of nucleic acid components.

    Blazej, D C; Peticolas, W L


    The first resonant Raman excitation profile using UV as well as visible radiation is presented. Measurements of the intensity of the Raman spectrum of adenosine 5'-monophosphate as a function of the frequency of the incident laser light are presented in the range from 20 to 38 kK (1000 cm-1). The scattering intensity per molecule increases by about 10(5) as the laser is tuned from low to high frequencies. The Raman excitation profile has been calculated by using a simple form of the vibronic theory of Raman scattering. The theoretical curves are found to adequately fit the data using only the frequencies of the excited electronic states of AMP and their corresponding vibronic linewidths as adjustable parameters. The Raman bands at 1484 cm-1 and 1583 cm-1 appear to obtain virtually all of their intensity from a weak electronic transition at 276 nm. The set of Raman bands in the range 1300 cm-1-1400 cm-1 appear to derive at least part of their intensity from an electronic band whose 0-0 transition is in the 269-259 nm region although the possibility of some intensity arising from the vibronic mixing between these two electronic states cannot as yet be ruled out.

  14. Depth profiling of strain and carrier concentration by cleaved surface scanning of GaN Gunn-diode: confocal Raman microscopy

    Belyaev, A. E.; Strelchuk, V. V.; Nikolenko, A. S.; Romanyuk, A. S.; Mazur, Yu I.; Ware, M. E.; DeCuir, E. A., Jr.; Salamo, G. J.


    Confocal micro-Raman spectroscopy was applied to study the cleaved surface of vertical GaN Gunn-diode structure grown by molecular-beam epitaxy. The analysis of lateral scanning along the cleaved edge reveals the depth profile of elastic strain, quality of the crystal structure, and the concentration of charge carriers. Results are compared with that of axial confocal Raman depth profiling normal to the structure's surface. Decrease of compressive strain near the cleaved edge in the direction from the substrate to the structure's surface and in the growth plane towards the cleaved edge is shown. The decrease in charge carrier concentration in the undoped n0-GaN channel region in comparison with the n+-GaN contact region is identified. Peculiarities of the resulting spatial profiles of free charge carriers and their correlation with the initial doping profile are discussed.

  15. Excitation mechanism of A1g mode and origin of nonlinear temperature dependence of Raman shift of CVD-grown mono- and few-layer MoS2 films.

    Yang, Tianqi; Huang, Xiaoting; Zhou, Hong; Wu, Guangheng; Lai, Tianshu


    MoS2 films are grown on SiO2/Si substrates by chemical vapor deposition. The vibrational properties of optical phonons of mono-, bi- and multilayer MoS2 are studied by Raman scattering spectroscopy over temperature range from 90 to 540 K with 514.5 nm and 785 nm lasers. The Raman peaks of E2g1 and A1g modes are observed simultaneously for mono-, bi- and multilayer MoS2 with 514.5 nm laser, but only the Raman peak of E2g1 mode is seen for monolayer MoS2 as 785 nm laser is used, revealing electron-phonon exchange excitation mechanism of A1g mode for the first time. The Raman shifts of E2g1 and A1g modes present obvious nonlinear temperature dependence. A semi-quantitative model is used to fit the nonlinear temperature dependence of Raman shifts which matches well to experimental data. Meanwhile, the fitting results reveal that the nonlinear temperature dependence of Raman shifts of E2g1 mode mainly originates from three-phonon anharmonic effect, while one of A1g mode is contributed by stronger three- and weaker four-phonon anharmonic effects cooperatively but two contributions are comparable in intensity.

  16. Early time excited-state structural evolution of pyranine in methanol revealed by femtosecond stimulated Raman spectroscopy.

    Wang, Yanli; Liu, Weimin; Tang, Longteng; Oscar, Breland; Han, Fangyuan; Fang, Chong


    To understand chemical reactivity of molecules in condensed phase in real time, a structural dynamics technique capable of monitoring molecular conformational motions on their intrinsic time scales, typically on femtoseconds to picoseconds, is needed. We have studied a strong photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS, pK(a)* ≈ 0) in pure methanol and observed that excited-state proton transfer (ESPT) is absent, in sharp contrast with our previous work on HPTS in aqueous solutions wherein ESPT prevails following photoexcitation. Two transient vibrational marker bands at ~1477 (1454) and 1532 (1528) cm(-1) appear in CH3OH (CD3OD), respectively, rising within the instrument response time of ~140 fs and decaying with 390-470 (490-1400) fs and ~200 ps time constants in CH3OH (CD3OD). We attribute the mode onset to small-scale coherent proton motion along the pre-existing H-bonding chain between HPTS and methanol, and the two decay stages to the low-frequency skeletal motion-modulated Franck-Condon relaxation within ~1 ps and subsequent rotational diffusion of H-bonding partners in solution before fluorescence. The early time kinetic isotope effect (KIE) of ~3 upon methanol deuteration argues active proton motions particularly within the first few picoseconds when coherent skeletal motions are underdamped. Pronounced quantum beats are observed for high-frequency modes consisting of strong phenolic COH rocking (1532 cm(-1)) or H-out-of-plane wagging motions (952 cm(-1)) due to anharmonic coupling to coherent low-frequency modes impulsively excited at ca. 96, 120, and 168 cm(-1). The vivid illustration of atomic motions of HPTS in varying H-bonding geometry with neighboring methanol molecules unravels the multidimensional energy relaxation pathways immediately following photoexcitation, and provides compelling evidence that, in lieu of ESPT, the photoacidity of HPTS promptly activates characteristic low-frequency skeletal motions to search phase

  17. The Temporal Profiles of Changes in Nerve Excitability Indices in Familial Amyloid Polyneuropathy.

    Hsing-Jung Lai

    Full Text Available Familial amyloid polyneuropathy (FAP caused by a mutation in transthyretin (TTR gene is an autosomal dominant inherited disorder. The aim of this study is to explore the pathophysiological mechanism of FAP. We prospectively recruited 12 pauci-symptomatic carriers, 18 patients who harbor a TTR mutation, p.A97S, and two-age matched control groups. Data of nerve excitability test (NET from ulnar motor and sensory axons were collected.NET study of ulnar motor axons of patients shows increased threshold and rheobase, reduced threshold elevation during hyperpolarizing threshold electrotonus (TE, and increased refractoriness. In sensory nerve studies, there are increased threshold reduction in depolarizing TE, lower slope of recovery and delayed time to overshoot after hyperpolarizing TE, increased refractoriness and superexcitability in recovery cycle. NET profiles obtained from the ulnar nerve of carriers show the increase of threshold and rheobase, whereas no significant threshold changes in hyperpolarizing TE and superexcitability. The regression models demonstrate that the increase of refractoriness and prolonged relative refractory period are correlated to the disease progression from carriers to patients. The marked increase of refractoriness at short-width stimulus suggests a defect in sodium current which may represent an early, pre-symptomatic pathophysiological change in TTR-FAP. Focal disruption of basal lamina and myelin may further increase the internodal capacity, manifested by the lower slope of recovery and delayed time to overshoot after hyperpolarization TE as well as the increase of superexcitability. NET could therefore make a pragmatic tool for monitoring disease progress from the very early stage of TTR-FAP.

  18. Distinct structures and environments for the three hemes of the cytochrome bc1 complex from Rhodospirillum rubrum. A resonance Raman study using B-band excitations.

    Le Moigne, C; Schoepp, B; Othman, S; Verméglio, A; Desbois, A


    The B-band excited resonance Raman (RR) spectra (100-1700 cm-1) of the bacterial cytochrome bc1 complex purified from Rhodospirillum rubrum are reported. Four redox states, i.e., the persulfate-oxidized, "as prepared", and ascorbate- and dithionite-reduced states of the complex, were investigated with the laser excitations at 406.7, 413.1, and 441.6 nm. Following the different absorption properties of the b- and c-type hemes and the different resonance enhancements of the vibrational modes of oxidized and reduced hemes, RR contributions from the b- and c-type hemes were characterized. For the nu2, nu10, and nu8 porphyrin vibrational modes, individual contributions of hemes c1, bH, and bL were determined. The data show that the macrocycle conformation of the three hemes of the cytochrome bc1 complex is different. In particular, the frequencies assigned to ferrous heme bL (1580, 1610, and 352 cm-1, respectively) reveal that its porphyrin is more strongly distorted than that of ferrous heme bH (1584, 1614, and 344 cm-1, respectively). The frequencies of the nu11 modes (1543, 1536, and 1526 cm-1 for ferrous heme c1, heme bH, and heme bL, respectively) confirm that the axial histidylimidazole ligands of heme bL have a marked anionic character. Strong differences in the peripheral interactions of the three hemes with the proteins were also detected through the frequency differences of the nu5, nu13, nu14, and nu42 modes. Considering that hemes bH and bL are inserted into a four-helice bundle, the RR data are interpreted in the frame of a strong protein constraint on heme bL.

  19. Atmospheric temperature profiling in the presence of clouds with a pure rotational Raman lidar by use of an interference-filter-based polychromator.

    Behrendt, A; Reichardt, J


    A lidar polychromator design for the measurement of atmospheric temperature profiles in the presence of clouds with the rotational Raman method is presented. The design utilizes multicavity interference filters mounted sequentially at small angles of incidence. Characteristics of this design are high signal efficiency and adjustable center wavelengths of the filters combined with a stable and relatively simple experimental setup. High suppression of the elastic backscatter signal in the rotational Raman detection channels allows temperature measurements independent of the presence of thin clouds or aerosol layers; no influence of particle scattering on the lidar temperature profile was observed in clouds with a backscatter ratio of at least 45. The minimum integration time needed for temperature profiling with a statistical temperature error of +/-1 K at, e.g., 20-km height and 960-m height resolution is 1.5 h.

  20. Continuous vertical aerosol profiling with a multi-wavelength Raman polarization lidar over the Pearl River Delta, China

    B. Heese


    Full Text Available A dataset of particle optical properties of the highly polluted atmosphere over the Pearl River Delta (PRD, Guangzhou, China, is presented in this paper. The data were derived from the measurements of a multi-wavelength Raman and depolarization lidar PollyXT and a co-located AERONET sun photometer. The measurement campaign was conducted from November 2011 to mid-June 2012. These are the first Raman lidar measurements in the PRD that lasted for several months. A mean value of aerosol optical depth (AOD of 0.54 ± 0.33 was observed by the sun photometer at 500 nm in the polluted atmosphere over this megacity for the whole measurement period. The lidar profiles frequently show lofted aerosol layers, which reach altitudes of up to 2 to 3 km and, especially during the spring season, up to 5 km. These layers contain between 12 and 56 % of the total AOD, with the highest values in spring. The aerosol types in these lofted layers are classified by their optical properties. The observed lidar ratio values range from 30 to 80 sr with a mean value of 48.0 ± 10.7 sr at 532 nm. The linear particle depolarization ratio at 532 nm lies mostly below 5 %, with a mean value of 3.6 ± 3.7 %. The majority of the Ångström exponents lie between 0.5 and 1.5, indicating a mixture of fine- and coarse-mode aerosols. These results reveal that mostly urban pollution particles mixed with particles produced from biomass and industrial burning are present in the atmosphere above the Pearl River Delta. Trajectory analyses show that these pollution mixtures arise mainly from local and regional sources.

  1. Continuous vertical aerosol profiling with a multi-wavelength Raman polarization lidar over the Pearl River Delta, China

    Heese, Birgit; Baars, Holger; Bohlmann, Stephanie; Althausen, Dietrich; Deng, Ruru


    A dataset of particle optical properties of the highly polluted atmosphere over the Pearl River Delta (PRD), Guangzhou, China, is presented in this paper. The data were derived from the measurements of a multi-wavelength Raman and depolarization lidar PollyXT and a co-located AERONET sun photometer. The measurement campaign was conducted from November 2011 to mid-June 2012. These are the first Raman lidar measurements in the PRD that lasted for several months. A mean value of aerosol optical depth (AOD) of 0.54 ± 0.33 was observed by the sun photometer at 500 nm in the polluted atmosphere over this megacity for the whole measurement period. The lidar profiles frequently show lofted aerosol layers, which reach altitudes of up to 2 to 3 km and, especially during the spring season, up to 5 km. These layers contain between 12 and 56 % of the total AOD, with the highest values in spring. The aerosol types in these lofted layers are classified by their optical properties. The observed lidar ratio values range from 30 to 80 sr with a mean value of 48.0 ± 10.7 sr at 532 nm. The linear particle depolarization ratio at 532 nm lies mostly below 5 %, with a mean value of 3.6 ± 3.7 %. The majority of the Ångström exponents lie between 0.5 and 1.5, indicating a mixture of fine- and coarse-mode aerosols. These results reveal that mostly urban pollution particles mixed with particles produced from biomass and industrial burning are present in the atmosphere above the Pearl River Delta. Trajectory analyses show that these pollution mixtures arise mainly from local and regional sources.

  2. Noninvasive detection of concealed explosives: depth profiling through opaque plastics by time-resolved Raman spectroscopy.

    Petterson, Ingeborg E Iping; López-López, María; García-Ruiz, Carmen; Gooijer, Cees; Buijs, Joost B; Ariese, Freek


    The detection of explosives concealed behind opaque, diffusely scattering materials is a challenge that requires noninvasive analytical techniques for identification without having to manipulate the package. In this context, this study focuses on the application of time-resolved Raman spectroscopy (TRRS) with a picosecond pulsed laser and an intensified charge-coupled device (ICCD) detector for the noninvasive identification of explosive materials through several millimeters of opaque polymers or plastic packaging materials. By means of a short (250 ps) gate which can be delayed several hundred picoseconds after the laser pulse, the ICCD detector allows for the temporal discrimination between photons from the surface of a sample and those from deeper layers. TRRS was applied for the detection of the two main isomers of dinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene as well as for various other components of explosive mixtures, including akardite II, diphenylamine, and ethyl centralite. Spectra were obtained through different diffuse scattering white polymer materials: polytetrafluoroethylene (PTFE), polyoxymethylene (POM), and polyethylene (PE). Common packaging materials of various thicknesses were also selected, including polystyrene (PS) and polyvinyl chloride (PVC). With the demonstration of the ability to detect concealed, explosives-related compounds through an opaque first layer, this study may have important applications in the security and forensic fields.

  3. Measurement of vibrationally excited N2(v) in an atmospheric-pressure air pulsed corona discharge using coherent anti-Stokes Raman scattering

    Teramoto, Yoshiyuki; Ono, Ryo


    Vibrationally excited N2(v = 1, 2) in an atmospheric-pressure air pulsed corona discharge was measured using coherent anti-Stokes Raman scattering (CARS). In a dry air discharge, the vibrational temperature determined from the ratio N2(v = 2)/N2(v = 0), Tv2, was approximately 500 K higher than that determined from N2(v = 1)/N2(v = 0), Tv1, immediately after the discharge pulse. Both vibrational temperatures reached equilibrium within 100 μs after the discharge pulse by the vibration-to-vibration (V-V) process of N2-N2. The translational temperature was also measured using CARS. The rise in the translational temperature due to vibration-to-translation (V-T) energy transfer was not observed for a postdischarge time of 5 μs-1 ms in the dry-air discharge. However, when the air was humidified, a significant V-T energy transfer was observed. It was due to an extremely rapid V-T process of H2O-H2O following the V-V process of N2-H2O. Measurements showed that the humidification of the ambient air accelerated the decrease in the N2 vibrational temperature and increased the translational temperature. N2(v) was generated mostly in the secondary streamer, not in the primary one, according to estimation from the measured N2(v) density.

  4. Potential of polarization/Raman lidar to separate fine dust, coarse dust, maritime, and anthropogenic aerosol profiles

    Mamouri, Rodanthi-Elisavet; Ansmann, Albert


    We applied the recently introduced polarization lidar-photometer networking (POLIPHON) technique for the first time to triple-wavelength polarization lidar measurements at 355, 532, and 1064 nm. The lidar observations were performed at Barbados during the Saharan Aerosol Long-Range Transport and Aerosol-Cloud-Interaction Experiment (SALTRACE) in the summer of 2014. The POLIPHON method comprises the traditional lidar technique to separate mineral dust and non-dust backscatter contributions and the new, extended approach to separate even the fine and coarse dust backscatter fractions. We show that the traditional and the advanced method are compatible and lead to a consistent set of dust and non-dust profiles at simplified, less complex aerosol layering and mixing conditions as is the case over the remote tropical Atlantic. To derive dust mass concentration profiles from the lidar observations, trustworthy extinction-to-volume conversion factors for fine, coarse, and total dust are needed and obtained from an updated, extended Aerosol Robotic Network sun photometer data analysis of the correlation between the fine, coarse and total dust volume concentration and the respective fine, coarse, and total dust extinction coefficient for all three laser wavelengths. Conversion factors (total volume to extinction) for pure marine aerosol conditions and continental anthropogenic aerosol situations are presented in addition. As a new feature of the POLIPHON data analysis, the Raman lidar method for particle extinction profiling is used to identify the aerosol type (marine or anthropogenic) of the non-dust aerosol fraction. The full POLIPHON methodology was successfully applied to a SALTRACE case and the results are discussed. We conclude that the 532 nm polarization lidar technique has many advantages in comparison to 355 and 1064 nm polarization lidar approaches and leads to the most robust and accurate POLIPHON products.

  5. Dynamical theory of spectroscopy with femtosecond pulse excitation(Ⅲ)——Transient rate equation in Liouville space

    陆靖; 范康年


    A dynamical theory of spectroscopy with femtosecond pulse excitation is developed in Liouville space. By using density matrix formalism, the transient rate equation that can be reduced to the classical KHD expression in CW case is obtained. This theory is applied to the Raman excitation profile of IBr and the results are in agreement with the experiments.

  6. Age related depth profiles of human Stratum Corneum barrier-related molecular parameters by confocal Raman microscopy in vivo.

    Choe, ChunSik; Schleusener, Johannes; Lademann, Jürgen; Darvin, Maxim E


    In this study, stratum corneum (SC) depth profiles of hydrogen bound water molecule types, intercellular lipid (ICL) ordering, concentration of natural moisturizing factor (NMF) and keratin folding/unfolding properties are investigated in vivo for older (mean 50 years old) and younger (mean 29 years old) human skin using confocal Raman microscopy. The results show that the SC of the older group is modestly thicker (p <0.1), has more hydrogen bound water molecules at the depth 20-30% of the SC thickness (p <0.05), has a higher ordered organization of ICL (p <0.1) and higher concentration of NMF (p <0.05) at the depth 20-40% of the SC thickness compared to the younger group. This study also reveals, that the hydrogen bonding state of water highly correlates with NMF and the lateral structure of ICL but not with keratin's folding/unfolding properties. The presented results let suggest, that the decreased trans-epidermal water loss (TEWL) with increasing age cannot be sufficiently explained by only the increased SC thickness, but additionally by the increase of ICL ordering, higher NMF concentration and thus larger amount of hydrogen bound water molecules at the depth 20-40% of the SC thickness. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Confocal Raman Microscopy

    Dieing, Thomas; Toporski, Jan


    Confocal Raman Microscopy is a relatively new technique that allows chemical imaging without specific sample preparation. By integrating a sensitive Raman spectrometer within a state-of-the-art microscope, Raman microscopy with a spatial resolution down to 200nm laterally and 500nm vertically can be achieved using visible light excitation. Recent developments in detector and computer technology as well as optimized instrument design have reduced integration times of Raman spectra by orders of magnitude, so that complete images consisting of tens of thousands of Raman spectra can be acquired in seconds or minutes rather than hours, which used to be standard just one decade ago. The purpose of this book is to provide the reader a comprehensive overview of the rapidly developing field of Confocal Raman Microscopy and its applications.

  8. A Profile Analysis of Raman-scattered O VI Bands at 6825 Å and 7082 Å in Sanduleak’s Star

    Heo, Jeong-Eun; Angeloni, Rodolfo; Di Mille, Francesco; Palma, Tali; Lee, Hee-Won


    We present a detailed modeling of the two broad bands observed at 6825 and 7082 Å in Sanduleak’s star, a controversial object in the Large Magellanic Cloud. These bands are known to originate from Raman scattering of O vi λ λ 1032 and 1038 photons with atomic hydrogen and are only observed in bona fide symbiotic stars. Our high-resolution spectrum obtained with the Magellan Inamori Kyocera Echelle spectrograph at the Magellan-Clay Telescope reveals, quite surprisingly, that the profiles of the two bands look very different: while the Raman 6825 Å band shows a single broad profile with a redward extended bump, the Raman 7082 Å band exhibits a distinct triple-peak profile. Our model suggests that the O vi emission nebula can be decomposed into a red, blue, and central emission region from an accretion disk, a bipolar outflow, and a further compact, optically thick region. We also perform Monte Carlo simulations with the aim of fitting the observed flux ratio F(6825)/F(7082) ˜ 4.5, which indicates that the neutral region in Sanduleak’s star is characterized by the column density N H i ˜ 1 × 1023 cm-2.

  9. Dynamics of the time-resolved stimulated Raman scattering spectrum in presence of transient vibronic inversion of population on the example of optically excited trans-β-apo-8{sup ′}-carotenal

    Kardaś, T. M., E-mail:; Ratajska-Gadomska, B.; Gadomski, W. [Department of Chemistry, University of Warsaw, Zwirki Wigury 101, 02-089 Warsaw (Poland); Lapini, A.; Righini, R.; Di Donato, M. [European Laboratory for Non-linear Spectroscopy (LENS), Universita di Firenze, Via Nello Carrara 1, I-50019 Sesto Fiorentino (Italy); Department of Chemistry, University of Florence, via della Lastruccia 3-13, 50019 Sesto Fiorentino (Italy); INO (Istituto Nazionale di Ottica), Largo Fermi 6, 50125 Firenze (Italy); Ragnoni, E. [European Laboratory for Non-linear Spectroscopy (LENS), Universita di Firenze, Via Nello Carrara 1, I-50019 Sesto Fiorentino (Italy); INO (Istituto Nazionale di Ottica), Largo Fermi 6, 50125 Firenze (Italy); Foggi, P. [European Laboratory for Non-linear Spectroscopy (LENS), Universita di Firenze, Via Nello Carrara 1, I-50019 Sesto Fiorentino (Italy); INO (Istituto Nazionale di Ottica), Largo Fermi 6, 50125 Firenze (Italy); Department of Chemistry, University of Perugia, via Elce di Sotto 8, 06123 Perugia (Italy)


    We have studied the effect of transient vibrational inversion of population in trans-β-apo-8{sup ′}-carotenal on the time-resolved femtosecond stimulated Raman scattering (TR-FSRS) signal. The experimental data are interpreted by applying a quantum mechanical approach, using the formalism of projection operators for constructing the theoretical model of TR-FSRS. Within this theoretical frame we explain the presence of transient Raman losses on the Stokes side of the TR-FSRS spectrum as the effect of vibrational inversion of population. In view of the obtained experimental and theoretical results, we conclude that the excited S{sub 2} electronic level of trans-β-apo-8{sup ′}-carotenal relaxes towards the S{sub 0} ground state through a set of four vibrational sublevels of S{sub 1} state.

  10. Determination of in-depth damaged profile by Raman line scan in a pre-cut He2+ irradiated UO2

    Guimbretière, G.; Desgranges, L.; Canizarès, A.; Carlot, G.; Caraballo, R.; Jégou, C.; Duval, F.; Raimboux, N.; Ammar, M. R.; Simon, P.


    Raman measurements were carried out to probe the spectroscopic signatures of the ion beam irradiation-induced damage and their in-depth profiles on a Uranium dioxide sample previously cut and polished prior to performing a 25 MeV He2+ cyclotron beam irradiation. Raman spectra clearly show the creation of three defects bands (U1 ≈ 530, U2 ≈ 575, and U3 ≈ 635 cm-1) resulting from the ion irradiation and also some changes in the T2g peak of UO2. Their in-depth distribution inside the sample exhibits a clear increase of the damage from the surface up to the position of the implanted He.

  11. Qualitative study of ethanol content in tequilas by Raman spectroscopy and principal component analysis

    Frausto-Reyes, C.; Medina-Gutiérrez, C.; Sato-Berrú, R.; Sahagún, L. R.


    Using Raman spectroscopy, with an excitation radiation source of 514.5 nm, and principal component analysis (PCA) was elaborated a method to study qualitatively the ethanol content in tequila samples. This method is based in the OH region profile (water) of the Raman spectra. Also, this method, using the fluorescence background of the Raman spectra, can be used to distinguish silver tequila from aged tequilas. The first three PCs of the Raman spectra, that provide the 99% of the total variance of the data set, were used for the samples classification. The PCA1 and PCA2 are related with the water (or ethanol) content of the sample, whereas the PCA3 is related with the fluorescence background of the Raman spectra.

  12. Narrow-band, narrow-field-of-view Raman lidar with combined day and night capability for tropospheric water-vapor profile measurements.

    Bisson, S E; Goldsmith, J E; Mitchell, M G


    We describe a high-performance Raman lidar system with combined day and night capability for tropospheric water-vapor profile measurements. The system incorporates high-performance UV interference filters and a narrow-band, dual-field-of-view receiver for rejection of background sunlight. Daytime performance has been demonstrated up to 5 km with 150-m vertical and 5-min temporal averaging. The nighttime performance is significantly better with measurements routinely extending from 10 to 12 km with 75-m range resolution and a 5-min temporal average. We describe design issues for daytime operation and a novel daytime calibration technique.

  13. Effect Of The Focusing Magnetostatic Field Profile On The Diffraction Radiation Oscillator Excitation

    E.M. Khutoryan


    Full Text Available Effect of the focusing magnetostatic field (FMF profile on the output characteristics of diffraction radiation oscillator (DRO is studied experimentally. The laboratory prototype of the mm range DRO produced in IRE NAS of Ukraine was used in the research. Peculiarities of the output power, oscillation frequency, starting current and other DRO characteristics for the cases of the decreasing, sagging and increasing magnetostatic field along the direction of the electron flow motion were determined. Prospects for the use of the increasing FMF in DRO are shown.

  14. Vertical excitation profile in diffusion injected multi-quantum well light emitting diode structure

    Riuttanen, L.; Kivisaari, P.; Svensk, O.; Vasara, T.; Myllys, P.; Oksanen, J.; Suihkonen, S.


    Due to their potential to improve the performance of light-emitting diodes (LEDs), novel device structures based on nanowires, surface plasmons, and large-area high-power devices have received increasing amount of interest. These structures are almost exclusively based on the double hetero junction (DHJ) structure, that has remained essentially unchanged for decades. In this work we study a III-nitride diffusion injected light-emitting diode (DILED), in which the active region is located outside the pn-junction and the excitation of the active region is based on bipolar diffusion of charge carriers. This unorthodox approach removes the need of placing the active region in the conventional current path and thus enabling carrier injection in device structures, which would be challenging to realize with the conventional DHJ design. The structure studied in this work is has 3 indium gallium nitride / gallium nitride (InGaN/GaN) quantum wells (QWs) under a GaN pn-junction. The QWs are grown at diferent growth temperatures for obtaining distinctive luminescence peaks. This allows to obtain knowledge on the carrier diffusion in the structure. When the device is biased, all QWs emit light indicating a significant diffusion current into the QW stack.

  15. Raman spectroscopy an intensity approach

    Guozhen, Wu


    This book summarizes the highlights of our work on the bond polarizability approach to the intensity analysis. The topics covered include surface enhanced Raman scattering, Raman excited virtual states and Raman optical activity (ROA). The first chapter briefly introduces the Raman effect in a succinct but clear way. Chapter 2 deals with the normal mode analysis. This is a basic tool for our work. Chapter 3 introduces our proposed algorithm for the Raman intensity analysis. Chapter 4 heavily introduces the physical picture of Raman virtual states. Chapter 5 offers details so that the readers can have a comprehensive idea of Raman virtual states. Chapter 6 demonstrates how this bond polarizability algorithm is extended to ROA intensity analysis. Chapters 7 and 8 offer details on ROA, showing many findings on ROA mechanism that were not known or neglected before. Chapter 9 introduces our proposed classical treatment on ROA which, as combined with the results from the bond polarizability analysis, leads to a com...

  16. Raman spectra of semiconductor nanoparticles: Disorder-activated phonons

    Ingale, Alka; Rustagi, K. C.


    We present Raman spectra of four semiconductor doped glasses and a single crystal of CdS0.55Se0.45 in the range 30-800 cm-1 in the backscattering geometry. This includes the first-order Raman scattering from the disorder-activated zone-edge phonons and the LO phonons. TO phonon modes are not observed, as in bulk CdS, for the excitation well above the lowest gap. We show that the asymmetric line profile of the LO phonon structure can be understood as a composite of two phonon modes: the zone center and the zone edge phonons. Disorder-activated modes in the (30-130)-cm-1 range and the higher-order Raman spectra are also observed and found to be consistent with this assignment.

  17. Time dependent density functional theory investigation of the resonance Raman properties of the julolidinemalononitrile push-pull chromophore in various solvents.

    Guthmuller, Julien; Champagne, Benoît


    The absorption and resonance Raman spectra have been investigated for the first excited state of the julolidinemalononitrile push-pull chromophore in cyclohexane, dichloromethane, and acetonitrile by means of time dependent density functional theory calculations. The effect of nonlocal exchange has been considered by using three different hybrid exchange-correlation functionals containing 20%, 35%, and 50% of exact Hartree-Fock exchange. The interactions with the solvent have been described by the polarizable continuum model. The short-time approximation expression has been used to evaluate the resonance Raman intensities, while the vibronic theory of resonance Raman spectroscopy has been employed to determine both the intensities and the excitation profiles. It is shown that a consistent description of the vibronic structure of the excited state and resonance Raman spectra can be obtained provided that an adequate amount, close to 35%, of exact exchange is included in the exchange-correlation functional. The effect of increasing the polarity of the solvent is well represented by the polarizable continuum model, both for the absorption spectra and resonance Raman intensities. In particular, these simulations can reproduce the observed variations of the 1560 cm(-1) band intensity and attribute them to elongations of a CC double bond upon electronic excitation. Moreover, the short-time approximation has been found sufficient to reproduce most of the results of the more evolved vibronic theory of resonance Raman spectroscopy, which includes summations over vibrational excited states, for both the spectral signatures and their solvent dependencies.

  18. Evaluation of drug delivery profiles in geometric three-layered tablets with various mechanical properties, in vitro-in vivo drug release, and Raman imaging.

    Choi, Du Hyung; Kim, Ki Hyun; Park, Jun Sang; Jeong, Seong Hoon; Park, Kinam


    Even though various multi-layered tablets have been developed for sustained release formulations, evaluations of mechanical properties during dissolution with drug release and imaging in the tablets have been limited. A novel geometric system consisting of an inner immediate release layer and two extended release barrier layers with swellable hydrophilic polymers was suggested as a once-a-day formulation. To evaluate drug release mechanisms with geometric properties, various mechanical characteristics during swelling were investigated to comprehend the relationship among in vitro drug release, human pharmacokinetics, and geometric characteristics. Imaging of drug movement was also studied in real-time using Raman spectroscopy. Drug delivery in the tablets might be divided into three processes through the geometric properties. When exposed to aqueous environments, the drug in the mid-layer was released until wrapped by the swollen barrier layers. Then, the drug in the mid-layer was mainly delivered to the barrier layers and a small amount of the drug was delivered to the contact region of the swollen barrier layers. Finally, the delivered drug to the barrier layers was consistently released out in response to the characteristics of the polymer of the barrier layers. Using Raman spectroscopy, these processes were confirmed in real-time analysis. Moreover, in vitro drug release profiles and human pharmacokinetics showed consistent results suggesting that drug release might be dependent on the various geometric properties and be modified consistently during the formulation development. © 2013.

  19. Protein expression guided chemical profiling of living cells by the simultaneous observation of Raman scattering and anti-Stokes fluorescence emission

    Chiu, Liang-da; Ichimura, Taro; Sekiya, Takumasa; Machiyama, Hiroaki; Watanabe, Tomonobu; Fujita, Hideaki; Ozawa, Takeaki; Fujita, Katsumasa


    Our current understanding of molecular biology provides a clear picture of how the genome, transcriptome and proteome regulate each other, but how the chemical environment of the cell plays a role in cellular regulation remains much to be studied. Here we show an imaging method using hybrid fluorescence-Raman microscopy that measures the chemical micro-environment associated with protein expression patterns in a living cell. Simultaneous detection of fluorescence and Raman signals, realised by spectrally separating the two modes through the single photon anti-Stokes fluorescence emission of fluorescent proteins, enables the accurate correlation of the chemical fingerprint of a specimen to its physiological state. Subsequent experiments revealed the slight chemical differences that enabled the chemical profiling of mouse embryonic stem cells with and without Oct4 expression. Furthermore, using the fluorescent probe as localisation guide, we successfully analysed the detailed chemical content of cell nucleus and Golgi body. The technique can be further applied to a wide range of biomedical studies for the better understanding of chemical events during biological processes. PMID:28272392

  20. Study of vibrational and magnetic excitations in Ni sub c Mg sub 1 sub - sub c O solid solutions by Raman spectroscopy

    Cazzanelli, E; Mariotto, G; Mironova-Ulmane, N


    The Raman scattering by phonons and magnons was studied for the first time in the polycrystalline solid solutions Ni sub c Mg sub 1 sub - sub c O. The experimental Raman spectrum for c = 0.9 is similar to that of NiO and consists of six well resolved bands, whose origins are the disorder-induced one-phonon scattering (bands at 400 and 500 cm sup - sup 1), two-phonon scattering (bands at 750, 900, and 1100 cm sup - sup 1), and two-magnon scattering (the broad band at approx 1400 cm sup - sup 1). We found that the dependence of the two-magnon band in solid solutions on the composition and temperature is consistent with their magnetic phase diagram. We also observed that the relative contribution of two-phonon scattering decreases strongly upon dilution with magnesium ions and disappears completely at c < 0.5. Such behaviour is explained in terms of a disorder-induced effect, which increases the probability of the one-phonon scattering processes.

  1. Raman spectroscopy

    Raman spectroscopy has gained increased use and importance in recent years for accurate and precise detection of physical and chemical properties of food materials, due to the greater specificity and sensitivity of Raman techniques over other analytical techniques. This book chapter presents Raman s...

  2. Theory of elementary excitations in quasiperiodic structures

    Albuquerque, E. L.; Cottam, M. G.


    The aim of this work is to present a comprehensive and up-to-date review of the main physical properties (such as energy profiles, localization, scale laws, multifractal analysis, transmission spectra, transmission fingerprints, electronic structures, magnetization curves and thermodynamic properties) of the elementary excitations that can propagate in multilayered structures with constituents arranged in a quasiperiodic fashion. These excitations include plasmon-polaritons, spin waves, light waves and electrons, among others. A complex fractal or multifractal profile of the energy spectra is the common feature among these excitations. The quasiperiodic property is formed by the incommensurate arrangement of periodic unit cells and can be of the type referred to as deterministic (or controlled) disorder. The resulting excitations are characterized by the nature of their Fourier spectrum, which can be dense pure point (as for the Fibonacci sequence) or singular continuous (as for the Thue-Morse and double-period sequences). These sequences are described in terms of a series of generations that obey particular recursion relations, and they can be considered as intermediate systems between a periodic crystal and the random amorphous solids, thus defining a novel description of disorder. A discussion is also included of some spectroscopic techniques used to probe the excitations, emphasizing Raman and Brillouin light scattering.

  3. Raman and SEM analysis of a biocolonised hot spring travertine terrace in Svalbard, Norway

    Jorge-Villar Susana E


    Full Text Available Abstract Background A profile across 8 layers from a fossil travertine terrace from a low temperature geothermal spring located in Svalbard, Norway has been studied using both Raman spectroscopy and SEM (Scanning Electron Microscopy techniques to identify minerals and organic life signals. Results Calcite, anatase, quartz, haematite, magnetite and graphite as well as scytonemin, three different carotenoids, chlorophyll and a chlorophyll-like compound were identified as geo- and biosignatures respectively, using 785 and/or 514 nm Raman laser excitation wavelengths. No morphological biosignatures representing remnant microbial signals were detected by high-resolution imaging, although spectral analyses indicated the presence of organics. In contrast, in all layers, Raman spectra identified a series of different organic pigments indicating little to no degradation or change of the organic signatures and thus indicating the preservation of fossil biomarker compounds throughout the life time of the springs despite the lack of remnant morphological indicators. Conclusion With a view towards planetary exploration we discuss the implications of the differences in Raman band intensities observed when spectra were collected with the different laser excitations. We show that these differences, as well as the different detection capability of the 785 and 514 nm laser, could lead to ambiguous compound identification. We show that the identification of bio and geosignatures, as well as fossil organic pigments, using Raman spectroscopy is possible. These results are relevant since both lasers have been considered for miniaturized Raman spectrometers for planetary exploration.

  4. Surface-enhanced Raman scattering from AgNP-graphene-AgNP sandwiched nanostructures

    Wu, Jian; Xu, Yijun; Xu, Pengyu; Pan, Zhenghui; Chen, Sheng; Shen, Qishen; Zhan, Li; Zhang, Yuegang; Ni, Weihai


    We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials.We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials. Electronic supplementary information (ESI) available: Additional SEM images, electric field enhancement profiles, Raman scattering spectra, and structure-dependent peak ratios. See DOI: 10.1039/c5nr04500b

  5. Observation of Vibrational Relaxation Dynamics in X(sup 3)Sigma(sup -)(sub g) Oxygen Following Stimulated Raman Excitation to the v=1 Level: Implications for the RELIEF Flow Tagging Technique

    Diskin, Glenn S.; Lempert, Walter R.; Miles, Richard B.


    The vibrational relaxation of ground-state molecular oxygen (O2, X(sup 3)Sigma(sup -)(sub g)) has been observed, following stimulated Raman excitation to the first excited vibrational level (v=1). Time delayed laser-induced fluorescence probing of the ro-vibrational population distribution was used to examine the temporal relaxation behavior. In the presence of water vapor, the relaxation process is rapid, and is dominated by near-resonant vibrational energy exchange between the v=1 level of O2 and the n2 bending mode of H2O. In the absence of H2O, reequilibration proceeds via homogeneous vibrational energy transfer, in which a collision between two v=1 O2 molecules leaves one molecule in the v=2 state and the other in the v=0 state. Subsequent collisions between molecules in v=1 and v>1 result in continued transfer of population up the vibrational ladder. The implications of these results for the RELIEF flow tagging technique are discussed.

  6. Implementation of Deep Ultraviolet Raman Spectroscopy

    Liu, Chuan

    , with particular focus on obtaining high quality of the final measurements. This naturally involves themes such as spectral resolution, sensitivity, elimination of background noise, and so on. Compared to Raman spectra excited with visible light, the DUV excited Raman spectra tend to have a markedly lower spectral...... resolution. The spectral resolution is an important factor to consider when using the DUV excited Raman spectroscopy. In line with this insight is the fact that we found a way to improve the knowledge on the spectral resolution of the DUV excited spectrum. A new method was invented during the project...... (absorption, condensation) are described. We have found a way to solve the problems, and our solution, using a special designed gas gap cell to obtain measurements of extraordinary high quality, are presented. The DUV Raman spectra of gasoline were excited by three different wavelengths, 257.3, 244.0 and 229...

  7. A depth-dependent profile of the lipid conformation and lateral packing order of the stratum corneum in vivo measured using Raman microscopy.

    Choe, ChunSik; Lademann, Jürgen; Darvin, Maxim E


    The intercellular lipid structure of the stratum corneum (SC) plays a key role in skin barrier function. A depth profile of the intercellular lipid conformation and the lipid lateral packing order were measured in vivo in the human SC using confocal Raman microscopy. The depth profiles of the 2880 cm(-1)/2850 cm(-1) peak ratio intensity, which represent the C-H stretching and lateral packing order of lipids, and the 1080 cm(-1)/(1130 cm(-1) + 1060 cm(-1)) peak ratio, which represents the C-C skeleton vibration and trans-gauche conformation order of lipids, were investigated. The influence of keratin on the lipid peaks at 2850 cm(-1) and 2880 cm(-1) was excluded by the developed mathematical algorithm. The results show that the trans-conformation and lateral packing order of the intercellular lipids reach their maximum value in the SC at 20-40% of its depth and then decrease towards the stratum granulosum. These results show that at a depth of 20-40% (normally corresponding to a depth of 4-8 μm) the SC exhibits the most ordered lipids and therefore the highest skin barrier function. The lateral packing of lipids is more disordered on the surface and in the deeper parts of the SC, which may be associated with a reduced skin barrier function.

  8. An overview of the first decade of PollyNET: an emerging network of automated Raman-polarization lidars for continuous aerosol profiling

    Baars, Holger; Kanitz, Thomas; Engelmann, Ronny; Althausen, Dietrich; Heese, Birgit; Komppula, Mika; Preißler, Jana; Tesche, Matthias; Ansmann, Albert; Wandinger, Ulla; Lim, Jae-Hyun; Ahn, Joon Young; Stachlewska, Iwona S.; Amiridis, Vassilis; Marinou, Eleni; Seifert, Patric; Hofer, Julian; Skupin, Annett; Schneider, Florian; Bohlmann, Stephanie; Foth, Andreas; Bley, Sebastian; Pfüller, Anne; Giannakaki, Eleni; Lihavainen, Heikki; Viisanen, Yrjö; Hooda, Rakesh Kumar; Nepomuceno Pereira, Sérgio; Bortoli, Daniele; Wagner, Frank; Mattis, Ina; Janicka, Lucja; Markowicz, Krzysztof M.; Achtert, Peggy; Artaxo, Paulo; Pauliquevis, Theotonio; Souza, Rodrigo A. F.; Prakesh Sharma, Ved; Gideon van Zyl, Pieter; Beukes, Johan Paul; Sun, Junying; Rohwer, Erich G.; Deng, Ruru; Mamouri, Rodanthi-Elisavet; Zamorano, Felix


    A global vertically resolved aerosol data set covering more than 10 years of observations at more than 20 measurement sites distributed from 63° N to 52° S and 72° W to 124° E has been achieved within the Raman and polarization lidar network PollyNET. This network consists of portable, remote-controlled multiwavelength-polarization-Raman lidars (Polly) for automated and continuous 24/7 observations of clouds and aerosols. PollyNET is an independent, voluntary, and scientific network. All Polly lidars feature a standardized instrument design with different capabilities ranging from single wavelength to multiwavelength systems, and now apply unified calibration, quality control, and data analysis. The observations are processed in near-real time without manual intervention, and are presented online at"target="_blank"> The paper gives an overview of the observations on four continents and two research vessels obtained with eight Polly systems. The specific aerosol types at these locations (mineral dust, smoke, dust-smoke and other dusty mixtures, urban haze, and volcanic ash) are identified by their Ångström exponent, lidar ratio, and depolarization ratio. The vertical aerosol distribution at the PollyNET locations is discussed on the basis of more than 55 000 automatically retrieved 30 min particle backscatter coefficient profiles at 532 nm as this operating wavelength is available for all Polly lidar systems. A seasonal analysis of measurements at selected sites revealed typical and extraordinary aerosol conditions as well as seasonal differences. These studies show the potential of PollyNET to support the establishment of a global aerosol climatology that covers the entire troposphere.

  9. Raman and coherent anti-Stokes Raman scattering microspectroscopy for biomedical applications

    Krafft, Christoph; Dietzek, Benjamin; Schmitt, Michael; Popp, Jürgen


    A tutorial article is presented for the use of linear and nonlinear Raman microspectroscopies in biomedical diagnostics. Coherent anti-Stokes Raman scattering (CARS) is the most frequently applied nonlinear variant of Raman spectroscopy. The basic concepts of Raman and CARS are introduced first, and subsequent biomedical applications of Raman and CARS are described. Raman microspectroscopy is applied to both in-vivo and in-vitro tissue diagnostics, and the characterization and identification of individual mammalian cells. These applications benefit from the fact that Raman spectra provide specific information on the chemical composition and molecular structure in a label-free and nondestructive manner. Combining the chemical specificity of Raman spectroscopy with the spatial resolution of an optical microscope allows recording hyperspectral images with molecular contrast. We also elaborate on interfacing Raman spectroscopic tools with other technologies such as optical tweezing, microfluidics and fiber optic probes. Thereby, we aim at presenting a guide into one exciting branch of modern biophotonics research.

  10. Discrimination of urinary tract infection pathogens by means of their growth profiles using surface enhanced Raman scattering.

    Avci, Ertug; Kaya, Nur Selin; Ucankus, Gizem; Culha, Mustafa


    Urinary tract infection (UTI) is a widespread infection and affects millions of people around the globe. The gold standard for identification of microorganisms causing infection is urine culture. However, current methods require at least 24 h for the results. In clinical settings, identification and discrimination of bacteria with less time-consuming and cheaper methods are highly desired. In recent years, the power of surface-enhanced Raman scattering (SERS) for fast identification of bacteria and biomolecules has been demonstrated. In this study, we show discrimination of urinary tract infection causative pathogens within 1 h of incubation using principal component analysis (PCA) of SERS spectra of seven different UTI causative bacterial species. In addition, we showed differentiation of them at their different growth phases. We also analyzed origins of bacterial SERS spectra and demonstrated the highly dynamic structure of the bacteria cell wall during their growth. Graphical Abstract Collection of bacteria from urine sample, and their discrimination using their SERS spectra and multivariate analysis.

  11. Blood analysis by Raman spectroscopy

    Enejder, Annika M. K.; Koo, Tae-Woong; Oh, Jeankun; Hunter, Martin; Sasic, Slobodan; Feld, Michael S.; Horowitz, Gary L.


    Concentrations of multiple analytes were simultaneously measured in whole blood with clinical accuracy, without sample processing, using near-infrared Raman spectroscopy. Spectra were acquired with an instrument employing nonimaging optics, designed using Monte Carlo simulations of the influence of light-scattering-absorbing blood cells on the excitation and emission of Raman light in turbid medium. Raman spectra were collected from whole blood drawn from 31 individuals. Quantitative predictions of glucose, urea, total protein, albumin, triglycerides, hematocrit, and hemoglobin were made by means of partial least-squares (PLS) analysis with clinically relevant precision (r2 values >0.93). The similarity of the features of the PLS calibration spectra to those of the respective analyte spectra illustrates that the predictions are based on molecular information carried by the Raman light. This demonstrates the feasibility of using Raman spectroscopy for quantitative measurements of biomolecular contents in highly light-scattering and absorbing media.

  12. Confocal Raman depth-scanning spectroscopic study of phonon-plasmon modes in GaN epilayers

    Strelchuk, V. V.; Bryksa, V. P.; Avramenko, K. A.; Valakh, M. Ya.; Belyaev, A. E.; Mazur, Yu. I.; Ware, M. E.; DeCuir, E. A.; Salamo, G. J.


    Coupled longitudinal-optical (LO)-phonon-plasmon excitations were studied using confocal micro-Raman spectroscopy. The high-quality Si-doped GaN epilayers were grown in a Gunn diode structure on (0001) sapphire substrates by plasma assisted molecular beam epitaxy. Depth-profiled Raman spectra exhibit a spatial variation of both low, ω-, and high, ω+, frequency coupled phonon-plasmon modes (CPPMs) in the n-GaN layers. To describe the features of the CPPMs in the Raman spectra a self-consistent model that includes both the electro-optic and deformation-potential as well as charge-density fluctuation mechanisms as important processes for light scattering in n-GaN has been proposed. An agreement between the theoretical and experimental line shapes of the Raman spectra is obtained. From the best line-shape fitting of the CPPMs the depth profiles of the plasmon and phonon damping, plasmon frequency, free carrier concentrations, and electron mobility as well as the contributions of the electron-phonon interaction and charge density fluctuations to the Raman cross section in the GaN layers are determined. It is found that these depth profiles exhibit considerable nonuniformity and change at different laser pump-power excitations. Despite the high electron concentration in the n+-GaN layers, a strong peak of the unscreened A1(LO) phonon is also observed. A possible origin for the appearance of this mode is discussed.

  13. Raman spectroscopy as a tool for reagent free estimation

    Kumar, S


    We present results of Raman spectroscopic studies of urine to determine the suitability of near-infrared Raman spectroscopy for quantitative estimation of urinary urea. The Raman spectra were acquired from the urine samples with an inbuilt Raman spectroscopy setup that employs a 785-nm diode laser as the Raman excitation source. A multivariate algorithm based on partial least square (PLS) regression was developed to predict the concentration of urea depending on the measured sets of Raman spectra and the reference urea concentration. The computed results shows that Raman spectroscopy in amalgamation with PLS-based multivariate chemometric algorithm can detect urea in urine samples with an accuracy of >90 %.

  14. NIR FT-Raman microspectroscopy of fluid inclusions: Comparisons with VIS Raman and FT-IR microspectroscopies

    Pironon, J.; Dubessy, J. (CREGU and GDR CNRS-CREGU, Vandoeuvre-les-Nancy (France)); Sawatzki, J. (BRUKER Analytische Messtechnik Gmbh, Karlsruhe (Germany))


    The first Raman spectra of hydrocarbon inclusions using Fourier transform (FT) Raman microspectroscopy were obtained with a 1,064 nm laser excitation in the near-infrared range (NIR FT-Raman). Some inclusions reveal the typical CH vibrational bands of organic compounds, but most of the inclusions that are fluorescent during visible Raman microspectroscopy (514 nm excitation) are still fluorescent in the NIR range. These Raman spectra are presented and compared to the conventional visible (VIS) Raman and FT-IR spectra. For spectra obtained on the same nonfluorescent inclusion, the signal/background ratio is lower in NIR FT-Raman than in VIS Raman. This ratio should be improved by application of more sensitive detectors. The increase of the power density (laser power/impact laser area) could be a future improvement in the limit of thermal background excitation and pyrolysis of the oils trapped in inclusions.

  15. Resonance Raman Spectroscopy of the Excited State Structural Dynamics of 6-N,N-Dimethyladenine%6-N,N-二甲基腺嘌呤激发态结构动力学的共振拉曼光谱

    刘崇; 杜蕊; 赵彦英; 王惠钢; 郑旭明


    The A- and B-band electronic excitations and the excited state structural dynamics of 6-N, N-dimethyladenine (DMA) were studied by resonance Raman spectroscopy and density functional theory calculations.The πH→πL* transition is the main part of the A-band absorption and its calculated oscillator strength occupies 79% of the A-band absorption.n→Ryd and πH→Ryd transitions where Ryd denotes the diffuse Rydberg orbital play important roles in the B-band electronic transitions and their calculated oscillator strengths occupy about 62% of the B-band absorption.The oscillator strength for the πH→πL* transition, which dominates the A-band electronic transition only occupies about 33% of the B-band absorption.The foundamental vibrations of the purine ring deformation stretch plus the C8H/N9H bend mode ν23 and the 5 member ring deformation stretch plus the C8H bend mode ν13, and their overtones and combination bands occupy most of the A-band resonance Raman intensities.Therefore, the 1πHπL* excited state structural dynamics of DMA is mainly along the ν23 and ν13 reaction coordinates.The majority of the B-band resonance Raman intensities are dominated by the fundamental vibrations of ν10, ν29, ν21, ν26, ν40,and their overtones and combination bands.This suggests the B-band excited state structural dynamics of DMA is mostly along the purine ring deformation, the C6N10 stretch, the N9H/C8H/C2H bend and the N(CH3)2 antisymmetric stretch.The appearance of ν26 and ν12 in the A-band resonance Raman spectrum is correlated to the Franck-Condon region 1nπ*/1ππ* conical intersection.The activation of ν21 in the B-band resonance Raman spectrum is correlated to the Franck-Condon region 1ππ*/1πσ* N9H conical intersection.%采用共振拉曼光谱技术和密度泛函理论方法研究了6-N,N-二甲基腺嘌呤(DMA)的A带和B带电子激发和Franck-Condon区域结构动力学.πH→π*L跃迁是A带吸收的主体,其振子强

  16. Raman facility

    Federal Laboratory Consortium — Raman scattering is a powerful light scattering technique used to diagnose the internal structure of molecules and crystals. In a light scattering experiment, light...

  17. Water Vapor Profiles up to the UT/LS from Raman Lidar at Reunion Island (21°S, 55°E) : Technical Description, Data Processing and Comparison with Sondes

    Vérèmes, Hélène; Keckhut, Philippe; Baray, Jean-Luc; Cammas, Jean-Pierre; Dionisi, Davide; Payen, Guillaume; Duflot, Valentin; Gabarrot, Franck; Leclair De Bellevue, Jimmy; Posny, Françoise; Evan, Stéphanie; Meier, Susanne; Vömel, Holger; Dirksen, Ruud


    The Maïdo high-altitude observatory located in Reunion Island (21°S, 55°E) is equipped with an innovative lidar designed to monitor the water vapor in the whole troposphere up to the lower stratosphere with a Raman system and to monitor, simultaneously, the temperature in the stratosphere and in the mesosphere based on a Rayleigh scattering technique. Several improvements have been performed on the new instrument to optimize the water vapor mixing ratio measurements thanks to the experience of the previous system. The choice of the operational configuration of the system and the calibration methodology were realized during the campaign MALICCA-1 (MAïdo LIdar Calibration CAmpaign) which provided simultaneous measurements of water vapor and ozone in April 2013. The lidar water vapor profiles are calibrated with water vapor columns obtained from a collocated GNSS receiver. By comparing CFH and Vaisala radiosondes and satellites water vapor mixing ratio profiles with the Raman lidar profiles, the performances of the lidar are shown to be good in the troposphere. With a suitable integration time period, the ability of measuring quantities of a few ppmv in the lower stratosphere is demonstrated. This Raman lidar will provide regular measurements to international networks with high vertical resolution profiles of water vapor in order to document various studies and to insure a long-term survey of the troposphere and of the lower stratosphere.

  18. Investigation of germanium implanted with aluminum by multi-laser micro-Raman spectroscopy

    Sanson, A., E-mail: [Dipartimento di Fisica e Astronomia, Università di Padova, Via Marzolo 8, I-35131 Padova (Italy); Napolitani, E. [MATIS IMM-CNR at Dipartimento di Fisica e Astronomia, Università di Padova, Via Marzolo 8, I-35131 Padova (Italy); Impellizzeri, G. [MATIS IMM-CNR and Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia 64, I-95123 Catania (Italy); Giarola, M. [Dipartimento di Informatica, Università di Verona, Strada le Grazie 15, I-37134 Verona (Italy); De Salvador, D. [Dipartimento di Fisica e Astronomia, Università di Padova, Via Marzolo 8, I-35131 Padova (Italy); Privitera, V.; Priolo, F. [MATIS IMM-CNR and Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia 64, I-95123 Catania (Italy); Mariotto, G. [Dipartimento di Informatica, Università di Verona, Strada le Grazie 15, I-37134 Verona (Italy); Carnera, A. [Dipartimento di Fisica e Astronomia, Università di Padova, Via Marzolo 8, I-35131 Padova (Italy)


    Germanium samples, implanted with aluminum and annealed, have been investigated by micro-Raman spectroscopy using different excitation lines with the aim of gaining insights about the Al distribution at different depths beneath the sample surface and to correlate the Raman spectra with the electrical and chemical profiles, obtained by Spreading Resistance Profiling (SRP) and Secondary Ions Mass Spectrometry (SIMS) measurements, respectively. The intensity of the Al–Ge Raman peak at about 370 cm{sup −1}, due to the local vibrational mode of the substitutional Al atoms in the Ge matrix, has been directly related to the SRP behavior, while no correlation has been observed with SIMS profiles. These findings show that the electrically active content is entirely due to the substitutional Al atoms. Finally, a clear down shift is observed for the Ge–Ge Raman peak at ∼ 300 cm{sup −1}, which also seems to be directly related to the active content of Al dopant atoms. This work shows that micro-Raman spectroscopy can be a suitable tool for the study of doping profiles in Ge. - Highlights: ► Al-implanted Ge and annealed were studied by micro-Raman spectroscopy. ► Using different laser lines we have investigated the implants at different depths. ► The Al–Ge Raman peak at about 370 cm{sup −1} is directly related to the SRP behavior. ► The electrically active content is entirely due to the substitutional Al atoms. ► Carrier effects are observed on the Ge–Ge peak at ∼ 300 cm{sup −1}.

  19. Giant Raman gain in silicon nanocrystals

    Sirleto, Luigi; Ferrara, Maria Antonietta; Nikitin, Timur; Novikov, Sergei; Khriachtchev, Leonid


    ... of next generation nonlinear photonic devices. Here we report the first observation of stimulated Raman scattering in silicon nanocrystals embedded in a silica matrix under non-resonant excitation at infrared wavelengths (~1.5 μm...

  20. Raman spectroscopy and its urological applications

    Vishwanath S Hanchanale


    Conclusion: Raman spectroscopy is an exciting tool for real-time diagnosis and in vivo evaluation of living tissue. The potential applications of Raman spectroscopy may herald a new future in the management of various malignant, premalignant, and other benign conditions in urology.

  1. Sub-50 fs excited state dynamics of 6-chloroguanine upon deep ultraviolet excitation.

    Mondal, Sayan; Puranik, Mrinalini


    The photophysical properties of natural nucleobases and their respective nucleotides are ascribed to the sub-picosecond lifetime of their first singlet states in the UV-B region (260-350 nm). Electronic transitions of the ππ* type, which are stronger than those in the UV-B region, lie at the red edge of the UV-C range (100-260 nm) in all isolated nucleobases. The lowest energetic excited states in the UV-B region of nucleobases have been investigated using a plethora of experimental and theoretical methods in gas and solution phases. The sub-picosecond lifetime of these molecules is not a general attribute of all nucleobases but specific to the five primary nucleobases and a few xanthine and methylated derivatives. To determine the overall UV photostability, we aim to understand the effect of more energetic photons lying in the UV-C region on nucleobases. To determine the UV-C initiated photophysics of a nucleobase system, we chose a halogen substituted purine, 6-chloroguanine (6-ClG), that we had investigated previously using resonance Raman spectroscopy. We have performed quantitative measurements of the resonance Raman cross-section across the Bb absorption band (210-230 nm) and constructed the Raman excitation profiles. We modeled the excitation profiles using Lee and Heller's time-dependent theory of resonance Raman intensities to extract the initial excited state dynamics of 6-ClG within 30-50 fs after photoexcitation. We found that imidazole and pyrimidine rings of 6-ClG undergo expansion and contraction, respectively, following photoexcitation to the Bb state. The amount of distortions of the excited state structure from that of the ground state structure is reflected by the total internal reorganization energy that is determined at 112 cm(-1). The contribution of the inertial component of the solvent response towards the total reorganization energy was obtained at 1220 cm(-1). In addition, our simulation also yields an instantaneous response of the first

  2. Profiles of second- to third-order moments of turbulent temperature fluctuations in the convective boundary layer: first measurements with Rotational Raman Lidar

    A. Behrendt


    Full Text Available The rotational Raman lidar of the University of Hohenheim (UHOH measures atmospheric temperature profiles during daytime with high resolution (10 s, 109 m. The data contain low noise errors even in daytime due to the use of strong UV laser light (355 nm, 10 W, 50 Hz and a very efficient interference-filter-based polychromator. In this paper, we present the first profiling of the second- to forth-order moments of turbulent temperature fluctuations as well as of skewness and kurtosis in the convective boundary layer (CBL including the interfacial layer (IL. The results demonstrate that the UHOH RRL resolves the vertical structure of these moments. The data set which is used for this case study was collected in western Germany (50°53'50.56′′ N, 6°27'50.39′′ E, 110 m a.s.l. within one hour around local noon on 24 April 2013 during the Intensive Observations Period (IOP 6 of the HD(CP2 Observational Prototype Experiment (HOPE, which is embedded in the German project HD(CP2 (High-Definition Clouds and Precipitation for advancing Climate Prediction. First, we investigated profiles of the noise variance and compared it with estimates of the statistical temperature measurement uncertainty Δ T based on Poisson statistics. The agreement confirms that photon count numbers obtained from extrapolated analog signal intensities provide a lower estimate of the statistical errors. The total statistical uncertainty of a 20 min temperature measurement is lower than 0.1 K up to 1050 m a.g.l. at noontime; even for single 10 s temperature profiles, it is smaller than 1 K up to 1000 m a.g.l.. Then we confirmed by autocovariance and spectral analyses of the atmospheric temperature fluctuations that a temporal resolution of 10 s was sufficient to resolve the turbulence down to the inertial subrange. This is also indicated by the profile of the integral scale of the temperature fluctuations, which was in the range of 40 to 120 s in the CBL. Analyzing then

  3. Ultraviolet Resonant Raman Enhancements in the Detection of Explosives

    Short Jr., Billy Joe [Naval Postgraduate School, Monterey, CA (United States)


    Raman-based spectroscopy is potentially militarily useful for standoff detection of high explosives. Normal (non-resonance) and resonance Raman spectroscopies are both light scattering techniques that use a laser to measure the vibrational spectrum of a sample. In resonance Raman, the laser is tuned to match the wavelength of a strong electronic absorbance in the molecule of interest, whereas, in normal Raman the laser is not tuned to any strong electronic absorbance bands. The selection of appropriate excitation wavelengths in resonance Raman can result in a dramatic increase in the Raman scattering efficiency of select band(s) associated with the electronic transition. Other than the excitation wavelength, however, resonance Raman is performed experimentally the same as normal Raman. In these studies, normal and resonance Raman spectral signatures of select solid high explosive (HE) samples and explosive precursors were collected at 785 nm, 244 nm and 229 nm. Solutions of PETN, TNT, and explosive precursors (DNT & PNT) in acetonitrile solvent as an internal Raman standard were quantitatively evaluated using ultraviolet resonance Raman (UVRR) microscopy and normal Raman spectroscopy as a function of power and select excitation wavelengths. Use of an internal standard allowed resonance enhancements to be estimated at 229 nm and 244 nm. Investigations demonstrated that UVRR provided ~2000-fold enhancement at 244 nm and ~800-fold improvement at 229 nm while PETN showed a maximum of ~25-fold at 244 nm and ~190-fold enhancement at 229 nm solely from resonance effects when compared to normal Raman measurements. In addition to the observed resonance enhancements, additional Raman signal enhancements are obtained with ultraviolet excitation (i.e., Raman scattering scales as !4 for measurements based on scattered photons). A model, based partly on the resonance Raman enhancement results for HE solutions, is presented for estimating Raman enhancements for solid HE samples.

  4. Spot profile analysis and lifetime mapping in ultrafast electron diffraction: Lattice excitation of self-organized Ge nanostructures on Si(001

    T. Frigge


    Full Text Available Ultrafast high energy electron diffraction in reflection geometry is employed to study the structural dynamics of self-organized Germanium hut-, dome-, and relaxed clusters on Si(001 upon femtosecond laser excitation. Utilizing the difference in size and strain state the response of hut- and dome clusters can be distinguished by a transient spot profile analysis. Surface diffraction from {105}-type facets provide exclusive information on hut clusters. A pixel-by-pixel analysis of the dynamics of the entire diffraction pattern gives time constants of 40, 160, and 390 ps, which are assigned to the cooling time constants for hut-, dome-, and relaxed clusters.

  5. Raman measurement of carotenoid composition in human skin

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner


    The carotenoids lycopene and beta-carotene are powerful antioxidants in skin and are thought to act as scavengers for free radicals and singlet oxygen. The role of carotenoid species in skin health is of strong current interest. We demonstrate the possibility to use Resonance Raman spectroscopy for fast, non-invasive, highly specific, and quantitative detection of beta-carotene and lycopene in human skin. Analyzing Raman signals originating from the carbon-carbon double bond stretch vibrations of the carotenoid molecules under blue and green laser excitation, we were able to characterize quantitatively the relative concentrations of each carotenoid species in-vivo. In the selective detection, we take advantage of different Raman cross-section spectral profiles for beta-carotene and lycopene molecules, and obtain a quantitative assessment of individual long-chain carotenoid species in the skin rather than their cumulative levels. Preliminary dual-wavelength Raman measurements reveal significant differences in the carotenoid composition of different subjects. The technique holds promise for rapid screening of carotenoid compositions in human skin in large populations and may be suitable in clinical studies for assessing the risk for cutaneous diseases.

  6. Raman spectroscopy of white wines.

    Martin, Coralie; Bruneel, Jean-Luc; Guyon, François; Médina, Bernard; Jourdes, Michael; Teissedre, Pierre-Louis; Guillaume, François


    The feasibility of exploiting Raman scattering to analyze white wines has been investigated using 3 different wavelengths of the incoming laser radiation in the near-UV (325 nm), visible (532 nm) and near infrared (785 nm). To help in the interpretation of the Raman spectra, the absorption properties in the UV-visible range of two wine samples as well as their laser induced fluorescence have also been investigated. Thanks to the strong intensity enhancement of the Raman scattered light due to electronic resonance with 325 nm laser excitation, hydroxycinnamic acids may be detected and analyzed selectively. Fructose and glucose may also be easily detected below ca. 1000 cm(-1). This feasibility study demonstrates the potential of the Raman spectroscopic technique for the analysis of white wines. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Analysis of the in vivo confocal Raman spectral variability in human skin

    Mogilevych, Borys; dos Santos, Laurita; Rangel, Joao L.; Grancianinov, Karen J. S.; Sousa, Mariane P.; Martin, Airton A.


    Biochemical composition of the skin changes in each layer and, therefore, the skin spectral profile vary with the depth. In this work, in vivo Confocal Raman spectroscopy studies were performed at different skin regions and depth profile (from the surface down to 10 μm) of the stratum corneum, to verify the variability and reproducibility of the intra- and interindividual Raman data. The Raman spectra were collected from seven healthy female study participants using a confocal Raman system from Rivers Diagnostic, with 785 nm excitation line and a CCD detector. Measurements were performed in the volar forearm region, at three different points at different depth, with the step of 2 μm. For each depth point, three spectra were acquired. Data analysis included the descriptive statistics (mean, standard deviation and residual) and Pearson's correlation coefficient calculation. Our results show that inter-individual variability is higher than intraindividual variability, and variability inside the SC is higher than on the skin surface. In all these cases we obtained r values, higher than 0.94, which correspond to high correlation between Raman spectra. It reinforces the possibility of the data reproducibility and direct comparison of in vivo results obtained with different study participants of the same age group and phototype.

  8. The effects of machine parameters on residual stress determined using micro-Raman spectroscopy

    Sparks, R.G.; Enloe, W.S.; Paesler, M.A.


    The effects of machine parameters on residual stresses in single point diamond turned silicon and germanium have been investigated using micro-Raman spectroscopy. Residual stresses were sampled across ductile feed cuts in < 100 > silicon and germanium which were single point diamond turned using a variety of feed rates, rake angles and clearance angles. High spatial resolution micro-Raman spectra (1{mu}m spot) were obtained in regions of ductile cutting where no visible surface damage was present. The use of both 514-5nm and 488.0nm excitation wavelengths, by virtue of their differing characteristic penetration depths in the materials, allowed determinations of stress profiles as a function of depth into the sample. Previous discussions have demonstrated that such Raman spectra will exhibit asymmetrically broadened peaks which are characteristic of the superposition of a continuum of Raman scatterers from the various depths probed. Depth profiles of residual stress were obtained using computer deconvolution of the resulting asymmetrically broadened raman spectra.

  9. In vivo confocal Raman microscopic determination of depth profiles of the stratum corneum lipid organization influenced by application of various oils.

    Choe, ChunSik; Schleusener, Johannes; Lademann, Jürgen; Darvin, Maxim E


    The intercellular lipids (ICL) of stratum corneum (SC) play an important role in maintaining the skin barrier function. The lateral and lamellar packing order of ICL in SC is not homogenous, but rather depth-dependent. This study aimed to analyze the influence of the topically applied mineral-derived (paraffin and petrolatum) and plant-derived (almond oil and jojoba oil) oils on the depth-dependent ICL profile ordering of the SC in vivo. Confocal Raman microscopy (CRM), a unique tool to analyze the depth profile of the ICL structure non-invasively, is employed to investigate the interaction between oils and human SC in vivo. The results show that the response of SC to oils' permeation varies in the depths. All oils remain in the upper layers of the SC (0-20% of SC thickness) and show predominated differences of ICL ordering from intact skin. In these depths, skin treated with plant-derived oils shows more disordered lateral and lamellar packing order of ICL than intact skin (p0.1), except plant-derived oils at the depth 30% of SC thickness. In the deeper layers of the SC (60-100% of SC thickness), no difference between ICL lateral packing order of the oil-treated and intact skin can be observed, except that at the depths of 70-90% of the SC thickness, where slight changes with more disorder states are measured for plant-derived oil treated skin (p<0.1), which could be explained by the penetration of free fatty acid fractions in the deep-located SC areas. Both oil types remain in the superficial layers of the SC (0-20% of the SC thickness). Skin treated with mineral- and plant-derived oils shows significantly higher disordered lateral and lamellar packing order of ICL in these layers of the SC compared to intact skin. Plant-derived oils significantly changed the ICL ordering in the depths of 30% and 70-90% of the SC thickness, which is likely due to the penetration of free fatty acids in the deeper layers of the SC. Copyright © 2017 Japanese Society for

  10. Spatially offset Raman spectroscopy based on a line-scan hyperspectral Raman system

    Spatially offset Raman spectroscopy (SORS) is a technique that can obtain subsurface layered information by collecting Raman spectra from a series of surface positions laterally offset from the excitation laser. The current methods of SORS measurement are typically either slow due to mechanical move...

  11. Raman Lidar Temperature Profiler Project

    National Aeronautics and Space Administration — Aircraft wake vortices is especially hazardous during the landing and taking-off phases of flight. It is essential to obtain an accurate atmospheric temperature...

  12. On surface Raman scattering and luminescence radiation in boron carbide.

    Werheit, H; Filipov, V; Schwarz, U; Armbrüster, M; Leithe-Jasper, A; Tanaka, T; Shalamberidze, S O


    The discrepancy between Raman spectra of boron carbide obtained by Fourier transform Raman and conventional Raman spectrometry is systematically investigated. While at photon energies below the exciton energy (1.560 eV), Raman scattering of bulk phonons of boron carbide occurs, photon energies exceeding the fundamental absorption edge (2.09 eV) evoke additional patterns, which may essentially be attributed to luminescence or to the excitation of Raman-active processes in the surface region. The reason for this is the very high fundamental absorption in boron carbide inducing a very small penetration depth of the exciting laser radiation. Raman excitations essentially restricted to the boron carbide surface region yield spectra which considerably differ from bulk phonon ones, thus indicating structural modifications.

  13. Enhanced Raman scattering from nano-SnO2 grains

    Ding Shuo; Liu Jin-Quan; Liu Yu-Long


    We present the Raman spectra of nano-SnO2 grains with sizes from 4nm to 80nm excited by 532nm and 1.06μm lines. The enhanced Raman scattering of the nanograins is observed for both exciting lines when the grain size is less than 8nm. The less the grain size is, the more intensely the Raman scattering is enhanced. According to our results,the enhancements of the Raman intensity are a few tenfolds and different for different exciting lines when the grain size is 4nm. It can be attributed to enhanced Raman scattering by electron-hole pair excitations in the nanograins that originate from sub-microscopic (10nm) size and other defect- and surface-related features. A critical size that divides respective predominance of bulk properties and the defect-, surface-, and size-related features can be determined to be about 8nm.

  14. Depth profiling of thin film solar cell components by synchrotron excited Soft X-ray emission spectroscopy (SXES)

    Moenig, Harry; Grimm, Alexander; Lux-Steiner, Martha; Saez-Araoz, Rodrigo; Fischer, Christian-Herbert [Freie Universitaet Berlin (Germany); Baer, Markus [University of Las Vegas (United States); Camus, Christian; Ennaoui, Ahmed; Kaufmann, Christian; Koerber, Paul; Kropp, Timo; Lauermann, Iver; Lehmann, Sebastian; Muenchenberg, Tim; Pistor, Paul; Puttnins, Stefan; Schock, Hans-Werner; Sokoll, Stefan [Hahn-Meitner-Institut Berlin (Germany); Jung, Christian [BESSY GmbH Berlin (Germany)


    Depending on the elemental composition of a material, SXES provides an information depth of 50-1000 nm. For studies of thin multilayer structures tuning of this parameter is highly desirable. One possibility is the variation of the excitation energy, which is accompanied by variation of photoionisation cross sections. Alternatively, we performed angle resolved SXES on the solar cell absorber material Cu(In,Ga)Se{sub 2} covered by CdS or Zn(S,O) buffer layers (10-50 nm). Due to our setup geometry, the emission spectra clearly display increased surface sensitivity at small (grazing exit) and large (grazing incidence) exit angles. A model based on Beer-Lamberts law and setup geometry is in reasonable agreement with our experimental data.The presented results show that angle resolved SXES measurements yield depth-dependent information on multilayer structures. The increased surface sensitivity at grazing exit and grazing incidence angles allows the detection of extremely thin cover layers at reasonable recording times.

  15. Stimulated Raman Scattering in Nanorod Silicon Carbide Films


    When the film is excited by a very low excitation energy, the spontaneous Raman scattering emerges. The intensity of Raman scattering is proportional to the excitation power below the threshold excitation. When the excited power reaches the excitation threshold, the intensity of Stokes light strongly increases. Meanwhile an anti-Stokes light at 495nm and multiple order but small Stokes peaks occur. The intensity of Stokes light is much larger than that of anti-Stokes. The full width of half maximum (FWHM) of Stokes peak is reduced from 0.4nm to less than 0.2nm, the scattering angle between both Stokes and incident lights becomes less than 1°, and the angle between the Stokes and anti-Stokes lights is about 3°. When the exciting power is in excess of the threshold, anti-Stokes and multiple Raman scattering peaks reappear. These experiments can be unlimitedly repeated. From this experiment, we can exclude the possibility of spontaneous Raman scattering. It is suggested that the nanorods are a quantum line dimension having a large surface. There will be Raman differential scattering section so long as the nanorod films become very strong scattering media; the surface-enhanced Raman scattering will be produced, the nanorod films of SiC will form a strong multiple scattering resonance cavities so as to form the stimulated Raman scattering oscillation.

  16. Analyzing the fundamental properties of Raman amplification in optical fibers

    Rottwitt, Karsten; Povlsen, Jørn Hedegaard


    The Raman response of germanosilicate fibers is presented. This includes not only the material dependence but also the relation between the spatial-mode profile of the light and the Raman response in the time and frequency domain. From the Raman-gain spectrum, information is derived related...

  17. The Stimulated Raman Spectrum of Cyanogen

    Bermejo; Escribano; Santos


    The Raman spectrum of cyanogen 12C214N2 has been investigated at nearly Doppler resolution by means of the Stimulated Raman technique. The regions around the Q branches of the nu1 (2330 cm-1) and nu2 (845 cm-1) vibrations have been recorded. Besides the fundamentals, hot bands arising from v5 = 1, v5 = 2, and v4 = 1 have been observed. The spectra have been analyzed, and rotational constants for the excited states have been obtained. Computer simulations of the Raman contours have been carried out as a test of the assignments. Copyright 1997 Academic Press. Copyright 1997Academic Press

  18. Excited State Dynamics of γ-Crotonolactone:Resonance Raman Spectroscopy and Complete Active Space†Self-consistent Field(CASSCF) Study%γ-巴豆酰内酯激发态动力学的共振拉曼光谱和完全活性空间自洽场(CASSCF)计算研究

    欧阳冰; 薛佳丹; 郑旭明


    The structural dynamics and decay mechanisms of γ-crotonolactone in the light-absorbing S2 excited states were studied by resonance Raman spectroscopy and complete active space self-consistent field(CASSCF) computations. The electronic spectra assignments and the vibrational assignments were done on the basis of the density-functional theory computations and the results of corresponding spectra. The reso-nance Raman spectra at four excitation wavelength which covered A-band were obtained. CASSCF method was carried out to determine the minimal excitation energies and excited geometries of S1,min , S2,min , T1,min , T2,min , T 3,min , as well as some conical intersection points. The relation between the structures of excited state S2,min as well as internal conversion point CI(S2 / S1 ) and the intensity mode of resonance Raman spectra was studied. The efficiency of various intersystem crossing is evaluated on the basis of the El-Sayed’s rule, and two major decay channels from S2,FC to ground state S0 were proposed. One is the internal conversion channel and the other is the intersystem crossing channel.%采用共振拉曼光谱和完全活性空间自洽场(CASSCF)方法研究了γ-巴豆酰内酯的光吸收 S2态的结构动力学和衰变机制。采用含时密度泛函理论方法结合光谱实验确认了紫外光谱和振动光谱。获得了涵盖A-带吸收的4个激发波长下的共振拉曼光谱。用 CASSCF 计算得到了 S1,min , S2,min , T1,min , T2,min和 T3,min及其相关势能面交叉点的结构与能量。研究了 A-带共振拉曼光谱强度模式与 S2,min和 CI(S2/ S1)交叉点结构的关系。借助 El-Sayed 规则分析了各系间窜跃路径的效率,提出了γ-巴豆酰内酯从 S2,FC弛豫到基态 S0的2条主要路径:内转换路径和系间窜跃路径。

  19. Detection of biologically active diterpenoic acids by Raman Spectroscopy

    Talian, Ivan; Orinak, Andrej; Efremov, Evtim V.


    Three poorly detectable, biologically active diterpenoic acids, kaurenoic, abietic, and gibberellic acid, were studied by using different modes of Raman spectroscopy. Because of their structural similarities, in the absence of strongly polarizable groups, conventional Raman spectroscopy...... is not suitable for their unambiguous identification, especially not in solution. We attempted to increase the sensitivity by applying UV-resonance Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) techniques. The UV-Raman spectra of the three compounds in ethanol/water 50 : 50 showed only very...... few enhanced Raman lines. SERS spectra with 514-nm excitation with Ag colloids were also relatively weak. The best SERS spectrawere obtained with 785-nm excitation on a novel nanostructured substrate, 'black silicon' coated with a 400-nm gold layer. The spectra showed clear differences...

  20. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.


    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...

  1. Stimulated terahertz emission due to electronic Raman scattering in silicon

    Pavlov, S. G.; Bottger, U.; Hovenier, J. N.; Abrosimov, N. V.; Riemann, H.; Zhukavin, R. K.; Shastin, V. N.; Redlich, B.; van der Meer, A. F. G.; Hubers, H. W.


    Stimulated Raman emission in the terahertz frequency range (4.8-5.1 THz and 5.9-6.5 THz) has been realized by optical excitation of arsenic donor centers in silicon at low temperatures. The Stokes shift of the observed laser emission is 5.42 THz which is equal to the Raman-active donor electronic tr

  2. Terahertz Raman laser based on silicon doped with phosphorus

    Pavlov, S. G.; Hubers, H. W.; Bottger, U.; Zhukavin, R. K.; Shastin, V. N.; Hovenier, J. N.; Redlich, B.; Abrosimov, N. V.; Riemann, H.


    Raman-type stimulated emission at frequencies between 5.0 and 5.2 THz as well as between 6.1 and 6.4 THz has been realized in silicon crystals doped by phosphorus donors. The Raman laser operates at around 5 K under optical excitation by a pulsed, frequency-tunable infrared free electron laser. The

  3. Fast Resonance Raman Spectroscopy of Short-Lived Radicals

    Pagsberg, Palle Bjørn; Wilbrandt, Robert Walter; Hansen, Karina Benthin


    We report the first application of pulsed resonance Raman spectroscopy to the study of short-lived free radicals produced by pulse radiolysis. A single pulse from a flash-lamp pumped tunable dye laser is used to excite the resonance Raman spectrum of the p-terphenyl anion radical with an initial...

  4. Detection of diamond in ore using pulsed laser Raman spectroscopy

    Lamprecht, GH


    Full Text Available The viability of using pulsed laser excited Raman spectroscopy as a method for diamond detection from ore, has been investigated. In this method the spontaneous Stokes Raman signal is used as indicator of diamond, and a dual channel system...

  5. Triplet State Resonance Raman Spectrum of all-trans-diphenylbutadiene

    Wilbrandt, Robert Walter; Grossman, W.E.L.; Killough, P.M


    The resonance Raman spectrum of all-trans-diphenylbutadiene (DPB) in its ground state and the resonance Raman spectrum (RRS) of DPB in its short-lived electronically excited triplet state are reported. Transient spectra were obtained by a pump-probe technique using two pulsed lasers...

  6. All-fiber Raman Probe using Higher Order Modes

    Larsen, Stine Højer Møller; Rishøj, Lars Søgaard; Rottwitt, Karsten


    We demonstrate the first all-fiber Raman probe utilizing higher order modes for the excitation. The spectrum of cyclohexane is measured using both the fundamental mode as well as in-fiber-generated Bessel-like modes.......We demonstrate the first all-fiber Raman probe utilizing higher order modes for the excitation. The spectrum of cyclohexane is measured using both the fundamental mode as well as in-fiber-generated Bessel-like modes....

  7. Multiwavelength Raman fiber ring laser with the spectrum profile broadened by parametric four wave mixing in highly nonlinear dispersion-shifted fibers

    Yan Wang; Qing Wang; Wei Zhang; Xiaoming Liu; Jiangde Peng


    @@ A broadband multiwavelength Raman fiber ring laser (RFRL) covering the whole C-band at room temperature are presented. The effect of the intracavity highly nonlinear dispersion-shifted fiber on broadening and flattening the output spectrum envelope is discussed and experimentally demonstrated. More than 45-dB extinction-ratio multiwavelength output from 1527.76 to 1566.86 nm with 100-GHz channel spacing and 2.1-dB power ripple has been achieved by carefully controlling the individual powers of three pump lasers.

  8. On-Line Multichannel Raman Spectroscopic Detection System For Capillary Zone Electrophoresis


    An on-line multichannel Raman spectroscopic detection system for capillary electrophoresis was established by using an Ar+ laser and a cryogenically cooled ICCD. Resonant excitation Raman spectra of methyl red and methyl orange were employed to test the system. The result shows that it could yield on-line electrophoretogram and time series of Raman spectra.

  9. Resonant Raman Study Of ZnSe Epitaxial Layers Grown On GaAs Substrates

    Djibladze, Merab I.; Dorosh, I. I.; Zlenko, A. A.; Kekelidze, George N.; Pashinin, Vladimir P.; Prokhorov, Kirill A.


    Quantitative difference between Raman and resonant Raman scattering spectra of thin ZnSe layers on GaAs substrates is presented. The dynamics of changing of Raman scattering properties while shortenning the exciting light wavelength for ZnSe/GaAs heterojunction is given. The difference in polarization spectra is demonstrated.

  10. Cryogenic exciter

    Bray, James William [Niskayuna, NY; Garces, Luis Jose [Niskayuna, NY


    The disclosed technology is a cryogenic static exciter. The cryogenic static exciter is connected to a synchronous electric machine that has a field winding. The synchronous electric machine is cooled via a refrigerator or cryogen like liquid nitrogen. The static exciter is in communication with the field winding and is operating at ambient temperature. The static exciter receives cooling from a refrigerator or cryogen source, which may also service the synchronous machine, to selected areas of the static exciter and the cooling selectively reduces the operating temperature of the selected areas of the static exciter.

  11. Resonance raman studies of phenylcyclopropane radical cations

    Godbout, J.T.; Zuilhof, H.; Heim, G.; Gould, I.R.; Goodman, J.L.; Dinnocenzo, J.P.; Myers Kelley, A.


    Resonance Raman spectra of the radical cations of phenylcyclopropane and trans-1-phenyl-2-methylcyclopropane are reported. A near-UV pump pulse excites a photosensitizer which oxidizes the species of interest, and a visible probe pulse delayed by 35 ns obtains the spectrum of the radical ion. The tr

  12. Ultraviolet Raman scattering from persistent chemical warfare agents

    Kullander, Fredrik; Wästerby, Pär.; Landström, Lars


    Laser induced Raman scattering at excitation wavelengths in the middle ultraviolet was examined using a pulsed tunable laser based spectrometer system. Droplets of chemical warfare agents, with a volume of 2 μl, were placed on a silicon surface and irradiated with sequences of laser pulses. The Raman scattering from V-series nerve agents, Tabun (GA) and Mustard gas (HD) was studied with the aim of finding the optimum parameters and the requirements for a detection system. A particular emphasis was put on V-agents that have been previously shown to yield relatively weak Raman scattering in this excitation band.

  13. Surface-Enhanced Raman Scattering Physics and Applications

    Kneipp, Katrin; Kneipp, Harald


    Almost 30 years after the first reports on surface-enhanced Raman signals, the phenomenon of surface-enhanced Raman scattering (SERS) is now well established. Yet, explaining the enhancement of a spectroscopic signal by fouteen orders of magnitude continues to attract the attention of physicists and chemists alike. And, at the same time and rapidly growing, SERS is becoming a very useful spectroscopic tool with exciting applications in many fields. SERS gained particular interest after single-molecule Raman spectroscopy had been demonstrated. This bookl summarizes and discusses present theoretical approaches that explain the phenomenon of SERS and reports on new and exciting experiments and applications of the fascinating spectroscopic effect.

  14. Raman spectroscopic investigation of blood and related materials

    Gnyba, M.; Jedrzejewska-Szczerska, M.; Wróbel, M. S.


    This paper reports preliminary studies on use of Raman spectroscopy for investigation of blood. High quality blood spectra were recorded in-vitro with excitation wavelengths of 830 nm. Because of complex composition of the blood as well as by light attenuation and scattering in the tissues, spectra set up from wide, low-intensive Raman bands and intensive optical background. To get information about origin of bands in Raman spectra it is necessary to create phantom, which would show influence of this parameter and can be used to calibrate the Raman measurement system. Spectra of phantoms of selected blood components were acquired and discussed.

  15. Experimental characterization of Raman overlaps between mode-groups

    Christensen, Erik Nicolai; Koefoed, Jacob Gade; Friis, Søren Michael Mørk;


    -equalized gain. In this paper, we present an experimental characterization of the intermodal Raman intensity overlaps of a few-mode fiber using backward-pumped Raman amplification. By varying the input pump power and the degree of higher order mode-excitation for the pump and the signal in a 10km long two......-mode fiber, we are able to characterize all intermodal Raman intensity overlaps. Using these results, we perform a Raman amplification measurement and demonstrate a mode-differential gain of only 0.25dB per 10dB overall gain. This is, to the best of our knowledge, the lowest mode differential gain achieved...

  16. Raman properties of GaSb nanoparticles embedded in SiO2 films

    Liu Fa-Min; Wang Tian-Min; Zhang Li-De


    The Raman shifts of nanocrystalline GaSb excited by an Ar+ ion laser at wavelengths 514.5, 496.5, 488.0, 476.5,and 457.9nm are studied by an SPEX-1403 laser Raman spectrometer respectively, and they are explained by phonon confinement, tensile stress, resonant Raman scattering and quantum size effects. The Stokes and anti-Stokes Raman spectra of GaSb nanocrystals strongly support the Raman feature of GaSb nanocrystals. The calculated optical spectra compare well with experimental data on Raman scattering GaSb nanocrystals.


    V. G. Savitski


    Full Text Available The linewidth of a KGd(WO42 pulsed Raman laser is analysed experimentally for different configurations of the Raman and pump resonators: with narrow and broadband pump emission profiles, with and without linewidth narrowing elements in the Raman laser resonator, with and without injection seeding into the Raman cavity. The benefits of a narrow linewidth pump source in combination with linewidth narrowing elements in the Raman laser cavity for the efficient linewidth narrowing of the Raman emission are explained. 20 kW peak-power pulses at 1156 nm with 0,43 cm -1 emission linewidth are demonstrated from an injection seeded KGW Raman laser. 

  18. Modelos para dispersão Raman em polímeros conjugados Raman dispersion models in conjugated polymers

    Ricardo P. Millen


    Full Text Available Raman dispersion refers to the dependence of the position of Raman bands on the energy of the exciting radiation. In this work, the three main models currently used to explain this phenomenon (Conjugated Length Model, Amplitude Mode Model and Effective Conjugation Coordinate Model are discussed. Raman dispersion is a consequence of pi electron delocalization, but each model describes in a different way how pi electron delocalization affects the position of Raman bands. Here the features, qualities and problems of the three models are highlighted.

  19. Raman spectroscopy for cancer detection: instrument development and tissue diagnosis

    Manoharan, Ramasamy; Wang, Yang; Boustany, Nada N.; Brennan, James F., III; Baraga, Joseph J.; Dasari, Ramachandra R.; Van Dam, Jacques; Singer, Samuel; Feld, Michael S.


    Raman spectroscopy can provide quantitative molecular information about the biochemical composition of human tissues exhibiting various stages of disease. Fluorescence interference is ubiquitous in Raman spectra of biological samples excited with visible light. However, it can be avoided by using near-infrared (NIR) or ultraviolet (UV) excitation. We are exploring the potential of these methods for detecting precancerous/cancerous changes in human tissues. The NIR studies use 830 nm excitation from a Ti:sapphire laser. Raman signals are collected by an imaging spectrograph/deep-depletion CCD detection system. High quality tissue spectra can be obtained in a few seconds or less. The UV resonance Raman studies employ wavelengths below 300 nm for selective excitation of nucleic acids, proteins and lipids. Excitation is provided by a frequency tripled/quadrupled mode-locked Ti:sapphire laser, and Raman light is collected by a one meter spectrograph/UV-enhanced CCD detector. The two systems can be coupled to appropriate microscopes for extracting morphological and biochemical information at the cellular level, which is important for understanding the origin of the Raman spectra of bulk tissue. The results of the initial studies for cancer detection in various human tissues are reported here.

  20. 拉曼散射激光雷达反演二氧化碳测量结果的可靠性分析%Reliability analysis of Raman scattering lidar for measurement of atmospheric carbon dioxide profiles

    苑克娥; 张世国; 胡顺星; 林金明; 邵石生; 曹开法; 黄见; 徐之海; 徐惠玲


    Raman scattering lidar is an important technique, which has the high space-time resolution, can measure atmospheric carbon dioxide mixture ratio profiles in real time. It is based on the Raman scattering frequency shift caused by laser and atmospheric CO2 or N2 interaction. A Raman scattering lidar system developed by Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, was introduced. And the theory and method for atmospheric CO2 space-time measurement were expatiated on. Two CO2 analyzers prior calibrated by each other, which tested the lidar′s results reliability, were placed in the sites of transmitting terminal and one kilometer distance along the laser path. Experiment results displayed the two analyzers have good consistency with the lidar′s in near-end and far-end respectively, where there are 0.8 ppm and 3.51 ppm difference in whole night averaged values. It was explained that the difference of CO2 mixture ratio in near-end and far-end. Thus atmospheric CO2 profiles monitored by Raman scattering lidar have authenticity and reliability.%拉曼散射法测量大气二氧化碳(CO2)是一种利用大气中CO2分子和N2分子与激光相互作用产生Raman散射频移来实现探测CO2混合比分布的探测技术。介绍了中国科学院安徽光学精密机械研究所自主研制的拉曼散射激光雷达系统,以及用于大气CO2时空间分布测量的原理和方法。将两台事先校准过的CO2分析仪布置在激光雷达水平光路的发射端和1 km位置进行同时测量,实验结果表明:两台分析仪分别与激光雷达近端和远端得到的CO2混合比随时间的变化具有较好的一致性,统计一整夜测量结果的平均值分别相差0.8 ppm和3.51 ppm;结合激光光路下垫面的不同对近端与远端结果的差异进行了分析说明,充分表明了拉曼散射激光雷达测量结果的可靠性。

  1. Cascade correlation-enhanced Raman scattering in atomic vapors

    Ma, Hong-Mei; Chen, Li-Qing; Yuan, Chun-Hua


    A new Raman process can be used to realize efficient Raman frequency conversion by coherent feedback at low light intensity [Chen B, Zhang K, Bian C L, Qiu C, Yuan C H, Chen L Q, Ou Z Y, and Zhang W P 2013 Opt. Express 21, 10490]. We present a theoretical model to describe this enhanced Raman process, termed as cascade correlation-enhanced Raman scattering, which is a Raman process injected by a seeded light field. It is correlated with the initially prepared atomic spin excitation and driven by the quasi-standing-wave pump fields, and the processes are repeated until the Stokes intensities are saturated. Such an enhanced Raman scattering may find applications in quantum information, nonlinear optics, and optical metrology due to its simplicity. Project supported by the National Natural Science Foundation of China (Grant Nos. 11474095, 11274118, and 91536114).

  2. Coherent anti-Stokes Raman spectroscopy: Understanding the essentials

    Ariunbold, Gombojav O.; Altangerel, Narangerel


    This paper is a brief overview to coherent anti- Stokes Raman spectroscopic technique and introduces the strengths and barriers to its use all based on the interpretation of simple theoretical formulae. The use of the Gaussian ultrashort pulses is highlighted as a practical elucidatory reconstruction tool of coherent Raman spectra. The paper presents the integral formulae for coherent anti-Stokes and Stokes Raman scattering, and discusses the closed-form solutions, its complex error function, and the delay time formula for enhancement of the inferred pure coherent Raman spectra. As an example, the timeresolved coherent Stokes Raman scattering experimental observations are quantitatively elucidated.Understanding the essentials of coherent Raman spectroscopy, therefore, promotes the importance of a number of experiments including the ones utilizing a broadband excitation with a narrowband delayed probing for successful background suppression.

  3. Raman scattering in the atmospheres of the major planets

    Cochran, W. D.; Trafton, L. M.


    A technique is developed to calculate the detailed effects of Raman scattering in an inhomogeneous anisotropically scattering atmosphere. The technique is applied to evaluations of Raman scattering by H2 in the atmosphere of the major planets. It is noted that Raman scattering produces an insufficient decrease in the blue and ultraviolet regions to explain the albedos of all planets investigated. For all major planets, the filling-in of solar line cores and the generation of the Raman-shifted ghosts of the Fraunhofer spectrum are observed. With regard to Uranus and Neptune, Raman scattering is seen to exert a major influence on the formation and profile of strong red and near infrared CH4 bands, and Raman scattering by H2 explains the residual intensity in the cores of these bands. Raman scattering by H2 must also be taken into account in the scattering of photons into the cores of saturated absorption bands.

  4. Exciter switch

    Mcpeak, W. L.


    A new exciter switch assembly has been installed at the three DSN 64-m deep space stations. This assembly provides for switching Block III and Block IV exciters to either the high-power or 20-kW transmitters in either dual-carrier or single-carrier mode. In the dual-carrier mode, it provides for balancing the two drive signals from a single control panel located in the transmitter local control and remote control consoles. In addition to the improved switching capabilities, extensive monitoring of both the exciter switch assembly and Transmitter Subsystem is provided by the exciter switch monitor and display assemblies.

  5. Raman spectroscopy of thin films

    Burgess, James Shaw

    Raman spectroscopy was used in conjunction with x-ray diffraction and x-ray photoelectron spectroscopy to elucidate structural and compositional information on a variety of samples. Raman was used on the unique La 2NiMnO6 mixed double perovskite which is a member of the LaMnO3 family of perovskites and has multiferroic properties. Raman was also used on nanodiamond films as well as some boron-doped carbon compounds. Finally, Raman was used to identify metal-dendrimer bonds that have previously been overlooked. Vibrational modes for La2NiMnO6 were ascribed by comparing spectra with that for LaMnO3 bulk and thin film spectra. The two most prominent modes were labeled as an asymmetric stretch (A g) centered around 535 cm-1 and a symmetric stretch (B g) centered around 678 cm. The heteroepitaxial quality of La2NiMnO 6 films on SrTiO3 (100) and LaAlO3 (100) substrates were examined using the Raman microscope by way of depth profile experiments and by varying the thickness of the films. It was found that thin films (10 nm) had much greater strain on the LaAlO3 substrate than on the SrTiO3 substrate by examining the shifts of the Ag and the Bg modes from their bulk positions. Changes in the unit cell owing to the presence of oxygen defects were also monitored using Raman spectroscopy. It was found that the Ag and Bg modes shifted between samples formed with different oxygen partial pressures. These shifts could be correlated to changes in the symmetry of the manganese centers due to oxygen defects. Raman spectroscopy was used to examine the structural and compositional characteristics of carbon materials. Nanocrystalline diamond coated cutting tools were examined using the Raman Microscope. Impact, abrasion, and depth profile experiments indicated that delamination was the primary cause of film failure in these systems. Boron doped material of interest as catalyst supports were also examined. Monitoring of the G-mode and intensities of the D- and G-modes indicated that

  6. Singlet internal conversion processes in the order of 1Bu+→3Ag-→1Bu-→2Ag-→1Ag- in all- trans-spheroidene and lycopene as revealed by subpicosecond time-resolved Raman spectroscopy

    Rondonuwu, Ferdy S.; Kakitani, Yoshinori; Tamura, Hiroshi; Koyama, Yasushi


    Key Raman lines ascribable to the 1Bu+, 3Ag-, 1Bu- and 2Ag- states were identified in the subpicosecond time-resolved Raman spectra of spheroidene and lycopene having 10 and 11 conjugated double bonds, respectively. The sequential rise-and-decay of the key Raman lines showed the internal conversion processes of 1Bu+→3Ag-→1Bu-→2Ag-→1Ag- (ground). The time constant in each step of internal conversion reflects the energy gap between the relevant states that had been determined by measurement of resonance - Raman excitation profiles [K. Furuichi, T. Sashima, Y. Koyama, Chem. Phys. Lett. 356 (2002) 547].

  7. Electronic absorption and resonance Raman spectroscopy from ab initio quantum molecular dynamics

    Ben-Nun, M.; Martinez, T.J.


    The absorption and resonance Raman excitation profiles of ethylene following {pi} {yields} {pi}* excitation and taking full account of anharmonicity and Duschinsky rotation effects are calculated from first principles molecular dynamics using the ab initio multiple spawning (AIMS) method and a correlation function approach. The AIMS method solves the nuclear and electronic Schroedinger equations simultaneously and it associates a unique nuclear wave function with each electronic state. The compound absorption spectrum has a full width at half maximum of 9,800 and 1,300 cm{sup {minus}1} (in agreement with the experimental value, 9,500 cm{sup {minus}1}) and a high-frequency structure spaced by 800 and 10 cm{sup {minus}1}, attributed to C{double{underscore}bond}C stretching. The resonance Raman excitation profile exhibits fundamental activity in all totally symmetric modes with the C{double{underscore}bond}C stretching mode being the most dominant. In addition, overtone activity is observed in the torsional motion, out-of-plane wagging motions and the out-of-plane rocking motions. The activity is consistent with the observation that the first excited state is twisted and one of the CH{sub 2} groups is pyramidalized. The coordinate dependence of the electronic transition dipole is investigated, and they find that it depends very strongly on the torsional coordinate and less so on the pyramidalization and C{double{underscore}bond}C stretching coordinates. However, within the approximations used in this paper this dependence does not influence the spectra significantly and the Condon approximation is quite accurate.

  8. Chromophore conformational analysis in phycocyanin and in related chromopeptides by surface enhanced Raman spectroscopy.

    Debreczeny, M; Gombos, Z; Csizmadia, V; Várkonyi, Z; Szalontai, B


    Chromopeptides got from phycocyanin by proteolytic digestion do not preserve the extended chromophore conformations characteristic to the native protein. Chromophore conformations in the chromopeptides showed heterogenity varying between completely folded and semi-extended states. Indications were found that the silver sol-phycocyanin interaction involves the UV electronic transition of the biliprotein which may explain why the visible excited surface enhanced Raman spectra were similar not to the visible excited but to the UV-excited resonance Raman spectrum of phycocyanin.

  9. Condensing Raman spectrum for single-cell phenotype analysis

    Sun, Shiwei


    Background In recent years, high throughput and non-invasive Raman spectrometry technique has matured as an effective approach to identification of individual cells by species, even in complex, mixed populations. Raman profiling is an appealing optical microscopic method to achieve this. To fully utilize Raman proling for single-cell analysis, an extensive understanding of Raman spectra is necessary to answer questions such as which filtering methodologies are effective for pre-processing of Raman spectra, what strains can be distinguished by Raman spectra, and what features serve best as Raman-based biomarkers for single-cells, etc. Results In this work, we have proposed an approach called rDisc to discretize the original Raman spectrum into only a few (usually less than 20) representative peaks (Raman shifts). The approach has advantages in removing noises, and condensing the original spectrum. In particular, effective signal processing procedures were designed to eliminate noise, utilising wavelet transform denoising, baseline correction, and signal normalization. In the discretizing process, representative peaks were selected to signicantly decrease the Raman data size. More importantly, the selected peaks are chosen as suitable to serve as key biological markers to differentiate species and other cellular features. Additionally, the classication performance of discretized spectra was found to be comparable to full spectrum having more than 1000 Raman shifts. Overall, the discretized spectrum needs about 5storage space of a full spectrum and the processing speed is considerably faster. This makes rDisc clearly superior to other methods for single-cell classication.

  10. High-wavenumber FT-Raman spectroscopy for in vivo and ex vivo measurements of breast cancer

    Garcia-Flores, A. F.; Raniero, L.; Canevari, R. A.;


    The identification of normal and cancer breast tissue of rats was investigated using high-frequency (HF) FT-Raman spectroscopy with a near-infrared excitation source on in vivo and ex vivo measurements. Significant differences in the Raman intensities of prominent Raman bands of lipids and protei...

  11. Coherent Raman spectroscopy

    Eesley, G L


    Coherent Raman Spectroscopy provides a unified and general account of the fundamental aspects of nonlinear Raman spectroscopy, also known as coherent Raman spectroscopy. The theoretical basis from which coherent Raman spectroscopy developed is described, along with its applications, utility, and implementation as well as advantages and disadvantages. Experimental data which typifies each technique is presented. This book is comprised of four chapters and opens with an overview of nonlinear optics and coherent Raman spectroscopy, followed by a discussion on nonlinear transfer function of matter

  12. Hollow-core photonic crystal fiber-optic probes for Raman spectroscopy.

    Konorov, Stanislav O; Addison, Christopher J; Schulze, H Georg; Turner, Robin F B; Blades, Michael W


    We have implemented a new Raman fiber-optic probe design based on a hollow-core photonic-crystal excitation fiber surrounded by silica-core collection fibers. The photonic-crystal fiber offers low attenuation at the pump radiation wavelength, mechanical flexibility, high radiation stability, and low background noise. Because the excitation beam is transmitted through air inside the hollow-core fiber, silica Raman scattering is much reduced, improving the quality of the spectra obtained using probes of this design. Preliminary results show that the new probe design decreases the Raman background from the silica by approximately an order of magnitude compared to solid-core silica Raman probes.

  13. Raman Probe Based on Optically-Poled Double-Core Fiber

    Brunetti, Anna Chiara; Margulis, Walter; Rottwitt, Karsten


    A Raman probe based on an optically-poled double-core fiber. In-fiber SHG allows for Raman spectroscopy of DMSO at 532nm when illuminating the fiber with 1064nm light. The fiber structure provides independent excitation and collection paths.......A Raman probe based on an optically-poled double-core fiber. In-fiber SHG allows for Raman spectroscopy of DMSO at 532nm when illuminating the fiber with 1064nm light. The fiber structure provides independent excitation and collection paths....

  14. Water Vapor Measurements by Mobile Raman Lidar Over The Mediterranean Sea in the Framework of HyMex: Application to Multi-Platform Validation of Moisture Profiles

    Totems Julien


    Full Text Available The Water Aerosol Lidar (WALI system, deployed for 14 weeks during 2012 & 2013 on the island of Menorca, provided the Hydrological cycle in the Mediterranean eXperiment (HyMeX with an opportunity to perform a multi-platform comparison on moisture retrievals at the timescales relevant for extreme precipitation events in the West Mediterranean basin. After calibration, the WALI lidar yields nighttime profiles of water vapor with ~7% accuracy from the ground up to 7 km, and daytime coverage of the lower layers, alongside common aerosol retrievals. It is used to characterize the water vapor profile product given by the IASI instrument on-board MetOp-B, and the fields simulated by the Météo-France AROME-WMED model and the open-source WRF model. IASI is found to be reliable above 1 km altitude, and the two models obtain similar high scores in the middle troposphere; WRF beneficiates from a more accurate modelling of the planetary boundary layer.

  15. Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

    Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu


    Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

  16. Excited states

    Lim, Edward C


    Excited States, Volume I reviews radiationless transitions, phosphorescence microwave double resonance through optical spectra in molecular solids, dipole moments in excited states, luminescence of polar molecules, and the problem of interstate interaction in aromatic carbonyl compounds. The book discusses the molecular electronic radiationless transitions; the double resonance techniques and the relaxation mechanisms involving the lowest triplet state of aromatic compounds; as well as the optical spectra and relaxation in molecular solids. The text also describes dipole moments and polarizab

  17. Analysis of lipsticks using Raman spectroscopy.

    Gardner, P; Bertino, M F; Weimer, R; Hazelrigg, E


    In this study, 80 lipsticks were obtained and evaluated using Raman spectroscopy at excitation wavelengths of 532 and 780 nm. Fluorescence severely limited analysis with the 532 nm line while the 780 nm line proved useful for all samples analyzed. It was possible to differentiate 95% of the lipsticks evaluated based on one or more Raman peaks. However, there were no peak trends observed that could be used to identify a manufacturer or categorize a sample. In situ analysis of lipstick smears was found to be possible even from several Raman active substrates, but was occasionally limited by background fluorescence and in extreme cases, photodegradation. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  18. Gain Variation with Raman Amplifier Parameters and Its Restoration


    We demonstrate that gain profile of a distributed Raman amplifier is sensitive to its parameter variation, such as loss/gain coefficients change or partial pump failure. Gain flatness can be restored by adjusting power of pump lasers.

  19. Determination of the spontaneous raman linewidth of CF 4 by measurements of stimulated raman scattering in both transient and steady states

    Pochon, E.


    The spontaneous Raman linewith Δ v of the v1 mode of gaseous CF 4 is determined from 30 to 360 amagat by comparison of stimulated Raman scattering threshold intensity measurements performed with picosecond and nanosecond laser excitation. At high densities Δ v = 0.20 cm -1 is constant. A possible explanation of this effect is given in terms of collisional narrowing

  20. Compact single-channel Raman detector for macular pigments

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner


    Raman detection of macular pigments (MP) holds promise as a novel noninvasive technology for the quantification of lutein and zeaxanthin carotenoids, which are thought to prevent or delay the onset of age-related macular degeneration. Using resonant excitation in the visible, we measure the Raman signals that originate from the double-bond stretch vibrations of the p-conjugated carotenoid molecule's carbon backbone. In this paper we describe the construction and performance of a new, compact, and low-cost MP Raman instrument using dielectric, angle-tuned band-pass filters for wavelength selection and single-channel photo-multiplier detection of carotenoid Raman responses. MP concentration measurements are fast and accurate, as seen in experiments with model eyes and living human eyes. The ease and rapidity of Raman MP measurements, the relative simplicity of the instrumentation, the high accuracy of the measurements, and the lack of significant systematic errors should make this technology useful for widespread clinical research.

  1. Diamagnetic Raman Optical Activity of Chlorine, Bromine, and Iodine Gases.

    Šebestík, Jaroslav; Kapitán, Josef; Pačes, Ondřej; Bouř, Petr


    Magnetic Raman optical activity of gases provides unique information about their electric and magnetic properties. Magnetic Raman optical activity has recently been observed in a paramagnetic gas (Angew. Chem. Int. Ed. 2012, 51, 11058; Angew. Chem. 2012, 124, 11220). In diamagnetic molecules, it has been considered too weak to be measurable. However, in chlorine, bromine and iodine vapors, we could detect a significant signal as well. Zeeman splitting of electronic ground-state energy levels cannot rationalize the observed circular intensity difference (CID) values of about 10(-4). These are explicable by participation of paramagnetic excited electronic states. Then a simple model including one electronic excited state provides reasonable spectral intensities. The results suggest that this kind of scattering by diamagnetic molecules is a general event observable under resonance conditions. The phenomenon sheds new light on the role of excited states in the Raman scattering, and may be used to probe molecular geometry and electronic structure.

  2. Micro-Raman spectroscopy of single leukemic cells

    Changmei Cai; Rong Chen; Juqiang Lin; Yongzeng Li; Shangyuan Feng


    The Raman spectra from leukemic cell line (HL60) and normal human peripheral blood mononuclear cells (PBMCs) are obtained by confocal micro-Raman spectroscopy using near-infrared laser (785 nm) excitation. The scanning range is from 500 to 2000 cm-1. The two average Raman spectra of normal PBMCs and carcinoma cells have clear differences because their structure and amount of nucleic acid, protein, and other major molecules are changed. The spectra are also compared and analyzed by principal component analysis (PCA) to demonstrate the two distinct clusters of normal and transformed cells. The sensitivity of this technique for identifying transformed cells is 100%.

  3. Polarized Raman optical activity of menthol and related molecules

    Barron, L. D.; Hecht, L.; Blyth, S. M.


    Polarized and depolarized Raman optical activity spectra of menthol, menthyl chloride, neomenthol and neothiomenthol from 800 to 1500 cm -1 are reported. Despite axial symmetry in all the bonds, the presence of the heteroatoms O or S seems to induce large deviations from the expected ratio of 2:1 between the polarized and depolarized Raman optical activity intensities, but Cl does not. These deviations might originate in large electric quadrupole contributions induced by excited state interactions involving O or S Rydberg p orbitals and valence orbitals on other parts of the molecule. Such interactions appear to undermine the bond polarizability theory of Raman intensities.

  4. Surface enhanced raman spectroscopy analytical, biophysical and life science applications

    Schlücker, Sebastian


    Covering everything from the basic theoretical and practical knowledge to new exciting developments in the field with a focus on analytical and life science applications, this monograph shows how to apply surface-enhanced Raman scattering (SERS) for solving real world problems. From the contents: * Theory and practice of SERS * Analytical applications * SERS combined with other analytical techniques * Biophysical applications * Life science applications including various microscopies Aimed at analytical, surface and medicinal chemists, spectroscopists, biophysicists and materials scientists. Includes a Foreword by the renowned Raman spectroscopist Professor Wolfgang Kiefer, the former Editor-in-Chief of the Journal of Raman Spectroscopy.

  5. Highly birefringent crystal for Raman transitions with phase modulators

    Arias, Nieves; Abediyeh, Vahide; Hamzeloui, Saeed; Jeronimo-Moreno, Yasser; Gomez, Eduardo


    We present a system to excite Raman transitions with minimum phase noise. The system uses a phase modulator to generate the phase locked beams required for the transition. We use a long calcite crystal to filter out one of the sidebands, avoiding the cancellation that appears at high detunings for phase modulation. The measured phase noise is limited by the quality of the microwave synthesizer. We use the calcite crystal a second time to produce a co-propagating Raman pair with perpendicular polarizations to drive velocity insensitive Raman transitions. Support from CONACYT and Fundacion Marcos Moshinsky.

  6. Identification and discrimination of polycyclic aromatic hydrocarbons using Raman spectroscopy

    Cloutis, Edward; Szymanski, Paul; Applin, Daniel; Goltz, Douglas


    Polycyclic aromatic hydrocarbons (PAHs) are widely present throughout the Solar System and beyond. They have been implicated as a contributor to unidentified infrared emission bands in the interstellar medium, comprise a substantial portion of the insoluble organic matter in carbonaceous chondrites, are expected stable components of organic matter on Mars, and are present in a wide range of terrestrial hydrocarbons and as components of biomolecules. However, PAH structures can be very complicated, making their identification challenging. Raman spectroscopy is known to be especially sensitive to the highly polarizable C-C and C=C bonds found in PAHs, and therefore, can be a powerful tool for PAH structural and compositional elucidation. This study examined Raman spectra of 48 different PAHs to determine the degree to which Raman spectroscopy could be used to uniquely identify different species, factors that control the positions of major Raman peaks, the degree to which induced fluorescence affects the intensity of Raman peaks, its usefulness for PAH discrimination, and the effects of varying excitation wavelength on some PAH Raman spectra. It was found that the arrangement and composition of phenyl (benzene) rings, and the type and position of functional groups can greatly affect fluorescence, positions and intensities of Raman peaks associated with the PAH backbone, and the introduction of new Raman peaks. Among the functional groups found on many of the PAHs that were analyzed, only a few Raman peaks corresponding to the molecular vibrations of these groups could be clearly distinguished. Comparison of the PAH Raman spectra that were acquired with both 532 and 785 nm excitation found that the longer wavelength resulted in reduced fluorescence, consistent with previous studies.

  7. Power Budget Analysis for Waveguide-Enhanced Raman Spectroscopy.

    Wang, Zilong; Pearce, Stuart J; Lin, Yung-Chun; Zervas, Michalis N; Bartlett, Philip N; Wilkinson, James S


    Waveguide-enhanced Raman spectroscopy (WERS) is emerging as an attractive alternative to plasmonic surface-enhanced Raman spectroscopy approaches as it can provide more reproducible quantitative spectra on a robust chip without the need for nanostructured plasmonic materials. Realizing portable WERS systems with high sensitivity using low-cost laser diodes and compact spectrometers requires a detailed analysis of the power budget from laser to spectrometer chip. In this paper, we describe theoretical optimization of planar waveguides for maximum Raman excitation efficiency, demonstrate WERS for toluene on a silicon process compatible high index contrast tantalum pentoxide waveguide, measure the absolute conversion efficiency from pump power to received power in an individual Raman line, and compare this with a power budget analysis of the complete system including collection with an optical fiber and interfacing to a compact spectrometer. Optimized 110 nm thick Ta2O5 waveguides on silica substrates excited at a wavelength of 637 nm are shown experimentally to yield overall system power conversion efficiency of ∼0.5 × 10(-12) from the pump power in the waveguide to the collected Raman power in the 1002 cm(-1) Raman line of toluene, in comparison with a calculated efficiency of 3.9 × 10(-12) Collection efficiency is dictated by the numerical and physical apertures of the spectral detection system but may be improved by further engineering the spatial and angular Raman scattering distributions.

  8. Solvatochromism of 9,10-phenanthrenequinone: an electronic and resonance Raman spectroscopic study.

    Ravi Kumar, Venkatraman; Rajkumar, Nagappan; Umapathy, Siva


    Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-π(1)*; S1 state) and the shorter (1π-π(1)*; S2 state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S2 state relative to the ground state. Raman excitation profiles of PQ (400-1800 cm(-1)) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C2ν symmetry constraint on the S2 state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling.

  9. Raman Spectra of Glasses


    17), Raman spectra, plus a , . theoretical treatment of the data, f complex fluorozirconate 14 I anions in ZBLAN glasses and melts (16), and...based ZBLAN glasses ) 17. ICORS (International Conference on Raman Spectroscopy) Proceedings, London, England. Conferencf 5-9 Sep 88. (Molten silica...RESEARCH FINAL REPORT DTIC CONTRACT N00014-81-K-0501 &JELECTE 1 MAY 81 -- 30 NOV 86 EJJAN041989 V "RAMAN SPECTRA OF GLASSES " 0 During the five years of the

  10. Waveguide-coupled directional Raman radiation for surface analysis.

    Chen, Chen; Li, Jin-Yang; Wang, Li; Lu, Dan-Feng; Qi, Zhi-Mei


    Kretschmann-type waveguide structures, including Plasmon Waveguide (PW) and Resonant Mirror (RM), have been applied in interfacial Raman spectroscopy due to the following unique features: (1) unlike the classic surface enhanced Raman scattering (SERS) substrates made of either gold or silver, both PW and RM can be prepared using a large variety of inexpensive materials; (2) the field enhancement factors using these structures can be theoretically predicted and experimentally controlled, which enables us to manipulate the surface Raman sensitivity with high repeatability; (3) the use of transverse electric (TE) and transverse magnetic (TM) modes for Raman excitation allows us to evaluate the orientation of target molecules immobilized on the waveguide surface; (4) the unwanted impact of noble metals on the Raman fingerprints of target molecules, which is often observed for conventional SERS substrates, can be avoided upon the use of dielectric waveguides. In this paper, guided-mode-coupled directional Raman emission, which is an additional important feature of the waveguide Raman technique, was theoretically investigated based on the optical reciprocity theorem combined with the Fresnel equations. The simulation results indicate that the directional Raman emission from a dipole located within the field confinement and penetration depth of a guided mode depends on both the orientation of the dipole and its distance from the waveguide surface. Raman light from the TE-oriented dipoles is launched into the prism coupler at the TE-mode resonance angle and that from the non-TE-oriented dipoles propagates at the TM-mode resonance angle. The intensity of the guided-mode-excited Raman signal propagating at the mode resonance angle is proportional to the fourth power of the mode field (E(4)) at the depth of the dipole from the waveguide surface. This means that the guided-mode-excited and guided-mode-coupled directional Raman spectroscopy has a detection depth that is as

  11. The Raman Spectrum of the Squarate (C4O4-2 Anion: An Ab Initio Basis Set Dependence Study

    Miranda Sandro G. de


    Full Text Available The Raman excitation profile of the squarate anion, C4O4-2 , was calculated using ab initio methods at the Hartree-Fock using Linear Response Theory (LRT for six excitation frequencies: 632.5, 514.5, 488.0, 457.9, 363.8 and 337.1 nm. Five basis set functions (6-31G*, 6-31+G*, cc-pVDZ, aug-cc-pVDZ and Sadlej's polarizability basis set were investigated aiming to evaluate the performance of the 6-31G* set for numerical convergence and computational cost in relation to the larger basis sets. All basis sets reproduce the main spectroscopic features of the Raman spectrum of this anion for the excitation interval investigated. The 6-31G* basis set presented, on average, the same accuracy of numerical results as the larger sets but at a fraction of the computational cost showing that it is suitable for the theoretical investigation of the squarate dianion and its complexes and derivatives.

  12. A Novel Technique for Raman Analysis of Highly Radioactive Samples Using Any Standard Micro-Raman Spectrometer.

    Colle, Jean-Yves; Naji, Mohamed; Sierig, Mark; Manara, Dario


    A novel approach for the Raman measurement of nuclear materials is reported in this paper. It consists of the enclosure of the radioactive sample in a tight capsule that isolates the material from the atmosphere. The capsule can optionally be filled with a chosen gas pressurized up to 20 bars. The micro-Raman measurement is performed through an optical-grade quartz window. This technique permits accurate Raman measurements with no need for the spectrometer to be enclosed in an alpha-tight containment. It therefore allows the use of all options of the Raman spectrometer, like multi-wavelength laser excitation, different polarizations, and single or triple spectrometer modes. Some examples of measurements are shown and discussed. First, some spectral features of a highly radioactive americium oxide sample (AmO2) are presented. Then, we report the Raman spectra of neptunium oxide (NpO2) samples, the interpretation of which is greatly improved by employing three different excitation wavelengths, (17)O doping, and a triple mode configuration to measure the anti-stokes Raman lines. This last feature also allows the estimation of the sample surface temperature. Finally, data that were measured on a sample from Chernobyl lava, where phases are identified by Raman mapping, are shown.

  13. Indirect exciton luminescense and Raman scattering in CdI 2

    Hayashi, T.; Ohata, T.; Koshino, S.


    Intrinsic luminescence and Raman scattering in 4HCdI 2 have been investigated at 2 K. Weak emission bands observed near the absorption edge are attributed to the phonon-assistes indirect exciton luminescence. Several new Raman lines are observed under resonant excitation in addition to known lines. The symmetry of the phonon modes associated with the indirect transitions as well as with Raman scattering is discussed.

  14. Continuous-wave Raman Lasing in Aluminum Nitride Microresonators

    Liu, Xianwen; Xiong, Bing; Wang, Lai; Wang, Jian; Han, Yanjun; Hao, Zhibiao; Li, Hongtao; Luo, Yi; Yan, Jianchang; Wei, Tongbo; Zhang, Yun; Wang, Junxi


    We report the first investigation on continuous-wave Raman lasing in high-quality-factor aluminum nitride (AlN) microring resonators. Although wurtzite AlN is known to exhibit six Raman-active phonons, single-mode Raman lasing with low threshold and high slope efficiency is demonstrated. Selective excitation of A$_1^\\mathrm{TO}$ and E$_2^\\mathrm{high}$ phonons with Raman shifts of $\\sim$612 and 660 cm$^{-1}$ is observed by adjusting the polarization of the pump light. A theoretical analysis of Raman scattering efficiency within ${c}$-plane (0001) of AlN is carried out to help account for the observed lasing behavior. Bidirectional lasing is experimentally confirmed as a result of symmetric Raman gain in micro-scale waveguides. Furthermore, second-order Raman lasing with unparalleled output power of $\\sim$11.3 mW is obtained, which offers the capability to yield higher order Raman lasers for mid-infrared applications.

  15. Formation and characterization of varied size germanium nanocrystals by electron microscopy, Raman spectroscopy, and photoluminescence

    Ou, Haiyan; Ou, Yiyu; Liu, Chuan


    and crystallization. The samples of different size Ge nanocrystals embedded in the SiO2 matrix were characterized by Raman spectroscopy and photoluminescence. Interplayed size and strain effect of Ge nanocystals was demonstrated by Raman spectroscopy after excluding the thermal effect with proper excitation laser...

  16. Raman spectroscopic characterization of ZrO2 and yttrium stabilized zirconias

    Kjerulf-Jensen, N.; Berg, Rolf W.; Poulsen, Finn Willy


    forward. The spectral features of the Raman spectra do furthermore not only depend on the phase composition, but also depend on the frequency of the excitation, temperature of experiment and texture/orientation of zirconia crystallites under investigation. These effects are illustrated by Raman spectra...

  17. Line-scan spatially offset Raman spectroscopy for inspecting subsurface food safety and quality

    This paper presented a method for subsurface food inspection using a newly developed line-scan spatially offset Raman spectroscopy (SORS) technique. A 785 nm laser was used as a Raman excitation source. The line-shape SORS data was collected in a wavenumber range of 0–2815 cm-1 using a detection mod...

  18. Raman crystallography of RNA.

    Gong, Bo; Chen, Jui-Hui; Yajima, Rieko; Chen, Yuanyuan; Chase, Elaine; Chadalavada, Durga M; Golden, Barbara L; Carey, Paul R; Bevilacqua, Philip C


    Raman crystallography is the application of Raman spectroscopy to single crystals. This technique has been applied to a variety of protein molecules where it has provided unique information about biopolymer folding, substrate binding, and catalysis. Here, we describe the application of Raman crystallography to functional RNA molecules. RNA represents unique opportunities and challenges for Raman crystallography. One issue that confounds studies of RNA is its tendency to adopt multiple non-functional folds. Raman crystallography has the advantage that it isolates a single state of the RNA within the crystal and can evaluate its fold, metal ion binding properties (ligand identity, stoichiometry, and affinity), proton binding properties (identity, stoichiometry, and affinity), and catalytic potential. In particular, base-specific stretches can be identified and then associated with the binding of metal ions and protons. Because measurements are carried out in the hanging drop at ambient, rather than cryo, conditions and because RNA crystals tend to be approximately 70% solvent, RNA dynamics and conformational changes become experimentally accessible. This review focuses on experimental setup and procedures, acquisition and interpretation of Raman data, and determination of physicochemical properties of the RNA. Raman crystallographic and solution biochemical experiments on the HDV RNA enzyme are summarized and found to be in excellent agreement. Remarkably, characterization of the crystalline state has proven to help rather than hinder functional characterization of functional RNA, most likely because the tendency of RNA to fold heterogeneously is limited in a crystalline environment. Future applications of Raman crystallography to RNA are briefly discussed.

  19. Portable raman explosives detection

    Moore, David Steven [Los Alamos National Laboratory; Scharff, Robert J [Los Alamos National Laboratory


    Recent advances in portable Raman instruments have dramatically increased their application to emergency response and forensics, as well as homeland defense. This paper reviews the relevant attributes and disadvantages of portable Raman spectroscopy, both essentially and instrumentally, to the task of explosives detection in the field.

  20. Excited baryons

    Mukhopadhyay, N.C.


    The status of the theory of the low-energy approach to hadron structure is reviewed briefly by surveying a few relevant models. A few examples of tests needed to sort out the predictions of different models pertaining to the quark-gluon structure of hadrons are discussed, and given the resulting physics objectives, a few experimental options for excited baryon research at CFBAF are suggested. (LEW)

  1. Selection of stimulated Raman scattering signal by entangled photons

    Munkhbaatar, Purevdorj; Myung-Whun, Kim


    We propose an excitation-probe measurement method utilizing entangled photon pulses. The excitation-probe signal is dominated by stimulated Raman scattering as well as two-photon absorption when the time delay between the excitation pulse and the probe pulse is shorter than the pulse duration. We demonstrate that the two-photon-absorption signal can be suppressed when the photons of the pulses are entangled. The stimulated Raman scattering signal can be composed of many peaks distributed over broad photon energies owing to the transitions between numerous quantum states in complex materials. We show that the desired peaks among the many peaks can be selected by controlling the thickness of the nonlinear crystal, the pump pulse center frequency, and the polarization of the excitation pulse and probe pulse.

  2. Raman Tweezers Spectroscopy of Live, Single Red and White Blood Cells

    Bankapur, Aseefhali; Zachariah, Elsa; Chidangil, Santhosh; Valiathan, Manna; Mathur, Deepak


    An optical trap has been combined with a Raman spectrometer to make high-resolution measurements of Raman spectra of optically-immobilized, single, live red (RBC) and white blood cells (WBC) under physiological conditions. Tightly-focused, near infrared wavelength light (1064 nm) is utilized for trapping of single cells and 785 nm light is used for Raman excitation at low levels of incident power (few mW). Raman spectra of RBC recorded using this high-sensitivity, dual-wavelength apparatus has enabled identification of several additional lines; the hitherto-unreported lines originate purely from hemoglobin molecules. Raman spectra of single granulocytes and lymphocytes are interpreted on the basis of standard protein and nucleic acid vibrational spectroscopy data. The richness of the measured spectrum illustrates that Raman studies of live cells in suspension are more informative than conventional micro-Raman studies where the cells are chemically bound to a glass cover slip. PMID:20454686

  3. Early dental caries detection using a fibre-optic coupled polarization-resolved Raman spectroscopic system.

    Ko, Alex C-T; Hewko, Mark; Sowa, Michael G; Dong, Cecilia C S; Cleghorn, Blaine; Choo-Smith, Lin-P'ing


    A new fibre-optic coupled polarization-resolved Raman spectroscopic system was developed for simultaneous collection of orthogonally polarized Raman spectra in a single measurement. An application of detecting incipient dental caries based on changes observed in Raman polarization anisotropy was also demonstrated using the developed fibre-optic Raman spectroscopic system. The predicted reduction of polarization anisotropy in the Raman spectra of caries lesions was observed and the results were consistent with those reported previously with Raman microspectroscopy. The capability of simultaneous collection of parallel- and cross-polarized Raman spectra of tooth enamel in a single measurement and the improved laser excitation delivery through fibre-optics demonstrated in this new design illustrates its future clinical potential.

  4. Raman tweezers spectroscopy of live, single red and white blood cells.

    Aseefhali Bankapur

    Full Text Available An optical trap has been combined with a Raman spectrometer to make high-resolution measurements of Raman spectra of optically-immobilized, single, live red (RBC and white blood cells (WBC under physiological conditions. Tightly-focused, near infrared wavelength light (1064 nm is utilized for trapping of single cells and 785 nm light is used for Raman excitation at low levels of incident power (few mW. Raman spectra of RBC recorded using this high-sensitivity, dual-wavelength apparatus has enabled identification of several additional lines; the hitherto-unreported lines originate purely from hemoglobin molecules. Raman spectra of single granulocytes and lymphocytes are interpreted on the basis of standard protein and nucleic acid vibrational spectroscopy data. The richness of the measured spectrum illustrates that Raman studies of live cells in suspension are more informative than conventional micro-Raman studies where the cells are chemically bound to a glass cover slip.

  5. Non-invasive laser Raman detection of lycopene and ž-carotene antioxidants in skin

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner


    The predominant long-chain carotenoids found in the human skin are lycopene and β-carotene. They are powerful antioxidants and thought to act as scavengers for free radicals and single oxygen that are formed by excessive exposure of skin to sunlight. However the role of the particular representatives of the carotenoid antioxidants family in the skin defense mechanism is still unclear and has to be clarified. We demonstrate the opportunity for fast non-invasive selective quantitative detection of β-carotene and lycopene in human skin employing Raman spectroscopy. Analyzing Raman signals originating from the carbon-carbon double bond stretch vibrations of the molecules under blue and green laser excitation we were able to characterize quantitativly the concentrations of each carotenoid in alive human skin. In this method we take an advantage of different Raman cross-section spectral profile for β-carotene and lycopene molecules. This novel technique allows the quantitative assessment of individual carotenoid species in the skin rather then the cumulative level of long-chain carotenoids mixture as we could measure in our previous works. The required laser light exposure levels are well within safety standards. Prelimininary dichoromatic Raman measurements reveal significant differences in the carotenoid composition of different volunteer's skin: even in statistically small group of seven subjects the ratio of β-carotene-to-lycopene in their skin vary from 0.5 to 1.6. This technique holds promise as a method of rapid screening of carotenoids composition of human skin in large populations and suitable in clinical studies for assessing the risk for cutaneous diseases.

  6. a Study on Excited State Dynamics of Simple Molecules: Time Dependent Wavepacket Approach

    Ryu, Jae-Seok


    Potential energy surfaces for the excited states of ethylene and dihalomethanes are determined by utilizing all available information from absorption and resonance Raman experiments and ab initio calculations. The theoretical treatment of absorption and resonance Raman excitation profiles utilize the well developed wavepacket methodology. The electronic spectrum of ethylene in the 50,000 -66,000cm^{-1} region has been assigned to overlapping valence pipi ^* ("N --> V") and pi3s Rydberg ("N --> R") transitions. In this thesis the hypothesis is made and tested that all of the observed structure is due to one pipi^* excited state. For the pipi^* electronic N --> V transition of ethylene, the V-state potential is constructed by considering a dynamical torsional barrier height which changes with the C-C distance. The spectrum that results from this single surface does not provide adequate agreement with experiment. The standard overlapping N --> V plus pi3s description is then considered quantitatively. In order to fit the observed spectra it is necessary to use a very large value for the N --> R (3s) oscillator strength and a very small value for the N --> V transition strength. Both of these values disagree with the results of ab initio calculation. Use of a large C = C displacement for N --> V transition can increase the oscillator strength for this state but this results in the expectation of strong overtone intensity in the resonance Raman spectrum in disagreement with experiment. Hence, the traditional assignment is also rejected and an alternative is sought. The most likely explanation for the strong structured absorption beginning at 57,500cm^{-1} is that it results from transitions to two coupled surfaces due to the N --> V state with B_{1u} symmetry and another Rydberg state of pi3p _{y} origin with B_{1g} symmetry. This new assignment of the ethylene spectrum predicts a constant depolarization. The traditional assignment predicts strong dispersion which is

  7. Profiling cancer

    Ciro, Marco; Bracken, Adrian P; Helin, Kristian


    In the past couple of years, several very exciting studies have demonstrated the enormous power of gene-expression profiling for cancer classification and prediction of patient survival. In addition to promising a more accurate classification of cancer and therefore better treatment of patients......, gene-expression profiling can result in the identification of novel potential targets for cancer therapy and a better understanding of the molecular mechanisms leading to cancer....

  8. Profiling cancer

    Ciro, Marco; Bracken, Adrian P; Helin, Kristian


    In the past couple of years, several very exciting studies have demonstrated the enormous power of gene-expression profiling for cancer classification and prediction of patient survival. In addition to promising a more accurate classification of cancer and therefore better treatment of patients......, gene-expression profiling can result in the identification of novel potential targets for cancer therapy and a better understanding of the molecular mechanisms leading to cancer....

  9. Comment on "Raman spectra of misoriented bilayer graphene"

    Ni, Zhenhua; Wang, Yingying; Yu, Ting; You, Yumeng; Shen, Zexiang


    In a recent paper [Phys. Rev. B 78, 113407 (2008)], Poncharal et al. studied the Raman spectra of misoriented bilayer graphene. They found that the blueshift of 2D band of misoriented graphene relative to that of single layer graphene shows a strong dependence on the excitation laser energy. The blueshift increases with decreasing excitation energy. This finding contradicts our explanation of reduction of Fermi velocity of folded/misoriented graphene [Ni et al. Phys. Rev. B 77, 235403 (2008)]...

  10. Surface enhanced Raman scattering spectroscopic waveguide

    Lascola, Robert J; McWhorter, Christopher S; Murph, Simona H


    A waveguide for use with surface-enhanced Raman spectroscopy is provided that includes a base structure with an inner surface that defines a cavity and that has an axis. Multiple molecules of an analyte are capable of being located within the cavity at the same time. A base layer is located on the inner surface of the base structure. The base layer extends in an axial direction along an axial length of an excitation section. Nanoparticles are carried by the base layer and may be uniformly distributed along the entire axial length of the excitation section. A flow cell for introducing analyte and excitation light into the waveguide and a method of applying nanoparticles may also be provided.

  11. Surface enhanced Raman scattering spectroscopic waveguide

    Lascola, Robert J; McWhorter, Christopher S; Murph, Simona H


    A waveguide for use with surface-enhanced Raman spectroscopy is provided that includes a base structure with an inner surface that defines a cavity and that has an axis. Multiple molecules of an analyte are capable of being located within the cavity at the same time. A base layer is located on the inner surface of the base structure. The base layer extends in an axial direction along an axial length of an excitation section. Nanoparticles are carried by the base layer and may be uniformly distributed along the entire axial length of the excitation section. A flow cell for introducing analyte and excitation light into the waveguide and a method of applying nanoparticles may also be provided.

  12. NH and OH Concentration Profiles in a Stoichiometric CH4/N2O Flame by Laser Excited Fluorescence and Absorption Techniques.


    Molecular Beam Mass Spectrometry and Ultraviolet Absorption Spectroscopy, Combustion and Flane VoZ . 33, p. 5, 1978. 2 CattoZica, R.J., Yoon, S. and Knuth, E.L...National Bureau of Standards Special Publication 561/2, U.S. Government Printing Office, ’-..Washington, D.C., VoZ . II, Section VI, 1979. ?Anderson, W.R...Chm. Phys. VoZ . 43, p. 3237, 1965. 19 1Anderson, W.R., Decker, L.J., and KotZar, A.J., "Concentration Profiles of NH and OH in a Stoichiometric CH4

  13. Research on Raman Crosstalk in Broadband Wavelength Division Multiplexed Systems

    XUE Fei; QIU Kun


    After a theoretical model is put forward on the base of accurate description of the Raman gain profile and the physical quantity,maximum Raman crosstalk(MRC),which quantificationally depicts the intensity of Raman crosstalk is defined.The influences of launch power,fiber effective core area,fiber nonlinear index,fiber length,channel number and channel interval on MRC are deduced.The result indicates that compared with low speed and narrowband optical fiber communication system,serious Raman crosstalk lies in high speed and broadband system,which impacts the performance of the system badly.The result is useful for forecasting Raman crosstalk in broadband and high speed optical fiber communication system.

  14. Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii).

    Maguregui, M; Knuutinen, U; Trebolazabala, J; Morillas, H; Castro, K; Martinez-Arkarazo, I; Madariaga, J M


    Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.

  15. Raman scattering in crystals

    Edwards, D.F.


    A tutorial presentation is given of Raman scattering in crystals. The physical concepts are emphasized rather than the detailed mathematical formalism. Starting with an introduction to the concepts of phonons and conservation laws, the effects of photon-phonon interactions are presented. This interaction concept is shown for a simple cubic crystal and is extended to a uniaxial crystal. The correlation table method is used for determining the number and symmetry of the Raman active modes. Finally, examples are given to illustrate the relative ease of using this group theoretical method and the predictions are compared with measured Raman spectra. 37 refs., 17 figs., 6 tabs.

  16. Applications of Raman Spectroscopy to Inorganic Chemistry



    The renaissance in Raman spectroscopy some 25-30 years ago had particular and immediate impact on Inorganic Chemistry,viz in areas such as the study of deeply coloued compounds,structural changes on change of state,equilibria,vapour phase band contour analysis,Raman band intensities and the nature of the chemical bond,metal-metal bonding,species in melts,identification of species in solution and of radicals by time-resolved techniques,in bioinorganic chemistry,and of linear-chain semiconductors.More recently,much attention has been directed at the quantitative level at the evaluation of geometric changes in molecules on excitation by resonance Raman spectroscopy.At the qualitative level Raman microscopy is now recognised to be the most effective technique for the identification of pigments-particularly the inorganic ones-on medieval manuscripts and especially of the components(down to grain sizes of -1 um)of pigment mixtures,It is thus a very important technique at the Arts/Science borderling in conservation science.

  17. Raman microspectroscopy for visualization of peripheral nerves

    Minamikawa, Takeo; Harada, Yoshinori; Koizumi, Noriaki; Takamatsu, Tetsuro


    The peripheral nervous system plays an important role in motility, sensory, and autonomic functions of the human body. Preservation of peripheral nerves in surgery is essential for improving quality of life of patients. To preserve peripheral nerves, detection of ne peripheral nerves that cannot be identi ed by human eye or under white light imaging is necessary. In this study, we sought to provide a proof-of-principle demonstration of a label-free detection technique of peripheral nerve tissues against adjacent tissues that employs spontaneous Raman microspectroscopy. A line-illumination confocal Raman microscope was used for the experiment. A laser operating at the wavelength of 532 nm was used as an excitation laser light. We obtained Raman spectra of peripheral nerve, brous connective tissue, skeletal muscle, blood vessel, and adipose tissue of Wistar rats, and extracted speci c spectral features of peripheral nerves and adjacent tissues. By applying multivariate image analysis, peripheral nerves were clearly detected against adjacent tissues without any preprocessing neither xation nor staining. These results suggest the potential of the Raman spectroscopic observation for noninvasive and label-free nerve detection, and we expect this method could be a key technique for nerve-sparing surgery.

  18. Resonance Raman measurements of carotenoids using light emitting diodes

    Bergeson, S D; Eyring, N J; Fralick, J F; Stevenson, D N; Ferguson, S B


    We report on the development of a compact commercial instrument for measuring carotenoids in skin tissue. The instrument uses two light emitting diodes (LEDs) for dual-wavelength excitation and four photomultiplier tubes for multichannel detection. Bandpass filters are used to select the excitation and detection wavelengths. The f/1.3 optical system has high optical throughput and single photon sensitivity, both of which are crucial in LED-based Raman measurements. We employ a signal processing technique that compensates for detector drift and error. The sensitivity and reproducibility of the LED Raman instrument compares favorably to laser-based Raman spectrometers. This compact, portable instrument is used for non-invasive measurement of carotenoid molecules in human skin with a repeatability better than 10%.

  19. UV resonance Raman analysis of trishomocubane and diamondoid dimers

    Meinke, Reinhard, E-mail:; Thomsen, Christian; Maultzsch, Janina [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstr. 36, D-10623 Berlin (Germany); Richter, Robert; Merli, Andrea [Institut für Optik und Atomare Physik, Technische Universität Berlin, Hardenbergstr. 36, D-10623 Berlin (Germany); Fokin, Andrey A. [Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, D-35392 Giessen (Germany); Department of Organic Chemistry, Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev (Ukraine); Koso, Tetyana V.; Schreiner, Peter R. [Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, D-35392 Giessen (Germany); Rodionov, Vladimir N. [Department of Organic Chemistry, Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev (Ukraine)


    We present resonance Raman measurements of crystalline trishomocubane and diamantane dimers containing a C=C double bond. Raman spectra were recorded with excitation energies between 2.33 eV and 5.42 eV. The strongest enhancement is observed for the C=C stretch vibration and a bending mode involving the two carbon atoms of the C=C bond, corresponding to the B{sub 2g} wagging mode of ethylene. This is associated with the localization of the π-HOMO and LUMO and the elongation of the C=C bond length and a pyramidalization of the two sp{sup 2}-hybridized carbon atoms at the optical excitation. The observed Raman resonance energies of the trishomocubane and diamantane dimers are significantly lower than the HOMO-LUMO gaps of the corresponding unmodified diamondoids.

  20. Sexual excitement.

    Stoller, R J


    Sexual excitement depends on a scenario the person to be aroused has been writing since childhood. The story is an adventure, an autobiography disguised as fiction, in which the hero/heroine hides crucial intrapsychic conflicts, mysteries, screen memories of actual traumatic events and the resolution of these elements into a happy ending, best celebrated by orgasm. The function of the fantasy is to take these painful experiences and convert them to pleasure-triumph. In order to sharpen excitement-the vibration between the fear of original traumas repeating and the hope of a pleasurable conclusion this time-one introduces into the story elements of risk (approximations of the trauma) meant to prevent boredom and safety factors (sub-limnal signals to the storyteller that the risk are not truly dangerous). Sexual fantasy can be studied by means of a person's daydreams (including those chosen in magazines, books, plays, television, movies, and outright pornography), masturbatory behavior, object choice, foreplay, techniques of intercourse, or postcoital behavior.

  1. Raman study of a work of art fragment

    Scremin, Barbara Federica


    The purpose of the present report was the study and identification of an unspecified sample on a work of art by means only of a microscope coupled to a Raman spectrometer. The origin of the fragment was unknown. The Raman spectra on the virgin sample were giving no results because of a deteriorated surface treatment, in spite of the evident blue color identified by microscopic visual inspection. The sample fragmentation and the preparation of a KBr pellet allowed the distribution of the painting layers of the different components on a flat substrate reducing surface effects. Selecting the areas of different color and focusing there it was possible to identify the pigments from their Raman spectra locally acquired by selective excitation. Raman spectra were assigned by comparison with published databases. It was possible to connect Carbon Black and Orange iron oxide, as documented historically, as constituents of Azurite preparatory layer Morellone, according to a technique generally employed to allow the use ...

  2. Raman microscopy of individual living human embryonic stem cells

    Novikov, S. M.; Beermann, J.; Bozhevolnyi, S. I.; Harkness, L. M.; Kassem, M.


    We demonstrate the possibility of mapping the distribution of different biomolecules in living human embryonic stem cells grown on glass substrates, without the need for fluorescent markers. In our work we improve the quality of measurements by finding a buffer that gives low fluorescence, growing cells on glass substrates (whose Raman signals are relatively weak compared to that of the cells) and having the backside covered with gold to improve the image contrast under direct white light illumination. The experimental setup used for Raman microscopy is the commercially available confocal scanning Raman microscope (Alpha300R) from Witec and sub-μm spatially resolved Raman images were obtained using a 532 nm excitation wavelength.

  3. Nanophotonic waveguide enhanced Raman spectroscopy of biological submonolayers

    Dhakal, Ashim; Peyskens, Frédéric; Jans, Karolien; Thomas, Nicolas Le; Baets, Roel


    Characterizing a monolayer of biological molecules has been a major challenge. We demonstrate nanophotonic wave-guide enhanced Raman spectroscopy (NWERS) of monolayers in the near-infrared region, enabling real-time measurements of the hybridization of DNA strands and the density of sub-monolayers of biotin-streptavidin complex immobilized on top of a photonics chip. NWERS is based on enhanced evanescent excitation and collection of spontaneous Raman scattering near nanophotonic waveguides, which for a one centimeter silicon nitride waveguide delivers a signal that is more than four orders of magnitude higher in comparison to a confocal Raman microscope. The reduced acquisition time and specificity of the signal allows for a quantitative and real-time characterization of surface species, hitherto not possible using Raman spectroscopy. NWERS provides a direct analytic tool for monolayer research and also opens a route to compact microscope-less lab-on-a-chip devices with integrated sources, spectrometers and d...

  4. Generation of Pseudoscalar Bosons by Stimulated Raman Scattering of Light in Dielectric Media

    Gorelik V.S.


    Full Text Available The conditions of pseudoscalar excitations of liquids and crystals vibration states in spontaneous and stimulated Raman spectra revealing are reported. The selection rules for pseudoscalar modes of molecules and crystals observation have been obtained. The experiments on observation of spontaneous and stimulated Raman scattering on pseudoscalar modes of molecules and crystals have been fulfilled. The excitation of stimulated Raman scattering was with using of solid state laser YAG:Nd3+, generating intense (up to 1 TW/cm2 ultrashort (60 ps laser pulses with energy 10 mJ and frequency repetition 10 Hz. The relationship between pseudoscalar bosons of dielectric media and axion of vacuum is analyzed.

  5. Evaluation of variations of biomolecular constituents in human skin in vivo by near-infrared Raman spectroscopy

    Huang, Zhiwei; Zeng, Haishan; MacAulay, Calum E.; Hamzavi, Iltefat; McLean, David I.; Lui, Harvey


    A portable and rapid near-infrared (NIR) Raman spectroscopy system together with a tissue Raman probe was developed and utilized to acquire in vivo skin Raman spectra at 785 nm excitation. We demonstrated that good quality in vivo skin Raman spectra free of interferences of fiber fluorescence and silica Raman signals can be acquired within 5 seconds. Distinct Raman peaks in the 800-1800 cm-1 range can be discerned clearly from various skin sites of the body. The intensity ratio of the Raman band at 1655 cm-1 to that at 1445 cm-1 was used to evaluate the variation of the protein/lipid depositions in the skin. The results show that the regional variations in the molecular composition and structure can be determined in vivo, suggesting that NIR Raman spectroscopy will be useful to non-invasively measure important biochemical parameters of human skin.

  6. Random Raman lasing

    Hokr, Brett H; Mason, John D; Beier, Hope T; Rockwll, Benjamin A; Thomas, Robert J; Noojin, Gary D; Petrov, Georgi I; Golovan, Leonid A; Yakovlev, Vladislav V


    Propagation of light in a highly scattering medium is among the most fascinating optical effect that everyone experiences on an everyday basis and possesses a number of fundamental problems which have yet to be solved. Conventional wisdom suggests that non-linear effects do not play a significant role because the diffusive nature of scattering acts to spread the intensity, dramatically weakening these effects. We demonstrate the first experimental evidence of lasing on a Raman transition in a bulk three-dimensional random media. From a practical standpoint, Raman transitions allow for spectroscopic analysis of the chemical makeup of the sample. A random Raman laser could serve as a bright Raman source allowing for remote, chemically specific, identification of powders and aerosols. Fundamentally, the first demonstration of this new light source opens up an entire new field of study into non-linear light propagation in turbid media, with the most notable application related to non-invasive biomedical imaging.

  7. Micro-Raman spectroscopy of Si nanowires: Influence of diameter and temperature

    Torres, A.; Martín-Martín, A.; Martínez, O.; Prieto, A. C.; Hortelano, V.; Jiménez, J.; Rodríguez, A.; Sangrador, J.; Rodríguez, T.


    Raman spectroscopy provides nondestructive information about nanoscaled semiconductors by modeling the phonon confinement effect. However, the Raman spectrum is also sensitive to the temperature, which can mix with the size effects borrowing the interpretation of the Raman spectrum. We present an analysis of the Raman spectra of Si nanowires (NWs). The influence of the excitation conditions and the temperature increase in the NWs are discussed. The interpretation of the data is supported by the calculation of the temperature inside the NWs with different diameters.

  8. A flow cytometer for the measurement of Raman spectra.

    Watson, Dakota A; Brown, Leif O; Gaskill, Daniel F; Naivar, Mark; Graves, Steven W; Doorn, Stephen K; Nolan, John P


    Multiparameter measurements in flow cytometry are limited by the broad emission spectra of fluorescent labels. By contrast, Raman spectra are notable for their narrow spectral features. To increase the multiparameter analysis capabilities of flow cytometry, we investigated the possibility of measuring Raman signals in a flow cytometry-based system. We constructed a Raman Spectral Flow Cytometer, substituting a spectrograph and CCD detector for the traditional mirrors, optical filters, and photomultiplier tubes. Excitation at 633 nm was provided by a HeNe laser, and forward-angle light scatter is used to trigger acquisition of complete spectra from individual particles. Microspheres were labeled with nanoparticle surface enhanced Raman scattering (SERS) tags and measured using the RSFC. Fluorescence and Raman spectra from labeled microspheres were acquired using the Raman Spectral Flow Cytometer. SERS spectral intensities were dependent on integration time, laser power, and detector pixel binning. Spectra from particles labeled with one each of four different SERS tags could be distinguished by either a virtual bandpass approach using commercial flow cytometry data analysis software or by principal component analysis. Raman flow cytometry opens up new possibilities for highly multiparameter and multiplexed measurements of cells and other particles using a simple optical design and a single detector and light source.

  9. Surface enhanced Raman spectroscopy using a single mode nanophotonic-plasmonic platform

    Peyskens, Frédéric; Van Dorpe, Pol; Thomas, Nicolas Le; Baets, Roel


    Surface Enhanced Raman Spectroscopy (SERS) is a well-established technique for enhancing Raman signals. Recently photonic integrated circuits have been used, as an alternative to microscopy based excitation and collection, to probe SERS signals from external metallic nanoparticles. However, in order to develop quantitative on-chip SERS sensors, integration of dedicated nanoplasmonic antennas and waveguides is desirable. Here we bridge this gap by demonstrating for the first time the generation of SERS signals from integrated bowtie nanoantennas, excited and collected by a single mode waveguide, and rigorously quantify the enhancement process. The guided Raman power generated by a 4-Nitrothiophenol coated bowtie antenna shows an 8 x 10^6 enhancement compared to the free-space Raman scattering. An excellent correspondence is obtained between the theoretically predicted and observed absolute Raman power. This work paves the way towards fully integrated lab-on-a-chip systems where the single mode SERS-probe can b...

  10. Noninvasive Spatiotemporal Profiling of the Processes of Impregnation and Drying within Mo/Al2O3 Catalyst Bodies by a Combination of X-ray Absorption Tomography and Diagonal Offset Raman Spectroscopy

    Gibson, E.K.; Zandbergen, M.W.; Jacques, S.D.M.; Biao, C.; Cernik, R.J.; O’Brien, M.G.; Di Michiel, M.; Weckhuysen, B.M.; Beale, A.M.


    A combination of X-ray absorption microcomputed tomography (μ-CT) and diagonal offset raman spectroscopy (DORS) have been used to follow in real time the 2-D and 3-D evolution of Mo species within 3 mm γ-Al2O3 extrudates during catalyst impregnation and drying processes. In a first set of experiment

  11. Raman transitions between hyperfine clock states in a magnetic trap

    Naber, J B; Hubert, T; Spreeuw, R J C


    We present our experimental investigation of an optical Raman transition between the magnetic clock states of $^{87}$Rb in an atom chip magnetic trap. The transfer of atomic population is induced by a pair of diode lasers which couple the two clock states off-resonantly to an intermediate state manifold. This transition is subject to destructive interference of two excitation paths, which leads to a reduction of the effective two-photon Rabi-frequency. Furthermore, we find that the transition frequency is highly sensitive to the intensity ratio of the diode lasers. Our results are well described in terms of light shifts in the multi-level structure of $^{87}$Rb. The differential light shifts vanish at an optimal intensity ratio, which we observe as a narrowing of the transition linewidth. We also observe the temporal dynamics of the population transfer and find good agreement with a model based on the system's master equation and a Gaussian laser beam profile. Finally, we identify several sources of decoheren...

  12. Raman spectra of carotenoids in natural products

    Withnall, Robert; Chowdhry, Babur Z.; Silver, Jack; Edwards, Howell G. M.; de Oliveira, Luiz F. C.


    Resonance Raman spectra of naturally occurring carotenoids have been obtained from nautilus, periwinkle ( Littorina littorea) and clam shells under 514.5 nm excitation and these spectra are compared with the resonance Raman spectra obtained in situ from tomatoes, carrots, red peppers and saffron. The tomatoes, carrots and red peppers gave rise to resonance Raman spectra exhibiting a ν1 band at ca. 1520 cm -1, in keeping with its assignment to carotenoids with ca. nine conjugated carboncarbon double bonds in their main chains, whereas the resonance Raman spectrum of saffron showed a ν1 band at 1537 cm -1 which can be assigned to crocetin, having seven conjugated carboncarbon double bonds. A correlation between ν1 wavenumber location and effective conjugated chain length has been used to interpret the data obtained from the shells, and the wavenumber position (1522 cm -1) of the ν1 band of the carotenoid in the orange clam shell suggests that it contains nine conjugated double bonds in the main chain. However, the black periwinkle and nautilus shells exhibit ν1 bands at 1504 and 1496 cm -1, respectively. On the basis of the correlation between ν1 wavenumber location and effective conjugated chain length, this indicates that they contain carotenoids with longer conjugated chains, the former having ca. 11 double bonds and the latter ca. 13 or even more. Raman spectra of the nautilus, periwinkle and clam shells also exhibited a strong band at 1085 cm -1 and a doublet with components at 701 and 705 cm -1, which can be assigned to biogenic calcium carbonate in the aragonite crystallographic form.

  13. Resonance Raman of BCC and normal skin

    Liu, Cheng-hui; Sriramoju, Vidyasagar; Boydston-White, Susie; Wu, Binlin; Zhang, Chunyuan; Pei, Zhe; Sordillo, Laura; Beckman, Hugh; Alfano, Robert R.


    The Resonance Raman (RR) spectra of basal cell carcinoma (BCC) and normal human skin tissues were analyzed using 532nm laser excitation. RR spectral differences in vibrational fingerprints revealed skin normal and cancerous states tissues. The standard diagnosis criterion for BCC tissues are created by native RR biomarkers and its changes at peak intensity. The diagnostic algorithms for the classification of BCC and normal were generated based on SVM classifier and PCA statistical method. These statistical methods were used to analyze the RR spectral data collected from skin tissues, yielding a diagnostic sensitivity of 98.7% and specificity of 79% compared with pathological reports.

  14. Enhancement of photoluminescence and raman scattering in one-dimensional photonic crystals based on porous silicon

    Gonchar, K. A., E-mail: [Moscow State University, Physics Faculty (Russian Federation); Musabek, G. K.; Taurbayev, T. I. [Al Farabi Kazakh National University, Physics Department (Kazakhstan); Timoshenko, V. Yu. [Moscow State University, Physics Faculty (Russian Federation)


    In porous-silicon-based multilayered structures that exhibit the properties of one-dimensional photonic crystals, an increase in the photoluminescence and Raman scattering intensities is observed upon optical excitation at the wavelength 1.064 {mu}m. When the excitation wavelength falls within the edge of the photonic band gap of the structures, a multiple increase (by a factor larger than 400) in the efficiency of Raman scattering is detected. The effect is attributed to partial localization of excitation light and, correspondingly, to the much longer time of interaction of light with the material in the structures.

  15. Femtosecond stimulated Raman study of the photoactive flavoprotein AppABLUF

    Hall, Christopher R.; Heisler, Ismael A.; Jones, Garth A.; Frost, James E.; Gil, Agnieszka A.; Tonge, Peter J.; Meech, Stephen R.


    Femtosecond stimulated Raman spectroscopy (FSRS) is applied to study the photocycle of a blue light using flavin (BLUF) domain photoreceptor, AppABLUF. It is shown that FSRS spectra are sensitive to the light adapted state of the protein and probe its excited state dynamics. The dominant contribution to the most sensitive excited state Raman active modes is from flavin ring modes. However, TD-DFT calculations for excited state structures indicate that reproduction and assignment of the experimentally observed spectral shift will require high level calculations on the flavin in its specific protein environment.

  16. Raman and surface enhanced Raman spectroscopic investigation on Lamiaceae plants

    Rösch, P.; Popp, J.; Kiefer, W.


    The essential oils of Thymus vulgaris and Origanum vulgaris are studied by means of micro-Raman spectroscopy. The containing monoterpenes can be identified by their Raman spectra. Further the essential oils are investigated in their natural environment, the so-called oil cells of these Lamiaceae plants, with surface enhanced Raman spectroscopy (SERS). This method has the advantage to enhance Raman signals and furthermore the SERS effect leads to fluorescence quenching.

  17. Multiphonon Resonance Raman Scattering in InGaN

    Ager III, J.W.; Walukiewicz, W.; Shan, W.; Yu, K.M.; Li, S.X.; Haller, E.E.; Lu, H.; Schaff, W.J.


    In In{sub x}Ga{sub 1-x}N epitaxial films with 0.37 < x < 1 and free electron concentrations in the 10{sup 18} cm{sup -3} range, strong resonant Raman scattering of A{sub 1}(LO) phonon is observed for laser excitation in Raman scattering when excited above the direct band gaps. Examination of films with direct band gaps between 0.7 and 1.9 eV using laser energies from 1.9 to 2.7 eV shows that the resonance is broad, extending to up to 2 eV above the direct gap. Multiphonon Raman scattering with up to 5 LO phonons is also observed for excitation close to resonance in alloy samples; this is the highest number of phonon overtones ever observed for multiphonon scattering in a III-V compound under ambient conditions. Coupling of the electron plasmon to the LO phonon to form a longitudinal plasmon coupled mode of the type which is observed in the Raman spectra of n-GaN, appears not to occur in In{sub x}Ga{sub 1-x}N for x > 0.37.

  18. Confocal Raman microspectroscopy: measuring the effects of topical moisturizers on stratum corneum water gradient in vivo

    Sieg, Anke; Crowther, Jonathan; Blenkiron, Peter; Marcott, Curtis; Matts, Paul J.


    The stratum corneum (SC) water concentration gradient is fundamental to skin's role as a barrier, regulating its physical and biochemical properties. Standard instruments utilizing changes in SC electrical properties to estimate SC water concentration provide simple, rapid measurements but cannot provide true interval data as a function of depth. Confocal Raman spectroscopy (CRS) of human subjects provides non-invasive, real-time, in vivo measures of molecular concentration profiles. A state-of-the-art confocal Raman microspectrometer equipped with a fiber-coupled laser source operating at a wavelength of 671 nm was used to obtain measurements in the high wavenumber region (~2400-4000 cm -1). An aircooled, high-sensitivity back-illuminated, deep-depletion CCD camera captured radiation scattered inelastically from focal planes within the skin in vivo (a high-precision, computer-controlled piezo-electric stage and objective allowing depth resolutions of niacinamide on SC water concentration gradient, as measured by CRS, in vivo. The approach to compare SC water gradient effects will be discussed and the utility of this exciting new method will be compared and contrasted to existing methodology.

  19. Optimization of surface enhanced Raman scattering (SERS) assay for the transition from benchtop to handheld Raman systems

    Schechinger, Monika; Marks, Haley; Locke, Andrea; Choudhury, Mahua; Coté, Gerard


    Human biomarkers are indicative of the body's relative state prior to the onset of disease, and sometimes before symptoms present. While blood biomarker detection has achieved considerable success in laboratory settings, its clinical application is lagging and commercial point-of-care devices are rare. A physician's ability to detect biomarkers such as microRNA-17, a potential epigenetic indicator of preeclampsia in pregnant woman, could enable early diagnosis and preventive intervention as early as the 1st trimester. One detection approach employing DNA-functionalized nanoparticles to detect microRNA-17, in conjunction with surface-enhanced Raman spectroscopy (SERS), has shown promise but is hindered, in part, by the use of large and expensive benchtop Raman microscopes. However, recent strides have been made in developing portable Raman systems for field applications. Characteristics of the SERS assay responsible for strengthening the assay's plasmonic response were explored, whilst comparing the results from both benchtop and portable Raman systems. The Raman spectra and intensity of three different types of photoactive molecules were compared as potential Raman reporter molecules: chromophores, fluorophores, and highly polarizable small molecules. Furthermore, the plasmonic characteristics governing the formation of SERS colloidal nanoparticle assemblies in response to DNA/miRNA hybridization were investigated. There were significant variations in the SERS enhancement in response to microRNA-17 using our assay depending on the excitation lasers at wavelengths of 532 nm and 785 nm, depending on which of the three different Raman systems were used (benchtop, portable, and handheld), and depending on which of the three different Raman reporters (chromophore, fluorophore, or Raman active molecule) were used. Analysis of data obtained did indicate that signal enhancement was better for the chromophore (MGITC) and Raman active molecule (DTNB) than it was for the

  20. Raman spectroscopy in astrobiology.

    Jorge Villar, Susana E; Edwards, Howell G M


    Raman spectroscopy is proposed as a valuable analytical technique for planetary exploration because it is sensitive to organic and inorganic compounds and able to unambiguously identify key spectral markers in a mixture of biological and geological components; furthermore, sample manipulation is not required and any size of sample can be studied without chemical or mechanical pretreatment. NASA and ESA are considering the adoption of miniaturised Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for extinct or extant life signals. In this paper we review the advantages and limitations of Raman spectroscopy for the analysis of complex specimens with relevance to the detection of bio- and geomarkers in extremophilic organisms which are considered to be terrestrial analogues of possible extraterrestial life that could have developed on planetary surfaces.

  1. Raman fiber lasers

    Supradeepa, V. R.; Feng, Yan; Nicholson, Jeffrey W.


    High-power fiber lasers have seen tremendous development in the last decade, with output powers exceeding multiple kilowatts from a single fiber. Ytterbium has been at the forefront as the primary rare-earth-doped gain medium owing to its inherent material advantages. However, for this reason, the lasers are largely confined to the narrow emission wavelength region of ytterbium. Power scaling at other wavelength regions has lagged significantly, and a large number of applications rely upon the diversity of emission wavelengths. Currently, Raman fiber lasers are the only known wavelength agile, scalable, high-power fiber laser technology that can span the wavelength spectrum. In this review, we address the technology of Raman fiber lasers, specifically focused on the most recent developments. We will also discuss several applications of Raman fiber lasers in laser pumping, frequency conversion, optical communications and biology.

  2. Raman spectrum of asphaltene

    Abdallah, Wael A.


    Asphaltenes extracted from seven different crude oils representing different geological formations from around the globe were analyzed using the Raman spectroscopic technique. Each spectrum is fitted with four main peaks using the Gaussian function. On the basis of D1 and G bands of the Raman spectrum, asphaltene indicated an ordered structure with the presence of boundary defected edges. The average aromatic sheet size of the asphaltene molecules is estimated within the range of 1.52-1.88 nm, which represents approximately seven to eight aromatic fused rings. This estimation is based on the integrated intensity of D1 and G bands, as proposed by Tunistra and Koenig. The results here are in perfect agreement with so many other used techniques and indicate the potential applicability of Raman measurements to determine the average aromatic ring size and its boundary. © 2012 American Chemical Society.

  3. Raman spectroscopy as a process analytical technology for pharmaceutical manufacturing and bioprocessing.

    Esmonde-White, Karen A; Cuellar, Maryann; Uerpmann, Carsten; Lenain, Bruno; Lewis, Ian R


    Adoption of Quality by Design (QbD) principles, regulatory support of QbD, process analytical technology (PAT), and continuous manufacturing are major factors effecting new approaches to pharmaceutical manufacturing and bioprocessing. In this review, we highlight new technology developments, data analysis models, and applications of Raman spectroscopy, which have expanded the scope of Raman spectroscopy as a process analytical technology. Emerging technologies such as transmission and enhanced reflection Raman, and new approaches to using available technologies, expand the scope of Raman spectroscopy in pharmaceutical manufacturing, and now Raman spectroscopy is successfully integrated into real-time release testing, continuous manufacturing, and statistical process control. Since the last major review of Raman as a pharmaceutical PAT in 2010, many new Raman applications in bioprocessing have emerged. Exciting reports of in situ Raman spectroscopy in bioprocesses complement a growing scientific field of biological and biomedical Raman spectroscopy. Raman spectroscopy has made a positive impact as a process analytical and control tool for pharmaceutical manufacturing and bioprocessing, with demonstrated scientific and financial benefits throughout a product's lifecycle.

  4. Interference-free optical detection for Raman spectroscopy

    Nguyen, Quang-Viet (Inventor); Fischer, David G (Inventor); Kojima, Jun (Inventor)


    An architecture for spontaneous Raman scattering (SRS) that utilizes a frame-transfer charge-coupled device (CCD) sensor operating in a subframe burst gating mode to realize time-resolved combustion diagnostics is disclosed. The technique permits all-electronic optical gating with microsecond shutter speeds (<5 .mu.s), without compromising optical throughput or image fidelity. When used in conjunction with a pair of orthogonally-polarized excitation lasers, the technique measures time-resolved vibrational Raman scattering that is minimally contaminated by problematic optical background noise.

  5. Resonant Raman Scattering from Silicon Nanoparticles Enhanced by Magnetic Response

    Dmitriev, Pavel A; Milichko, Valentin A; Makarov, Sergey V; Mukhin, Ivan S; Samusev, Anton K; Krasnok, Alexander E; Belov, Pavel A; Kivshar, Yuri S


    Enhancement of optical response with high-index dielectric nanoparticles is attributed to the excitation of their Mie-type magnetic and electric resonances. Here we study Raman scattering from crystalline silicon nanoparticles and reveal that magnetic dipole modes have much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of Raman signal from individual silicon spherical nanoparticles at the magnetic dipole resonance. Our results confirm the importance of the optically-induced magnetic response of subwavelength dielectric nanoparticles for enhancing light-matter interactions.

  6. Raman spectroscopic determination of norbixin and tartrazine in sugar.

    Uhlemann, Ute; Strelau, Katharina K; Weber, Karina; Da Costa Filho, Paulo Augusto; Rösch, Petra; Popp, Jürgen


    In this paper, a method for the detection of norbixin and tartrazine in sugar by means of resonance Raman spectroscopy is presented. The extraction was done in four steps using methanol and the measurements were performed in aqueous solution. The excitation wavelength was 514 nm for norbixin and 488 nm for tartrazine samples. The characteristic resonance Raman signals of the dyes were fitted by different functions. Depending on the R² values of the different fits, each spectrum was classified as positive or negative response. A detection limit of 250 ng g⁻¹ for norbixin and 989 ng g⁻¹ for tartrazine in solid sugar samples could be reached by logistic regression.

  7. FT-Raman spectroscopy study of human breast tissue

    Bitar Carter, Renata A.; Martin, Airton A.; Netto, Mario M.; Soares, Fernando A.


    Optical spectroscopy has been extensively studied as a potential in vivo diagnostic tool to provide information about the chemical and morphologic structure of tissue. Raman Spectroscpy is an inelastic scattering process that can provide a wealth of spectral features that can be related to the specific molecular structure of the sample. This article reports results of an in vitro study of the FT-Raman human breast tissue spectra. An Nd:YAG laser at 1064nm was used as the excitation source in the FT-Raman Spectrometer. The neoplastic human breast samples, both Fibroadenoma and ICD, were obtained during therapeutical routine medical procedures required by the primary disease, and the non-diseased human tissue was obtained in plastic surgery. No sample preparation was needed for the FT-Raman spectra collection. The FT-Raman spectra were recorded from normal, benign (Fibroadenomas) and malignant (IDC-Intraductal Carcinoma) samples, adding up 51 different areas. The main spectral differences of a typical FT-Raman spectra of a Normal (Non-diseased), Fibroadenoma, and Infiltrating Ductal Carcinoma (IDC) breast tissue at the interval of 600 to 1800cm-1, which may differentiate diagnostically the sample, were found in the bands of 1230 to 1295cm-1, 1440 to 1460 cm-1 and 1650 to 1680 cm-1, assigned to the vibrational bands of the carbohydrate-amide III, proteins and lipids, and carbohydrate-amide I, respectively.

  8. Common Raman Spectral Markers among Different Tissues for Cancer Detection

    Zohreh Dehghani-Bidgoli


    Full Text Available Introduction Raman spectroscopy is a vibrational spectroscopic technique, based on inelastic scattering of monochromatic light. This technique can provide valuable information about biomolecular changes, associated with neoplastic transformation. The purpose of this study was to find Raman spectral markers for distinguishing normal samples from cancerous ones in different tissues. Materials and Methods Ten tissue samples from the breast, colon, pancreas, and thyroid were collected. A Raman system was used for Raman spectroscopic measurement of tissues at 532 nm laser excitation. Five to six Raman spectra were acquired from each sample (a total of 52 spectra. Raman spectra were investigated in important bands associated with Amid1, CH2 (scissoring, Amid3, d(NH, n(C-C, and das (CH3 in both normal and cancerous groups. In addition, common spectral markers, which discriminated between normal and cancerous samples in the above tissues, were investigated. Results Common spectral markers among different tissues included intensities of Amid3 and CH2 (scissoring and intensity ratios of I(Amid1/I(CH2, I(n(C-C/I(CH2, and I(d(NH/I(CH2. This study showed that Amid1-, n(C-C-, and d(NH-to-CH2 intensity ratios can discriminate between normal and cancerous samples, with an accuracy of 84.6%, 82.7%, and 82.7% in all studied tissues, respectively. Conclusion This study demonstrates the presence of common spectral markers, associated with neoplastic changes, among different tissues.

  9. Potential of Raman and Infrared Spectroscopy for Plant Analysis

    Schulz, H.


    Various mid-infrared (MIR) and Raman spectroscopic methods applied to the analysis of valuable plant substances or quality parameters in selected horticultural and agricultural crops are presented. Generally, both spectroscopy techniques allow to identify simultaneously characteristic key bands of individual plant components (e.g. carotenoids, alkaloids, polyacetylenes, fatty acids, amino acids, terpenoids). In contrast to MIR methods Raman spectroscopy mostly does not need any sample pre-treatment; even fresh plant material can be analysed without difficulty because water shows only weak Raman scattering properties. In some cases a significant sensivity enhancement of Raman signals can be achieved if the exciting laser wavelength is adjusted to the absorption range of particular plant chromophores such as carotenoids (Resonance Raman effect). Applying FT-IR or FT Raman micro-spectroscopy the distribution of certain plant constituents in the cell wall can be identified without the need for any physical separation. Furthermore it is also possible to analyse secondary metabolites occurring in the cell vacuoles if significant key bands do not coincide with the spectral background of the plant matrix.

  10. RAMAN spectroscopy imaging improves the diagnosis of papillary thyroid carcinoma

    Rau, Julietta V.; Graziani, Valerio; Fosca, Marco; Taffon, Chiara; Rocchia, Massimiliano; Crucitti, Pierfilippo; Pozzilli, Paolo; Onetti Muda, Andrea; Caricato, Marco; Crescenzi, Anna


    Recent investigations strongly suggest that Raman spectroscopy (RS) can be used as a clinical tool in cancer diagnosis to improve diagnostic accuracy. In this study, we evaluated the efficiency of Raman imaging microscopy to discriminate between healthy and neoplastic thyroid tissue, by analyzing main variants of Papillary Thyroid Carcinoma (PTC), the most common type of thyroid cancer. We performed Raman imaging of large tissue areas (from 100 × 100 μm2 up to 1 × 1 mm2), collecting 38 maps containing about 9000 Raman spectra. Multivariate statistical methods, including Linear Discriminant Analysis (LDA), were applied to translate Raman spectra differences between healthy and PTC tissues into diagnostically useful information for a reliable tissue classification. Our study is the first demonstration of specific biochemical features of the PTC profile, characterized by significant presence of carotenoids with respect to the healthy tissue. Moreover, this is the first evidence of Raman spectra differentiation between classical and follicular variant of PTC, discriminated by LDA with high efficiency. The combined histological and Raman microscopy analyses allow clear-cut integration of morphological and biochemical observations, with dramatic improvement of efficiency and reliability in the differential diagnosis of neoplastic thyroid nodules, paving the way to integrative findings for tumorigenesis and novel therapeutic strategies.

  11. RAMAN spectroscopy imaging improves the diagnosis of papillary thyroid carcinoma

    Rau, Julietta V.; Graziani, Valerio; Fosca, Marco; Taffon, Chiara; Rocchia, Massimiliano; Crucitti, Pierfilippo; Pozzilli, Paolo; Onetti Muda, Andrea; Caricato, Marco; Crescenzi, Anna


    Recent investigations strongly suggest that Raman spectroscopy (RS) can be used as a clinical tool in cancer diagnosis to improve diagnostic accuracy. In this study, we evaluated the efficiency of Raman imaging microscopy to discriminate between healthy and neoplastic thyroid tissue, by analyzing main variants of Papillary Thyroid Carcinoma (PTC), the most common type of thyroid cancer. We performed Raman imaging of large tissue areas (from 100 × 100 μm2 up to 1 × 1 mm2), collecting 38 maps containing about 9000 Raman spectra. Multivariate statistical methods, including Linear Discriminant Analysis (LDA), were applied to translate Raman spectra differences between healthy and PTC tissues into diagnostically useful information for a reliable tissue classification. Our study is the first demonstration of specific biochemical features of the PTC profile, characterized by significant presence of carotenoids with respect to the healthy tissue. Moreover, this is the first evidence of Raman spectra differentiation between classical and follicular variant of PTC, discriminated by LDA with high efficiency. The combined histological and Raman microscopy analyses allow clear-cut integration of morphological and biochemical observations, with dramatic improvement of efficiency and reliability in the differential diagnosis of neoplastic thyroid nodules, paving the way to integrative findings for tumorigenesis and novel therapeutic strategies. PMID:27725756

  12. Nonlinearity in Intensity versus Concentration Dependence for the Deep UV Resonance Raman Spectra of Toluene and Heptane

    Liu, Chuan; Berg, Rolf W.


    by absorption and Resonance Raman effects. Raman spectra of toluene and heptane mixtures - with progressively increasing concentrations of heptane - were measured by use of 229 nm excitation. The results show that the characteristic band intensities are not directly proportional to the relative concentrations...... of the compounds and deviate due to absorption resonance effects. An approximated mathematical model is developed to demonstrate that the intensities of the normal Raman scattering bands are suppressed. An inhibition coefficient Ki is introduced to describe the situation and determine the penetration depth. Most......The relation between Raman scattering, resonance Raman scattering and absorption is reviewed to see to what extent quantitative analysis can be applied in Resonance Raman spectroscopy. In addition to this it is demonstrated experimentally that normal Raman spectra can be dramatically inhibited...

  13. Water Raman normalization of airborne laser fluorosensor measurements - A computer model study

    Poole, L. R.; Esaias, W. E.


    The technique for normalizing airborne lidar measurements of chlorophyll fluoresence by the water Raman scattering signal is investigated for laser-excitation wavelengths of 480 and 532 nm using a semianalytic Monte Carlo methodology (SALMON). The signal-integration depth for chlorophyll fluorescence Z(90,F), is found to be insensitive to excitation wavelength and ranges from a maximum of 4.5 m in clearest waters to less than 1 m at a chlorophyll concentration of 20 microgram/liter. For excitation at 532 nm, the signal-integration depth for Raman scattering, Z(90,R), is comparable to Z(90,F). For excitation at 480 nm, Z(90,R) is four times as large as Z(90,F) in clearest waters but nearly equivalent at chlorophyll concentrations greater than 2-3 microgram/liter. Absolute signal levels are stronger with excitation at 480 nm than with excitation at 532 nm, but this advantage must be weighed against potential ambiguities resulting from different integration depths for the fluorescence and Raman scattering signals in clearer waters. To the precision of the simulations, Raman normalization produces effectively linear response to chlorophyll concentration for both excitation wavelengths.

  14. Raman modes in transferred bilayer CVD graphene

    Niilisk Ahti


    Full Text Available A systematic experimental Raman spectroscopic study of twisted bilayer graphene (tBLG domains localized inside wide-area single layer graphene (SLG produced by low-pressure CVD on Cu foil and transferred onto SiO2/Si substrate has been performed. According to the Raman characterization the tBLG domains had a great variety of twisting angles θ between the bottom and top graphene layers (6° < θ < 25°. The twisting angle θ was estimated from the spectral position of the rotating R and R' modes in the Raman spectrum.Under G band resonance conditions the breathing mode ZO' with a frequency of 95- 97 cm−1 was detected, and a breathing mode ZO was found in the spectra between 804 cm−1 and 836 cm−1, its position depending on the twisting angle θ. An almost linear relationship was found between the frequencies ωZO and ωR. Also a few other spectral peculiarities were found, e.g. a high-energy excitation of the G band resonance, the 2G overtone appearing at 3170-3180 cm−1 by the G band resonance, revealing a linear dispersion of 80 cm−1/eV of the 2D band in tBLG

  15. Development of an inverted NIR-FT-Raman microscope for biomedical applications

    Dippel, B.; Tatsch, E.; Schrader, B.


    NIR-FT-Raman spectroscopy is the most suitable tool for investigation of biological samples, because the fluorescence of organic substances is reduced to a minimum. To examine the applicability of NIR excited FT-Raman spectroscopy to the study of cell cultures and tissues, measurements were made with an inverted Raman microscope, a modified Zeiss Axiovert 135. This system allows the collection of Raman spectra both by Koehler laser illumination and the confocal principle: • Koehler laser illumination avoids overheating and denaturation of the sample because the exciting laser beam illuminates the sample as an unfocused collimated beam. An integrative collection over the whole image of the microscope objective is necessary to increase the Raman light flux. • The confocal arrangement allows high spatial resolution which is reached by selective collection of the Raman scattering of details of the sample. A larger spatial resolution leads to a decreased light flux of the Raman scattering, this is compensated by a focused laser beam. We have used NIR-FT-Raman spectroscopy to investigate the spectra of normal breast tissues, potentially useful in the diagnosis of cancer.

  16. Stimulated Raman Adiabatic Passage for Improved Performance of a Cold Atom Electron and Ion Source

    Sparkes, B M; Taylor, R J; Spiers, R W; McCulloch, A J; Scholten, R E


    We experimentally implement high-efficiency coherent excitation to a Rydberg state using stimulated Raman adiabatic passage in a cold atom electron and ion source, leading to a peak efficiency of 85%, a 1.7 times improvement in excitation probability relative to incoherent pulsed-laser excitation. Using streak measurements and pulsed electric field ionization of the Rydberg atoms we demonstrate electron bunches with duration of 250 ps. High-efficiency excitation will increase source brightness, crucial for ultrafast electron diffraction experiments, while using coherent excitation to high-lying Rydberg states could allow for the reduction of internal bunch heating and the creation of a high-speed single ion source.

  17. Snapshot Raman Spectral Imager


    range is appealing in this regard as upper atmospheric absorption by oxygen and ozone eliminate almost all radiation in the Raman shifted range of a...customer wanted to replace a bulky Fourier-Transform Infrared ( FTIR ) system with a dispersive system to lower the cost and size of the instrument. AQT

  18. Magnetoelectric excitations in multiferroic N i3Te O6

    Skiadopoulou, Stella; Borodavka, Fedir; Kadlec, Christelle; Kadlec, Filip; Retuerto, Maria; Deng, Zheng; Greenblatt, Martha; Kamba, Stanislav


    The spin-order-induced ferroelectric antiferromagnet N i3Te O6 transcends the magnetoelectric performance of all other single-phase multiferroics because it exhibits nonhysteretic colossal magnetoelectric coupling [Y. S. Oh, S. Artyukhin, J. J. Yang, V. Zapf, J. W. Kim, D. Vanderbilt, and S.-W. Cheong, Nat Commun. 5, 3201 (2014), 10.1038/ncomms4201]. We investigated spin and lattice excitations in N i3Te O6 by a combination of infrared, Raman, and THz spectroscopies. Two spin excitations (near 13 and 35 c m-1 ) were observed simultaneously in Raman and time-domain THz spectra below the Néel temperature TN=53 K . We propose to assign them to electromagnons, which are activated by the dynamic magnetoelectric coupling. A third magnon is seen only in the Raman spectra near 206 c m-1 .

  19. Development and biological applications of optical tweezers and Raman spectroscopy

    Xie, Chang'an

    Optical tweezers is a three-dimensional manipulation tool that employs a gradient force that originates from the single highly focused laser beam. Raman spectroscopy is a molecular analytical tool that can give a highly unique "fingerprint" for each substance by measuring the unique vibrations of its molecules. The combination of these two optical techniques offers a new tool for the manipulation and identification of single biological cells and microscopic particles. In this thesis, we designed and implemented a Laser-Tweezers-Raman-Spectroscopy (LTRS) system, also called the Raman-tweezers, for the simultaneous capture and analysis of both biological particles and non-biological particles. We show that microparticles can be conveniently captured at the focus of a laser beam and the Raman spectra of trapped particles can be acquired with high quality. The LTRS system overcomes the intrinsic Brownian motion and cell motility of microparticles in solution and provides a promising tool for in situ identifying suspicious agents. In order to increase the signal to noise ratio, several schemes were employed in LTRS system to reduce the blank noise and the fluorescence signal coming from analytes and the surrounding background. These techniques include near-infrared excitation, optical levitation, confocal microscopy, and frequency-shifted Raman difference. The LTRS system has been applied for the study in cell biology at the single cell level. With the built Raman-tweezers system, we studied the dynamic physiological processes of single living cells, including cell cycle, the transcription and translation of recombinant protein in transgenic yeast cells and the T cell activation. We also studied cell damage and associated biochemical processes in optical traps, UV radiations, and evaluated heating by near-infrared Raman spectroscopy. These studies show that the Raman-tweezers system is feasible to provide rapid and reliable diagnosis of cellular disorders and can be

  20. Noise Gain Features of Fiber Raman Amplifier

    Georgii S. Felinskyi


    Full Text Available The formation dynamics of the optical noise in a silica single mode fiber (SMF as function of the pump power variation in the counter pumped fiber Raman amplifier (FRA is experimentally studied. The ratio between the power of amplified spontaneous emission and the power of incoherent optical noise is quantitatively determined by detailed analysis of experimental data in the pump powers range of 100–300 mW within the full band of Stokes frequencies, including FRA working wavelengths over the C + L transparency windows. It is found out the maximum of Raman gain coefficient for optical noise does not exceed ~60% of corresponding peak at the gain profile maximum of coherent signal. It is shown that the real FRA noise figure may be considerably less than 3 dB over a wide wavelength range (100 nm at a pump power of several hundreds of mW.

  1. Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

    Ravi Kumar, Venkatraman; Rajkumar, Nagappan; Umapathy, Siva, E-mail:


    Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-π{sup 1}*; S{sub 1} state) and the shorter (1π-π{sup 1}*; S{sub 2} state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S{sub 2} state relative to the ground state. Raman excitation profiles of PQ (400–1800 cm{sup −1}) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C{sub 2ν} symmetry constraint on the S{sub 2} state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling.

  2. Raman Imaging Techniques and Applications


    Raman imaging has long been used to probe the chemical nature of a sample, providing information on molecular orientation, symmetry and structure with sub-micron spatial resolution. Recent technical developments have pushed the limits of micro-Raman microscopy, enabling the acquisition of Raman spectra with unprecedented speed, and opening a pathway to fast chemical imaging for many applications from material science and semiconductors to pharmaceutical drug development and cell biology, and even art and forensic science. The promise of tip-enhanced raman spectroscopy (TERS) and near-field techniques is pushing the envelope even further by breaking the limit of diffraction and enabling nano-Raman microscopy.

  3. Coronagraphic Notch Filter for Raman Spectroscopy

    Cohen, David; Stirbl, Robert


    A modified coronagraph has been proposed as a prototype of improved notch filters in Raman spectrometers. Coronagraphic notch filters could offer alternatives to both (1) the large and expensive double or triple monochromators in older Raman spectrometers and (2) holographic notch filters, which are less expensive but are subject to environmental degradation as well as to limitations of geometry and spectral range. Measurement of a Raman spectrum is an exercise in measuring and resolving faint spectral lines close to a bright peak: In Raman spectroscopy, a monochromatic beam of light (the pump beam) excites a sample of material that one seeks to analyze. The pump beam generates a small flux of scattered light at wavelengths slightly greater than that of the pump beam. The shift in wavelength of the scattered light from the pump wavelength is known in the art as the Stokes shift. Typically, the flux of scattered light is of the order of 10 7 that of the pump beam and the Stokes shift lies in the wave-number range of 100 to 3,000 cm 1. A notch filter can be used to suppress the pump-beam spectral peak while passing the nearby faint Raman spectral lines. The basic principles of design and operation of a coronagraph offer an opportunity for engineering the spectral transmittance of the optics in a Raman spectrometer. A classical coronagraph may be understood as two imaging systems placed end to end, such that the first system forms an intermediate real image of a nominally infinitely distant object and the second system forms a final real image of the intermediate real image. If the light incident on the first telescope is collimated, then the intermediate image is a point-spread function (PSF). If an appropriately tailored occulting spot (e.g., a Gaussian-apodized spot with maximum absorption on axis) is placed on the intermediate image plane, then the instrument inhibits transmission of light from an on-axis source. However, the PSFs of off-axis light sources are

  4. Raman spectrum of Si nanowires: temperature and phonon confinement effects

    Anaya, J.; Torres, A.; Hortelano, V.; Jiménez, J.; Prieto, A. C.; Rodríguez, A.; Rodríguez, T.; Rogel, R.; Pichon, L.


    The Raman spectrum of Si nanowires (NWs) is a matter of controversy. Usually, the one-phonon band appears broadened and shifted. This behaviour is interpreted in terms of phonon confinement; however, similar effects are observed for NWs with dimensions for which phonon confinement does not play any relevant role. In this context, the temperature increase induced by the laser beam is recognized to play a capital role in the shape of the spectrum. The analysis of the Raman spectrum, under the influence of the heating induced by the laser beam, is strongly dependent on the excitation conditions and the properties of the NWs. We present herein an analysis of the Raman spectrum of Si NWs based on a study of the interaction between the laser beam and the NWs, for both ensembles of NWs and individual NWs, taking account of the temperature increase in the NWs under the focused laser beam and the dimensions of the NWs.

  5. Resonance Raman spectroscopy in one-dimensional carbon materials

    Dresselhaus Mildred S.


    Full Text Available Brazil has played an important role in the development and use of resonance Raman spectroscopy as a powerful characterization tool for materials science. Here we present a short history of Raman scattering research in Brazil, highlighting the important contributions to the field coming from Brazilian researchers in the past. Next we discuss recent and important contributions where Brazil has become a worldwide leader, that is on the physics of quasi-one dimensional carbon nanotubes. We conclude this article by presenting results from a very recent resonance Raman study of exciting new materials, that are strictly one-dimensional carbon chains formed by the heat treatment of very pure double-wall carbon nanotube samples.

  6. Decoupling of epitaxial graphene via gold intercalation probed by dispersive Raman spectroscopy

    Pillai, P. B., E-mail:, E-mail:; DeSouza, M., E-mail:, E-mail: [Semiconductor Materials and Device Group, Electronic and Electrical Engineering, University of Sheffield, Mappin Street, S1 3JD Sheffield (United Kingdom); Narula, R.; Reich, S. [Department of Physics, Freie Universität Berlin, Arnimallee 14, 14195 Berlin (Germany); Wong, L. Y.; Batten, T. [Renishaw, Old Town, Wotton-under-Edge, GL12 7DW Gloucestershire (United Kingdom); Pokorny, J. [Department of Materials Science and Engineering, Sir Robert Hadfield Building, Mappin Street, S1 3JD Sheffield (United Kingdom); Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Praha 8 (Czech Republic)


    Signatures of a superlattice structure composed of a quasi periodic arrangement of atomic gold clusters below an epitaxied graphene (EG) layer are examined using dispersive Raman spectroscopy. The gold-graphene system exhibits a laser excitation energy dependant red shift of the 2D mode as compared to pristine epitaxial graphene. The phonon dispersions in both the systems are mapped using the experimentally observed Raman signatures and a third-nearest neighbour tight binding electronic band structure model. Our results reveal that the observed excitation dependent Raman red shift in gold EG primarily arise from the modifications of the phonon dispersion in gold-graphene and shows that the extent of decoupling of graphene from the underlying SiC substrate can be monitored from the dispersive nature of the Raman 2D modes. The intercalated gold atoms restore the phonon band structure of epitaxial graphene towards free standing graphene.

  7. Fast and reliable identification of microorganisms by means of Raman spectroscopy

    Rösch, Petra; Harz, Michaela; Krause, Mario; Popp, Jürgen


    The identification of bacteria is necessary as fast as possible e.g. to provide an appropriate therapy for patients. Here the cultivation time should be kept to a minimum. Beside microbiological identification methods Raman spectroscopy is a valuable tool for bacteria identification. UV-resonance Raman spectroscopy enables selective monitoring of the cellular DNA/RNA content and allows for a genotaxonomic classification of the bacteria. Since UV excitation may lead to sample destruction the measurements are performed on rotated bacterial films. For a faster identification avoiding the cultivation step single bacteria analysis is necessary. Using micro-Raman spectroscopy a spatial resolution in the size range of the bacteria can be achieved. With this Raman excitation the chemical components of the whole cell are measured which leads to a phenotypic classification. For localization of bacteria inside complex matrices fluorescence labeling is achieved.

  8. Multiwavelength Raman spectroscopy analysis of a large sampling of disordered carbons extracted from the Tore Supra tokamak

    Pardanaud, Cedric; Roubin, P


    Disordered carbon often exhibit a complex Raman spectrum, with four to six components. Here, a large variety of disordered carbons, forming a collection of samples with a great variety of structures, are analysed using multi-wavelength Raman microscopy (325.0, 514.5, 785.0 nm). They allow us to extend Raman behaviour known for nano-crystalline graphite to amorphous carbons, (dependence with the excitation wavelength) and other known for amorphous carbons to nano-crystalline graphite, (differentiation of the smallest cluster size probed using different excitation wavelengths). Experimental spectra were compared to simulated spectra, built using known laws, to evidence a new source of broadening.

  9. Optimal design of gold nanomatryoshkas with embedded Raman reporters

    Khlebtsov, Nikolai G.; Khlebtsov, Boris N.


    Gold multilayered nanoparticles (nanomatryoshkas, NMs), in which Raman molecules are embedded in a nanometer-sized gap between Au layers, have great potential in biomedical applications as highly efficient surface enhanced Raman scattering (SERS) probes. Compared to other SERS tags, the Raman molecules in Au NM are protected from environmental conditions and subjected to a strongly enhanced electromagnetic (EM) field in the gap. However, the SERS efficiency of Au NMs is multifactorial and depends on their structure, excitation wavelength, resonance properties and loading of Raman reporters, etc. Here, we report a detailed analysis of EM enhancement in Au(core)/Gap/Au(shell) NMs as a function of the core/gap/shell dimensions, the gap refractive index, and the excitation wavelength. The applicability of classical treatment is justified by discussion of recent studies on non-local and quantum tunneling effects in plasmonic dimers. Our optimization strategy is based on efficient rigorous solution for internal EM fields in a layered sphere and explicit analytical solutions for the surface and volume averaged EM intensities within a particular layer and around the NM. SERS enhancement is shown to be strongly dependent, in a resonance manner, on the core/gap/shell dimensions. For four wavelengths of commercial Raman devices 532, 633, 785, and 1064 nm, the optimal NM structures are found. Simulation data are discussed in the light of practical constrains and illustrated by experimental data on Au NMs with embedded 1,4 benzenedithiol (BDT) molecules that serve both as spacers and Raman reporters. The physical insights acquired from this study is hoped to pave the way for rational design of new SERS tags based on plasmonic field enhancement in the nanometer-sized gaps.

  10. Raman spectroscopy and coherent anti-Stokes Raman scattering imaging: prospective tools for monitoring skeletal cells and skeletal regeneration

    Moura, Catarina Costa; Tare, Rahul S.; Oreffo, Richard O. C.; Mahajan, Sumeet


    The use of skeletal stem cells (SSCs) for cell-based therapies is currently one of the most promising areas for skeletal disease treatment and skeletal tissue repair. The ability for controlled modification of SSCs could provide significant therapeutic potential in regenerative medicine, with the prospect to permanently repopulate a host with stem cells and their progeny. Currently, SSC differentiation into the stromal lineages of bone, fat and cartilage is assessed using different approaches that typically require cell fixation or lysis, which are invasive or even destructive. Raman spectroscopy and coherent anti-Stokes Raman scattering (CARS) microscopy present an exciting alternative for studying biological systems in their natural state, without any perturbation. Here we review the applications of Raman spectroscopy and CARS imaging in stem-cell research, and discuss the potential of these two techniques for evaluating SSCs, skeletal tissues and skeletal regeneration as an exemplar. PMID:27170652

  11. Resonant Raman scattering in superconducting Ba1-xKxBiO3

    Menushenkov, AP; Troyan, IA; Eremets, MI


    The effect of the photon energy of the exciting laser radiation on the Raman spectra of Ba1 - xKxBiO3 with x = 0.25, 0.40, and 0.50 is studied. An increase in the laser wavelength from 488 to 750 nm scarcely affects the amplitudes and frequencies of the spectral lines in the Raman spectra of the non

  12. Resonance raman spectra and photochemical reactivity of transition metal α-diimine complexes

    Stufkens, D. J.

    In this article the application of resonance Raman spectroscopy to the study of metal to ligand charge transfer (MLCT) transitions of α-diimine complexes is described. From these spectra information is obtained about the character of the MLCT transitions and about the properties of the excited states. It is shown how these resonance Raman spectra can be used to interpret and predict the MLCT photo-chemistry of α-diimine and imine complexes.

  13. Raman Spectroscopy of Single Nanoparticles in a Double-Nanohole Optical Tweezer System

    Jones, Steven; Gordon, Reuven


    A double nanohole in a metal film was used to trap nanoparticles (20 nm diameter) and simultaneously record their Raman spectrum using the trapping laser as the excitation source. This allowed for the identification of characteristic Stokes lines for titania and polystyrene nanoparticles, showing the capability for material identification of nanoparticles once trapped. Increased Raman signal is observed for the trapping of multiple nanoparticles. This system combines the benefits of nanoparticle isolation and manipulation with unique identification.

  14. Concentration of Unknown Atomic Entangled States via Entanglement Swapping through Raman Interaction

    ZOU Jin-Hua; HU Xiang-Ming


    We show that entanglement concentration of unknown atomic entangled states is achieved via the implementation of entanglement swapping based on Raman interaction in cavity QED. A maximally entangled state is obtained from a pair of partially entangled states probabilistically. Due to Raman interaction of two atoms with a cavity mode and an external driving field, the influence of atomic spontaneous emission has been eliminated. Because of the virtual excitation of the cavity mode, the decoherence of cavity decay and thermal field is neglected.

  15. Raman spectroscopy of single nanoparticles in a double-nanohole optical tweezer system

    Jones, Steven; Balushi, Ahmed A. Al; Gordon, Reuven


    A double nanohole in a metal film was used to trap nanoparticles (20 nm diameter) and simultaneously record their Raman spectrum using the trapping laser as the excitation source. This allowed for the identification of characteristic Stokes lines for titania and polystyrene nanoparticles, showing the capability for material identification of nanoparticles once trapped. Increased Raman signal was observed for the trapping of multiple nanoparticles. This system combines the benefits of nanoparticle isolation and manipulation with unique identification.

  16. Stimulated Raman adiabatic control of a nuclear spin in diamond

    Coto, Raul; Jacques, Vincent; Hétet, Gabriel; Maze, Jerónimo R.


    Coherent manipulation of nuclear spins is a highly desirable tool for both quantum metrology and quantum computation. However, most of the current techniques to control nuclear spins lack fast speed, impairing their robustness against decoherence. Here, based on stimulated Raman adiabatic passage, and its modification including shortcuts to adiabaticity, we present a fast protocol for the coherent manipulation of nuclear spins. Our proposed Λ scheme is implemented in the microwave domain and its excited-state relaxation can be optically controlled through an external laser excitation. These features allow for the initialization of a nuclear spin starting from a thermal state. Moreover we show how to implement Raman control for performing Ramsey spectroscopy to measure the dynamical and geometric phases acquired by nuclear spins.

  17. Raman Lidar Profiles–Temperature (RLPROFTEMP) Value-Added Product

    Newsom, RK; Sivaraman, C; McFarlane, SA


    The purpose of this document is to describe the Raman Lidar Profiles–Temperature (RLPROFTEMP) value-added product (VAP) and the procedures used to derive atmospheric temperature profiles from the raw RL measurements. Sections 2 and 4 describe the input and output variables, respectively. Section 3 discusses the theory behind the measurement and the details of the algorithm, including calibration and overlap correction.

  18. Surface enhanced Raman scattering

    Furtak, Thomas


    In the course of the development of surface science, advances have been identified with the introduction of new diagnostic probes for analytical characterization of the adsorbates and microscopic structure of surfaces and interfaces. Among the most recently de­ veloped techniques, and one around which a storm of controversy has developed, is what has now been earmarked as surface enhanced Raman scattering (SERS). Within this phenomenon, molecules adsorbed onto metal surfaces under certain conditions exhibit an anomalously large interaction cross section for the Raman effect. This makes it possible to observe the detailed vibrational signature of the adsorbate in the ambient phase with an energy resolution much higher than that which is presently available in electron energy loss spectroscopy and when the surface is in contact with a much larger amount of material than that which can be tolerated in infrared absorption experiments. The ability to perform vibrational spectroscopy under these conditions would l...


    Baker, W.R.; Kerns, Q.A.; Riedel, J.


    An apparatus is presented for exciting a cavity resonator with a minimum of difficulty and, more specifically describes a sub-exciter and an amplifier type pre-exciter for the high-frequency cxcitation of large cavities. Instead of applying full voltage to the main oscillator, a sub-excitation voltage is initially used to establish a base level of oscillation in the cavity. A portion of the cavity encrgy is coupled to the input of the pre-exciter where it is amplified and fed back into the cavity when the pre-exciter is energized. After the voltage in the cavity resonator has reached maximum value under excitation by the pre-exciter, full voltage is applied to the oscillator and the pre-exciter is tunned off. The cavity is then excited to the maximum high voltage value of radio frequency by the oscillator.

  20. Low frequency Raman scattering for high resolution low temperature optical fiber sensors

    Rabia, M. K.; Jurdyc, A.-M.; Le Brusq, J.; Champagnon, B.; Vouagner, D.


    Raman distributed optical fiber temperature sensors are based on the intensity ratio of the anti-Stokes to the Stokes Raman band at 440 cm-1 of silica. In this paper we predict that the sensitivity of the Raman measurements for low temperatures can be improved by considering the Boson peak in the low frequency Raman scattering domain at 60 cm-1. In this way Raman temperature sensors can be performed down to cryogenic temperatures. It is further shown that the Boson peak is less dependent than the 440 cm-1 band to the polarization of light. For the usual excitation at 1550 nm the anti-Stokes Boson peak at 1536 nm is in the low loss transmission window of the silica fibers.

  1. Multi-wavelength Raman scattering of nanostructured Al-doped zinc oxide

    Russo, V.; Ghidelli, M.; Gondoni, P. [Dipartimento di Energia and NEMAS, Center for Nanoengineered Materials and Surfaces, Politecnico di Milano, via Ponzio 34/3, I-20133 Milano (Italy); Casari, C. S.; Li Bassi, A. [Dipartimento di Energia and NEMAS, Center for Nanoengineered Materials and Surfaces, Politecnico di Milano, via Ponzio 34/3, I-20133 Milano (Italy); Center for Nano Science and Technology PoliMI, Istituto Italiano di Tecnologia, Via Pascoli 70/3, I-20133 Milano (Italy)


    In this work we present a detailed Raman scattering investigation of zinc oxide and aluminum-doped zinc oxide (AZO) films characterized by a variety of nanoscale structures and morphologies and synthesized by pulsed laser deposition under different oxygen pressure conditions. The comparison of Raman spectra for pure ZnO and AZO films with similar morphology at the nano/mesoscale allows to investigate the relation between Raman features (peak or band positions, width, relative intensity) and material properties such as local structural order, stoichiometry, and doping. Moreover Raman measurements with three different excitation lines (532, 457, and 325 nm) point out a strong correlation between vibrational and electronic properties. This observation confirms the relevance of a multi-wavelength Raman investigation to obtain a complete structural characterization of advanced doped oxide materials.

  2. Double-clad hollow core photonic crystal fiber for coherent Raman endoscope.

    Brustlein, Sophie; Berto, Pascal; Hostein, Richard; Ferrand, Patrick; Billaudeau, Cyrille; Marguet, Didier; Muir, Alistair; Knight, Jonathan; Rigneault, Hervé


    Performing label free coherent anti-Stokes Raman scattering (CARS) and stimulated Raman scattering (SRS) in endoscope imaging is a challenge, with huge potential clinical benefit. To date, this goal has remained inaccessible because of the inherent coherent Raman noise that is generated in the fiber itself. By developing double-clad hollow core photonic crystal fiber, we demonstrate coherent anti-Stokes Raman scattering and stimulated Raman scattering in an 'endoscope-like' scheme. Both the excitation beams and the collected CARS and SRS signals travel through the same fiber. No CARS and SRS signals are generated within the hollow core fiber even for temporally overlapping pump and Stokes beams, leading to excellent image quality. The CARS and SRS signals generated in the sample are coupled back into a high numerical aperture multimode cladding surrounding the central photonic crystal cladding. We demonstrate this scheme by imaging molecular vibrational bonds of organic crystal deposited on a glass surface.

  3. Fiber optic direct Raman imaging system based on a hollow-core fiber bundle

    Inoue, S.; Katagiri, T.; Matsuura, Y.


    A Raman imaging system which combined a hollow fiber bundle and a direct imaging technique was constructed for high-speed endoscopic Raman imaging. The hollow fiber bundle is fabricated by depositing a silver thin film on the inner surface of pre-drawn glass capillary bundle. It performs as a fiber optic probe which transmits a Raman image with high signal-to-noise ratio because the propagating light is confined into the air core inducing little light scattering. The field of view on the sample is uniformly irradiated by the excitation laser light via the probe. The back-scattered image is collected by the probe and captured directly by an image sensor. A pair of thin film tunable filters is used to select target Raman band. This imaging system enables flexible and high-speed Raman imaging of biological tissues.

  4. Quantitative determination of the human breast milk macronutrients by near-infrared Raman spectroscopy

    Motta, Edlene d. C. M.; Zângaro, Renato A.; Silveira, Landulfo, Jr.


    This work proposes the evaluation of the macronutrient constitution of human breast milk based on the spectral information provided by near-infrared Raman spectroscopy. Human breast milk (5 mL) from a subject was collected during the first two weeks of breastfeeding and stocked in -20°C freezer. Raman spectra were measured using a Raman spectrometer (830 nm excitation) coupled to a fiber based Raman probe. Spectra of human milk were dominated by bands of proteins, lipids and carbohydrates in the 600-1800 cm-1 spectral region. Raman spectroscopy revealed differences in the biochemical constitution of human milk depending on the time of breastfeeding startup. This technique could be employed to develop a classification routine for the milk in Human Milk Banking (HMB) depending on the nutritional facts.

  5. Surface Plasmons and Surface Enhanced Raman Spectra of Aggregated and Alloyed Gold-Silver Nanoparticles

    Y. Fleger


    Full Text Available Effects of size, morphology, and composition of gold and silver nanoparticles on surface plasmon resonance (SPR and surface enhanced Raman spectroscopy (SERS are studied with the purpose of optimizing SERS substrates. Various gold and silver films made by evaporation and subsequent annealing give different morphologies and compositions of nanoparticles and thus different position of the SPR peak. SERS measurements of 4-mercaptobenzoic acid obtained from these films reveal that the proximity of the SPR peak to the exciting laser wavelength is not the only factor leading to the highest Raman enhancement. Silver nanoparticles evaporated on top of larger gold nanoparticles show higher SERS than gold-silver alloyed nanoparticles, in spite of the fact that the SPR peak of alloyed nanoparticles is narrower and closer to the excitation wavelength. The highest Raman enhancement was obtained for substrates with a two-peak particle size distribution for excitation wavelengths close to the SPR.

  6. In Situ Raman Analysis of CO2—Assisted Drying of Fruit-Slices

    Andreas Siegfried Braeuer


    Full Text Available This work explores the feasibility of applying in situ Raman spectroscopy for the online monitoring of the supercritical carbon dioxide (SC-CO2 drying of fruits. Specifically, we investigate two types of fruits: mango and persimmon. The drying experiments were carried out inside an optical accessible vessel at 10 MPa and 313 K. The Raman spectra reveal: (i the reduction of the water from the fruit slice and (ii the change of the fruit matrix structure during the drying process. Two different Raman excitation wavelengths were compared: 532 nm and 785 nm. With respect to the quality of the obtained spectra, the 532 nm excitation wavelength was superior due to a higher signal-to-noise ratio and due to a resonant excitation scheme of the carotenoid molecules. It was found that the absorption of CO2 into the fruit matrix enhances the extraction of water, which was expressed by the obtained drying kinetic curve.

  7. Simple Raman Instrument for in Vivo Detection of Macular Pigments

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner


    Raman spectroscopy holds promise as a novel noninvasive technology for the quantification of the macular pigments (MP) lutein and zeaxanthin. These compounds, which are members of the carotenoid family, are thought to prevent or delay the onset of age-related macular degeneration, the leading cause of irreversible blindness in the elderly. It is highly likely that they achieve this protection through their function as optical filters and/or antioxidants. Using resonant excitation in the visib...

  8. Analytical Raman spectroscopy in a forensic art context: The non-destructive discrimination of genuine and fake lapis lazuli

    Ali, Esam M. A.; Edwards, Howell G. M.


    The differentiation between genuine and fake lapis lazuli specimens using Raman spectroscopy is assessed using laboratory and portable instrumentation operating at two longer wavelengths of excitation in the near-infrared, namely 1064 and 785 nm. In spite of the differences between the spectra excited here in the near infrared and those reported in the literature using visible excitation, it is clear that Raman spectroscopy at longer wavelengths can provide a means of differentiating between the fakes studied here and genuine lapis lazuli. The Raman spectra obtained from portable instrumentation can also achieve this result, which will be relevant for the verification of specimens which cannot be removed from collections and for the identification of genuine lapis lazuli inlays in, for example, complex jewellery and furniture. The non-destructive and non-contact character of the technique offers a special role for portable Raman spectroscopy in forensic art analysis.

  9. [Research Progress of Raman Spectroscopy on Dyestuff Identification of Ancient Relics and Artifacts].

    He, Qiu-ju; Wang, Li-qin


    As the birthplace of Silk Road, China has a long dyeing history. The valuable information about the production time, the source of dyeing material, dyeing process and preservation status were existed in organic dyestuff deriving from cultural relics and artifacts. However, because of the low contents, complex compositions and easily degraded of dyestuff, it is always a challenging task to identify the dyestuff in relics analyzing field. As a finger-print spectrum, Raman spectroscopy owns unique superiorities in dyestuff identification. Thus, the principle, characteristic, limitation, progress and development direction of micro-Raman spectroscopy (MRS/µ-Raman), near infrared reflection and Fourier transform Raman spectroscopy (NIR-FT-Raman), surface-enhanced Raman spectroscopy (SERS) and resonance raman spectroscopy (RRS) have been introduced in this paper. Furthermore, the features of Raman spectra of gardenia, curcumin and other natural dyestuffs were classified by MRS technology, and then the fluorescence phenomena of purpurin excitated with different wavelength laser was compared and analyzed. At last, gray green silver colloidal particles were made as the base, then the colorant of madder was identified combining with thin layer chromatography (TLC) separation technology and SERS, the result showed that the surface enhancement effect of silver colloidal particles could significantly reduce fluorescence background of the Raman spectra. It is pointed out that Raman spectroscopy is a rapid and convenient molecular structure qualitative methodology, which has broad application prospect in dyestuff analysis of cultural relics and artifacts. We propose that the combination of multi-Raman spectroscopy, separation technology and long distance transmission technology are the development trends of Raman spectroscopy.

  10. Discriminant Analysis of Raman Spectra for Body Fluid Identification for Forensic Purposes

    Vitali Sikirzhytski


    Full Text Available Detection and identification of blood, semen and saliva stains, the most common body fluids encountered at a crime scene, are very important aspects of forensic science today. This study targets the development of a nondestructive, confirmatory method for body fluid identification based on Raman spectroscopy coupled with advanced statistical analysis. Dry traces of blood, semen and saliva obtained from multiple donors were probed using a confocal Raman microscope with a 785-nm excitation wavelength under controlled laboratory conditions. Results demonstrated the capability of Raman spectroscopy to identify an unknown substance to be semen, blood or saliva with high confidence.

  11. Noninvasive laser Raman detection of carotenoid antioxidants in living human skin

    Gellermann, Werner; Ermakov, Igor V.; Ermakova, Maia R.; McClane, Robert W.


    We have used resonance Raman scattering as a novel non- invasive optical technology to measure carotenoid antioxidants in human skin of healthy volunteers. Using blue-green laser excitation, clearly distinguishable carotenoid Raman spectra are obtained which are superimposed on a large skin autofluorescence background. The Raman spectra are obtained rapidly, i.e. within about 30 seconds, and the required laser light exposure levels are well within safety standards. Our technique can be used for rapid screening of carotenoid antioxidant levels in large populations and may have applications for assessing the risk for cutaneous diseases.

  12. Multivariate reference technique for quantitative analysis of fiber-optic tissue Raman spectroscopy.

    Bergholt, Mads Sylvest; Duraipandian, Shiyamala; Zheng, Wei; Huang, Zhiwei


    We report a novel method making use of multivariate reference signals of fused silica and sapphire Raman signals generated from a ball-lens fiber-optic Raman probe for quantitative analysis of in vivo tissue Raman measurements in real time. Partial least-squares (PLS) regression modeling is applied to extract the characteristic internal reference Raman signals (e.g., shoulder of the prominent fused silica boson peak (~130 cm(-1)); distinct sapphire ball-lens peaks (380, 417, 646, and 751 cm(-1))) from the ball-lens fiber-optic Raman probe for quantitative analysis of fiber-optic Raman spectroscopy. To evaluate the analytical value of this novel multivariate reference technique, a rapid Raman spectroscopy system coupled with a ball-lens fiber-optic Raman probe is used for in vivo oral tissue Raman measurements (n = 25 subjects) under 785 nm laser excitation powers ranging from 5 to 65 mW. An accurate linear relationship (R(2) = 0.981) with a root-mean-square error of cross validation (RMSECV) of 2.5 mW can be obtained for predicting the laser excitation power changes based on a leave-one-subject-out cross-validation, which is superior to the normal univariate reference method (RMSE = 6.2 mW). A root-mean-square error of prediction (RMSEP) of 2.4 mW (R(2) = 0.985) can also be achieved for laser power prediction in real time when we applied the multivariate method independently on the five new subjects (n = 166 spectra). We further apply the multivariate reference technique for quantitative analysis of gelatin tissue phantoms that gives rise to an RMSEP of ~2.0% (R(2) = 0.998) independent of laser excitation power variations. This work demonstrates that multivariate reference technique can be advantageously used to monitor and correct the variations of laser excitation power and fiber coupling efficiency in situ for standardizing the tissue Raman intensity to realize quantitative analysis of tissue Raman measurements in vivo, which is particularly appealing in

  13. Optical diagnosis of dengue virus infection in human blood serum using Raman spectroscopy

    Saleem, M.; Bilal, M.; Anwar, S.; Rehman, A.; Ahmed, M.


    We present the optical diagnosis of dengue virus infection in human blood serum using Raman spectroscopy. Raman spectra were acquired from 18 blood serum samples using a laser at 532 nm as the excitation source. A multivariate regression model based on partial least-squares regression is developed that uses Raman spectra to predict dengue infection with leave-one-sample-out cross validation. The prediction of dengue infection by our model yields correlation coefficient r2 values of 0.9998 between the predicted and reference clinical results. The model was tested for six unknown human blood sera and found to be 100% accurate in accordance with the clinical results.

  14. Cell Imaging by Spontaneous and Amplified Raman Spectroscopies

    Giulia Rusciano


    Full Text Available Raman spectroscopy (RS is a powerful, noninvasive optical technique able to detect vibrational modes of chemical bonds. The high chemical specificity due to its fingerprinting character and the minimal requests for sample preparation have rendered it nowadays very popular in the analysis of biosystems for diagnostic purposes. In this paper, we first discuss the main advantages of spontaneous RS by describing the study of a single protozoan (Acanthamoeba, which plays an important role in a severe ophthalmological disease (Acanthamoeba keratitis. Later on, we point out that the weak signals that originated from Raman scattering do not allow probing optically thin samples, such as cellular membrane. Experimental approaches able to overcome this drawback are based on the use of metallic nanostructures, which lead to a huge amplification of the Raman yields thanks to the excitation of localized surface plasmon resonances. Surface-enhanced Raman scattering (SERS and tip-enhanced Raman scattering (TERS are examples of such innovative techniques, in which metallic nanostructures are assembled on a flat surface or on the tip of a scanning probe microscope, respectively. Herein, we provide a couple of examples (red blood cells and bacterial spores aimed at studying cell membranes with these techniques.

  15. Identification of color development potential of quartz by Raman spectroscopy

    Alkmim, Danielle G.; Lameiras, Fernando S.; Almeida, Frederico O.T., E-mail:, E-mail: [Centro e Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horionte, MG (Brazil)


    Colorless quartz is usually exposed to ionizing radiation (gamma rays or high energy electron beams) to acquire different colors for jewelry. Color development is due to the presence of traces of some elements such as aluminum, iron, hydrogen, lithium, or sodium. Most quartz crystals are extracted colorless from nature and it is necessary to separate those that can develop colors from those that cannot. Irradiation tests can be used to accomplish this separation, but they take a long time. Infrared signature of colorless quartz can also be used. However, infrared spectroscopy is quite expensive, especially when using portable devices. Raman spectroscopy is now available as an inexpensive and portable technique that could provide identification of the samples of colorless quartz still in the field, facilitating the prediction for their economic exploitation. In addition, Raman spectroscopy usually requires a minimum or no sample preparation. This paper presents an investigation of the feasibility of using Raman spectroscopy as a substitute for infrared spectroscopy to predict the potential for color development of quartz. A band at 3595 cm{sup -1} in the Raman shift spectrum was observed only along the c axis of a prasiolite excited by a high power 514 nm laser. This band was not observed in quartz samples that do not develop color after irradiation. Further studies are required to identify the potential for color development by Raman spectroscopy of other types of colorless quartz. (author)

  16. Simple Raman instrument for in vivo detection of macular pigments.

    Ermakov, Igor V; Ermakova, Maia R; Gellermann, Werner


    Raman spectroscopy holds promise as a novel noninvasive technology for the quantification of the macular pigments (MP) lutein and zeaxanthin. These compounds, which are members of the carotenoid family, are thought to prevent or delay the onset of age-related macular degeneration, the leading cause of irreversible blindness in the elderly. It is highly likely that they achieve this protection through their function as optical filters and/or antioxidants. Using resonant excitation in the visible region, we measure and quantify the Raman signals that originate from the carbon double bond (C=C) stretch vibrations of the pi-conjugated molecule backbone. In this manuscript we describe the construction and performance of a novel compact MP Raman instrument utilizing dielectric angle-tuned band-pass filters for wavelength selection and a single-channel photo-multiplier for the detection of MP Raman responses. MP concentration measurements are fast and accurate, as seen in our experiments with model eyes and living human eyes. The ease and rapidity of Raman MP measurements, the simplicity of the instrumentation, the high accuracy of the measurements, and the lack of significant systematic errors should make this technology attractive for widespread clinical research.

  17. Spatially offset Raman spectroscopy (SORS) for liquid screening

    Loeffen, Paul W.; Maskall, Guy; Bonthron, Stuart; Bloomfield, Matthew; Tombling, Craig; Matousek, Pavel


    Recently, Spatially Offset Raman Spectroscopy (SORS) has been discussed as a novel method for the screening of liquids, aerosols and gels (LAGs) at airports and for other security applications. SORS is an optical spectroscopic method which enables the precise chemical identification of substances from a reference list and, due to the rich spectral information, has an inherently high probability of detection and low false alarm rate. The method is generally capable of screening substances inside non-metallic containers such as plastic and glass bottles. SORS is typically successful through opaque plastic and coloured glass, which are often challenging for conventional backscatter Raman spectroscopy. SORS is performed in just a few seconds by shining a laser light onto the container and then measuring the Raman signal at the excitation point but also at one or more offset positions. Each measurement has different relative orthogonal contributions from the container and contents Raman spectra, so that, with no prior knowledge, the pure Raman spectra of both the container and contents can be extracted - either by scaled subtraction or via multivariate statistical methods in an automated process. In this paper, the latest results will be described from a prototype SORS device designed for aviation security and the advantages and limitations of SORS will be discussed.

  18. Time-resolved spatially offset Raman spectroscopy for depth analysis of diffusely scattering layers.

    Iping Petterson, Ingeborg E; Dvořák, Patrick; Buijs, Joost B; Gooijer, Cees; Ariese, Freek


    The objective of this study is to use time-resolved (TR) Raman spectroscopy, spatially offset Raman spectroscopy (SORS), and a combination of these approaches to obtain high quality Raman spectra from materials hidden underneath an opaque layer. Both TR Raman and SORS are advanced techniques that allow for an increased relative selectivity of photons from deeper layers within a sample. Time-resolved detection reduces fluorescence background, and the selectivity for the second layer is improved. By combining this with spatially offset excitation we additionally increased selectivity for deeper layers. Test samples were opaque white polymer blocks of several mm thicknesses. Excitation was carried out with a frequency-doubled Ti:sapphire laser at 460 nm, 3 ps pulse width and 76 MHz repetition rate. Detection was either with a continuous-wave CCD camera or in time-resolved mode using an intensified CCD camera with a 250 ps gate width. The Raman photons were collected in backscatter mode, with or without lateral offset. By measuring the delay of the Raman signal from the second layer (polyethylene terephthalate/PET/Arnite), the net photon migration speeds through Teflon, polythene, Delrin and Nylon were determined. Raman spectra could be obtained from a second layer of PET through Teflon layers up to 7 mm of thickness. The ability to obtain chemical information through layers of diffusely scattering materials has powerful potential for biomedical applications.

  19. Passively mode locked Raman laser

    Liang, W; Savchenkov, A A; Matsko, A B; Seidel, D; Maleki, L


    We report on the observation of a novel mode locked optical comb generated at the Raman offset (Raman comb) in an optically pumped crystalline whispering gallery mode resonator. Mode locking is confirmed via measurement of the radio-frequency beat note produced by the optical comb on a fast photodiode. Neither the conventional Kerr comb nor hyper-parametric oscillation is observed when the Raman comb is present.

  20. Raman Scattering of Inorganic Fibers


    We have examined evolution of Raman spectra of carbon fibers and SiC fibers through structural transformations caused by heat treatment. Raman spectra of the SiC fibers indicate that the fibers consist of amorphous or microcrystalline SiC and graphitic microcrystals. We discuss the correlation between the tensile strength of the fibers and their microscopic structure deduced from the Raman data.

  1. Practical Raman spectroscopy an introduction

    Vandenabeele, Peter


    This text offers an open-learning approach to Raman spectroscopy providing detail on instrumentation, applications and discussions questions throughout the book. It provides a valuable guide to assist with teaching Raman spectroscopy which is gaining attention in (analytical) chemistry, and as a consequence, teaching programs have followed. Today, education in Raman spectroscopy is often limited to theoretical aspects (e.g. selection rules), but practical aspects are usually disregarded. With these course notes, the author hopes to fill this gap and include information about Raman instrumentat

  2. a simple a simple excitation control excitation control excitation ...


    brushes for low power generators or brushless for high-power ... produce the primary dc fluxes are usually placed on the ... motor and the study was extended to over-excitation schemes ... automatic voltage controller (AVR) around this range.

  3. Raman Spectroscopic Profile of Ethanol Fermentation in High Gravity Cassava Starch Brewing%浓醪乙醇发酵的单细胞拉曼光谱表征

    李自达; 赖钧灼; 廖威; 刘军贤; 王桂文


    应用激光镊子拉曼光谱技术收集500 L发酵罐中木薯淀粉浓醪乙醇发酵过程底物、产物及酵母单细胞的拉曼光谱,以期从单细胞水平为乙醇发酵提供新的认识.结果显示:1)拉曼光谱可以实时监测浓醪乙醇发酵过程底物与产物的变化;2)酵母细胞胞内物质的变化存在类似于产物变化的前发酵期、主发酵期和后发酵期3个阶段,但出现的时间要比产物变化晚约4 h;3)为适应浓醪发酵环境,酵母细胞的生理状态和胞内物质在不断地进行调整,随着环境乙醇浓度的升高,酵母细胞在胞内累积蛋白质和脂类物质,蛋白质二级结构逐渐变为以无规则卷曲为主;4)发酵后期,酵母细胞在胞内累积大量的嘌呤类物质,但细胞间含量存在异质性.上述结果表明,单细胞拉曼光谱技术提供了一种研究微生物发酵的新方法,可从新的角度获知乙醇发酵过程酵母细胞内外的变化信息.%Raman spectroscopy is used to characterize the process of ethanol fermentation and look into the Saccharomyces cerevisiae cells at single-cell level. The ethanol fermentation using high-concentration cassava starch as feedstock is processed in a 500 L fermentor and the Raman spectra of substrate, product and individual yeast cell are acquired by using laser tweezers Raman spectroscopy (LTRS). Major results are as follows: 1) Raman spectroscopy can monitor the dynamic changes of substrate and product during the ethanol fermentation; 2) the changes of intracellular components of yeast cells exhibit three stages, I. E., primary fermentation, main fermentation and later fermentation, which are similar to those of products, but there is a delay of about 4 hi 3) yeast cells amend its physiological state and intracellular compounds to adapt to the high osmotic stress at the initial stage and the high ethanol concentration at the later stage of fermentation. Random coiling dominates the secondary structure of

  4. Shape-dependent surface-enhanced Raman scattering in gold-Raman probe-silica sandwiched nanoparticles for biocompatible applications.

    Li, Ming; Cushing, Scott K; Zhang, Jianming; Lankford, Jessica; Aguilar, Zoraida P; Ma, Dongling; Wu, Nianqiang


    To meet the requirement of Raman probes (labels) for biocompatible applications, a synthetic approach has been developed to sandwich the Raman-probe (malachite green isothiocyanate, MGITC) molecules between the gold core and the silica shell in gold-SiO₂ composite nanoparticles. The gold-MGITC-SiO₂ sandwiched structure not only prevents the Raman probe from leaking out but also improves the solubility of the nanoparticles in organic solvents and in aqueous solutions even with high ionic strength. To amplify the Raman signal, three types of core, gold nanospheres, nanorods and nanostars, have been chosen as the substrates of the Raman probe. The effect of the core shape on the surface-enhanced Raman scattering (SERS) has been investigated. The colloidal nanostars showed the highest SERS enhancement factor while the nanospheres possessed the lowest SERS activity under excitation with 532 and 785 nm lasers. Three-dimensional finite-difference time domain (FDTD) simulation showed significant differences in the local electromagnetic field distributions surrounding the nanospheres, nanorods, and nanostars, which were induced by the localized surface plasmon resonance (LSPR). The electromagnetic field was enhanced remarkably around the two ends of the nanorods and around the sharp tips of the nanostars. This local electromagnetic enhancement made the dominant contribution to the SERS enhancement. Both the experiments and the simulation revealed the order nanostars > nanorods > nanospheres in terms of the enhancement factor. Finally, the biological application of the nanostar-MGITC-SiO₂ nanoparticles has been demonstrated in the monitoring of DNA hybridization. In short, the gold–MGITC-SiO₂ sandwiched nanoparticles can be used as a Raman probe that features high sensitivity, good water solubility and stability, low-background fluorescence, and the absence of photobleaching for future biological applications.

  5. Effect of boron doping on first-order Raman scattering in superconducting boron doped diamond films

    Kumar, Dinesh; Chandran, Maneesh; Ramachandra Rao, M. S.


    Aggregation of impurity levels into an impurity band in heavily boron doped diamond results in a background continuum and discrete zone centre phonon interference during the inelastic light scattering process. In order to understand the Raman scattering effect in granular BDD films, systematically heavily doped samples in the semiconducting and superconducting regimes have been studied using the excitation wavelengths in the UV and visible regions. A comprehensive analysis of the Fano resonance effect as a function of the impurity concentrations and the excitation frequencies is presented. Various Raman modes available in BDD including signals from the grain boundaries are discussed.

  6. Electron-enhanced Raman scattering: a history of its discovery and spectroscopic applications to solution and interfacial chemistry.

    Yui, Hiroharu


    Raman scattering spectroscopy can be used to distinguish highly similar molecules and obtain useful information on local physical and chemical environments at their functional group levels. However, obtaining a high-quality Raman spectrum requires high-power excitation and a long acquisition time owing to the inherently small Raman scattering cross section, which is problematic in the analyses of living cells and real-time environmental monitoring. Herein, a new Raman enhancement technique, electron-enhanced Raman scattering (EERS), is described in which artificially generated electrons affect the polarizability of target molecular systems and enhance their inherent Raman cross sections. The EERS technique stands in contrast to the well-known SERS technique, which requires roughened metal surfaces. The history of EERS and its spectroscopic applications to aqueous solutions are presented.

  7. Excitation of knotted vortex lines in matter waves

    Maucher, F.; Gardiner, S. A.; Hughes, I. G.


    We study the creation of knotted ultracold matter waves in Bose-Einstein condensates via coherent two-photon Raman transitions with a Λ level configuration. The Raman transition allows an indirect transfer of atoms from the internal state | a> to the target state | b> via an excited state | e> , that would be otherwise dipole-forbidden. This setup enables us to imprint three-dimensional knotted vortex lines embedded in the probe field to the density in the target state. We elaborate on experimental feasibility as well as on subsequent dynamics of the matter wave.

  8. Non-destructive analysis of the nuclei of transgenic living cells using laser tweezers and near-infrared raman spectroscopic technique

    Tang, Wei; Newton, Ronald J; Xie, Chang An; Li, Yong Qing; Whitley, Nicki


    ...) system in this investigation. A low power diode laser at 785 nm was used for both laser optical trapping of single transgenic cells and excitation for near-infrared Raman spectroscopy of the nuclei of synchronized cells, which...

  9. Portable vibration exciter

    Beecher, L. C.; Williams, F. T.


    Gas-driven vibration exciter produces a sinusoidal excitation function controllable in frequency and in amplitude. It allows direct vibration testing of components under normal loads, removing the possibility of component damage due to high static pressure.

  10. Studies of Minerals, Organic and Biogenic Materials through Time-Resolved Raman Spectroscopy

    Garcia, Christopher S.; Abedin, M. Nurul; Ismail, Syed; Sharma, Shiv K.; Misra, Anupam K.; Nyugen, Trac; Elsayed-Ali, hani


    A compact remote Raman spectroscopy system was developed at NASA Langley Research center and was previously demonstrated for its ability to identify chemical composition of various rocks and minerals. In this study, the Raman sensor was utilized to perform time-resolved Raman studies of various samples such as minerals and rocks, Azalea leaves and a few fossil samples. The Raman sensor utilizes a pulsed 532 nm Nd:YAG laser as excitation source, a 4-inch telescope to collect the Raman-scattered signal from a sample several meters away, a spectrograph equipped with a holographic grating, and a gated intensified CCD (ICCD) camera system. Time resolved Raman measurements were carried out by varying the gate delay with fixed short gate width of the ICCD camera, allowing measurement of both Raman signals and fluorescence signals. Rocks and mineral samples were characterized including marble, which contain CaCO3. Analysis of the results reveals the short (approx.10-13 s) lifetime of the Raman process, and shows that Raman spectra of some mineral samples contain fluorescence emission due to organic impurities. Also analyzed were a green (pristine) and a yellow (decayed) sample of Gardenia leaves. It was observed that the fluorescence signals from the green and yellow leaf samples showed stronger signals compared to the Raman lines. Moreover, it was also observed that the fluorescence of the green leaf was more intense and had a shorter lifetime than that of the yellow leaf. For the fossil samples, Raman shifted lines could not be observed due the presence of very strong short-lived fluorescence.

  11. Analysis of root surface properties by fluorescence/Raman intensity ratio.

    Nakamura, Shino; Ando, Masahiro; Hamaguchi, Hiro-O; Yamamoto, Matsuo


    The aim of this study is to evaluate the existence of residual calculus on root surfaces by determining the fluorescence/Raman intensity ratio. Thirty-two extracted human teeth, partially covered with calculus on the root surface, were evaluated by using a portable Raman spectrophotometer, and a 785-nm, 100-mW laser was applied for fluorescence/Raman excitation. The collected spectra were normalized to the hydroxyapatite Raman band intensity at 960 cm(-1). Raman spectra were recorded from the same point after changing the focal distance of the laser and the target radiating angle. In seven teeth, the condition of calculus, cementum, and dentin were evaluated. In 25 teeth, we determined the fluorescence/Raman intensity ratio following three strokes of debridement. Raman spectra collected from the dentin, cementum, and calculus were different. After normalization, spectra values were constant. The fluorescence/Raman intensity ratio of calculus region showed significant differences compared to the cementum and dentin (p < 0.05). The fluorescence/Raman intensity ratio decreased with calculus debridement. For this analysis, the delta value was defined as the difference between the values before and after three strokes, with the final 2 delta values close to zero, indicating a gradual asymptotic curve and the change in intensity ratio approximating that of individual constants. Fluorescence/Raman intensity ratio was effectively used to cancel the angle- and distance-dependent fluctuations of fluorescence collection efficiency during measurement. Changes in the fluorescence/Raman intensity ratio near zero suggested that cementum or dentin was exposed, and calculus removed.

  12. Diffusion measurements by Raman spectroscopy

    Hansen, Susanne Brunsgaard; Shapiro, Alexander; Berg, Rolf W.;

    Poster "Diffusion measurements by Raman spectroscopy", See poster at "Diffusion measurements by Raman spectroscopy", See poster at

  13. Diffusion measurements by Raman spectroscopy

    Hansen, Susanne Brunsgaard; Shapiro, Alexander; Berg, Rolf W.

    Poster "Diffusion measurements by Raman spectroscopy", See poster at "Diffusion measurements by Raman spectroscopy", See poster at

  14. Quantum profiles

    Bernstein, Jeremy


    For the prominent science writer Jeremy Bernstein, the profile is the most congenial way of communicating science. Here, in what he labels a "series of conversations carried on in the reader's behalf and my own," he evokes the tremendous intellectual excitement of the world of modern physics, especially the quantum revolution. Drawing on his well-known talent for explaining the most complex scientific ideas for the layperson, Bernstein gives us a lively sense of what the issues of quantum mechanics are and of various ways in which individual physicists approached them.The author begins this se

  15. Raman Spectroscopy for Clinical Oncology

    Michael B. Fenn


    Full Text Available Cancer is one of the leading causes of death throughout the world. Advancements in early and improved diagnosis could help prevent a significant number of these deaths. Raman spectroscopy is a vibrational spectroscopic technique which has received considerable attention recently with regards to applications in clinical oncology. Raman spectroscopy has the potential not only to improve diagnosis of cancer but also to advance the treatment of cancer. A number of studies have investigated Raman spectroscopy for its potential to improve diagnosis and treatment of a wide variety of cancers. In this paper the most recent advances in dispersive Raman spectroscopy, which have demonstrated promising leads to real world application for clinical oncology are reviewed. The application of Raman spectroscopy to breast, brain, skin, cervical, gastrointestinal, oral, and lung cancers is reviewed as well as a special focus on the data analysis techniques, which have been employed in the studies.

  16. All-Fiber Raman Probe

    Brunetti, Anna Chiara

    The design and development of an all-in-fiber probe for Raman spectroscopy are presented in this Thesis. Raman spectroscopy is an optical technique able to probe a sample based on the inelastic scattering of monochromatic light. Due to its high specificity and reliability and to the possibility...... to perform real-time measurements with little or no sample preparation, Raman spectroscopy is now considered an invaluable analytical tool, finding application in several fields including medicine, defense and process control. When combined with fiber optics technology, Raman spectroscopy allows...... for the realization of flexible and minimally-invasive devices, able to reach remote or hardly accessible samples, and to perform in-situ analyses in hazardous environments. The work behind this Thesis focuses on the proof-of-principle demonstration of a truly in-fiber Raman probe, where all parts are realized...

  17. The development of a wide-field, high-resolution UV Raman hyperspectral imager

    Gomer, Nathaniel R.; Nelson, Matthew P.; Angel, S. M.


    Raman spectroscopy is a valuable tool for the investigation and analysis of explosive and biological analytes because it provides a unique molecular fingerprint that allows for unambiguous target identification. Raman can be advantageous when utilized with deep UV excitation, but typical deep UV Raman systems have numerous limitations that hinder their performance and make their potential integration onto a field portable platform difficult. These systems typically offer very low throughput, are physically large and heavy, and can only probe an area the size of a tightly focused laser, severely diminishing the ability of the system to investigate large areas efficiently. The majority of these limitations are directly related to a system's spectrometer, which is typically dispersive grating based and requires a very narrow slit width and long focal length optics to achieve high spectral resolution. To address these shortcomings, ChemImage Sensor Systems (CISS), teaming with the University of South Carolina, are developing a revolutionary wide-field Raman hyperspectral imaging system capable of providing wide-area, high resolution measurements with greatly increased throughput in a small form factor, which would revolutionize the way Raman is conducted and applied. The innovation couples a spatial heterodyne spectrometer (SHS), a novel slit-less spectrometer that operates similar to Michelson interferometer, with a fiber array spectral translator (FAST) fiber array, a two-dimensional imaging fiber for hyperspectral imagery. This combination of technologies creates a novel wide-field, high throughput Raman hyperspectral imager capable of yielding very high spectral resolution measurements using defocused excitation, giving the system a greater area coverage and faster search rate than traditional Raman systems. This paper will focus on the need for an innovative UV Raman system, provide an overview of spatial heterodyne Raman spectroscopy, and discuss the development

  18. Optimally shaped narrowband picosecond pulses for femtosecond stimulated Raman spectroscopy.

    Hoffman, David P; Valley, David; Ellis, Scott R; Creelman, Mark; Mathies, Richard A


    A comparison between a Fabry-Pérot etalon filter and a conventional grating filter for producing the picosecond (ps) Raman pump pulses for femtosecond stimulated Raman spectroscopy (FSRS) is presented. It is shown that for pulses of equal energy the etalon filter produces Raman signals twice as large as that of the grating filter while suppressing the electronically resonant background signal. The time asymmetric profile of the etalon-generated pulse is shown to be responsible for both of these observations. A theoretical discussion is presented which quantitatively supports this hypothesis. It is concluded that etalons are the ideal method for the generation of narrowband ps pulses for FSRS because of the optical simplicity, efficiency, improved FSRS intensity and reduced backgrounds.

  19. Raman Spectroscopy and instrumentation for monitoring soil carbon systems.

    Stokes, D.L.


    This work describes developments in the application of Raman scattering and surface-enhanced Raman scattering (SERS) towards the assessment/characterization of carbon in soil. In the past, the nonspecific total carbon mass content of soil samples has generally been determined through mass loss techniques and elemental analysis. However, because of the concern over CO{sub 2} buildup in the atmosphere and its possible role in the ''Greenhouse Effect,'' there is a need for better-defined models of global cycling of carbon. As a means towards this end, there is a need to know more about the structure and functionality of organic materials in soil. Raman spectroscopy may therefore prove to be an exceptional tool in soil carbon analysis. Based on vibrational transitions of irradiated molecules, it provides structural information that is often suitable for sample identification. Furthermore, Raman scattering yields very fine spectral features which offer the potential for multicomponent sample analysis with minimal or no sample pretreatment. Although the intensity of Raman scattering is generally extremely low, the surface-enhanced Raman scattering (SERS) effect can greatly enhance Raman signals (10{sup 6}-10{sup 8} range) through the adsorption of compounds on specially roughened metal surfaces. In our laboratory, we have investigated copper, gold and silver as possible substrate metals in the fabrication of SERS substrates. These substrates have included metal-coated microparticles, metal island films, and redox-roughened metal foils. We have evaluated several laser excitation sources spanning the 515-785 nm range for both Raman and SERS analysis. For this particular study, we have selected fulvic and humic acids as models for establishing the feasibility of using Raman and SERS in soil carbon analysis. Our studies thus far have demonstrated that copper substrates perform best in the SERS detection of humic and fulvic acids, particularly when coupled

  20. Spectroscopic (FT-IR, FT-Raman, UV, 1H and 13C NMR) profiling and computational studies on methyl 5-methoxy-1H-indole-2-carboxylate: A potential precursor to biologically active molecules

    Almutairi, Maha S.; Xavier, S.; Sathish, M.; Ghabbour, Hazem A.; Sebastian, S.; Periandy, S.; Al-Wabli, Reem I.; Attia, Mohamed I.


    Methyl 5-methoxy-1H-indole-2-carboxylate (MMIC) was prepared via esterification of commercially available 5-methoxyindole-2-carboxylic acid. The title molecule MMIC was characterised using FT-IR and FT-Raman in the ranges of 4000-500 and 4000-50 cm-1, respectively. The fundamental modes of the vibrations were assigned and the UV-visible spectrum of the MMIC molecule was recorded in the range of 200-400 nm to explore its electronic nature. The HOMO-LUMO energy distribution was calculated and the bonding and anti-bonding structures of the title molecule were studied and analysed using the natural bond orbital (NBO) approach. The reactivity of the MMIC molecule was also investigated and both the positive and negative centres of the molecule were identified using chemical descriptors and molecular electrostatic potential (MEP) analysis. The chemical shifts of the 1H and 13C NMR spectra were noted and the magnetic field environment of the MMIC molecule are discussed. The non-linear optical (NLO) properties of the title molecule were studied based on its calculated values of polarisability and hyperpolarisability. All computations were obtained by DFT methods using the 6-311++G (d,p) basis set.

  1. Surface-enhanced Raman spectroscopy at single-molecule scale and its implications in biology

    Wang, Yuling; Irudayaraj, Joseph


    Single-molecule (SM) spectroscopy has been an exciting area of research offering significant promise and hope in the field of sensor development to detect targets at ultra-low levels down to SM resolution. To the experts and developers in the field of surface-enhanced Raman spectroscopy (SERS), this has often been a challenge and a significant opportunity for exploration. Needless to say, the opportunities and excitement of this multidisciplinary area impacts span the fields of physics, chemi...

  2. A Theoretical Distinction Between Time-Resolved Resonance Raman andResonance Fluorescence

    LU Jing; DU Si-De; FAN Kang-Nian; Lee Soo-Ying


    Based on the time-dependent theory, an analysis of the distinction between resonance Raman (RR) and resonance fluorescence (RF) with pulse excitation was presented. The real population of the intermediate state gives two optical components-the independent time evolution of intermediate ket and bra states generates RR while RF originates from the phase coherent between ket and bra states. In cw limit, the transition probability of spontaneous emission with pulse excitation can be reduced to the classical theory.

  3. Multi-frequency excitation

    Younis, Mohammad I.


    Embodiments of multi-frequency excitation are described. In various embodiments, a natural frequency of a device may be determined. In turn, a first voltage amplitude and first fixed frequency of a first source of excitation can be selected for the device based on the natural frequency. Additionally, a second voltage amplitude of a second source of excitation can be selected for the device, and the first and second sources of excitation can be applied to the device. After applying the first and second sources of excitation, a frequency of the second source of excitation can be swept. Using the methods of multi- frequency excitation described herein, new operating frequencies, operating frequency ranges, resonance frequencies, resonance frequency ranges, and/or resonance responses can be achieved for devices and systems.

  4. Hong-Ou-Mandel Interference between Two Deterministic Collective Excitations in an Atomic Ensemble

    Li, Jun; Zhou, Ming-Ti; Jing, Bo; Wang, Xu-Jie; Yang, Sheng-Jun; Jiang, Xiao; Mølmer, Klaus; Bao, Xiao-Hui; Pan, Jian-Wei


    We demonstrate deterministic generation of two distinct collective excitations in one atomic ensemble, and we realize the Hong-Ou-Mandel interference between them. Using Rydberg blockade we create single collective excitations in two different Zeeman levels, and we use stimulated Raman transitions to perform a beam-splitter operation between the excited atomic modes. By converting the atomic excitations into photons, the two-excitation interference is measured by photon coincidence detection with a visibility of 0.89(6). The Hong-Ou-Mandel interference witnesses an entangled NOON state of the collective atomic excitations, and we demonstrate its two times enhanced sensitivity to a magnetic field compared with a single excitation. Our work implements a minimal instance of boson sampling and paves the way for further multimode and multiexcitation studies with collective excitations of atomic ensembles.

  5. Adiabatic Tip-Plasmon Focusing for Nano-Raman Spectroscopy

    Berweger, Samuel; Atkin, Joanna M.; Olmon, Robert L.; Raschke, Markus Bernd


    True nanoscale optical spectroscopy requires the efficient delivery of light for a spatially nanoconfined excitation. We utilize adiabatic plasmon focusing to concentrate an optical field into the apex of a scanning probe tip of {approx}10 nm in radius. The conical tips with the ability for two-stage optical mode matching of the surface plasmon polariton (SPP) grating-coupling and the adiabatic propagating SPP conversion into a localized SPP at the tip apex represent a special optical antenna concept for far-field transduction into nanoscale excitation. The resulting high nanofocusing efficiency and the spatial separation of the plasmonic grating coupling element on the tip shaft from the near-field apex probe region allows for true background-free nanospectroscopy. As an application, we demonstrate tip-enhanced Raman spectroscopy (TERS) of surface molecules with enhanced contrast and its extension into the near-IR with 800 nm excitation.

  6. Vibrational fingerprinting of bacterial pathogens by surface enhanced Raman scattering (SERS)

    Premasiri, W. Ranjith; Moir, D. T.; Ziegler, Lawrence D.


    The surface enhanced Raman scattering (SERS) spectra of vegetative whole-cell bacteria were obtained using in-situ grown gold nanoparticle cluster-covered silicon dioxide substrates excited at 785 nm. SERS spectra of Gram-negative bacteria; E. coli and S. typhimurium, and Gram-positive bacteria; B. subtilis, B. cereus, B. thuringeinsis and B. anthracis Sterne, have been observed. Raman enhancement factors of ~104-105 per cell are found for both Gram positive and Gram negative bacteria on this novel SERS substrate. The bacterial SERS spectra are species specific and exhibit greater species differentiation and reduced spectral congestion than their corresponding non-SERS (bulk) Raman spectra. Fluorescence observed in the 785 nm excited bulk Raman emission of Bacillus species is not apparent in the corresponding SERS spectra. The surface enhancement effect allows the observation of Raman spectra at the single cell level excited by low incident laser powers (blood serum, has an observable effect on the bacterial SERS spectra. However, reproducible, species specific SERS vibrational fingerprints are still obtained. The potential of SERS for detection and identification of bacteria with species specificity on these gold nanoparticle coated substrates is demonstrated by these results.

  7. Detection and characterization of stomach cancer and atrophic gastritis with fluorescence and Raman spectroscopy

    Li, Xiaozhou; Lin, Junxiu; Jia, Chunde; Wang, Rong


    In this paper, we attempt to find a valid method to distinguish gastric cancer and atrophic gastritis. Auto-fluorescence and Raman spectroscopy of laser induced (514.5 nm and 488.0 nm) was measured. The serum spectrum is different between normal and cancer. Average value of diagnosis parameter for normal serum, red shift is less than 12 nm and Raman relative intensity of peak C by 514.5 nm excited is stronger than that of 488.0 nm. To gastric cancer, its red shift of average is bigger than 12 nm and relative intensity of Raman peak C by 514.5 nm excited is weaker than that by 488.0 nm. To atrophic gastritis, the distribution state of Raman peaks is similar with normal serum and auto-fluorescence spectrum's shape is similar to that of gastric cancer. Its average Raman peak red shift is bigger than 12 nm and the relative intensity of peak C by 514.5 excited is stronger than that of by 488.0. We considered it as a criterion and got an accuracy of 85.6% for diagnosis of gastric cancer compared with the result of clinical diagnosis.

  8. Research on the photochemical kinetics process of gold nanoparticle-doped photopolymer system using Raman spectroscopy

    Li, Ruoping; Yang, Jingliang; Li, Yanmeng; Han, Junhe; Huang, Mingju


    A photopolymer system doped with gold nanoparticles (Au NPs) was studied using Surface Enhanced Raman Scattering (SERS) technique in this work. In the system, polyvinyl alcohol is a binder, acrylamide and methylene-bisacrylamide are two monomers, methylene blue (MB) is a photosensitizer and triethanolamine is an initiator. Two types of Au NPs-- bare Au NPs with 13nm and 25nm diameter, and their corresponding SiO2 shell-isolated Au (Au@SiO2) NPs with 2nm shell thickness, were prepared and doped into the photopolymer for reducing the shrinkage of holograms. The shield of SiO2 shell avoids the dark reaction originating from electron transfer between Au NPs and MB molecules. More importantly, under 633nm laser excitation, the resonance Raman scattering of MB can be triggered, and the Raman signal of MB can be enhanced greatly due to the local enhanced electromagnetic field by Au@SiO2 NPs. Both of them made the in-situ Raman detection of the photopolymer more feasible. The experimental results not only show the excitation process of MB but also display the polymerization process of the photopolymer. In addition, the excitation rate of MB and the polymerization rate of monomers can also be obtained using their time Raman spectra. This provides an experimental tool for detecting the photochemical kinetics process of the photopolymer.

  9. Simulations of the polarisation-dependent Raman intensity of β-carotene in photosystem II crystals

    Brose, K., E-mail: [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin (Germany); Zouni, A. [Institut für Chemie, Max-Volmer-Laboratorium, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany); Müh, F. [Institut für Theoretische Physik, Johannes Kepler Universität Linz, Altenberger Straße 69, 4040 Linz (Austria); Mroginski, M.A. [Institut für Chemie, Max-Volmer-Laboratorium, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany); Maultzsch, J. [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin (Germany)


    Highlights: • First polarisation-dependent Raman spectroscopy on photosystem II crystals. • Orientation-dependent Raman intensity simulations for di- and monomeric crystals. • Simulations account for all β-carotenes (β-Car) in the unit cell for the first time. • Prediction for identificationy of the β-Car cation in side-path electron transport. - Abstract: In order to clarify possibilities to identify the β-carotene (β-Car) radicals in secondary electron transfer (ET) reactions in the photosystem II core complex (PSIIcc), Raman intensities of all 96 β-Car cofactors in the unit cell of PSIIcc-dimer crystals as a function of polarisation and crystal orientation were simulated based on the 2.9 Å resolution structure. The Raman-active symmetry A{sub g} in the C{sub 2h} group is assigned to the β-Car modes ν{sub 66} and ν{sub 67}. Simulations are in agreement with experiment for off-resonant excitation at 1064 nm. Resonant measurements at 476 and 532 nm excitation can not be explained, which is attributed to mode mixing in the excited state and the existence of different spectral pools. The identity of the β-Car oxidised in secondary ET can not be resolved by Raman measurements on PSIIcc-dimer crystals. Additional simulations show that similar measurements on PSIIcc-monomer crystals could provide a possible route to solve this issue.

  10. Resonance Raman Spectroscopy of Extreme Nanowires and Other 1D Systems

    Smith, David C.; Spencer, Joseph H.; Sloan, Jeremy; McDonnell, Liam P.; Trewhitt, Harrison; Kashtiban, Reza J.; Faulques, Eric


    This paper briefly describes how nanowires with diameters corresponding to 1 to 5 atoms can be produced by melting a range of inorganic solids in the presence of carbon nanotubes. These nanowires are extreme in the sense that they are the limit of miniaturization of nanowires and their behavior is not always a simple extrapolation of the behavior of larger nanowires as their diameter decreases. The paper then describes the methods required to obtain Raman spectra from extreme nanowires and the fact that due to the van Hove singularities that 1D systems exhibit in their optical density of states, that determining the correct choice of photon excitation energy is critical. It describes the techniques required to determine the photon energy dependence of the resonances observed in Raman spectroscopy of 1D systems and in particular how to obtain measurements of Raman cross-sections with better than 8% noise and measure the variation in the resonance as a function of sample temperature. The paper describes the importance of ensuring that the Raman scattering is linearly proportional to the intensity of the laser excitation intensity. It also describes how to use the polarization dependence of the Raman scattering to separate Raman scattering of the encapsulated 1D systems from those of other extraneous components in any sample. PMID:27168195

  11. Raman imaging of extraterrestrial materials

    Wang, Alian; Korotev, Randy L.; Jolliff, Bradley L.; Ling, Zongcheng


    Laser Raman Spectroscopy has been proposed and is under extensive development for surface exploration missions to planetary bodies of our Solar System. It reveals information on molecular structure and chemistry. The spatial distribution of molecular species in natural geological samples and planetary materials has significance for the geological processes by which they formed. Raman imaging is the best way to combine the molecular identification and characterization of geologic materials with their spatial distribution. This paper reports Raman imaging studies of five types of extraterrestrial materials and three terrestrial samples using a state-of-the-art Raman imaging system. The Raman spectral features of major, minor, and trace species in these samples, together with their spatial correlations revealed by these Raman imaging studies indicate the genetic relationships and the geological processes that these materials have been experienced. For robotic planetary surface exploration mission, a simple yet very useful molecular map of a sample can be generated by using line-scan or grid-scan of an in situ Raman system with tightly focused laser beam.

  12. Chemical aerosol Raman detector

    Aggarwal, R. L.; Farrar, L. W.; Di Cecca, S.; Amin, M.; Perkins, B. G.; Clark, M. L.; Jeys, T. H.; Sickenberger, D. W.; D'Amico, F. M.; Emmons, E. D.; Christesen, S. D.; Kreis, R. J.; Kilper, G. K.


    A sensitive chemical aerosol Raman detector (CARD) has been developed for the trace detection and identification of chemical particles in the ambient atmosphere. CARD includes an improved aerosol concentrator with a concentration factor of about 40 and a CCD camera for improved detection sensitivity. Aerosolized isovanillin, which is relatively safe, has been used to characterize the performance of the CARD. The limit of detection (SNR = 10) for isovanillin in 15 s has been determined to be 1.6 pg/cm3, which corresponds to 6.3 × 109 molecules/cm3 or 0.26 ppb. While less sensitive, CARD can also detect gases. This paper provides a more detailed description of the CARD hardware and detection algorithm than has previously been published.

  13. Combined quantum mechanics (TDDFT) and classical electrodynamics (Mie theory) methods for calculating surface enhanced Raman and hyper-Raman spectra.

    Mullin, Jonathan; Valley, Nicholas; Blaber, Martin G; Schatz, George C


    Multiscale models that combine quantum mechanics and classical electrodynamics are presented, which allow for the evaluation of surface-enhanced Raman (SERS) and hyper-Raman scattering spectra (SEHRS) for both chemical (CHEM) and electrodynamic (EM) enhancement mechanisms. In these models, time-dependent density functional theory (TDDFT) for a system consisting of the adsorbed molecule and a metal cluster fragment of the metal particle is coupled to Mie theory for the metal particle, with the surface of the cluster being overlaid with the surface of the metal particle. In model A, the electromagnetic enhancement from plasmon-excitation of the metal particle is combined with the chemical enhancement associated with a static treatment of the molecule-metal structure to determine overall spectra. In model B, the frequency dependence of the Raman spectrum of the isolated molecule is combined with the enhancements determined in model A to refine the enhancement estimate. An equivalent theory at the level of model A is developed for hyper-Raman spectra calculations. Application to pyridine interacting with a 20 nm diameter silver sphere is presented, including comparisons with an earlier model (denoted G), which combines plasmon enhanced fields with gas-phase Raman (or hyper-Raman) spectra. The EM enhancement factor for spherical particles at 357 nm is found to be 10(4) and 10(6) for SERS and SEHRS, respectively. Including both chemical and electromagnetic mechanisms at the level of model A leads to enhancements on the order of 10(4) and 10(9) for SERS and SEHRS.

  14. Scanning angle Raman spectroscopy: Investigation of Raman scatter enhancement techniques for chemical analysis

    Meyer, Matthew W. [Iowa State Univ., Ames, IA (United States)


    This thesis outlines advancements in Raman scatter enhancement techniques by applying evanescent fields, standing-waves (waveguides) and surface enhancements to increase the generated mean square electric field, which is directly related to the intensity of Raman scattering. These techniques are accomplished by employing scanning angle Raman spectroscopy and surface enhanced Raman spectroscopy. A 1064 nm multichannel Raman spectrometer is discussed for chemical analysis of lignin. Extending dispersive multichannel Raman spectroscopy to 1064 nm reduces the fluorescence interference that can mask the weaker Raman scattering. Overall, these techniques help address the major obstacles in Raman spectroscopy for chemical analysis, which include the inherently weak Raman cross section and susceptibility to fluorescence interference.

  15. From spin flip excitations to the spin susceptibility enhancement of a two-dimensional electron gas.

    Perez, F; Aku-leh, C; Richards, D; Jusserand, B; Smith, L C; Wolverson, D; Karczewski, G


    The g-factor enhancement of the spin-polarized two-dimensional electron gas was measured directly over a wide range of spin polarizations, using spin flip resonant Raman scattering spectroscopy on two-dimensional electron gases embedded in Cd(1-x)Mn(x)Te semimagnetic quantum wells. At zero Raman transferred momentum, the single-particle spin flip excitation, energy Z*, coexists in the Raman spectrum with the spin flip wave of energy Z, the bare giant Zeeman splitting. We compare the measured g-factor enhancement with recent spin-susceptibility enhancement theories and deduce the spin-polarization dependence of the mass renormalization.

  16. Raman Spectroscopy at High Pressures

    Alexander F. Goncharov


    Full Text Available Raman spectroscopy is one of the most informative probes for studies of material properties under extreme conditions of high pressure. The Raman techniques have become more versatile over the last decades as a new generation of optical filters and multichannel detectors become available. Here, recent progress in the Raman techniques for high-pressure research and its applications in numerous scientific disciplines including physics and chemistry of materials under extremes, earth and planetary science, new materials synthesis, and high-pressure metrology will be discussed.

  17. ExoMars Raman laser spectrometer for Exomars

    Rull, F.; Sansano, A.; Díaz, E.; Canora, C. P.; Moral, A. G.; Tato, C.; Colombo, M.; Belenguer, T.; Fernández, M.; Manfredi, J. A. R.; Canchal, R.; Dávila, B.; Jiménez, A.; Gallego, P.; Ibarmia, S.; Prieto, J. A. R.; Santiago, A.; Pla, J.; Ramos, G.; Díaz, C.; González, C.


    The Raman Laser Spectrometer (RLS) is one of the Pasteur Payload instruments, within the ESA's Aurora Exploration Programme, ExoMars mission. ExoMars 2018 main Scientific objective is "Searching for evidence of past and present life on Mars". Raman Spectroscopy is used to analyze the vibrational modes of a substance either in the solid, liquid or gas state. It relies on the inelastic scattering (Raman Scattering) of monochromatic light produced by atoms and molecules. The radiation-matter interaction results in the energy of the exciting photons to be shifted up or down. The shift in energy appears as a spectral distribution and therefore provides an unique fingerprint by which the substances can be identified and structurally analyzed. The RLS is being developed by an European Consortium composed by Spanish, French, German and UK partners. It will perform Raman spectroscopy on crushed powdered samples inside the Rover's Analytical Laboratory Drawer. Instrument performances are being evaluated by means of simulation tools and development of an instrument prototype.

  18. Raman Laser Spectrometer for 2020 ExoMars

    Moral, Andoni G.; Pérez, Carlos; INTA, University of Valladolid, INSA, Leicester University, IRAP, RAL, OHB


    The Raman Laser Spectrometer (RLS) is one of the Pasteur Payload instruments, within the ESA's Aurora Exploration Programme, ExoMars mission.ExoMars 2020 main scientific objective is "Searching for evidence of past and present life on Mars".Raman Spectroscopy is used to analyze the vibrational modes of a substance either in the solid, liquid or gas state. It relies on the inelastic scattering (Raman Scattering) of monochromatic light produced by atoms and molecules. The radiation-matter interaction results in the energy of the exciting photons to be shifted up or down. The shift in energy appears as a spectral distribution and therefore provides an unique fingerprint by which the substances can be identified and structurally analyzed.The RLS is being developed by an European Consortium composed by Spanish, UK, French and German partners. It will perform Raman spectroscopy on crushed powdered samples, obtained from 2 meters depth under Mars surface, inside the Rover's Analytical Laboratory Drawer.After a wide campaign for evaluating Instrument performances by means of simulation tools and development of an instrument prototype, Instrument Structural and Thermal Model was successfully delivered on February 2015, and the Engineering and Qualification Model has been manufactured and is expected to be delivered by November 2016, after a testing campaign developed during Q2 & Q3 of 2016.A summary of main Instrument performances obtained during the last months, achieving high levels of spectral resolution and accuracy in the obtained spectra.

  19. Proliferation detection using a remote resonance Raman chemical sensor

    Sedlacek, A.J.; Chen, C.L.; Dougherty, D.R.


    The authors discussed the potential of the resonance Raman chemical sensor as a remote sensor that can be used for gases, liquids or solids. This spectroscopy has the fundamental advantage that it is based on optical fingerprints that are insensitive to environmental perturbations or excitation frequency. By taking advantage of resonance enhancement, the inelastic scattering cross-section can increase anywhere from 4 to 6 orders of magnitude which translates into increased sensing range or lower detection limits. It was also shown that differential cross-sections as small as 10{sup {minus}27} cm{sup 2}/sr do not preclude the use of this technique as being an important component in one`s remote-sensing arsenal. The results obtained in the early 1970s on various pollutants and the more recent work on atmospheric water cast a favorable light on the prospects for the successful development of a resonance Raman remote sensor. Currently, of the 20 CW agent-related {open_quotes}signature{close_quotes} chemicals that the authors have investigated, 18 show enhancements ranging from 3 to 6 orders of magnitude. The absolute magnitudes of the measured resonance enhanced Raman cross-sections for these 18 chemicals suggest that detection and identification of trace quantities of the {open_quotes}signature{close_quotes} chemicals, through a remote resonance Raman chemical sensor, could be achieved.

  20. Raaka-aineiden tunnistus Raman-spektroskopialla


    Opinnäytetyön aiheena on Raman-spektroskopian käyttö raaka-aineiden tunnistuksessa. Raman-spektroskopia perustuu Raman-sirontaan, jonka Raman havaitsi 1928. Raman-sirontaa tapahtuu, kun molekyylin kemialliset sidokset kohtaavat valon fotonit ja fotonien energia muuttuu. Raman-sironta on hyvin heikkoa ja mittausta häiritsee huomattavasti voimakkaammat Rayleigh-sironta ja fluoresenssi. Vasta 1980-luvulla tekniikka oli riittävän kehittynyttä, että Raman-spektroskopiaa pystyttiin hyödyntämään käy...

  1. Surface-enhanced resonance Raman spectroscopy of copper chlorophyllin on silver and gold colloids

    Hildebrandt, P.; Spiro, T.G.


    Surface-enhanced resonance Raman spectra (SERRS) are reported for copper chlorophyllin a (CuChl) adsorbed on silver and gold colloids. The surface species are shown to be monomeric, by comparison with solution resonance Raman (RR) spectra, although lowering the pH of the gold colloid to 2.0 induces spectral changes suggestive of surface aggregation. The similarity of CuChl monomer RR and SERRS spectra is consistent with electromagnetic enhancement of the RR spectra via the metal particles, with no indication of a chemical interaction that would perturb the electronic states. The SERRS spectra change markedly with excitation wavelength in ways that can be explained on the basis of the different Raman enhancement pattern expected for resonance with the different chlorin excited states. The SERRS spectra are highly resolved and are useful in suggesting new assignments for chlorin vibrational modes.

  2. Femtosecond time-resolved impulsive stimulated Raman spectroscopy using sub-7-fs pulses: Apparatus and applications

    Kuramochi, Hikaru; Takeuchi, Satoshi; Tahara, Tahei


    We describe details of the setup for time-resolved impulsive stimulated Raman spectroscopy (TR-ISRS). In this method, snapshot molecular vibrational spectra of the photoreaction transients are captured via time-domain Raman probing using ultrashort pulses. Our instrument features transform-limited sub-7-fs pulses to impulsively excite and probe coherent nuclear wavepacket motions, allowing us to observe vibrational fingerprints of transient species from the terahertz to 3000-cm-1 region with high sensitivity. Key optical components for the best spectroscopic performance are discussed. The TR-ISRS measurements for the excited states of diphenylacetylene in cyclohexane are demonstrated, highlighting the capability of our setup to track femtosecond dynamics of all the Raman-active fundamental molecular vibrations.

  3. Anomalous lattice vibrations of monolayer MoS 2 probed by ultraviolet Raman scattering

    Liu, Hsiang Lin


    We present a comprehensive Raman scattering study of monolayer MoS2 with increasing laser excitation energies ranging from the near-infrared to the deep-ultraviolet. The Raman scattering intensities from the second-order phonon modes are revealed to be enhanced anomalously by only the ultraviolet excitation wavelength 354 nm. We demonstrate theoretically that such resonant behavior arises from a strong optical absorption that forms near the Γ point and of the band structure and an inter-valley resonant electronic scattering by the M-point phonons. These results advance our understanding of the double resonance Raman scattering process in low-dimensional semiconducting nanomaterials and provide a foundation for the technological development of monolayer MoS2 in the ultraviolet frequency range. © the Owner Societies 2015.

  4. Continuous Flow-Resonance Raman Spectroscopy of an Intermediate Redox State of Cytochrome-C

    Forster, M.; Hester, R. E.; Cartling, B.


    An intermediate redox state of cytochrome c at alkaline pH, generated upon rapid reduction by sodium dithionite, has been observed by resonance Raman (RR) spectroscopy in combination with the continuous flow technique. The RR spectrum of the intermediate state is reported for excitation both...

  5. Raman scattering and quantum confinement in heavily electron-irradiated alkali halides

    Shtyrkov, E.I.; Klimovitskii, A.; Hartog, H.W. den; Vainshtein, D.I.


    In this paper we will study the properties of several unusual Raman scattering peaks in heavily irradiated NaCl with vast amounts of colloidal sodium and chlorine precipitates. It appears that the laser excitation light interacts with both the electronic and vibration systems of the Na colloids, whi

  6. Three-phonon stimulated Raman scattering in an orthorhombic LuAlO3 crystal

    Kaminskii, A. A.


    High-order stimulated Raman scattering (SRS) has been revealed in a LuAlO3 crystal upon stationary picosecond laser excitation. All recorded Stokes and anti-Stokes χ(3)-nonlinear laser components are attributed to three SRS-promoting A g vibrational modes of its octahedral anionic units (AlO3)-3.


    A compact diode laser/fiber-optic Raman spectrometer is used for quantitative detection of environmentally important dyes. This system is based on diode laser excitation at 782 mm, fiber optic probe technology, an imaging spectrometer, and state-of-the-art scientific CCD camera. ...

  8. On the Increasing Fragility of Human Teeth with Age: ADeep-Ultraviolet Resonance Raman Study

    Ager III, J.W.; Nalla, R.K.; Balooch, G.; Kim, G.; Pugach, M.; Habelitz, S.; Marshall, G.W.; Kinney, J.H.; Ritchie, R.O.


    Ultraviolet resonance Raman spectroscopy (UVRRS) using 244nm excitation was used to investigate the impact of aging on humandentin. The intensity of a spectroscopic feature from the peptide bondsin the collagen increases with tissue age, similar to a finding reportedpreviously for human cortical bone.

  9. Structural Evolution in Photoactive Yellow Protein Studied by Femtosecond Stimulated Raman Spectroscopy

    Yoshizawa M.


    Full Text Available Ultrafast structural evolution in photoactive yellow protein (PYP is studied by femtosecond stimulated Raman spectroscopy. A comparison between wild-type PYP and E46Q mutant reveals that the hydrogen-bonding network surrounding the chromophore of PYP is immediately rearranged in the electronic excited state.

  10. Stimulated Raman spectroscopy and nanoscopy of molecules using near field photon induced forces without resonant electronic enhancement gain

    Tamma, Venkata Ananth; Huang, Fei; Nowak, Derek; Kumar Wickramasinghe, H.


    We report on stimulated Raman spectroscopy and nanoscopy of molecules, excited without resonant electronic enhancement gain, and recorded using near field photon induced forces. Photon-induced interaction forces between the sharp metal coated silicon tip of an Atomic Force Microscope (AFM) and a sample resulting from stimulated Raman excitation were detected. We controlled the tip to sample spacing using the higher order flexural eigenmodes of the AFM cantilever, enabling the tip to come very close to the sample. As a result, the detection sensitivity was increased compared with previous work on Raman force microscopy. Raman vibrational spectra of azobenzene thiol and l-phenylalanine were measured and found to agree well with published results. Near-field force detection eliminates the need for far-field optical spectrometer detection. Recorded images show spatial resolution far below the optical diffraction limit. Further optimization and use of ultrafast pulsed lasers could push the detection sensitivity towards the single molecule limit.

  11. Raman imaging to study structural and chemical features of the dentin enamel junction

    Alebrahim, M. Anwar; Krafft, C.; Popp, J.


    The structure and chemical features of the human dentin enamel junction (DEJ) were characterized using Raman spectroscopic imaging. Slices were prepared from 10 German, and 10 Turkish teeth. Raman images were collected at 785 nm excitation and the average Raman spectra were calculated for analysis. Univariate and multivariate spectral analysis were applied for investigation. Raman images were obtained based on the intensity ratios of CH at 1450 cm-1 (matrix) to phosphate at 960 cm-1 (mineral), and carbonate to phosphate (1070/960) ratios. Different algorithms (HCA, K-means cluster and VCA) also used to study the DEJ. The obtained results showed that the width of DEJ is about 5 pm related to univariate method while it varies from 6 to 12 μm based on multivariate spectral technique. Both spectral analyses showed increasing in carbonate content inside the DEJ compared to the dentin, and the amide I (collagen) peak in dentin spectra is higher than DEJ spectra peak.

  12. Raman spectroscopic measurements of beta-carotene and lycopene in human skin

    Darvin, M. E.; Gerzonde, I.; Ey, S.; Brandt, Nikolai N.; Albrecht, Hansjoerg; Gonchukov, Sergei A.; Sterry, Wolfram; Lademann, Juergen


    The antioxidant β-carotene and lycopene substances were detected non-invasively, in vivo in human skin using resonance Raman spectroscopy. Both substances were detected simultaneously. To distinguish between the substances, the Raman signals were excited at 488 nm and 514,5 nm simultaneously using a multilane Ar+ laser. The application of a fiber based optical imaging system allowed the detection of β-carotene and lycopene on any skin area. The disturbance of the measurements because of non-homogeneous skin pigmentation was avoided by using a measuring area of 28 mm2. The minimum power density for registration of the Raman signals and their optimum relation was determined. The Raman spectroscopic method is well suited for the evaluation of the efficacy of topically or systematically applied amounts of β-carotene and lycopene.

  13. Surface-enhanced Raman scattering from AgNP-graphene-AgNP sandwiched nanostructures.

    Wu, Jian; Xu, Yijun; Xu, Pengyu; Pan, Zhenghui; Chen, Sheng; Shen, Qishen; Zhan, Li; Zhang, Yuegang; Ni, Weihai


    We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a "hot surface" for enhancing the Raman response of two-dimensional materials.

  14. Surface-enhanced Raman scattering: a new optical probe in molecular biophysics and biomedicine

    Kneipp, J.; Wittig, B.; Bohr, Henrik


    Sensitive and detailed molecular structural information plays an increasing role in molecular biophysics and molecular medicine. Therefore, vibrational spectroscopic techniques, such as Raman scattering, which provide high structural information content are of growing interest in biophysical...... of the free electrons in the metal. This effect of surface-enhanced Raman scattering (SERS) allows us to push vibrational spectroscopy to new limits in detection sensitivity, lateral resolution, and molecular structural selectivity. This opens up exciting perspectives also in molecular biospectroscopy...... and biomedical research. Raman spectroscopy can be revolutionized when the inelastic scattering process takes place in the very close vicinity of metal nanostructures. Under these conditions, strongly increased Raman signals can be obtained due to resonances between optical fields and the collective oscillations...

  15. Fast discrimination of hydroxypropyl methyl cellulose using portable Raman spectrometer and multivariate methods

    Song, Biao; Lu, Dan; Peng, Ming; Li, Xia; Zou, Ye; Huang, Meizhen; Lu, Feng


    Raman spectroscopy is developed as a fast and non-destructive method for the discrimination and classification of hydroxypropyl methyl cellulose (HPMC) samples. 44 E series and 41 K series of HPMC samples are measured by a self-developed portable Raman spectrometer (Hx-Raman) which is excited by a 785 nm diode laser and the spectrum range is 200-2700 cm-1 with a resolution (FWHM) of 6 cm-1. Multivariate analysis is applied for discrimination of E series from K series. By methods of principal components analysis (PCA) and Fisher discriminant analysis (FDA), a discrimination result with sensitivity of 90.91% and specificity of 95.12% is achieved. The corresponding receiver operating characteristic (ROC) is 0.99, indicting the accuracy of the predictive model. This result demonstrates the prospect of portable Raman spectrometer for rapid, non-destructive classification and discrimination of E series and K series samples of HPMC.

  16. Intense Raman bands and low luminescence of thin films of heme proteins on silica

    Sonois, Vanessa; Bacsa, Wolfgang; Faller, Peter


    We use resonance Raman spectroscopy to study cytochrome c, hemoglobin and myoglobin from 50 μM solutions dried on a SiO 2 surface. Intense Raman spectra were observed with low luminescent background when excited at 488 nm with low laser power levels (0.6 mW) and relative short acquisition times (120 s). We estimate that 1 picogram of heme proteins can be detected. A polarization sensitive Raman band in cytochrome c near the edge of dried droplets suggests that the proteins line up in the ring deposit. This preferential orientation is suggested to contribute to the low luminescence back ground signal and to the larger Raman intensity compared to the heme proteins in powder form.

  17. Potential application of Raman spectroscopy for determining burial duration of skeletal remains.

    McLaughlin, Gregory; Lednev, Igor K


    Raman spectroscopy was used to study trends in chemical composition of bones in a burial environment. A turkey bone was sectioned and buried for short intervals between 12 and 62 days. Buried sections were analyzed using Raman microspectroscopy with 785 nm excitation. The results indicate that chemical changes in bone due to soil bacteria are time-dependent. Spectroscopic trends within buried bone segments were correlated to burial duration. A preliminary model was constructed using peak integration of Raman bands. Data collected within buried bone segments fit very well in this model. The model constructed is sensitive to changes in bone composition in a scale of days. This study illustrates the great potential of Raman spectroscopy as a non-destructive method for estimating the burial duration of bone for forensic purposes.

  18. Computer simulation of surface-enhanced Raman scattering in nanostructured metamaterials

    Boyarintsev, S. O.; Sarychev, A. K.


    The simulation of local field fluctuations and surface-enhanced Raman scattering in percolation systems at the percolation threshold is described. An approximate real-space renormalization group method was used in the simulation. It allows one to radically reduce the computation time compared to an exact calculation and to obtain detailed information about the electromagnetic field. The local fields in real macroscopic systems can be calculated by using this approximation. A computer simulation of the local fields in metal island (percolation) films has been performed by the developed method. The calculation has confirmed the existence of giant local field fluctuations. In turn, the local electric field excites Raman scattering. The local fields of surface-enhanced Raman scattering have been calculated for the first time. The dependence of the Raman scattering enhancement factor on the reference frequency and Stokes shift has been derived. An experimental observation of this dependence could be considered as a confirmation of the electromagnetic nature of the enhancement.

  19. Mapping residual stress fields from Vickers hardness indents using Raman microprobe spectroscopy

    Sparks, R.G.; Enloe, W.S.; Paesler, M.A.


    Micro-Raman spectroscopy is used to map the residual stress fields in the vicinity of Vickers hardness indents. Both 514.5 and 488.0 nm, light is used to excite the effect and the resulting shifted and broadened Raman peaks are analyzed using computer deconvolution. Half-wave plates are used to vary the orientation of the incident later light`s polarization state with respect to crystal orientation. The Raman scattered light is then analyzed for polarization dependences which are indicative of the various components of the Raman scattering tensor. Such studies can yield valuable information about the orientation of stress components in a well known stress field. The results can then be applied to the determination of stress components in machined semiconductor materials.

  20. Raman spectroscopy of Cd1-xMnxS quantum dots

    Romcevic, N.; Kostic, R.; Romcevic, M.; Comor, M. I.; Nedeljkovic, J. M.


    Powders consisting of 44 Å Cd1-xMnxS (x = 0; 0.05; 0.1; 0.15; 0.3) quantum dots (QDs) were synthesized using the colloidal chemistry method and characterized by Raman scattering measurements. The dominant Raman line of the 44 Å Cd1-xMnxS QDs was at about 300 cm-1 showing asymmetric broadening for ω < 300 cm-1. A significant change in the intensity of the first harmonic for different x and excitation energies was noticed. Also, the second harmonic of confined Raman modes was experimentally observed. A theoretical model was used to calculate the relative contributions of the confined Raman scattering modes for the 44 Å CdS QDs and satisfactory agreement with experimental results was found.

  1. Raman spectroscopy of Cd{sub 1-x}Mn{sub x}S quantum dots

    Romcevic, N [Institute of Physics, Pregrevica 118, 11080 Belgrade (Serbia and Montenegro); Kostic, R [Institute of Physics, Pregrevica 118, 11080 Belgrade (Serbia and Montenegro); Romcevic, M [Institute of Physics, Pregrevica 118, 11080 Belgrade (Serbia and Montenegro); Comor, M I [Vinca Institute of Nuclear Sciences, PO Box 522, 11001 Belgrade (Serbia and Montenegro); Nedeljkovic, J M [Vinca Institute of Nuclear Sciences, PO Box 522, 11001 Belgrade (Serbia and Montenegro)


    Powders consisting of 44 A Cd{sub 1-x}Mn{sub x}S (x = 0; 0.05; 0.1; 0.15; 0.3) quantum dots (QDs) were synthesized using the colloidal chemistry method and characterized by Raman scattering measurements. The dominant Raman line of the 44 A Cd{sub 1-x}Mn{sub x}S QDs was at about 300 cm{sup -1} showing asymmetric broadening for {omega} < 300 cm{sup -1}. A significant change in the intensity of the first harmonic for different x and excitation energies was noticed. Also, the second harmonic of confined Raman modes was experimentally observed. A theoretical model was used to calculate the relative contributions of the confined Raman scattering modes for the 44 A CdS QDs and satisfactory agreement with experimental results was found.

  2. CN rotational excitation

    Palazzi, E.; Mandolesi, N.; Crane, Philippe


    We report the results of a search for new lines of sight in which to study the CN excitation and a statistical analysis of all the excitation temperatures measured using interstellar CN. This data set strongly confirms that the cosmic background radiation (CBR) is the dominant contributor to the excitation of CN, and demonstrates the homogeneity of the CBR. Thirty-five observations is a sufficiently large sample to look for the presence of systematic effects in the CN excitation. The weighted average of the CN excitation temperatures exceeds the T(CBR) obtained by COBE and the Canadian rocket by 82 +/- 30 mK. With the aim of looking at the origin of this difference, we have considered in detail the known mechanisms that could contribute to exciting the CN molecule. None of the data necessary to quantify these mechanisms are of sufficient quality to provide a clean explanation of the observed difference.

  3. On the excited-state multi-dimensionality in cyanines

    Dietzek, Benjamin; Brüggemann, Ben; Persson, Petter; Yartsev, Arkady


    Vibrational coherences in a photoexcited cyanine dye are preserved for the time-scale of diffusive torsional motion to the bottom of the excited-state potential. The coherently excited modes are virtually unaffected by solvent friction and thus distinct from the bond-twisting motion, which is strongly coupled to the surrounding solvent. We correlate the modes apparent in the resonance Raman and the four-wave mixing signal of 1,1'-diethyl-2,2'-cyanine with the understanding of optimal control of isomerization. In turn, the experimental results illustrate that optimal control might be used to obtain vibrational information complementary to conventional spectroscopic data.

  4. Raman Studies of Carbon Nanostructures

    Jorio, Ado; Souza Filho, Antonio G.


    This article reviews recent advances on the use of Raman spectroscopy to study and characterize carbon nanostructures. It starts with a brief survey of Raman spectroscopy of graphene and carbon nanotubes, followed by recent developments in the field. Various novel topics, including Stokes-anti-Stokes correlation, tip-enhanced Raman spectroscopy in two dimensions, phonon coherence, and high-pressure and shielding effects, are presented. Some consequences for other fields—quantum optics, near-field electromagnetism, archeology, materials and soil sciences—are discussed. The review ends with a discussion of new perspectives on Raman spectroscopy of carbon nanostructures, including how this technique can contribute to the development of biotechnological applications and nanotoxicology.

  5. Population of highly excited intermediate resonance states by electron transfer and excitation

    Schuch, R. (Manne Siegbahn Institute of Physics, S-104 05 Stockholm, Sweden (SE)); Justiniano, E. (Department of Physics, East Carolina University, Greenville, North Carolina 27858-4353 (USA)); Schulz, M.; Datz, S.; Dittner, P.F.; Giese, J.P.; Krause, H.F.; Schoene, H.; Vane, R. (Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6377 (USA)); Shafroth, S. (Department of Physics, North Carolina University, Chapel Hill, North Carolina 27599-3255 (USA))


    Coincidences between two sulfur {ital K} x rays were detected from collisions of hydrogenlike S ions with H{sub 2} gas in the projectile energy range between 150 and 225 MeV. These {ital K} x rays are emitted in the decay of doubly excited states formed in the collisions via transfer and excitation. The excitation function for two coincident {ital K}{beta} transitions peaks at about 175 MeV, slightly above the expected {ital KMM} resonance energy for resonant transfer and excitation (RTE). This demonstrates the occurrence of {Delta}{ital N}{ge}2 transitions (i.e., {ital KMM} and higher resonances) in the RTE process. The cross sections for the population of the very highly excited states are higher than those predicted by theoretical calculations that use dielectronic recombination rates folded with the Compton profile for the bound electrons.

  6. Excited states 2

    Lim, Edward C


    Excited States, Volume 2 is a collection of papers that deals with molecules in the excited states. The book describes the geometries of molecules in the excited electronic states. One paper describes the geometries of a diatomic molecule and of polyatomic molecules; it also discusses the determination of the many excited state geometries of molecules with two, three, or four atoms by techniques similar to diatomic spectroscopy. Another paper introduces an ordered theory related to excitons in pure and mixed molecular crystals. This paper also presents some experimental data such as those invo

  7. Excited states v.6

    Lim, Edward C


    Excited States, Volume 6 is a collection of papers that discusses the excited states of molecules. The first paper discusses the linear polyene electronic structure and potential surfaces, considering both the theoretical and experimental approaches in such electronic states. This paper also reviews the theory of electronic structure and cites some experimental techniques on polyene excitations, polyene spectroscopic phenomenology, and those involving higher states of polyenes and their triplet states. Examples of these experimental studies of excited states involve the high-resolution one-pho

  8. Guided-mode-resonance coupled localized surface plasmons for dually resonance enhanced Raman scattering sensing

    Wang, Zheng; Liu, Chao; Li, Erwen; Chakravarty, Swapnajit; Xu, Xiaochuan; Wang, Alan X.; Fan, D. L.; Chen, Ray T.


    Raman scattering spectroscopy is a unique tool to probe vibrational, rotational, and other low-frequency modes of a molecular system and therefore could be utilized to identify chemistry and quantity of molecules. However, the ultralow efficient Raman scattering, which is only 1/109 1/1014 of the excitation light due to the small Raman scattering cross-sections of molecules, have significantly hindered its development in practical sensing applications. The discovery of surface-enhanced Raman scattering (SERS) in the 1970s and the significant progress in nanofabrication technique, provide a promising solution to overcome the inherent issues of Raman spectroscopy. It is found that In the vicinity of nanoparticles and their junctions, the Raman signals of molecules can be significantly improved by an enhancement factor as high as 1010, due to the ultrahigh electric field generated by the localized surface plasmons resonance (LSPR), where the intensity of Raman scattering is proportional to the |E|4. In this work, we propose and demonstrate a new approach combining LSPR from nanocapsules with densely assembled silver nanoparticles (NC-AgNPs) and guidemode- resonance (GMR) from dielectric photonic crystal slabs (PCSs) for SERS substrates with robustly high performance.

  9. Insights into Protein Structure and Dynamics by Ultraviolet and Visible Resonance Raman Spectroscopy.

    López-Peña, Ignacio; Leigh, Brian S; Schlamadinger, Diana E; Kim, Judy E


    Raman spectroscopy is a form of vibrational spectroscopy based on inelastic scattering of light. In resonance Raman spectroscopy, the wavelength of the incident light falls within an absorption band of a chromophore, and this overlap of excitation and absorption energy greatly enhances the Raman scattering efficiency of the absorbing species. The ability to probe vibrational spectra of select chromophores within a complex mixture of molecules makes resonance Raman spectroscopy an excellent tool for studies of biomolecules. In this Current Topic, we discuss the type of molecular insights obtained from steady-state and time-resolved resonance Raman studies of a prototypical photoactive protein, rhodopsin. We also review recent efforts in ultraviolet resonance Raman investigations of soluble and membrane-associated biomolecules, including integral membrane proteins and antimicrobial peptides. These examples illustrate that resonance Raman is a sensitive, selective, and practical method for studying the structures of biological molecules, and the molecular bonding, geometry, and environments of protein cofactors, the backbone, and side chains.

  10. Raman Tweezers as a Diagnostic Tool of Hemoglobin-Related Blood Disorders

    Giulia Rusciano


    Full Text Available This review presents the development of a Raman Tweezers system for detecting hemoglobin-related blood disorders at a single cell level. The study demonstrates that the molecular fingerprint insight provided by Raman analysis holds great promise for distinguishing between healthy and diseased cells in the field of biomedicine. Herein a Raman Tweezers system has been applied to investigate the effects of thalassemia, a blood disease quite diffuse in the Mediterranean Sea region. By resonant excitation of hemoglobin Raman bands, we examined the oxygenation capability of normal, alpha- and beta-thalassemic erythrocytes. A reduction of this fundamental red blood cell function, particularly severe for beta-thalassemia, has been found. Raman spectroscopy was also used to draw hemoglobin distribution inside single erythrocytes; the results confirmed the characteristic anomaly (target shape, occurring in thalassemia and some other blood disorders. The success of resonance Raman spectroscopy for thalassemia detection reported in this review provide an interesting starting point to explore the application of a Raman Tweezers system in the analysis of several blood disorders.

  11. Triplet State Resonance Raman Spectroscopy

    Wilbrandt, Robert Walter; Jensen, N. H.; Pagsberg, Palle Bjørn


    Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied......Makes the first report on the resonance Raman spectrum of a molecule in its triplet state generated by pulse radiolysis. A solution of 0.01 mol dm-3 of p-terphenyl in benzene was studied...

  12. Tip-enhanced Raman spectroscopy: From concepts to practical applications

    Jiang, Nan; Kurouski, Dmitry; Pozzi, Eric A.; Chiang, Naihao; Hersam, Mark C.; Van Duyne, Richard P.


    Tip-enhanced Raman spectroscopy (TERS) is a powerful technique that integrates the vibrational fingerprinting of Raman spectroscopy and the sub-nanometer resolution of scanning probe microscopy (SPM). As a result, TERS is capable of obtaining chemical maps of analyzed specimens with exceptional lateral resolution. This is extremely valuable for the study of interactions between molecules and substrates, in addition to structural characterization of biological objects, such as viruses and amyloid fibrils, 2D polymeric materials, and monitoring electrochemical and photo-catalytic processes. In this mini-review, we discuss the most significant advances of TERS, including: super high resolution chemical imaging, monitoring of catalytic processes, incorporation of pulsed-excitation techniques, single-site electrochemistry, biosensing, and art conservation. We begin with a short overview of TERS, comparing it with other surface analytical techniques, followed by an overview of recent developments and future applications in TERS.

  13. Radiative processes in air excited by an ArF laser

    Laufer, Gabriel; Mckenzie, Robert L.; Huo, Winifred M.


    The emission spectrum of air that is excited by an ArF laser has been investigated experimentally and theoretically to determine the conditions under which fluorescence from O2 can be used for the measurement of temperature in aerodynamic flows. In addition to the expected fluorescence from O2, the spectrum from excitation with an intense laser beam is shown to contain significant contributions from the near-resonant Raman fundamental and overtone bands, the four-photon fluorescence excitation of C produced from ambient CO2, and possibly the three-photon excitation of O(2+). The nature of the radiative interactions contributing to these additional features is described.

  14. Raman mapping for kinetic analysis of crystallization of amorphous drug based on distributional images.

    Ueda, Hiroshi; Ida, Yasuo; Kadota, Kazunori; Tozuka, Yuichi


    The feasibility of Raman mapping for understanding the crystallization mechanism of an amorphous drug was investigated using described images. The crystallization tendency of amorphous indomethacin under dry condition at 30 °C was kinetically evaluated by means of Raman mapping and X-ray powder diffraction (XRPD) with change in the calculated crystallinities. Raman images directly revealed the occurrence of particle size-dependent non-uniform crystallization; slow crystallization of large particles, but fast crystallization of small particles. Kinetic analysis by fitting to the Kolmogorov-Johnson-Mehl-Avrami equation was performed for the crystallization profiles of both Raman mapping and XRPD data. For the Raman mapping data, the distribution of large particles was characterized and examined. The kinetic parameters calculated from the whole Raman image area agreed well with those of XRPD, suggesting accurate prediction of both techniques for the entire crystallization. Raman images revealed the change in the crystallization mechanism for the focused area; the large particles showed a reduced crystallization rate constant and an increase in the dimensional crystal growth exponent. Raman mapping is an attractive tool for quantitative and kinetic investigation of the crystallization mechanism with distributional images.

  15. Phonon and crystal field excitations in geometrically frustrated rare earth titanates

    Lummen, T. T. A.; Handayani, I. P.; Donker, M. C.; Fausti, D.; Dhalenne, G.; Berthet, P.; Revcolevschi, A.; van Loosdrecht, P. H. M.


    The phonon and crystal field excitations in several rare earth titanate pyrochlores are investigated. Magnetic measurements on single crystals of Gd2Ti2O7 , Tb2Ti2O7 , Dy2Ti2O7 , and Ho2Ti2O7 are used for characterization, while Raman spectroscopy and terahertz time domain spectroscopy are employed to probe the excitations in the materials. The lattice excitations are found to be analogous across the compounds over the whole temperature range investigated (295-4 K). The resulting full phononic characterization of the R2Ti2O7 pyrochlore structure is then used to identify crystal field excitations observed in the materials. Several crystal field excitations have been observed in Tb2Ti2O7 in Raman spectroscopy, among which all of the previously reported excitations. The presence of additional crystal field excitations, however, suggests the presence of two inequivalent Tb3+ sites in the low-temperature structure. Furthermore, the crystal field level at approximately 13cm-1 is found to be both Raman and dipole active, indicating broken inversion symmetry in the system and thus undermining its current symmetry interpretation. In addition, evidence is found for a significant crystal field-phonon coupling in Tb2Ti2O7 . The additional crystal field information on Tb2Ti2O7 adds to the recent discussion on the low temperature symmetry of this system and may serve to improve its theoretical understanding.

  16. Spectroscopic (FT-IR, FT-Raman, UV, 1H and 13C NMR) profiling and theoretical calculations of (2E)-2-[3-(1H-imidazol-1-yl)-1-phenylpropylidene]hydrazinecarboxamide: An anticonvulsant agent

    Haress, Nadia G.; Govindarajan, Munusamy; AL-Wabli, Reem I.; Almutairi, Maha S.; Al-Alshaikh, Monirah A.; Al-Saadi, Abdulaziz A.; Attia, Mohamed I.


    Vibrational characteristics of the anticonvulsant agent, (2E)-2-[3-(1H-imidazol-1-yl)-1-phenylpropylidene]hydrazinecarboxamide ((2E)-IPHC) have been investigated. The computational data are obtained by adopting ab initio Hartree-Fock (HF) and DFT/B3LYP/6-31 + G(d,p) methods. The most stable conformer is identified by a potential energy scan. The optimized geometrical parameters indicated that the overall symmetry of the most stable conformer is CS. Atoms in molecules (AIM) analysis is contained out and the chemical bondings between the atoms are as characterized. Mulliken atomic charges and simulated thermo-molecular (heat capacity and enthalpy) characteristics of the (2E)-IPHC molecule also have been analyzed. The magnitude of the molecular electrostatic potential (MEP) of oxygen, hydrogen, and nitrogen atoms as well as phenyl and imidazole rings in the title molecule were investigated along with their contribution to the biological activity. The energy gap between HOMO and LUMO orbitals has been found to be 5.1334 eV in the gaseous phase. Excitation energies, oscillator strength and wavelengths were computed by the time-dependent density function theory (TD-DFT) approach. Predicted wavenumbers have been assigned and they are consistent with the experimental values. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the (2E)-IPHC molecule were computed by the gauge independent atomic orbital (GIAO) method and were compared with the experimental results.

  17. Dependence of Raman and absorption spectra of stacked bilayer MoS2 on the stacking orientation.

    Park, Seki; Kim, Hyun; Kim, Min Su; Han, Gang Hee; Kim, Jeongyong


    Stacked bilayer molybdenum disulfide (MoS2) exhibits interesting physical properties depending on the stacking orientation and interlayer coupling strength. Although optical properties, such as photoluminescence, Raman, and absorption properties, are largely dependent on the interlayer coupling of stacked bilayer MoS2, the origin of variations in these properties is not clearly understood. We performed comprehensive confocal Raman and absorption mapping measurements to determine the dependence of these spectra on the stacking orientation of bilayer MoS2. The results indicated that with 532-nm laser excitation, the Raman scattering intensity gradually increased upon increasing the stacking angle from 0° to 60°, whereas 458-nm laser excitation resulted in the opposite trend of decreasing Raman intensity with increasing stacking angle. This opposite behavior of the Raman intensity dependence was explained by the varying resonance condition between the Raman excitation wavelength and C exciton absorption energy of bilayer MoS2. Our work sheds light on the intriguing effect of the subtle interlayer interaction in stacked MoS2 bilayers on the resulting optical properties.

  18. Raman scattering enhanced by plasmonic clusters and its application to single-molecule imaging

    Yasuike, Tomokazu [The Open University of Japan, Wakaba 2-11, Mihama-ku, Chiba 261-8586 (Japan); ESICB, Kyoto University, Kyoto daigaku-Katsura, Nishikyo-ku, Kyoto 615-8530 (Japan); Nobusada, Katsuyuki [Institute for Molecular Science and SOKENDAI, Nishigonaka 38, Okazaki, 444-8585 (Japan); ESICB, Kyoto University, Kyoto daigaku-Katsura, Nishikyo-ku, Kyoto 615-8530 (Japan)


    The optical response of the linear Au{sub 8} cluster is investigated by the linear response theory based on the density functional theory. It is revealed that the observed many peaks in the visible region originate from the interaction of the ideal plasmonic excitation along the molecular axis with the background d-electron excitations, i.e., the Landau damping. In spite of the existence of the damping, the Raman scattering is shown to be enhanced remarkably by the incident light resonant to the visible excitations. The novel imaging experiment with the atomic resolution is proposed by utilizing a plasmonic cluster as the probing tip.

  19. 2 nm continuously tunable 488nm micro-integrated diode-laser-based SHG light source for Raman spectroscopy

    Braune, M.; Maiwald, M.; Sumpf, B.; Tränkle, G.


    Raman spectroscopy in the visible spectral range is of great interest due to resonant Raman effects. Nevertheless, fluorescence and ambient light can mask the weak Raman lines. Shifted excitation Raman difference spectroscopy is a demonstrated tool to overcome this drawback. To apply this method, a light source with two alternating wavelengths is necessary. The spectral distance between these two wavelengths has to be adapted to the width of the Raman signal. According to the sample under investigation the width of the Raman signal could be in the range of 3 cm-1 - 12 cm-1. In this work, a micro-integrated light source emitting at 488 nm with a continuous wavelength tuning range up to 2 nm (83 cm-1) is presented. The pump source, a DFB laser emitting at 976 nm, and a periodically poled lithium niobate (PPLN) ridge waveguide crystal is used for the second harmonic generation (SHG). Both components are mounted on a μ-Peltier-element for temperature control. Here, a common wavelength tuning of the pump wavelength and the acceptance bandwidth of the SHG crystal via temperature is achieved. With the results the light source is suitable for portable Raman and SERDS experiments with a flexible spectral distance between both excitation wavelengths for SERDS with respect to the sample under investigation.

  20. Fermi energy dependence of first- and second-order Raman spectra in graphene: Kohn anomaly and quantum interference effect

    Hasdeo, Eddwi H.; Nugraha, Ahmad R. T.; Dresselhaus, Mildred S.; Saito, Riichiro


    Intensities of the first- and the second-order Raman spectra are calculated as a function of the Fermi energy. We show that the Kohn anomaly effect, i.e., phonon frequency renormalization, in the first-order Raman spectra originates from the phonon renormalization by the interband electron-hole excitation, whereas in the second-order Raman spectra, a competition between the interband and intraband electron-hole excitations takes place. By this calculation, we confirm the presence of different dispersive behaviors of the Raman peak frequency as a function of the Fermi energy for the first- and the second-order Raman spectra, as observed in some previous experiments. Moreover, the calculated results of the Raman intensity sensitively depend on the Fermi energy for both the first- and the second-order Raman spectra, indicating the presence of the quantum interference effect. The electron-phonon matrix element plays an important role in the intensity increase (decrease) of the combination (overtone) phonon modes as a function of the Fermi energy.

  1. Study on forward stimulated Brillouin scattering in a backward pumped fiber Raman amplifier

    Zaixuan Zhang(张在宣); Dawei Fang(方达伟); Songlin Zhuang(庄松林); Laixiao Li(李来晓); Dan Geng(耿丹); Bizhi Dai(戴碧智); Yongxing Jin(金永兴); Honglin Liu(刘红林); Insoo S.Kim; Jianfeng Wang(王剑锋); Xiaobiao Wu(吴孝彪)


    Strong multi-order forward stimulated Brillouin scattering (SBS) has been observed in the backward pumped S-band distributed fiber Raman amplifier (FRA) with tunable narrow signal source (less than 100 MHz) when the pump power of FRA reached the SBS threshold. This does not obey the theory that only weak backward SBS lines exist according to the conservation of energy and momentum and the wave vector selected rule. This is because the sound waveguide characteristic weakens the wave vector rule, and the forward transmitted sound waveguide Brillouin scattering lines are generated and amplified in FRA.When the pump power is further increased, 11 orders of SBS lines and comb-like profile are observed. For the excited line, the frequency is 197.2296 THz and the power is 0 dBm. The even order SBS lines are stronger than odd order SBS lines, the power of the 2nd and 4th order SBS lines is 1.75 dBm, which is 16 dB higher than that of the 1st and 3rd order SBS lines. The odd order SBS lines are named BrillouinRayleigh scattering lines.

  2. The origin of relative intensity fluctuations in single-molecule tip-enhanced Raman spectroscopy.

    Sonntag, Matthew D; Chulhai, Dhabih; Seideman, Tamar; Jensen, Lasse; Van Duyne, Richard P


    An explanation of the relative intensity fluctuations observed in single-molecule Raman experiments is described utilizing both single-molecule tip-enhanced Raman spectroscopy and time-dependent density functional theory calculations. No correlation is observed in mode to mode intensity fluctuations indicating that the changes in mode intensities are completely independent. Theoretical calculations provide convincing evidence that the fluctuations are not the result of diffusion, orientation, or local electromagnetic field gradients but rather are the result of subtle variations of the excited-state lifetime, energy, and geometry of the molecule. These variations in the excited-state properties will provide information on adsorbate-adsorbate and adsorbate-substrate interactions and may allow for inversion of experimental results to obtain these excited-state properties.

  3. Classification of oral cancers using Raman spectroscopy of serum

    Sahu, Aditi; Talathi, Sneha; Sawant, Sharada; Krishna, C. Murali


    Oral cancers are the sixth most common malignancy worldwide, with low 5-year disease free survival rates, attributable to late detection due to lack of reliable screening modalities. Our in vivo Raman spectroscopy studies have demonstrated classification of normal and tumor as well as cancer field effects (CFE), the earliest events in oral cancers. In view of limitations such as requirement of on-site instrumentation and stringent experimental conditions of this approach, feasibility of classification of normal and cancer using serum was explored using 532 nm excitation. In this study, strong resonance features of β-carotenes, present differentially in normal and pathological conditions, were observed. In the present study, Raman spectra of sera of 36 buccal mucosa, 33 tongue cancers and 17 healthy subjects were recorded using Raman microprobe coupled with 40X objective using 785 nm excitation, a known source of excitation for biomedical applications. To eliminate heterogeneity, average of 3 spectra recorded from each sample was subjected to PC-LDA followed by leave-one-out-cross-validation. Findings indicate average classification efficiency of ~70% for normal and cancer. Buccal mucosa and tongue cancer serum could also be classified with an efficiency of ~68%. Of the two cancers, buccal mucosa cancer and normal could be classified with a higher efficiency. Findings of the study are quite comparable to that of our earlier study, which suggest that there exist significant differences, other than β- carotenes, between normal and cancerous samples which can be exploited for the classification. Prospectively, extensive validation studies will be undertaken to confirm the findings.

  4. Mode-selective phonon excitation in gallium nitride using mid-infrared free-electron laser

    Kagaya, Muneyuki; Yoshida, Kyohei; Zen, Heishun; Hachiya, Kan; Sagawa, Takashi; Ohgaki, Hideaki


    The single-phonon mode was selectively excited in a solid-state sample. A mid-infrared free-electron laser, which was tuned to the target phonon mode, was irradiated onto a crystal cooled to a cryogenic temperature, where modes other than the intended excitation were suppressed. An A 1(LO) vibrational mode excitation on GaN(0001) face was demonstrated. Anti-Stokes Raman scattering was used to observe the excited vibrational mode, and the appearance and disappearance of the scattering band at the target wavenumber were confirmed to correspond to on and off switching of the pump free-electron laser and were fixed to the sample vibrational mode. The sum-frequency generation signals of the pump and probe lasers overlapped the Raman signals and followed the wavenumber shift of the pump laser.

  5. Design of an 1800nm Raman amplifier

    Svane, Ask Sebastian; Rottwitt, Karsten


    We present the experimental results for a Raman amplifier that operates at 1810 nm and is pumped by a Raman fiber laser at 1680 nm. Both the pump laser and the Raman amplifier is polarization maintaining. A challenge when scaling Raman amplifiers to longer wavelengths is the increase...... in transmission loss, but also the reduction in the Raman gain coefficient as the amplifier wavelength is increased. Both polarization components of the Raman gain is characterized, initially for linearly co-polarized signal and pump, subsequently linearly polarized orthogonal signal and pump. The noise...

  6. Characterization of Small-Diameter Carbon Nanotubes and Carbon Nanocaps on SiC(000\\bar{1}) Using Raman Spectroscopy

    Maruyama, Takahiro; Shiraiwa, Tomoyuki; Fujita, Naomi; Kawamura, Yasuyuki; Naritsuka, Shigeya; Kusunoki, Michiko


    The Raman spectra of carbon nanotubes (CNTs) formed on a 6H-SiC(000\\bar{1}) C-face substrate by surface decomposition were acquired using a 1064 nm Nd:YAG laser as the excitation source. Intense radial-breathing-mode Raman bands were successfully detected under resonant excitation from CNTs formed by the surface decomposition of SiC. Fine CNTs having diameters between 0.7 and 1.3 nm were observed on SiC after heating at 1700 °C in a vacuum electric furnace. These diameters are considerably smaller than those previously observed for CNTs grown by this technique.

  7. Performance analysis of multi-pump Raman+EDFA hybrid amplifiers for WDM systems

    Jardim Martini, Márcia M.; Pontes, Maria José; Ribeiro, Moisés. R. N.; Kalinowski, Hypolito José


    An approximated technique to optimize the gain profile of multi-pump broadband hybrid amplifiers (Raman+EDFA) under residual pump recycling is applied to a WDM system. The Optimized hybrid amplifier configurations with multi-pumping were analyzed considering different number of input channels in order to check the global gain saturation and the changes in the global gain profile that occur due to signal-pump, signal-signal, and pump-pump interactions. This work extends the optimization of the gain profile from Raman+EDFA hybrid amplifiers and studies the signal-signal interactions, signal-pumping and pumping-pumping WDM systems. Multiple input channels allowed the gain characterization of the Raman+EDFA hybrid amplifier in terms of global gain, ripple, and noise figure considering applications for WDM systems.

  8. Measurements of Raman scattering in the middle ultraviolet band from persistent chemical warfare agents

    Kullander, Fredrik; Landström, Lars; Lundén, Hampus; Mohammed, Abdesalam; Olofsson, Göran; Wästerby, Pär.


    The very low Raman scattering cross section and the fluorescence background limit the measuring range of Raman based instruments operating in the visible or infrared band. We are exploring if laser excitation in the middle ultraviolet (UV) band between 200 and 300 nm is useful and advantageous for detection of persistent chemical warfare agents (CWA) on various kinds of surfaces. The UV Raman scattering from tabun, mustard gas, VX and relevant simulants in the form of liquid surface contaminations has been measured using a laboratory experimental setup with a short standoff distance around 1 meter. Droplets having a volume of 1 μl were irradiated with a tunable pulsed laser swept within the middle UV band. A general trend is that the signal strength moves through an optimum when the laser excitation wavelength is swept between 240 and 300 nm. The signal from tabun reaches a maximum around 265 nm, the signal from mustard gas around 275 nm. The Raman signal from VX is comparably weak. Raman imaging by the use of a narrow bandpass UV filter is also demonstrated.

  9. Raman Spectroscopy for Homeland Security Applications

    Gregory Mogilevsky


    Full Text Available Raman spectroscopy is an analytical technique with vast applications in the homeland security and defense arenas. The Raman effect is defined by the inelastic interaction of the incident laser with the analyte molecule’s vibrational modes, which can be exploited to detect and identify chemicals in various environments and for the detection of hazards in the field, at checkpoints, or in a forensic laboratory with no contact with the substance. A major source of error that overwhelms the Raman signal is fluorescence caused by the background and the sample matrix. Novel methods are being developed to enhance the Raman signal’s sensitivity and to reduce the effects of fluorescence by altering how the hazard material interacts with its environment and the incident laser. Basic Raman techniques applicable to homeland security applications include conventional (off-resonance Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS, resonance Raman spectroscopy, and spatially or temporally offset Raman spectroscopy (SORS and TORS. Additional emerging Raman techniques, including remote Raman detection, Raman imaging, and Heterodyne imaging, are being developed to further enhance the Raman signal, mitigate fluorescence effects, and monitor hazards at a distance for use in homeland security and defense applications.

  10. Validation model for Raman based skin carotenoid detection.

    Ermakov, Igor V; Gellermann, Werner


    Raman spectroscopy holds promise as a rapid objective non-invasive optical method for the detection of carotenoid compounds in human tissue in vivo. Carotenoids are of interest due to their functions as antioxidants and/or optical absorbers of phototoxic light at deep blue and near UV wavelengths. In the macular region of the human retina, carotenoids may prevent or delay the onset of age-related tissue degeneration. In human skin, they may help prevent premature skin aging, and are possibly involved in the prevention of certain skin cancers. Furthermore, since carotenoids exist in high concentrations in a wide variety of fruits and vegetables, and are routinely taken up by the human body through the diet, skin carotenoid levels may serve as an objective biomarker for fruit and vegetable intake. Before the Raman method can be accepted as a widespread optical alternative for carotenoid measurements, direct validation studies are needed to compare it with the gold standard of high performance liquid chromatography. This is because the tissue Raman response is in general accompanied by a host of other optical processes which have to be taken into account. In skin, the most prominent is strongly diffusive, non-Raman scattering, leading to relatively shallow light penetration of the blue/green excitation light required for resonant Raman detection of carotenoids. Also, sizable light attenuation exists due to the combined absorption from collagen, porphyrin, hemoglobin, and melanin chromophores, and additional fluorescence is generated by collagen and porphyrins. In this study, we investigate for the first time the direct correlation of in vivo skin tissue carotenoid Raman measurements with subsequent chromatography derived carotenoid concentrations. As tissue site we use heel skin, in which the stratum corneum layer thickness exceeds the light penetration depth, which is free of optically confounding chromophores, which can be easily optically accessed for in vivo RRS

  11. Revealing silent vibration modes of nanomaterials by detecting anti-Stokes hyper-Raman scattering with femtosecond laser pulses

    Zeng, Jianhua; Chen, Lei; Dai, Qiaofeng; Lan, Sheng; Tie, Shaolong


    We proposed a scheme in which normal Raman scattering is coupled with hyper-Raman scattering for generating a strong anti-Stokes hyper-Raman scattering in nanomaterials by using femtosecond laser pulses. The proposal was experimentally demonstrated by using a single-layer MoS2 on a SiO2/Si substrate, a 17 nm-thick MoS2 on an Au/SiO2 substrate and a 9 nm-thick MoS2 on a SiO2-SnO2/Ag/SiO2 substrate which were confirmed to be highly efficient for second harmonic generation. A strong anti-Stokes hyper-Raman scattering was also observed in other nanomaterials possessing large second-order susceptibilities, such as silicon quantum dots self-assembled into ``coffee'' rings and tubular Cu-doped ZnO nanorods. In all the cases, many Raman inactive vibration modes were clearly revealed in the anti-Stokes hyper-Raman scattering. Apart from the strong anti-Stokes hyper-Raman scattering, Stokes hyper-Raman scattering with small Raman shifts was detected during the ablation process of thick MoS2 layers. It was also observed by slightly defocusing the excitation light. The detection of anti-Stokes hyper-Raman scattering may serve as a new technique for studying the Raman inactive vibration modes in nanomaterials.We proposed a scheme in which normal Raman scattering is coupled with hyper-Raman scattering for generating a strong anti-Stokes hyper-Raman scattering in nanomaterials by using femtosecond laser pulses. The proposal was experimentally demonstrated by using a single-layer MoS2 on a SiO2/Si substrate, a 17 nm-thick MoS2 on an Au/SiO2 substrate and a 9 nm-thick MoS2 on a SiO2-SnO2/Ag/SiO2 substrate which were confirmed to be highly efficient for second harmonic generation. A strong anti-Stokes hyper-Raman scattering was also observed in other nanomaterials possessing large second-order susceptibilities, such as silicon quantum dots self-assembled into ``coffee'' rings and tubular Cu-doped ZnO nanorods. In all the cases, many Raman inactive vibration modes were clearly

  12. Cone-shell Raman spectroscopy (CSRS) for depth-sensitive measurements in layered tissue.

    Khan, Khan Mohammad; Majumder, Shovan Kumar; Gupta, Pradeep Kumar


    We report the development of a depth-sensitive Raman spectroscopy system using the configuration of cone-shell excitation and cone detection. The system uses a 785 nm diode laser and three identical axicons for Raman excitation of the target sample in the form of a hollow conic section. The Raman scattered light from the sample, passed through the same (but solid) conic section, is collected for detection. Apart from its ability of probing larger depths (~ few mm), an important attraction of the system is that the probing depths can be varied by simply varying the separation between axicons in the excitation arm. Furthermore, no adjustment is required in the sample arm, which is a significant advantage for noncontact, depth-sensitive measurement. Evaluation of the performance of the developed setup on nonbiological phantom and biological tissue sample demonstrated its ability to recover Raman spectra of layers located at depths of ~2-3 mm beneath the surface. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Raman and SERS recognition of β-carotene and haemoglobin fingerprints in human whole blood.

    Casella, Michele; Lucotti, Andrea; Tommasini, Matteo; Bedoni, Marzia; Forvi, Elena; Gramatica, Furio; Zerbi, Giuseppe


    The present work reports on Raman and Surface Enhanced Raman Scattering (SERS) vibrational fingerprints of β-carotene and haemoglobin in fresh whole blood (i.e. right after blood test) with different laser excitations, i.e. visible (514 nm) and near-infrared (NIR, 785 nm). The use of colloidal silver nanoparticles significantly increases the Raman signal, thus providing a clear SERS spectrum of blood. The collected spectra have been examined and marker bands of β-carotene and of the haem prosthetic group of haemoglobin have been found. In particular, the fundamental features of β-carotene (514 nm excitation), blood proteins and haem molecules (785 nm excitation) were recognized and assigned. Moreover haemoglobin SERS signals can be identified and related with its oxygenation state (oxy-haemoglobin). The data reported show the prospects of Raman and SERS techniques to detect important bio-molecules in a whole blood sample with no pre-treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Identification of bacteria causing acute otitis media using Raman microspectroscopy

    Ayala, Oscar D.; Wakeman, Catherine A.; Skaar, Eric P.; Mahadevan-Jansen, Anita


    Otitis media (OM) is the leading cause of acute physician visits and prescription of antibiotics for children. Current standard techniques to diagnose acute otitis media (AOM) are limited by their ability to probe only changes in symptoms of the bacterial infection that cause AOM. Furthermore, they are not able to detect the presence of or identify bacteria causing AOM, which is important for diagnosis and proper antibiotic treatment. Our goal is to detect the presence of and identify the pathogens involved in causing AOM based on their biochemical profile using Raman spectroscopy (RS). An inVia confocal Raman microscope (Renishaw) at 785 nm was used to detect bacteria causing AOM in vitro. The three main bacteria that cause AOM, Haemophilus influenzae, Moraxella catarrhalis, and Streptococcus pneumoniae were cultured in chocolate agar and Mueller-Hinton agar to determine which agar type would minimize Raman signal from the growth agar. Preliminary results identified specific Raman spectral features characteristic of S. pneumoniae. RS has the potential to accurately diagnose AOM, which will help in identifying the antibiotic that will be most beneficial for the patient and ultimately decrease the course of infection.

  15. Evaluation of the potential of surface enhancement Raman spectroscopy for detection of tricyclic psychotropic drugs. Case studies on imipramine and its metabolite.

    Jaworska, Aleksandra; Wietecha-Posłuszny, Renata; Woźniakiewicz, Michał; Kościelniak, Paweł; Malek, Kamilla


    The potential use of surface Raman enhanced spectroscopy (SERS) for confirmatory identification and the semi-quantitative analysis of selected tricyclic antidepressants (TCAs) is examined utilizing a conventional silver colloid. Raman and SERS spectra of aqueous solutions of imipramine (Imi) and its metabolite, desipramine (Des), were recorded as the function of concentration using NIR excitation. A good linear correlation is observed for the dependence of the SERS signal at 684 cm(-1) (R(2) = 0.9997) on Imi concentration over the range of 0.75-7.5 μM. The limit of detection of imipramine in the silver colloidal solution is 0.98 μM. SERS spectra of Imi and Des were also recorded for blood plasma samples without prior purification as well as after the use of standard solid phase extraction. All spectra show the characteristic spectral profile of the molecules and moreover, stronger signal enhancement is observed for Imi in the "raw" samples as opposed to Imi extracted from a biological matrix.

  16. Label-free in vivo analysis of intracellular lipid droplets in the oleaginous microalga Monoraphidium neglectum by coherent Raman scattering microscopy.

    Jaeger, Daniel; Pilger, Christian; Hachmeister, Henning; Oberländer, Elina; Wördenweber, Robin; Wichmann, Julian; Mussgnug, Jan H; Huser, Thomas; Kruse, Olaf


    Oleaginous photosynthetic microalgae hold great promise as non-food feedstocks for the sustainable production of bio-commodities. The algal lipid quality can be analysed by Raman micro-spectroscopy, and the lipid content can be imaged in vivo in a label-free and non-destructive manner by coherent anti-Stokes Raman scattering (CARS) microscopy. In this study, both techniques were applied to the oleaginous microalga Monoraphidium neglectum, a biotechnologically promising microalga resistant to commonly applied lipid staining techniques. The lipid-specific CARS signal was successfully separated from the interfering two-photon excited fluorescence of chlorophyll and for the first time, lipid droplet formation during nitrogen starvation could directly be analysed. We found that the neutral lipid content deduced from CARS image analysis strongly correlated with the neutral lipid content measured gravimetrically and furthermore, that the relative degree of unsaturation of fatty acids stored in lipid droplets remained similar. Interestingly, the lipid profile during cellular adaption to nitrogen starvation showed a two-phase characteristic with initially fatty acid recycling and subsequent de novo lipid synthesis. This works demonstrates the potential of quantitative CARS microscopy as a label-free lipid analysis technique for any microalgal species, which is highly relevant for future biotechnological applications and to elucidate the process of microalgal lipid accumulation.

  17. Monitoring guanidinium-induced structural changes in ribonuclease proteins using Raman spectroscopy and 2D correlation analysis.

    Brewster, Victoria L; Ashton, Lorna; Goodacre, Royston


    Assessing the stability of proteins by comparing their unfolding profiles is a very important characterization and quality control step for any biopharmaceutical, and this is usually measured by fluorescence spectroscopy. In this paper we propose Raman spectroscopy as a rapid, noninvasive alternative analytical method and we shall show this has enhanced sensitivity and can therefore reveal very subtle protein conformational changes that are not observed with fluorescence measurements. Raman spectroscopy is a powerful nondestructive method that has a strong history of applications in protein characterization. In this work we describe how Raman microscopy can be used as a fast and reliable method of tracking protein unfolding in the presence of a chemical denaturant. We have compared Raman spectroscopic data to the equivalent samples analyzed using fluorescence spectroscopy in order to validate the Raman approach. Calculations from both Raman and fluorescence unfolding curves of [D]50 values and Gibbs free energy correlate well with each other and more importantly agree with the values found in the literature for these proteins. In addition, 2D correlation analysis has been performed on both Raman and fluorescence data sets in order to allow further comparisons of the unfolding behavior indicated by each method. As many biopharmaceuticals are glycosylated in order to be functional, we compare the unfolding profiles of a protein (RNase A) and a glycoprotein (RNase B) as measured by Raman spectroscopy and discuss the implications that glycosylation has on the stability of the protein.

  18. Raman spectroscopy under extreme conditions

    Goncharov, A F; Crowhurst, J C


    We report the results of Raman measurements of various materials under simultaneous conditions of high temperature and high pressure in the diamond anvil cell (DAC). High temperatures are generated by laser heating or internal resistive (ohmic) heating or a combination of both. We present Raman spectra of cubic boron nitride (cBN) to 40 GPa and up to 2300 K that show a continuous pressure and temperature shift of the frequency of the transverse optical mode. We have also obtained high-pressure Raman spectra from a new noble metal nitride, which we synthesized at approximately 50 GPa and 2000 K. We have obtained high-temperature spectra from pure nitrogen to 39 GPa and up to 2000 K, which show the presence of a hot band that has previously been observed in CARS measurements. These measurements have also allowed us to constrain the melting curve and to examine changes in the intramolecular potential with pressure.

  19. Rashba realization: Raman with RF

    Campbell, Daniel L


    We theoretically explore a Rashba spin-orbit coupling scheme which operates entirely in the absolute ground state manifold of an alkali atom, thereby minimizing all inelastic processes. An energy gap between ground eigenstates of the proposed coupling can be continuously opened or closed by modifying laser polarizations. Our technique uses far-detuned "Raman" laser coupling to create the Rashba potential, which has the benefit of low spontaneous emission rates. At these detunings, the Raman matrix elements that link $m_F$ magnetic sublevel quantum numbers separated by two are also suppressed. These matrix elements are necessary to produce the Rashba Hamiltonian within a single total angular momentum $f$ manifold. However, the far-detuned Raman couplings can link the three XYZ states familiar to quantum chemistry, which possess the necessary connectivity to realize the Rashba potential. We show that these XYZ states are essentially the hyperfine spin eigenstates of $^{87}\\text{Rb}$ dressed by a strong radio-fr...

  20. Status of miniature integrated UV resonance fluorescence and Raman sensors for detection and identification of biochemical warfare agents

    Hug, William F.; Bhartia, Rohit; Taspin, Alexandre; Lane, Arthur; Conrad, Pamela; Sijapati, Kripa; Reid, Ray D.


    Laser induced native fluorescence (LINF) is the most sensitive method of detection of biological material including microorganisms, virus', and cellular residues. LINF is also a sensitive method of detection for many non-biological materials as well. The specificity with which these materials can be classified depends on the excitation wavelength and the number and location of observation wavelengths. Higher levels of specificity can be obtained using Raman spectroscopy but a much lower levels of sensitivity. Raman spectroscopy has traditionally been employed in the IR to avoid fluorescence. Fluorescence rarely occurs at wavelength below about 270nm. Therefore, when excitation occurs at a wavelength below 250nm, no fluorescence background occurs within the Raman fingerprint region for biological materials. When excitation occurs within electronic resonance bands of the biological target materials, Raman signal enhancement over one million typically occurs. Raman sensitivity within several hundred times fluorescence are possible in the deep UV where most biological materials have strong absorption. Since the Raman and fluorescence emissions occur at different wavelength, both spectra can be observed simultaneously, thereby providing a sensor with unique sensitivity and specificity capability. We will present data on our integrated, deep ultraviolet, LINF/Raman instruments that are being developed for several applications including life detection on Mars as well as biochemical warfare agents on Earth. We will demonstrate the ability to discriminate organic materials based on LINF alone. Together with UV resonance Raman, higher levels of specificity will be demonstrated. In addition, these instruments are being developed as on-line chemical sensors for industrial and municipal waste streams and product quality applications.

  1. The Raman Laser Spectrometer for the ExoMars Rover Mission to Mars

    Rull, Fernando; Maurice, Sylvestre; Hutchinson, Ian; Moral, Andoni; Perez, Carlos; Diaz, Carlos; Colombo, Maria; Belenguer, Tomas; Lopez-Reyes, Guillermo; Sansano, Antonio; Forni, Olivier; Parot, Yann; Striebig, Nicolas; Woodward, Simon; Howe, Chris; Tarcea, Nicolau; Rodriguez, Pablo; Seoane, Laura; Santiago, Amaia; Rodriguez-Prieto, Jose A.; Medina, Jesús; Gallego, Paloma; Canchal, Rosario; Santamaría, Pilar; Ramos, Gonzalo; Vago, Jorge L.; RLS Team


    The Raman Laser Spectrometer (RLS) on board the ESA/Roscosmos ExoMars 2020 mission will provide precise identification of the mineral phases and the possibility to detect organics on the Red Planet. The RLS will work on the powdered samples prepared inside the Pasteur analytical suite and collected on the surface and subsurface by a drill system. Raman spectroscopy is a well-known analytical technique based on the inelastic scattering by matter of incident monochromatic light (the Raman effect) that has many applications in laboratory and industry, yet to be used in space applications. Raman spectrometers will be included in two Mars rovers scheduled to be launched in 2020. The Raman instrument for ExoMars 2020 consists of three main units: (1) a transmission spectrograph coupled to a CCD detector; (2) an electronics box, including the excitation laser that controls the instrument functions; and (3) an optical head with an autofocus mechanism illuminating and collecting the scattered light from the spot under investigation. The optical head is connected to the excitation laser and the spectrometer by optical fibers. The instrument also has two targets positioned inside the rover analytical laboratory for onboard Raman spectral calibration. The aim of this article was to present a detailed description of the RLS instrument, including its operation on Mars. To verify RLS operation before launch and to prepare science scenarios for the mission, a simulator of the sample analysis chain has been developed by the team. The results obtained are also discussed. Finally, the potential of the Raman instrument for use in field conditions is addressed. By using a ruggedized prototype, also developed by our team, a wide range of terrestrial analog sites across the world have been studied. These investigations allowed preparing a large collection of real, in situ spectra of samples from different geological processes and periods of Earth evolution. On this basis, we are working

  2. Excitable Scale Free Networks

    Copelli, Mauro


    When a simple excitable system is continuously stimulated by a Poissonian external source, the response function (mean activity versus stimulus rate) generally shows a linear saturating shape. This is experimentally verified in some classes of sensory neurons, which accordingly present a small dynamic range (defined as the interval of stimulus intensity which can be appropriately coded by the mean activity of the excitable element), usually about one or two decades only. The brain, on the other hand, can handle a significantly broader range of stimulus intensity, and a collective phenomenon involving the interaction among excitable neurons has been suggested to account for the enhancement of the dynamic range. Since the role of the pattern of such interactions is still unclear, here we investigate the performance of a scale-free (SF) network topology in this dynamic range problem. Specifically, we study the transfer function of disordered SF networks of excitable Greenberg-Hastings cellular automata. We obser...

  3. Stimulated Raman adiabatic passage for improved performance of a cold-atom electron and ion source

    Sparkes, B. M.; Murphy, D.; Taylor, R. J.; Speirs, R. W.; McCulloch, A. J.; Scholten, R. E.


    We implement high-efficiency coherent excitation to a Rydberg state using stimulated Raman adiabatic passage in a cold-atom electron and ion source. We achieve an efficiency of 60% averaged over the laser excitation volume with a peak efficiency of 82%, a 1.6 times improvement relative to incoherent pulsed-laser excitation. Using pulsed electric field ionization of the Rydberg atoms we create electron bunches with durations of 250 ps. High-efficiency excitation will increase source brightness, crucial for ultrafast electron diffraction experiments, and coherent excitation to high-lying Rydberg states could allow for the reduction of internal bunch heating and the creation of a high-speed single-ion source.

  4. Size-Dependent Raman Shifts for nanocrystals.

    Gao, Yukun; Zhao, Xinmei; Yin, Penggang; Gao, Faming


    Raman spectroscopy is a very sensitive tool for probing semiconductor nanocrystals. The underlying mechanism behind the size-dependent Raman shifts is still quite controversial. Here we offer a new theoretical method for the quantum confinement effects on the Raman spectra of semiconductor nanocrystals. We propose that the shift of Raman spectra in nanocrystals can result from two overlapping effects: the quantum effect shift and surface effect shift. The quantum effect shift is extracted from an extended Kubo formula, the surface effect shift is determined via the first principles calculations. Fairly good prediction of Raman shifts can be obtained without the use of any adjustable parameter. Closer analysis shows that the size-dependent Raman shifts in Si nanocrystals mainly result from the quantum effect shifts. For nanodiamond, the proportion of surface effect shift in Raman shift is up to about 40%. Such model can also provide a good baseline for using Raman spectroscopy as a tool to measure size.

  5. Higher order mode optical fiber Raman amplifiers

    Rottwitt, Karsten; Friis, Søren Michael Mørk; Usuga Castaneda, Mario A.


    We review higher order mode Raman amplifiers and discuss recent theoretical as well as experimental results including system demonstrations.......We review higher order mode Raman amplifiers and discuss recent theoretical as well as experimental results including system demonstrations....

  6. Design of Raman-parametric fiber amplifier for wavelength division multiplex transmission system

    Xiaohong Jiang; Chun Jiang; Xiaoming Zhang


    We optimize the novel configuration of a hybrid fiber amplifier-Raman assisted-fiber-based optical parametric amplifier (R-FOPA), in which the parametric gain and Raman gain profiles are combined to achieve a flat composite gain profile.The pump powers and the fiber length in the hybrid amplifier are effectively optimized by genetic algorithm (GA) scheme.The optimization results indicate that the R-FOPA can achieve a 200-nm flat bandwidth spectrum with the gain of 20 dB and ripple of less than 4 dB.

  7. Theory of Two-Magnon Raman Scattering in Iron Pnictides and Chalcogenides

    Chen, C. C.


    Although the parent iron-based pnictides and chalcogenides are itinerant antiferromagnets, the use of local moment picture to understand their magnetic properties is still widespread. We study magnetic Raman scattering from a local moment perspective for various quantum spin models proposed for this new class of superconductors. These models vary greatly in the level of magnetic frustration and show a vastly different two-magnon Raman response. Light scattering by two-magnon excitations thus provides a robust and independent measure of the underlying spin interactions. In accord with other recent experiments, our results indicate that the amount of magnetic frustration in these systems may be small.

  8. Rapid screening of wheat bran contaminated by deoxynivalenol mycotoxin using Raman spectroscopy: a preliminary experiment

    Mignani, A. G.; Ciaccheri, L.; Mencaglia, A. A.; De Girolamo, A.; Lippolis, V.; Pascale, M.


    Deoxynivalenol (DON) is a mycotoxin frequently occurring in cereals and derived products, and regulated in many countries. Raman spectroscopy performed using optical fibers, with excitation at 1064 nm and a dispersive detection scheme, was utilized to analyze wheat bran samples naturally contaminated with DON. A multivariate processing of the spectroscopic data allowed to distinguish two classes of contamination, with DON below and above 400 μg/kg, respectively. Only one highly contaminated sample was misclassified. This preliminary result demonstrates the potential of Raman spectroscopy as a useful analytical tool for the non-destructive and rapid analysis of mycotoxins in food.

  9. Characterisation of paint samples by infrared and Raman spectroscopy for criminalistic purposes

    Zięba-Palus, Janina; Michalska, Aleksandra; Wesełucha-Birczyńska, Aleksandra


    Infrared microspectrometry and Raman microscopy were applied in characterisation of paint coatings, i.e. in identification of pigments and in differentiation between paint samples of similar colour and shade. The use of different excitation lasers enabled us to reduce the fluorescence of the sample and identify the main pigments present in the sample. It was shown that Raman mapping has great potential for the forensic study of paint samples. It is useful because paints are usually chemically complex and heterogeneous mixtures and spectroscopic images allow an assessment of the chemical heterogeneity of a specimen in terms of the spatial distribution of the molecular constituents.

  10. Challenges in higher order mode Raman amplifiers

    Rottwitt, Karsten; Nielsen, Kristian; Friis, Søren Michael Mørk;


    A higher order Raman amplifier model that take random mode coupling into account ispresented. Mode dependent gain and signal power fluctuations at the output of the higher order modeRaman amplifier are discussed......A higher order Raman amplifier model that take random mode coupling into account ispresented. Mode dependent gain and signal power fluctuations at the output of the higher order modeRaman amplifier are discussed...

  11. Challenges in higher order mode Raman amplifiers

    Rottwitt, Karsten; Nielsen, Kristian; Friis, Søren Michael Mørk


    A higher order Raman amplifier model that take random mode coupling into account ispresented. Mode dependent gain and signal power fluctuations at the output of the higher order modeRaman amplifier are discussed......A higher order Raman amplifier model that take random mode coupling into account ispresented. Mode dependent gain and signal power fluctuations at the output of the higher order modeRaman amplifier are discussed...

  12. Monitoring and trace detection of hazardous waste and toxic chemicals using resonance Raman spectroscopy

    Sedlacek, A.J. III; Dougherty, D.R.; Chen, C.L.


    Raman scattering is a coherent, inelastic, two-photon process, which shifts the frequency of an outgoing photon according to the vibrational structure of the irradiated species, thereby providing a unique fingerprint of the molecule. When involving an allowed electronic transition (resonance Raman), this scattering cross section can be enhanced by 10{sup 4} to 10{sup 6} and provides the basis for a viable technique that can monitor and detect trace quantities of hazardous wastes and toxic chemicals. Resonance Raman spectroscopy (RRS) possesses many of the ideal characteristics for monitoring and detecting of hazardous waste and toxic chemicals. Some of these traits are: (1) very high selectivity (chemical specific fingerprints); (2) independence from the excitation wavelength (ability to monitor in the solar blind region); (3) chemical mixture fingerprints are the sum of its individual components (no spectral cross-talk); (4) near independence of the Raman fingerprint to its physical state (very similar spectra for gas, liquid, solid and solutions -- either bulk or aerosols); and (5) insensitivity of the Raman signature to environmental conditions (no quenching). Data from a few chemicals will be presented which illustrate these features. In cases where background fluorescence accompanies the Raman signals, an effective frequency modulation technique has been developed, which can completely eliminate this interference.

  13. Monitoring and trace detection of hazardous waste and toxic chemicals using resonance Raman spectroscopy

    Sedlacek, A.J. III; Dougherty, D.R.; Chen, C.L.


    Raman scattering is a coherent, inelastic, two-photon process, which shifts the frequency of an outgoing photon according to the vibrational structure of the irradiated species, thereby providing a unique fingerprint of the molecule. When involving an allowed electronic transition (resonance Raman), this scattering cross section can be enhanced by 10[sup 4] to 10[sup 6] and provides the basis for a viable technique that can monitor and detect trace quantities of hazardous wastes and toxic chemicals. Resonance Raman spectroscopy (RRS) possesses many of the ideal characteristics for monitoring and detecting of hazardous waste and toxic chemicals. Some of these traits are: (1) very high selectivity (chemical specific fingerprints); (2) independence from the excitation wavelength (ability to monitor in the solar blind region); (3) chemical mixture fingerprints are the sum of its individual components (no spectral cross-talk); (4) near independence of the Raman fingerprint to its physical state (very similar spectra for gas, liquid, solid and solutions -- either bulk or aerosols); and (5) insensitivity of the Raman signature to environmental conditions (no quenching). Data from a few chemicals will be presented which illustrate these features. In cases where background fluorescence accompanies the Raman signals, an effective frequency modulation technique has been developed, which can completely eliminate this interference.

  14. Diagnosis of atherosclerosis in human carotid artery by FT-Raman spectroscopy: Principal Components Analysis algorithm

    Nogueira, Grazielle V.; Silveira, Landulfo, Jr.; Martin, Airton A.; Zangaro, Renato A.; Pacheco, Marcos T.; Chavantes, Maria C.; Zampieri, Marcelo; Pasqualucci, Carlos A. G.


    FT- Raman Spectroscopy (FT-Raman) could allow identification and evaluation of human atherosclerotic lesions. A Raman spectrum can provide biochemical information of arteries which can help identifying the disease status and evolution. In this study, it is shown the results of FT-Raman for identification of human carotid arteries in vitro. Fragments of human carotid arteries were analyzed using a FT-Raman spectrometer with a Nd:YAG laser at 1064nm operating at an excitation power of 300mW. Spectra were obtained with 250 scans and spectral resolution of 4 cm-1. Each collection time was approximately 8 min. A total of 75 carotid fragments were spectroscopically scanned and FT-Raman results were compared with histopathology. Principal Components Analysis (PCA) was used to model an algorithm for tissue classification into three categories: normal, atherosclerotic plaque without calcification and atherosclerotic plaque with calcification. Non-atherosclerotic (normal) artery, atherosclerotic plaque and calcified plaque exhibit different spectral signatures related to biochemicals presented in each tissue type, such as, bands of collagen and elastin (proteins), cholesterol and its esters and calcium hydroxyapatite and carbonate apatite respectively. Results show that there is 96% match between classifications based on PCA algorithm and histopathology. The diagnostic applied over all 75 samples had sensitivity and specificity of about 89% and 100%, respectively, for atherosclerotic plaque and 100% and 98% for calcified plaque.

  15. Instant detection and identification of concealed explosive-related compounds: Induced Stokes Raman versus infrared.

    Elbasuney, Sherif; El-Sherif, Ashraf F


    The instant detection of explosives and explosive-related compounds has become an urgent priority in recent years for homeland security and counter-terrorism applications. Modern techniques should offer enhancement in selectivity, sensitivity, and standoff distances. Miniaturisation, portability, and field-ruggedisation are crucial requirements. This study reports on instant and standoff identification of concealed explosive-related compounds using customized Raman technique. Stokes Raman spectra of common explosive-related compounds were generated and spectrally resolved to create characteristic finger print spectra. The scattered Raman emissions over the band 400:2000cm(-1) were compared to infrared absorption using FTIR. It has been demonstrated that the two vibrational spectroscopic techniques were opposite and completing each other. Molecular vibrations with strong absorption in infrared (those involve strong change in dipole moments) induced weak signals in Raman and vice versa. The tailored Raman offered instant detection, high sensitivity, and standoff detection capabilities. Raman demonstrated characteristic fingerprint spectra with stable baseline and sharp intense peaks. Complete correlations of absorption/scattered signals to certain molecular vibrations were conducted to generate an entire spectroscopic profile of explosive-related compounds. This manuscript shades the light on Raman as one of the prevailing technologies for instantaneous detection of explosive-related compounds. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  16. Nanoparticle Based Surface-Enhanced Raman Spectroscopy

    Talley, C E; Huser, T R; Hollars, C W; Jusinski, L; Laurence, T; Lane, S M


    Surface-enhanced Raman scattering is a powerful tool for the investigation of biological samples. Following a brief introduction to Raman and surface-enhanced Raman scattering, several examples of biophotonic applications of SERS are discussed. The concept of nanoparticle based sensors using SERS is introduced and the development of these sensors is discussed.

  17. Surface enhanced raman spectroscopy on chip

    Hübner, Jörg; Anhøj, Thomas Aarøe; Zauner, Dan;


    is projected onto a CCD element and visualized by a computer. To enhance the otherwise rather weak Raman signal, a nanosurface is prepared and a sample solutions is impregnated on this surface. The surface enhanced Raman signal is picked up using a Raman probe and coupled into the spectrometer via an optical...

  18. Profilometry of thin films on rough substrates by Raman spectroscopy

    Ledinský, Martin; Paviet-Salomon, Bertrand; Vetushka, Aliaksei; Geissbühler, Jonas; Tomasi, Andrea; Despeisse, Matthieu; de Wolf, Stefaan; Ballif, Christophe; Fejfar, Antonín


    Thin, light-absorbing films attenuate the Raman signal of underlying substrates. In this article, we exploit this phenomenon to develop a contactless thickness profiling method for thin films deposited on rough substrates. We demonstrate this technique by probing profiles of thin amorphous silicon stripes deposited on rough crystalline silicon surfaces, which is a structure exploited in high-efficiency silicon heterojunction solar cells. Our spatially-resolved Raman measurements enable the thickness mapping of amorphous silicon over the whole active area of test solar cells with very high precision; the thickness detection limit is well below 1 nm and the spatial resolution is down to 500 nm, limited only by the optical resolution. We also discuss the wider applicability of this technique for the characterization of thin layers prepared on Raman/photoluminescence-active substrates, as well as its use for single-layer counting in multilayer 2D materials such as graphene, MoS2 and WS2.

  19. Profilometry of thin films on rough substrates by Raman spectroscopy

    Ledinský, Martin


    Thin, light-absorbing films attenuate the Raman signal of underlying substrates. In this article, we exploit this phenomenon to develop a contactless thickness profiling method for thin films deposited on rough substrates. We demonstrate this technique by probing profiles of thin amorphous silicon stripes deposited on rough crystalline silicon surfaces, which is a structure exploited in high-efficiency silicon heterojunction solar cells. Our spatially-resolved Raman measurements enable the thickness mapping of amorphous silicon over the whole active area of test solar cells with very high precision; the thickness detection limit is well below 1 nm and the spatial resolution is down to 500 nm, limited only by the optical resolution. We also discuss the wider applicability of this technique for the characterization of thin layers prepared on Raman/photoluminescence-active substrates, as well as its use for single-layer counting in multilayer 2D materials such as graphene, MoS2 and WS2.

  20. [Rapid detection of chlorinated organic mixture by laser Raman spectroscopy].

    Ma, Jing


    In order to realize the rapid, nondestructive detection of organic compounds, a two-dimensional analysis method based on technology of laser Raman spectroscopy was proposed. The results show that using 532 nm laser as excitation light source, the observation of 236.2, 348.9, 449.4 and 513.6 cm(-1), the four vibrational Raman spectra, and the intensity ratio of 6.4 : 1.7: 9.4 : 1.0 can determine the existence of tetrachloroethylene. The observation of 707.5, 1 087.9, 1 175.8 and 3 078.6 cm(-1), the four vibrational Raman spectra, and the intensity ratio of 9.6 : 6.4 : 1.0 : 3.9 can determine the existence of chlorobenzene. In other words, that through the comprehensive study of spectral lines and intensity ratio of some spectral lines, the presence of organic compounds in the mixed solution can be determined quickly. In the aspect of quantitative analysis, using multi-spectral analysis combined with least square fitting method can improve the reliability of the measurement, The accuracy of sample concentration was 98.4%. This spectral measurement method is a potential tool for organic component identification and concentration analysis which has a prosperous application prospects.

  1. Nonlinear microscopy, infrared, and Raman microspectroscopy for brain tumor analysis

    Meyer, Tobias; Bergner, Norbert; Bielecki, Christiane; Krafft, Christoph; Akimov, Denis; Romeike, Bernd F. M.; Reichart, Rupert; Kalff, Rolf; Dietzek, Benjamin; Popp, Jürgen


    Contemporary brain tumor research focuses on two challenges: First, tumor typing and grading by analyzing excised tissue is of utmost importance for choosing a therapy. Second, for prognostication the tumor has to be removed as completely as possible. Nowadays, histopathology of excised tissue using haematoxylin-eosine staining is the gold standard for the definitive diagnosis of surgical pathology specimens. However, it is neither applicable in vivo, nor does it allow for precise tumor typing in those cases when only nonrepresentative specimens are procured. Infrared and Raman spectroscopy allow for very precise cancer analysis due to their molecular specificity, while nonlinear microscopy is a suitable tool for rapid imaging of large tissue sections. Here, unstained samples from the brain of a domestic pig have been investigated by a multimodal nonlinear imaging approach combining coherent anti-Stokes Raman scattering, second harmonic generation, and two photon excited fluorescence microscopy. Furthermore, a brain tumor specimen was additionally analyzed by linear Raman and Fourier transform infrared imaging for a detailed assessment of the tissue types that is required for classification and to validate the multimodal imaging approach. Hence label-free vibrational microspectroscopic imaging is a promising tool for fast and precise in vivo diagnostics of brain tumors.

  2. In situ solution-phase Raman spectroscopy under forced convection.

    Zhu, Huanfeng; Wu, Jun; Shi, Qingfang; Wang, Zhenghao; Scherson, Daniel A


    In situ Raman spectra of solution-phase electrogenerated species have been recorded in a channel-type electrochemical cell incorporating a flat optically transparent window placed parallel to the channel plane that contains the embedded working electrode. A microscope objective with its main axis (Z) aligned normal to the direction of flow was used to focus the excitation laser beam (lambda exc = 532 nm) in the solution and also to collect the Raman scattered light from species present therein. Judicious adjustment of the cell position along Z allowed the depth of focus to overlap the diffusion boundary layer to achieve maximum detection sensitivity. Measurements were performed using a Au working electrode in iron hexacyanoferrate(II), [Fe(CN)6]4-, and nitrite, NO2-, containing aqueous solutions as a function of the applied potential, E. Linear correlations were found between both the gain and the loss of the integrated Raman intensity, IR, of bands, attributed to [Fe(CN)6]3- and [Fe(CN)6]4-, respectively, recorded downstream from the edge of the working electrode, and the current measured at the Au electrode as a function of E. The same overall trend was found for the gain in the IR of the NO3- band in the nitrite solution. Also included in this work is a ray trace analysis of the optical system.

  3. Feasibility Study of Using High-Temperature Raman Spectroscopy for On-Line Monitoring and Product Control of the Glass Vitrification Process

    Windisch, C.F. Jr.; Piepel, G.F.; Li, H.; Elliott, M.L.; Su, Y.


    A pulse-gating Raman spectroscopy setup was developed in this project. The setup was capable of performing in-situ high-temperature Raman measurements for glasses at temperatures as high as 1412 C. In the literature, high-temperature Raman measurements have only been performed on thin films of glass to minimize black-body radiation effects. The pulse-gating Raman setup allows making high-temperature measurements for bulk melts while effectively minimizing black-body radiation effects. A good correlation was found between certain Raman characteristic parameters and glass melt temperature for sodium silicate glasses measured in this project. Comparisons were made between the high-temperature Raman data from this study and literature data. The results suggest that an optimization of the pulse-gating Raman setup is necessary to further improve data quality (i.e., to obtain data with a higher signal-to-noise ratio). An W confocal Raman microspectrometer with continuous wave laser excitation using a 325 nm excitation line was evaluated selectively using a transparent silicate glass ad a deep-colored high-level waste glass in a bulk quantity. The data were successfully collected at temperatures as high as approximately 1500 C. The results demonstrated that the UV excitation line can be used for high-temperature Raman measurements of molten glasses without black-body radiation interference from the melt for both transparent and deep-color glasses. Further studies are needed to select the best laser system that can be used to develop high-temperature Raman glass databases.

  4. Determination of Salinity in Fluid Inclusions with Laser Raman Spectroscopy Technique


    A preliminary study was conducted to outline the laser Raman spectroscopy technique for determination of salinity in the aqueous phase in fluid inclusions. The skewing parameters of the Raman profiles of the calibration solutions determined were used to derive a calibration curve for the estimation of the equivalent mass fraction NaCl in aqueous solutions. This technique was also verified in the analysis of the natural fluid inclusions from Tongshankou porphyry Cu (Mo) deposit, Hubei Province, China. Although the analyses on the natural fluid inclusions are limited, an acceptable agreement has been reached on the salinities, for most fluid inclusions, determined by the Raman spectroscopy and microthermometry techniques, indicating the reliability of the Raman technique for determination of salinity in fluid inclusion studies.

  5. Investigating Effects of Proteasome Inhibitor on Multiple Myeloma Cells Using Confocal Raman Microscopy

    Jeon Woong Kang


    Full Text Available Due to its label-free and non-destructive nature, applications of Raman spectroscopic imaging in monitoring therapeutic responses at the cellular level are growing. We have recently developed a high-speed confocal Raman microscopy system to image living biological specimens with high spatial resolution and sensitivity. In the present study, we have applied this system to monitor the effects of Bortezomib, a proteasome inhibitor drug, on multiple myeloma cells. Cluster imaging followed by spectral profiling suggest major differences in the nuclear and cytoplasmic contents of cells due to drug treatment that can be monitored with Raman spectroscopy. Spectra were also acquired from group of cells and feasibility of discrimination among treated and untreated cells using principal component analysis (PCA was accessed. Findings support the feasibility of Raman technologies as an alternate, novel method for monitoring live cell dynamics with minimal external perturbation.

  6. Raman fingerprints on the Bloch sphere of a spinor Bose-Einstein condensate

    Schultz, Justin T.; Hansen, Azure; Murphree, Joseph D.; Jayaseelan, Maitreyi; Bigelow, Nicholas P.


    We explore the geometric interpretation of a diabatic, two-photon Raman process as a rotation on the Bloch sphere for a pseudo-spin-? system. The spin state of a spin-? quantum system can be described by a point on the surface of the Bloch sphere, and its evolution during a Raman pulse is a trajectory on the sphere determined by properties of the optical beams: the pulse area, the relative intensities and phases and the relative frequencies. We experimentally demonstrate key features of this model with a ?Rb spinor Bose-Einstein condensate, which allows us to examine spatially dependent signatures of the Raman beams. The two-photon detuning allows us to precisely control the spin density and imprinted relative phase profiles, as we show with a coreless vortex. With this comprehensive understanding and intuitive geometric interpretation, we use the Raman process to create and tailor as well as study and characterize exotic topological spin textures in spinor BECs.

  7. STIRAP on helium: Excitation to Rydberg states

    Yuan, Deqian

    Research in optically induced transitions between dierent atomic levels has a long history. For transitions between states driven by a coherent optical eld, the theoretical eciency could be ideally high as 100% but there could be many factors preventing this. In the three state helium atom excitation process, i.e. 23S→33P→nL , the stimulated emission from intermediate state makes it hard to achieve ecient population transfer to the nal state through an intuitive excitation order. One technique to achieve a higher eciency is Stimulated Raman Adiabatic Passage (STIRAP) which is being studied and under research in our lab. Unlike traditional three level excitation processes, STIRAP actually uses a counter intuitive pulsed laser beams timing arrangement. The excitation objects are metastable helium atoms traveling in a vacuum system with a longitudinal velocity of ~ 1070 m/s. We are using a 389 nm UV laser to connect the 23S and the 33P state and a frequency tunable ~790 nm IR laser to connect the 33P state and the dierent Rydberg states. A third 1083 nm wavelength laser beam drives the 23S → 23P transition to transversely separate the residual metastable atoms and the Rydberg atoms for eciency measurements. The data is taken by a stainless steel detector in the vacuum system. As the Rydberg atoms will get ionized by blackbody radiation under room temperature, we can utilize this for their detection. An ion detector sitting on the eld plate is capable to collect the ion signals of the Rydberg atoms for detection. So far the whole system has not been ready for data collection and measurement, so here we are using data and results from previous theses for discussions. The highest transition frequency that has ever been achieved in our lab is around 70% after corrections.

  8. Geometrical relaxation of excitations in one-dimensional conjugated polymers; Giichijigen kyoeki kobunshi reiki jotai no shusa kozo kanwa

    Yoshizawa, M. [Tohoku University, Sendai (Japan). Faculty of Engineering


    Large ultrafast optical nonlinearities in conjugated polymers have attracted much attention because of possible applications to nonlinear optical devices. One-dimensional systems such as conjugated polymers have localized excited states with geometrical relaxation. In this study, photoexcited states in polydiacetylene has been investigated by femtosecond Raman gain spectroscopy with 300-fs resolution. A new photoinduced Raman peak with lifetime of 1.5 ps has been observed at 1200cm{sup -1} for the first time. This peak indicates acetylene-like structure of the main chain relaxes to butatriene-like structure due to the formation of self-trapped exciting with the geometrical relaxation. The formation and decay kinetics of the Raman signals is consistent with the relaxation processes of exciting observed by femtosecond absorption spectroscopy. 8 refs., 5 figs.

  9. Single fiber laser based wavelength tunable excitation for CRS spectroscopy.

    Su, Jue; Xie, Ruxin; Johnson, Carey K; Hui, Rongqing


    We demonstrate coherent Raman spectroscopy (CRS) using a tunable excitation source based on a single femtosecond fiber laser. The frequency difference between the pump and the Stokes pulses was generated by soliton self-frequency shifting (SSFS) in a nonlinear optical fiber. Spectra of C-H stretches of cyclohexane were measured simultaneously by stimulated Raman gain (SRG) and coherent anti-Stokes Raman scattering (CARS) and compared. We demonstrate the use of spectral focusing through pulse chirping to improve CRS spectral resolution. We analyze the impact of pulse stretching on the reduction of power efficiency for CARS and SRG. Due to chromatic dispersion in the fiber-optic system, the differential pulse delay is a function of Stokes wavelength. This differential delay has to be accounted for when performing spectroscopy in which the Stokes wavelength needs to be scanned. CARS and SRG signals were collected and displayed in two dimensions as a function of both the time delay between chirped pulses and the Stokes wavelength, and we demonstrate how to find the stimulated Raman spectrum from the two-dimensional plots. Strategies of system optimization consideration are discussed in terms of practical applications.

  10. Electronic Raman Scattering in Graphene

    LU Hong-Yan; WANG Qiang-Hua


    Linear dispersion near the Dirac points in the band structure of graphenes can give rise to novel physical properties.We calculate the electronic contribution to the Raman spectra in graphenes, which also shows novel features.In the clean limit, the Raman spectrum in the undoped graphene is linear (with a universal slope against impurity scattering) at low energy due to the linear dispersion near the Dirac points, and it peaks at a position corresponding to the van Hove singularity in the band structure. In a doped graphene, the electronic Raman absorption is forbidden up to a vertical inter-band particle-hole gap. Beyond the gap the spectrum follows the undoped case. In the presence of impurities, absorption within the gap (in the otherwise clean case) is induced, which is identified as the intra-band contribution. The Drude-like intra-band contribution is seen to be comparable to the higher energy inter-band Raman peak. The results are discussed in connection to experiments.

  11. Raman spectroscopy for nanomaterials characterization


    First volume of a 40-volume series on nanoscience and nanotechnology, edited by the renowned scientist Challa S.S.R. Kumar. This handbook gives a comprehensive overview about Raman spectroscopy for the characterization of nanomaterials. Modern applications and state-of-the-art techniques are covered and make this volume essential reading for research scientists in academia and industry.

  12. Photonics crystal fiber Raman sensors

    Yang, Xuan; Bond, Tiziana C.; Zhang, Jin Z.; Li, Yat; Gu, Claire


    Hollow core photonic crystal fiber (HCPCF) employs a guiding mechanism fundamentally different from that in conventional index guiding fibers. In an HCPCF, periodic air channels in a glass matrix act as reflectors to confine light in an empty core. As a result, the interaction between light and glass can be very small. Therefore, HCPCF has been used in applications that require extremely low non-linearity, high breakdown threshold, and zero dispersion. However, their applications in optical sensing, especially in chemical and biological sensing, have only been extensively explored recently. Besides their well-recognized optical properties the hollow cores of the fibers can be easily filled with liquid or gas, providing an ideal sampling mechanism in sensors. Recently, we have demonstrated that by filling up a HCPCF with gas or liquid samples, it is possible to significantly increase the sensitivity of the sensors in either regular Raman or surface enhanced Raman scattering (SERS) applications. This is because the confinement of both light and sample inside the hollow core enables direct interaction between the propagating wave and the analyte. In this paper, we report our recent work on using HCPCF as a platform for Raman or SERS in the detection of low concentration greenhouse gas (ambient CO2), biomedically significant molecules (e.g., glucose), and bacteria. We have demonstrated that by filling up a HCPCF with gas or liquid samples, it is possible to significantly increase the sensitivity of the sensors in either regular Raman or SERS applications.

  13. Raman Spectroscopy of Ocular Tissue

    Ermakov, Igor V.; Sharifzadeh, Mohsen; Gellermann, Warner

    The optically transparent nature of the human eye has motivated numerous Raman studies aimed at the non-invasive optical probing of ocular tissue components critical to healthy vision. Investigations include the qualitative and quantitative detection of tissue-specific molecular constituents, compositional changes occurring with development of ocular pathology, and the detection and tracking of ocular drugs and nutritional supplements. Motivated by a better understanding of the molecular mechanisms leading to cataract formation in the aging human lens, a great deal of work has centered on the Raman detection of proteins and water content in the lens. Several protein groups and the hydroxyl response are readily detectable. Changes of protein compositions can be studied in excised noncataractous tissue versus aged tissue preparations as well as in tissue samples with artificially induced cataracts. Most of these studies are carried out in vitro using suitable animal models and conventional Raman techniques. Tissue water content plays an important role in optimum light transmission of the outermost transparent ocular structure, the cornea. Using confocal Raman spectroscopy techniques, it has been possible to non-invasively measure the water to protein ratio as a measure of hydration status and to track drug-induced changes of the hydration levels in the rabbit cornea at various depths. The aqueous humor, normally supplying nutrients to cornea and lens, has an advantageous anterior location for Raman studies. Increasing efforts are pursued to non-invasively detect the presence of glucose and therapeutic concentrations of antibiotic drugs in this medium. In retinal tissue, Raman spectroscopy proves to be an important tool for research into the causes of macular degeneration, the leading cause of irreversible vision disorders and blindness in the elderly. It has been possible to detect the spectral features of advanced glycation and advanced lipooxydation end products in

  14. Photoisomerization pathways and Raman activity of 1,1'-difluorostilbene

    Dobryakov, A. L.; Quick, M.; Richter, C.; Knie, C.; Ioffe, I. N.; Granovsky, A. A.; Mahrwald, R.; Ernsting, N. P.; Kovalenko, S. A.


    The photoisomerization of 1,1'-difluorostilbene, following S0→S1 optical excitation in solution, was studied with femtosecond broadband transient absorption and stimulated Raman spectroscopy, and by quantum-chemical calculations. In n-hexane, trans-to-cis (t →c ) isomerization starts with Franck-Condon relaxation (τ1 t = 0.07 ps) followed by nearly barrierless torsion around the ethylenic bond (τ2 t ≈ 0.3 ps) to a perpendicular conformation P. About 50% of the excited molecules are trapped in P, while others reach the S1(cis) conformation adiabatically. For the opposite cis-to-trans (c →t ) path, the dynamics in n-hexane (τ1 c = 0.04 ps, τ2 c = 0.7 ps) suggest a 5 kJ/mol barrier between the relaxed S1(cis) and P states. The subsequent P decay with τ3 = 0.4 ps is followed by much slower ground-state recovery (τ4 ≈ 3 ps), indicating an intermediate state X. The t →P and c →P torsion depend on solvent viscosity and polarity, whereas the P →X →S0 relaxation and residual torsion is viscosity-independent but still polarity-dependent. Photoisomerization yields are derived from the transient absorption data and compared to those from actinometric measurements. Low-frequency oscillations in the transient signal are assigned to nuclei motions. Transient and stationary stimulated Raman spectra are compared to calculations. Early Franck-Condon Raman spectra differ from those of the quasistationary trans or cis S1 state. The photoisomerization behavior of stilbene and vinyl-substituted derivatives is compared and the general features are discussed.

  15. Human brain cancer studied by resonance Raman spectroscopy

    Zhou, Yan; Liu, Cheng-Hui; Sun, Yi; Pu, Yang; Boydston-White, Susie; Liu, Yulong; Alfano, Robert R.


    The resonance Raman (RR) spectra of six types of human brain tissues are examined using a confocal micro-Raman system with 532-nm excitation in vitro. Forty-three RR spectra from seven subjects are investigated. The spectral peaks from malignant meningioma, stage III (cancer), benign meningioma (benign), normal meningeal tissues (normal), glioblastoma multiforme grade IV (cancer), acoustic neuroma (benign), and pituitary adenoma (benign) are analyzed. Using a 532-nm excitation, the resonance-enhanced peak at 1548 cm-1 (amide II) is observed in all of the tissue specimens, but is not observed in the spectra collected using the nonresonance Raman system. An increase in the intensity ratio of 1587 to 1605 cm-1 is observed in the RR spectra collected from meningeal cancer tissue as compared with the spectra collected from the benign and normal meningeal tissue. The peak around 1732 cm-1 attributed to fatty acids (lipids) are diminished in the spectra collected from the meningeal cancer tumors as compared with the spectra from normal and benign tissues. The characteristic band of spectral peaks observed between 2800 and 3100 cm-1 are attributed to the vibrations of methyl (-CH3) and methylene (-CH2-) groups. The ratio of the intensities of the spectral peaks of 2935 to 2880 cm-1 from the meningeal cancer tissues is found to be lower in comparison with that of the spectral peaks from normal, and benign tissues, which may be used as a distinct marker for distinguishing cancerous tissues from normal meningeal tissues. The statistical methods of principal component analysis and the support vector machine are used to analyze the RR spectral data collected from meningeal tissues, yielding a diagnostic sensitivity of 90.9% and specificity of 100% when two principal components are used.

  16. Applicability of confocal Raman microscopy for the signal detective of organic reagents in a PDMS microfluidic chip

    Choi, Seung Yeol; Choo, Jae Bum; Ahn, Yoo Min; Kim, Yang S. [Hanyang University, Ansan (Korea, Republic of)


    A PDMS microfluidic chip has been constructed using a photolithographic fabrication technique. Confocal laser-induced Raman microscopy has been utilized for the signal detection of chemical species in a PDMS microfluidic chip. The CC1{sub 4} benzene binary mixtures with different % concentrations have been prepared and injected into the PDMS chip using a microsyringe pump. Raman spectra were measured by focusing the Ar{sup +} laser on a microfluidic channel using a 10x objective lens. The concentration of each solvent mixture has been determined from the ratio of Raman intensity profiles, which were measured by integrating the area of characteristic Raman peaks for CC1{sub 4} and benzene. In this work, the feasibility of confocal laser-induced Raman microscopy for the quantitative analysis of organic reagents in a PDMS microfluidic chip will be demonstrated.

  17. Raman Lidar MERGE Value-Added Product

    Newsom, Rob [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Goldsmith, John [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sivaraman, Chitra [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    The U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility Raman lidars (RLs) are semi-autonomous, land-based, laser remote sensing systems that provide height- and time-resolved measurements of water vapor mixing ratio, temperature, aerosol backscatter, extinction, and linear depolarization ratio from about 200 m to greater than 10 km AGL. These systems transmit at a wavelength of 355 nm with 300 mJ, ~5 ns pulses, and a pulse repetition frequency of 30 Hz. The receiver incorporates nine detection channels, including two water vapor channels at 408 nm, two nitrogen channels at 387 nm, three elastic channels, and two rotational Raman channels for temperature profiling at 354 and 353 nm. Figure 1 illustrates the layout of the ARM RL receiver system. Backscattered light from the atmosphere enters the telescope and is directed into the receiver system (i.e., aft optics). This signal is then split between a narrow-field-of-view radiometer (NFOV) path (blue) and a wide-field-of-view zenith radiometer (WFOV) path (red). The WFOV (2 mrad) path contains three channels (water vapor, nitrogen, and unpolarized elastic), and the NFOV (0.3 mrad) path contains six channels (water vapor, nitrogen, parallel and perpendicular elastic, and two rotational Raman). All nine detection channels use Electron Tubes 9954B photomultiplier tubes (PMTs). The signals from each of the nine PMTs are acquired using transient data recorders from Licel GbR (Berlin, Germany). The Licel data recorders provide simultaneous measurements of both analog photomultiplier current and photon counts at height resolution of 7.5 m and a time resolution of 10 s. The analog signal provides good linearity in the strong signal regime, but poor sensitivity at low signal levels. Conversely, the photo counting signal provides good sensitivity in the weak signal regime, but is strongly nonlinear at higher signal levels. The advantage in recording both signals is that they can be

  18. Biophotonics of skin: method for correction of deep Raman spectra distorted by elastic scattering

    Roig, Blandine; Koenig, Anne; Perraut, François; Piot, Olivier; Gobinet, Cyril; Manfait, Michel; Dinten, Jean-Marc


    Confocal Raman microspectroscopy allows in-depth molecular and conformational characterization of biological tissues non-invasively. Unfortunately, spectral distortions occur due to elastic scattering. Our objective is to correct the attenuation of in-depth Raman peaks intensity by considering this phenomenon, enabling thus quantitative diagnosis. In this purpose, we developed PDMS phantoms mimicking skin optical properties used as tools for instrument calibration and data processing method validation. An optical system based on a fibers bundle has been previously developed for in vivo skin characterization with Diffuse Reflectance Spectroscopy (DRS). Used on our phantoms, this technique allows checking their optical properties: the targeted ones were retrieved. Raman microspectroscopy was performed using a commercial confocal microscope. Depth profiles were constructed from integrated intensity of some specific PDMS Raman vibrations. Acquired on monolayer phantoms, they display a decline which is increasing with the scattering coefficient. Furthermore, when acquiring Raman spectra on multilayered phantoms, the signal attenuation through each single layer is directly dependent on its own scattering property. Therefore, determining the optical properties of any biological sample, obtained with DRS for example, is crucial to correct properly Raman depth profiles. A model, inspired from S.L. Jacques's expression for Confocal Reflectance Microscopy and modified at some points, is proposed and tested to fit the depth profiles obtained on the phantoms as function of the reduced scattering coefficient. Consequently, once the optical properties of a biological sample are known, the intensity of deep Raman spectra distorted by elastic scattering can be corrected with our reliable model, permitting thus to consider quantitative studies for purposes of characterization or diagnosis.

  19. Raman detected differential scanning calorimetry of polymorphic transformations in acetaminophen.

    Kauffman, John F; Batykefer, Linda M; Tuschel, David D


    Acetaminophen is known to crystallize in three polymorphic forms. Thermally induced transformations between the crystalline forms and the super-cooled liquid have been observed by differential scanning calorimetry (DSC), but the assignment of calorimetric transitions to specific polymorphic transformations remains challenging, because the transition temperatures for several transformations are close to one another, and the characteristics of the observed transitions depend on experimental variables that are often poorly controlled. This paper demonstrates the simultaneous application of DSC and Raman microscopy for the observation of thermally driven transitions between polymorphs of pharmaceutical materials. Raman detected differential scanning calorimetry (RD-DSC) has been used to monitor the DSC thermograms of super-cooled liquid acetaminophen and confirms the assignment of two exothermic transitions to specific polymorphic transformations. Principal component analysis of the Raman spectra have been used to determine the number of independent components that participate in the phase transformations, and multivariate regression has been used to determine transition temperatures from the spectral data. The influence of the laser excitation source on measured DSC thermograms has also been investigated, and it has been demonstrated that a baseline shift occurs in RD-DSC when a polymorphic transformation occurs between crystalline and amorphous forms. RD-DSC has been used to examine the influence of sample aging and sample pan configuration on the observed polymorphic transformations, and both of these variables were found to influence the thermal behavior of the sample. The results demonstrate the advantage of simultaneous Raman spectroscopy and differential scanning calorimetry for the unambiguous assignment of thermally driven polymorphic transformations.

  20. Low noise Raman lasers for yellow-orange spectrum coverage

    Landru, Nicolas; Rouvillain, Julien; Le Bail, Guy; Georges, Thierry


    Diode lasers have been demonstrated to operate over a great part of the visible spectrum: InGaN diodes cover the violet-blue- green part (635 nm). Some fluorophorus in biotechnology applications are excited by intermediate wavelengths, from 540 to 630 nm. Optically pumped InGaAs lasers were demonstrated from 460 nm up to 580 nm. Standard frequency doubled diode pumped solid state (DPSS) lasers lack of suitable transition to cover the 565-650nm region. It is possible to modify the semiconductor composition to extend the frequency range or to frequency mix DPSS laser wavelengths, but it comes either with a significant R&D effort or with a complexity in the design. Raman scattering can red-shift the strong transitions of Nd or Yb lasers so that many wavelengths lying in the 1080-1300 nm range can be achieved. Recently several CW diode pumped Raman lasers were demonstrated, some of them including intra-cavity frequency doubling or mixing. The problems with these Raman lasers are the high pump threshold and the high noise. Based on monolithic cavities, we have built several visible Raman lasers with a reduced loss presenting a low pump threshold (<1W) and a high slope efficiency. Output powers in excess of 100 mW were achieved at 588 nm with a 2.5W 808 nm pump. Laser emissions from 556 nm up to more than 610 nm were demonstrated. Noise of these lasers was analyzed and means to reach low noise operation will be discussed at the conference.