Science.gov

Sample records for resonance raman study

  1. Resonance Raman Studies of Azulene and the Permanganate Ion.

    NASA Astrophysics Data System (ADS)

    Khodadoost, Baback

    This dissertation will present resonance Raman studies of the azulene molecule and the permanganate ion. Experimental measurements of the optical absorption spectra and the resonance Raman excitation profiles will be used along with the recently developed transform analysis. In the first part we have extended the frequency range of the previously measured resonance Raman profiles of azulene in solution. We have also measured, for the first time, profiles of two new Raman lines. Using transform techniques, we have calculated resonance Raman profile line shapes directly from our measured optical absorption spectra and the excited state vibrational frequencies. Our overall good profile line shape fits suggest that our model assumptions are basically correct for all the modes studied. Stokes loss analysis based on the good line shape fits indicates that possible deviations from these assumptions may be different for different modes. In the second part we have measured the visible absorption spectra of the permanganate ion with potassium perchlorate used as the host material as a function of pressure. These measurements indicate a blue shift of the absorption. The frequency of the breathing mode in the excited state increases with the pressure. From our absorption measurements we have also inferred a decrease in the Stokes loss parameter for this mode. We have also measured room temperature resonance Raman excitation profiles for the fundamental and the first two harmonics of the breathing mode, both at atmospheric and high pressures. Our Raman measurements indicate a linear increase in the ground state frequency of the breathing mode as a function of pressure. The use of the transform technique which relates absorption to resonance Raman profile line shape produces good agreements with our experimental data in all cases. As previously observed in the low pressure case we show that at high pressures it also is essential to use the excited state frequency in the

  2. Resonance and Variable Temperature Raman Studies of Chloroperoxidase and Methemoglobin.

    NASA Astrophysics Data System (ADS)

    Remba, Ronald David

    1980-12-01

    Raman spectra of the heme proteins chloroperoxidase and methemoglobin, chemically and temperature modified, are obtained for laser excitation near the Soret absorption band. Numerous biochemical and physical results are obtained. The following observations for chloroperoxidase have been made. The scattered intensity for resonance (406.7 nm) excitation is at least twenty times that for near resonance (457.9 nm) excitation. In resonance only totally symmetric modes are enhanced. The positions of marker band I ((TURN) 1370 cm(' -1)) for both the native and reduced enzymes are lower than expected for high-spin heme proteins indicating a strongly electron donating axial ligand. From shifts in spin-sensitive Raman peaks as the temperature is lowered, a high-spin to low-spin transition of the heme iron is inferred. Raman spectra of chloroperoxidase liganded with small ions indicate that there is a second anion binding site near the heme. Photo-dissociation of CO from reduced chloroperoxidase is observed. The position of marker band I in the CO complex indicates that electron density is transferred from the heme onto the CO. The resonance Raman spectra of chloroperoxidase and cytochrome P-450 are nearly identical and are very different from those of horseradish peroxidase and cytochrome c. These results, particularly for the reduced enzymes, indicate that the heme sites in chloroperoxidase and P -450 are essentially the same. Raman spectra of a number of methemoglobins complexed with various small ions are obtained as a function of temperature in the region of spin-sensitive marker band (II) ((TURN) 1500 cm('-1)) for laser excitation near the Soret absorption band. For certain ligands, H(,2)O, N(,3)('-), OCN('-), OH('-) and SCN('-), the iron spin state changes from high spin to low spin with decreasing temperature. The relative spin concentrations are monitored by measuring the Raman intensity ratio, I(,h)/I(,1), of the high-spin and low -spin versions of marker band (II

  3. Auger resonant Raman spectroscopy

    SciTech Connect

    Azuma, Y.; LeBrun, T.; MacDonald, M.; Southworth, S.H.

    1995-08-01

    As noted above, traditional spectroscopy of the electronic structure of the inner shells of atoms, molecules, and solids is limited by the lifetime broadening of the core-excited states. This limitation can also be avoided with the non-radiative analog of X-ray Raman scattering - resonant Auger Raman spectroscopy. We have used this technique to study the K-shell excitation spectrum of argon as the photon energy is continuously scanned across threshold.

  4. Resonance Raman spectroscopic study of fused multiporphyrin linear arrays

    NASA Astrophysics Data System (ADS)

    Jeong, Dae Hong; Jang, Sung Moon; Hwang, In-Wook; Kim, Dongho; Matsuzaki, Yoichi; Tanaka, Kazuyoshi; Tsuda, Akihiko; Nakamura, Takeshi; Osuka, Atsuhiro

    2003-09-01

    For prospective applications as molecular electric wires, triply linked fused porphyrin arrays have been prepared. As expected from their completely flat molecular structures, π-electron delocalization can be extended to the whole array manifested by a continuous redshift of the HOMO-LUMO transition band to infrared region up to a few μm as the number of porphyrin units in the array increases. To gain an insight into the relationship between the molecular structures and electronic properties, we have investigated resonance Raman spectra of fused porphyrin arrays depending on the number of porphyrin pigments in the array. We have carried out the normal mode analysis of fused porphyrin dimer based on the experimental results including Raman frequency shifts of two types of 13C-isotope substituted dimers, Raman enhancement pattern by changing excitation wavelength, and depolarization ratio measurements as well as normal-mode calculations at the B3LYP/6-31G level. In order to find the origins for the resonance Raman mode enhancement mechanism, we have predicted both the excited state geometry changes (A-term) and the vibronic coupling efficiencies (B-term) for the relevant electronic transitions based on the INDO/S-SCI method. A detailed normal mode analysis of the fused dimer allows us to extend successfully our exploration to longer fused porphyrin arrays. Overall, our investigations have provided a firm basis in understanding the molecular vibrations of fused porphyrin arrays in relation to their unique flat molecular structures and rich electronic transitions.

  5. Resonance Raman spectroscopic studies of enzymesubstrate intermediates at 5 K

    NASA Astrophysics Data System (ADS)

    Kim, Munsok; Carey, Paul R.

    1991-01-01

    A simple and versatile system for resonance Raman (RR) spectroscopic analysis of enzymesubstrate complexes at liquid helium temperatures is described. The system allows us to record high-quality RR spectra for dithioacyl papain intermediates (MeO-Phe-Gly- and MeO-Gly-Gly-Phe-Gly-C (dbnd S)S-papain) in ice matrices at 5 K. Based on established structure-spectra correlations, it is concluded that the active-site conformation of the intermediates about the φ', ψ' glycinic linkages and cysteine-25 side chain is B-G+-PH both in ice matrices at 5 K and in solution at room temperature.

  6. Human brain cancer studied by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhou, Yan; Liu, Cheng-Hui; Sun, Yi; Pu, Yang; Boydston-White, Susie; Liu, Yulong; Alfano, Robert R.

    2012-11-01

    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.

  7. Theoretical study of the resonance Raman spectra for meso-tetrakis(3,5-di-tertiarybutylphenyl)-porphyrin

    NASA Astrophysics Data System (ADS)

    Zheng, Ren-hui; Wei, Wen-mei; Zhu, Li-li; Shi, Qiang

    2014-12-01

    Applying time-dependent density functional theory (TDDFT), we study the resonance Raman spectra for the Q and B bands of the meso-tetrakis(3,5-di-tertiarybutylphenyl)-porphyrin (H2TBPP) molecule including both Raman A term (Franck-Condon term) and Raman B term (Herzberg-Teller term) contributions. It is found that Raman B term can be one order of magnitude larger than Raman A term and dominates resonance Raman for the Q band resonance. In comparison with the recent experimental Raman spectra of H2TBPP with incident light frequency 532 nm, we predict the absence of 1580 cm-1 band in the resonance Raman spectra which agrees well with the experimental results, whereas the previous theoretical calculation using non-resonance strategy failed to do so.

  8. Surface-enhanced resonance hyper-Raman scattering and surface-enhanced resonance Raman scattering of dyes adsorbed on silver electrode and silver colloid: a comparison study

    NASA Astrophysics Data System (ADS)

    Li, Wu-Hu; Li, Xiao-Yuan; Yu, Nai-Teng

    1999-10-01

    Surface-enhanced resonance hyper-Raman scattering (SERHRS) and surface-enhanced resonance Raman scattering (SERRS) of three dyes, rhodamine 6G, crystal violet and basic fuchsin, are studied comparatively on electrochemically roughened silver electrode and silver colloid, respectively. All three dyes show a better SERHRS efficiency on the silver colloid than on the silver electrode, a phenomenon just opposite to what we have recently observed for pyridine and pyrazine [Chem. Phys. Lett. 305 (1999) 303]. These results suggest that the efficiency of SEHRS depends not only on the active surfaces employed (colloidal metals versus roughened electrodes) but also on the types of the adsorbed molecules.

  9. Comparative study of resonance Raman and surface-enhanced resonance Raman chlorophyll a spectra using soret and red excitation

    SciTech Connect

    Thomas, L.L.; Kim, Jaeho; Cotton, T.M. )

    1990-12-05

    Surface-enhanced resonance Raman scattering (SERRS) spectra are reported for chlorophyll a adsorbed on a silver electrode at 298 and 77 K with 406.7-, 457.9-, 514.5-, and 647.1-nm excitation. Submerging the electrode in degassed water at 298 K was found to improve the spectral quality by minimizing sample heating and photooxidation. Spectral intensities and peak resolutions were greater at all excitation wavelengths at liquid nitrogen temperature. Most significantly, roughened silver at the low temperature quenched the fluorescence accompanying red excitation and minimized sample photooxidation, resulting in richly detailed SERRS spectra of chlorophyll a. The close correspondence between chlorophyll a resonance Raman (RR) and SERRS spectra suggests that an electromagnetic mechanism is the major source of the surface enhancement, rather than a chemical mechanism (e.g. a charge-transfer complex between chlorophyll a and the metal). The spectral similarities, together with the presence of the MgN{sub 4} vibration band in the SERRS spectra, also provide evidence that structural alterations (e.g. cleavage of ring V or loss of Mg) do not occur in chlorophyll a after adsorption at the electrode surface. A distinctive SERRS spectrum was obtained for each excitation wavelength. Selective excitation within the various electronic transitions can thus be utilized to verify assignments of the vibrational modes of chlorophyll a and to monitor its interactions and photochemical behavior in biomimetic systems.

  10. Resonant Raman scattering in antiferromagnets

    NASA Astrophysics Data System (ADS)

    Morr, Dirk K.; Chubukov, Andrey V.

    1997-10-01

    Two-magnon Raman scattering provides important information about electronic correlations in the insulating parent compounds of high-Tc materials. Recent experiments have shown a strong dependence of the Raman signal in B1g geometry on the frequency of the incoming photon. We present an analytical and numerical study of the Raman intensity in the resonant regime. It has been previously argued by Chubukov and Frenkel that the most relevant contribution to the Raman vertex at resonance is given by the triple resonance diagram. We derive an expression for the Raman intensity in which we simultaneously include the enhancement due to the triple resonance and a final-state interaction. We compute the two-magnon peak height (TMPH) as a function of incident frequency and find two maxima at ω(1)res~2Δ+3J and ω(2)res~2Δ+8J. We argue that the high-frequency maximum is cut only by a quasiparticle damping, while the low-frequency maximum has a finite amplitude even in the absence of damping. We also obtain an evolution of the Raman profile from an asymmetric form around ω(1)res to a symmetric form around ω(2)res. We further show that the TMPH depends on the fermionic quasiparticle damping, the next-nearest-neighbor hopping term t', and the corrections to the interaction vertex between light and the fermionic current. We discuss our results in the context of recent experiments by Blumberg et al. on Sr2CuO2Cl2 and YBa2Cu3O6.1 and Rübhausen et al. on PrBa2Cu3O7 and show that the triple resonance theory yields a qualitative and to some extent also quantitative understanding of the experimental data.

  11. Resonance Raman spectroscopic evaluation of skin carotenoids as a biomarker of carotenoid status for human studies

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Resonance Raman Spectroscopy (RRS) is a non-invasive method that has been developed to assess carotenoid status in human tissues including human skin in vivo. Skin carotenoid status, as assessed by RRS, has been suggested as a promising biomarker for use in human studies. This manuscript describes...

  12. Schumann-Runge resonance Raman scattering of O sub 2 : A rotationally resolved excitation profile study

    SciTech Connect

    Zhang, Y.P.; Ziegler, L.D. )

    1989-09-07

    Rotationally resolved resonance Raman spectra and excitation profiles of O{sub 2} excited with narrow-band radiation tunable throughout the {nu}{prime} = 5 absorption band of the Schumann-Runge (SR) region (190-192 nm) are reported. The pressure dependence and scattering polarization unambiguously identify all the observed resonant emission intensity as Raman scattering (both resonant and off-resonant), not resonance fluorescence. This characterization is in contrast to the description of the resonant emission of the SR absorption bands offered in recent laser-excited studies. Excitation profile analysis determines rotationally specific lifetimes of the {nu}{prime} = 5 level. A homogeneous line width of 2.05 {plus minus} 0.10 cm{sup {minus}1} is determined for the rotational levels of this vibronic band. Within experimental uncertainty, this line width/lifetime is independent of the rotational angular momentum of the resonant predissociative rovibronic levels of the {nu}{prime} = 5 band. This value is in excellent agreement with the results of the most recent SR absorption contour analysis but is not in quantitative agreement with the most recent theoretical modeling of the rovibronic dynamics of the SR absorption bands.

  13. Surface plasmon enhanced interfacial electron transfer and resonance Raman, surface-enhanced resonance Raman studies of cytochrome C mutants

    SciTech Connect

    Zheng, Junwei

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO{sub 2} were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO{sub 2}, large photoelectrocatalytic effect for the reduction of CO{sub 2} was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO{sub 2} in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

  14. Resonance Raman studies of bathorhodopsin: evidence for a protonated Schiff base linkage.

    PubMed

    Eyring, G; Mathies, R

    1979-01-01

    A dual beam pump/probe technique has been used with a 585-nm probe wavelength to obtain maximal resonance enhancement of the Raman lines of bathorhodopsin in a photostationary steady-state mixture at -160 degrees C. These studies show that bathorhodopsin has a protonated Schiff base vibration at 1657 cm(-1) which shifts upon deuteration to 1625 cm(-1). Within our experimental error (+/-2 cm(-1)) these frequencies are identical to those observed in rhodopsin and isorhodopsin. These effects show that the strength of the C=N bond and the degree of protonation of the Schiff base nitrogen are the same in bathorhodopsin, rhodopsin, and isorhodopsin. The implication of these results for the structure of the retinal chromophore in bathorhodopsin are discussed. The resonance Raman spectrum of pure bathorhodopsin has been generated by accurately subtracting the residual contributions of rhodopsin and isorhodopsin from spectra of the low temperature photostationary mixture. Bathorhodopsin is found to have lines at 853, 875, 920, 1006, 1166, 1210, 1278, 1323, 1536, and 1657 cm(-1). Also, by using an intensified vidicon detector, we have observed Raman scattering from bathorhodopsin at room temperature by generating a photostationary steady state with pulsed laser excitation. At room temperature the three characteristic lines of bathorhodopsin are found at 858, 873, and 920 cm(-1). The fact that the frequencies of these bathorhodopsin lines are nearly identical at both temperatures implies that the retinal conformation in bathorhodopsin formed at -160 degrees C is the same as that formed at room temperature. PMID:284349

  15. Intermediate and stable redox states of cytochrome c studied by low temperature resonance Raman spectroscopy.

    PubMed Central

    Cartling, B

    1983-01-01

    Stabilized intermediate redox states of cytochrome c are generated by radiolytic reduction of initially oxidized enzyme in glass matrices at liquid nitrogen temperature. In the intermediate states the heme group is reduced by hydrated electrons, whereas the protein conformation is restrained close to its oxidized form by the low-temperature glass matrix. The intermediate and stable redox states of cytochrome c at neutral and alkaline pH are studied by low-temperature resonance Raman spectroscopy using excitations in resonance with the B (Soret) and Q1 (beta) optical transitions. The assignments of the cytochrome c resonance Raman bands are discussed. The observed spectral characteristics of the intermediate states as well as of the alkaline transition in the oxidized state are interpreted in terms of oxidation-state marker modes, spin-state marker modes, heme iron--axial ligand stretching modes, totally symmetric in-plane porphyrin modes, nontotally symmetric in-plane modes, and out-of-plane modes. PMID:6311300

  16. Resonant Raman Scattering in Antiferromagnets

    NASA Astrophysics Data System (ADS)

    Chubukov, Andrey V.; Morr, Dirk K.

    1996-03-01

    Two-magnon Raman scattering provides important information about electronic correlations in the insulating parent compounds of high-Tc materials. Recent experiments have shown a strong dependence of the Raman signal in B_1g geometry on the frequency of the incoming photon. We present a detailed numerical study of the diagram which was previously identified(A.V. Chubukov and D.M. Frenkel, Phys. Rev. B 52), 9760 (1995) as the most relevant in the resonant regime. We found two maxima of the two-magnon peak hight at transferred frequencies of ω ≈ 3J and ω ≈ 8J. These results agree with recent experiments by Blumberg(G. Blumberg et al.), preprint et al. on Sr_2CuO_2Cl_2. Furthermore, we study how the two-magnon profile depends on a quasiparticle damping and a hopping between next-nearest neighbors. We also study resonance scattering in other scattering geometries, in particular, A_1g scattering.

  17. A resonance raman scattering study of vibrational dephasing in the mixed crystal of pentacene in naphthalene

    NASA Astrophysics Data System (ADS)

    de Bree, Philippus; Wiersma, Douwe A.

    1982-04-01

    Resonance Raman scattering is used to investigate vibrational dephasing in the mixed crystal of pentacene in naphthalene. It is shown that, as for the pure electronic transition, uncorrelated resonant phonon scattering processes in the ground and vibrationally excited state induce vibrational dephasing in this system.

  18. Spatial correlation between chemical and topological defects in vitreous silica: UV-resonance Raman study

    SciTech Connect

    Saito, M. D’Amico, F.; Bencivenga, F.; Cucini, R.; Gessini, A.; Principi, E.; Masciovecchio, C.

    2014-06-28

    A spatial correlation between chemical and topological defects in the tetrahedron network in vitreous silica produced by a fusion process of natural quartz crystals was found by synchrotron-based UV resonance Raman experiments. Furthermore, a quantitative correlation between these defects was obtained by comparing visible Raman and UV absorption spectra. These results indicate that in vitreous silica produced by the fusion process the topological defects disturb the surrounding tetrahedral silica network and induce further disorder regions with sub nanometric sizes.

  19. Ultraviolet Resonant Raman Enhancements in the Detection of Explosives

    SciTech Connect

    Short Jr., Billy Joe

    2009-06-01

    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.

  20. Multi-wavelength resonance Raman spectroscopy of bacteria to study the effects of growth condition

    NASA Astrophysics Data System (ADS)

    Kunapareddy, Nagapratima; Grun, Jacob; Lunsford, Robert; Gillis, David; Nikitin, Sergei; Wang, Zheng

    2012-06-01

    We will examine the use of multi-wavelength UV resonance-Raman signatures to identify the effects of growth phase on different types of bacteria. Gram positive and gram-negative species, Escherichia coli, Bacillus cereus, Citrobacter koseri and Citrobacter braakii were grown to logarithmic and stationary phases in different culture media. Raman spectra of bacteria were obtained by sequential illumination of samples between 220 and 260 nm; a range which encompasses the resonance frequencies of cellular components. In addition to the information contained in the single spectrum, this two-dimensional signature contains information reflecting variations in resonance cross sections with illumination wavelength. Results of our algorithms in identifying the differences between these germs are discussed. Preliminary results indicate that growth affects the Raman signature, but not to an extent that would negate identification of the species.

  1. On the Increasing Fragility of Human Teeth with Age: ADeep-Ultraviolet Resonance Raman Study

    SciTech Connect

    Ager III, J.W.; Nalla, R.K.; Balooch, G.; Kim, G.; Pugach, M.; Habelitz, S.; Marshall, G.W.; Kinney, J.H.; Ritchie, R.O.

    2006-07-14

    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.

  2. Resonance Raman spectroscopic studies of the interactions between trypsin and a competitive inhibitor.

    PubMed Central

    Dupaix, A; Bechet, J J; Yon, J; Merlin, J C; Delhaye, M; Hill, M

    1975-01-01

    Raman spectroscopy was used to study the interactions between bovine trypsin and a competitive inhibitor. For this purpose, a chromophoric substrate analogue, 4-amidino-4'-dimethylamine azobenzene, was synthesized. This compound competitively inhibits the enzyme with a 1:1 stoichiometry and an inhibition constant Ki of 2.3 muM at pH 6.08 and 15 degrees. Resonance Raman spectra in aqueous solution of free or enzyme-bound inhibitor were analyzed. The main spectral changes observed upon enzyme-inhibitor complex formation were changes in the relative intensities of four bands (1171, 1206, 1315, 1608 cm-1) while no large frequency shifts occurred. The binding of the inhibitor molecule to the enzyme did not induce a twisting of the phenyl groups around the N=N bond. Some modifications of the band widths are interpreted in terms of a restriction of rotational motions in the inhibitor molecule. The possible involvement of specific interactions between trypsin and the benzamidinium ion part of the inhibitor molecule is discussed. PMID:1060102

  3. Optical pathology study of human abdominal aorta tissues using confocal micro resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Cheng-hui; Boydston-White, Susie; Wang, Wubao; Sordillo, Laura A.; Shi, Lingyan; Weisberg, Arel; Tomaselli, Vincent P.; Sordillo, Peter P.; Alfano, Robert R.

    2016-03-01

    Resonance Raman (RR) spectroscopic technique has a high potential for label-free and in-situ detection of biomedical lesions in vivo. This study evaluates the ability of RR spectroscopy method as an optical histopathology tool to detect the atherosclerotic plaque states of abdominal aorta in vitro. This part demonstrates the RR spectral molecular fingerprint features from different sites of the atherosclerotic abdominal aortic wall tissues. Total 57 sites of five pieces aortic samples in intimal and adventitial wall from an autopsy specimen were examined using confocal micro Raman system of WITec 300R with excitation wavelength of 532nm. The preliminary RR spectral biomarkers of molecular fingerprints indicated that typical calcified atherosclerotic plaque (RR peak at 964cm-1) tissue; fibrolipid plaque (RR peaks at 1007, 1161, 1517 and 2888cm-1) tissue, lipid pool with the fatty precipitation cholesterol) with collagen type I (RR peaks at 864, 1452, 1658, 2888 and 2948cm-1) in the soft tissue were observed and investigated.

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

    SciTech Connect

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

    2015-01-14

    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.

  5. Resonance Raman spectroscopic and density functional theory study of p-nitroacetophenone (PNAP)

    NASA Astrophysics Data System (ADS)

    Pei, Kemei; Ma, Yufang; Zheng, Xuming; Li, Haiyang

    2007-03-01

    Resonance Raman spectra of p-nitroacetophenone(PNAP) have been obtained in resonance with the charge-transfer (CT) band using 252.7, 266 and 273.9 nm in methanol solvent. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mainly along the C dbnd O stretching ν8(1691 cm -1) and the benzene ring stretch ν10(1593 cm -1). A preliminary resonance Raman intensity analysis was done and the results for PNAP were compared with nitrobenzene and aceptophenone. Our results indicate that -NO 2 is more photoactive than -COCH 3. The isomerization process of PNAP takes place somewhere after the wave packet leaves the Franck-Condon region.

  6. Resonant photo-thermal modification of vertical gallium arsenide nanowires studied using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Walia, Jaspreet; Boulanger, Jonathan; Dhindsa, Navneet; LaPierre, Ray; (Shirley Tang, Xiaowu; Saini, Simarjeet S.

    2016-06-01

    Gallium arsenide nanowires have shown considerable promise for use in applications in which the absorption of light is required. When the nanowires are oriented vertically, a considerable amount of light can be absorbed, leading to significant heating effects. Thus, it is important to understand the threshold power densities that vertical GaAs nanowires can support, and how the nanowire morphology is altered under these conditions. Here, resonant photo-thermal modification of vertical GaAs nanowires was studied using both Raman spectroscopy and electron microscopy techniques. Resonant waveguiding, and subsequent absorption of the excited optical mode reduces the irradiance vertical GaAs nanowires can support relative to horizontal ones, by three orders of magnitude before the onset of structural changes occur. A power density of only 20 W mm‑2 was sufficient to induce local heating in the nanowires, resulting in the formation of arsenic species. Upon further increasing the power, a hollow nanowire morphology was realized. These findings are pertinent to all optical applications and spectroscopic measurements involving vertically oriented GaAs nanowires. Understanding the optical absorption limitations, and the effects of exceeding these limitations will help improve the development of all III–V nanowire devices.

  7. Resonant Raman scattering in nanoscale pentacene films

    NASA Astrophysics Data System (ADS)

    He, Rui; Dujovne, Irene; Chen, Liwei; Miao, Qian; Hirjibehedin, Cyrus F.; Pinczuk, Aron; Nuckolls, Colin; Kloc, Christian; Ron, Arza

    2004-02-01

    Resonant Raman scattering intensities from nanoscale films of pentacene display large resonant enhancements that enable observation of vibrational modes in monolayer cluster films. The resonant enhancements occur when the outgoing photon energy overlaps the free exciton optical transitions observed in luminescence. The results point to the significant potential of resonant Raman methods in the characterization of nanoscale structures of organic molecular semiconductors.

  8. G-band resonant Raman study of 62 isolated single-wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Jorio, A.; Souza Filho, A. G.; Dresselhaus, G.; Dresselhaus, M. S.; Swan, A. K.; Ünlü, M. S.; Goldberg, B. B.; Pimenta, M. A.; Hafner, J. H.; Lieber, C. M.; Saito, R.

    2002-04-01

    We report G-band resonance Raman spectra of single-wall carbon nanotubes (SWNTs) at the single-nanotube level. By measuring 62 different isolated SWNTs resonant with the incident laser, and having diameters dt ranging between 0.95 nm and 2.62 nm, we have conclusively determined the dependence of the two most intense G-band features on the nanotube structure. The higher-frequency peak is not diameter dependent (ω+G=1591 cm-1), while the lower-frequency peak is given by ω-G=ω+G-C/d2t, with C being different for metallic and semiconducting SWNTs (CM>CS). The peak frequencies do not depend on nanotube chiral angle. The intensity ratio between the two most intense features is in the range 0.1resonance conditions, i.e., SWNTs for which the incident photons are in resonance with the ES44 interband transition and scattered photons are in resonance with ES33. Since the Eii values depend sensitively on both nanotube diameter and chirality, the (n,m) SWNTs that should exhibit such a special G-band spectra can be predicted by resonance Raman theory. The agreement between theoretical predictions and experimental observations about these special G-band phenomena gives additional support for the (n,m) assignment from resonance Raman spectroscopy.

  9. Resonance Raman Spectroscopic Evaluation of Skin Carotenoids as a Biomarker of Carotenoid Status for Human Studies

    PubMed Central

    Mayne, Susan T.; Cartmel, Brenda; Scarmo, Stephanie; Jahns, Lisa; Ermakov, Igor V.; Gellermann, Werner

    2013-01-01

    Resonance Raman Spectroscopy (RRS) is a non-invasive method that has been developed to assess carotenoid status in human tissues including human skin in vivo. Skin carotenoid status has been suggested as a promising biomarker for human studies. This manuscript describes research done relevant to the development of this biomarker, including its reproducibility, validity, feasibility for use in field settings, and factors that affect the biomarker such as diet, smoking, and adiposity. Recent studies have evaluated the response of the biomarker to controlled carotenoid interventions, both supplement-based and dietary [e.g., provision of a high-carotenoid fruit and vegetable (F/V)-enriched diet], demonstrating consistent response to intervention. The totality of evidence supports the use of skin carotenoid status as an objective biomarker of F/V intake, although in the cross-sectional setting, diet explains only some of the variation in this biomarker. However, this limitation is also a strength in that skin carotenoids may effectively serve as an integrated biomarker of health, with higher status reflecting greater F/V intake, lack of smoking, and lack of adiposity. Thus, this biomarker holds promise as both a health biomarker and an objective indicator of F/V intake, supporting its further development and utilization for medical and public health purposes. PMID:23823930

  10. UV resonance Raman study of model complexes of the Cu B site of cytochrome c oxidase

    NASA Astrophysics Data System (ADS)

    Nagano, Yasutomo; Liu, Jin-Gang; Naruta, Yoshinori; Kitagawa, Teizo

    2005-02-01

    A newly designed model complex for the CuB site of cytochrome c oxidase (CcO), that is, Cu coordinated by two free imidazoles and an imidazole covalently linked to p-cresol [CuIIBIAIPBr]Br, (BIAIP =2-[4-[[Bis(1-methyl-1H-imidazol-2-ylmethyl)amino]methyl]-1H-imidazol-1-yl]-4-methylphenol), and related molecules have been investigated with absorption and ultraviolet resonance Raman (UVRR) spectroscopy employing the excitation wavelengths between 220 and 290 nm. Attention was focused on the electron delocalization through the cross-linkage between the phenol and imidazole rings, and the influences by the coordination of CuII to imidazole. In addition to the ν8a and ν8b modes of p-cresol, a number of Raman bands involving vibrations of the imidazole moiety have been intensity-enhanced despite Raman excitation in resonance with the π-π* transition of phenol, indicating appreciable mixing of the π systems of imidazole and phenol rings. Furthermore, two kinds of imidazoles seem to be differential; one is the imidazole linked to p-cresol which yielded Raman bands at 1249, 1191, and 1141 cm-1 for protonated CuII-BIAIP, and the other is one not linked to p-cresol, which yielded an intense band at 1488 cm-1 band. Raman enhancement of the latter mode seems to be caused by preresonance to the lowest π-π* transition of imidazole via the A-term mechanism. The Raman excitation profile (REP) of ν8a mode for the deprotonated phenol of the CuII-complex revealed a weak local maximum corresponding to the La band around 240 nm. Raman enhancement by the La band was relatively weaker for the CuII-complex than for the ZnII-complex and metal-free ligand, suggesting the more extensive mixing of π systems of p-cresol-imidazole through the cross-linkage for the Cu II-complex.

  11. Ultrafast protein dynamics of hemoglobin as studied by picosecond time-resolved resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Mizutani, Yasuhisa; Nagai, Masako

    2012-03-01

    Time-resolved resonance Raman spectroscopy on human adult hemoglobin (HbA) following ligand photolysis revealed that the frequency of the iron-histidine stretching [ν(Fe-His)] mode exhibited a 2-cm-1 downshift with a time constant of about 300 ps, suggesting a structural change in the heme pocket following the ligand photolysis. Low-frequency heme modes suggested that the primary metastable form of HbA has a more disordered orientation of propionates and a less strained environment than the deoxy form. The latter fact is consistent with the experimental observation that the ν(Fe-His) frequency of the metastable form is higher than the deoxy form. The present study shows that HbA adopts a metastable structure within the instrument response time and remains little changed in the subnanosecond to nanosecond time regime. Characteristics of the primary protein response of HbA based on the comparison of the results of HbA with those of the isolated chains and myoglobin are discussed.

  12. Resonance Raman studies of the HOOP modes in octopus bathorhodopsin with deuterium-labeled retinal chromophores

    SciTech Connect

    Deng, H.; Manor, D.; Weng, G.; Rath, P.; Callender, R.H. ); Koutalos, Y.; Ebrey, T. ); Gebhard, R.; Lugtenburg, J. ); Tsuda, M. )

    1991-05-07

    Resonance Raman spectra of the hydrogen out-of-plane (HOOP) vibrational modes in the retinal chromophore of octopus bathorhodopsin with deuterium label(s) along the polyene chain have been obtained. In clear contrast with bovine bathorhodopsin's HOOP modes, there are only two major HOOP bands at 887 and 940 cm{sup {minus}1} for octopus bathorhodopsin. On the basis of their isotopic shifts upon deuterium labeling, the authors have assigned the band at 887 cm{sup {minus}1} to C{sub 10}H and C{sub 14}H HOOP modes, and the band at 940 cm{sup {minus}1} to C{sub 11}H{double bond}C{sub 12}H A{sub u}-like HOOP mode. They found also that the C{sub 10}H and C{sub 14}H HOOP wags are also similar to those in the model-compound studies. However, they have found that the interaction between the C{sub 7}H and C{sub 8}H HOOP internal coordinates of the chromophore in octopus bathorhodopsin is different from that of the chromophore in solution. The twisted nature of the chromophore, semiquantitatively discussed here, likely affects the {lambda}{sub max} of the chromophore and its enthalpy. The nature of the HOOP modes of octopus bathorhodopsin differs substantially from those found in bovine bathorhodopsin.

  13. UV resonance Raman and DFT studies of arginine side chains in peptides: insights into arginine hydration.

    PubMed

    Hong, Zhenmin; Wert, Jonathan; Asher, Sanford A

    2013-06-20

    We examined the UV resonance Raman (UVRR) spectra of four models of the Arg side chain, guanidinium (Gdn), ethylguanidinium (EG), arginine (Arg), and Ac-Arg-OMe (AAO) in H2O and D2O, in order to identify spectral markers that report on the environment of the Arg side chain. To elucidate the resonance Raman enhancement mechanism of the Arg side chain, we used density functional theory (DFT) to calculate the equilibrium geometries of the electronic ground state and the first excited state. We determined the vibrational mode frequencies of the ground state and the first derivative of the first electronic excited state potential energy with respect to each vibrational normal mode of the electronic ground state at the electronic ground state equilibrium geometry. The DFT calculations and the potential energy distributions reveal that, in addition to the Gdn group C-N stretching vibrations, the C-N bond stretching vibration of the Gdn group-methylene linkage is also strongly resonance-enhanced in EG, Arg, and AAO. From the UVRR spectra, we find that the Raman cross section and frequency of the ~1170 cm(-1) vibration of the Arg side chain depends on its hydration state and can be used to determine the hydration state of the Arg side chain in peptides and proteins. We examined the hydration of the Arg side chain in two polyAla peptides and found that in the α-helical conformation the Arg side chain in the AEP peptide (sequence: A9RA3EA4RA2) is less hydrated than that in the AP peptide (sequence: A8RA4RA4RA2). PMID:23676082

  14. UV Resonance Raman and DFT Studies of Arginine Side Chains in Peptides: Insights into Arginine Hydration

    PubMed Central

    Hong, Zhenmin; Wert, Jonathan; Asher, Sanford A.

    2013-01-01

    We examined the UV resonance Raman (UVRR) spectra of four models of the arg side chain, guanidinium (gdn), ethylguanidinium (EG), arginine (arg) and Ac-arg-OMe (AAO) in H2O and D2O, in order to identify spectral markers that report on the environment of the arg side chain. To elucidate the resonance Raman enhancement mechanism of the arg side chain, we used DFT to calculate the equilibrium geometries of the electronic ground state and the first excited state. We determined the vibrational mode frequencies of the ground state and the first derivative of the first electronic excited state potential energy with respect to each vibrational normal mode of the electronic ground state at the electronic ground state equilibrium geometry. The DFT calculations and the potential energy distributions reveal that, in addition to the gdn group C-N stretching vibrations, the C-N bond stretching vibration of the gdn group-methylene linkage is also strongly resonance enhanced in EG, arg and AAO. From the UVRR spectra, we find that the Raman cross section and frequency of the ~1170 cm−1 vibration of the arg side chain depends on its hydration state and can be used to determine the hydration state of the arg side chain in peptides and proteins. We examined the hydration of the arg side chain in two polyala peptides and found that in the α-helical conformation the arg side chain in the AEP peptide (sequence: A9RA3EA4RA2) is less hydrated than that in the AP peptide (sequence: A8RA4RA4RA2). PMID:23676082

  15. X-ray resonant Raman spectroscopy

    SciTech Connect

    Cowan, P.L.; LeBrun, T.; Deslattes, R.D.

    1995-08-01

    X-ray resonant Raman scattering presents great promise as a high-resolution spectroscopic probe of the electronic structure of matter. Unlike other methods, the technique avoids the loss of energy resolution resulting from the lifetime broadening of short-lived core-excited states. In addition, measurements of polarization and angular anisotropies yield information on the symmetries of electronic states of atoms and molecules. We studied the L{sub 3} edge of xenon, where the lifetime broadening is a major feature of the spectra recorded previously. X-ray fluorescence spectra were taken of both the L{alpha}{sub l,2} and L{beta}{sub 2,15} peaks over a range of energies from 10 eV below the edge to 40 eV above. These spectra show the evolution of resonant Raman scattering into characteristic fluorescence as the photon energy is scanned across the edge, and confirm several features of these spectra such as asymmetries in resonant peak shapes due to the onset of the ionization continuum. These results constitute the most comprehensive study of X-ray resonant Raman scattering to date, and were submitted for publication. Studies of other cases are under way, and new instruments that would match the unique characteristics of the APS - and thus render a new range of experiments possible - are under consideration.

  16. Al-doped MgB2 materials studied using electron paramagnetic resonance and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Bateni, Ali; Erdem, Emre; Repp, Sergej; Weber, Stefan; Somer, Mehmet

    2016-05-01

    Undoped and aluminum (Al) doped magnesium diboride (MgB2) samples were synthesized using a high-temperature solid-state synthesis method. The microscopic defect structures of Al-doped MgB2 samples were systematically investigated using X-ray powder diffraction, Raman spectroscopy, and electron paramagnetic resonance. It was found that Mg-vacancies are responsible for defect-induced peculiarities in MgB2. Above a certain level of Al doping, enhanced conductive properties of MgB2 disappear due to filling of vacancies or trapping of Al in Mg-related vacancy sites.

  17. Resonance IR: a coherent multidimensional analogue of resonance Raman.

    PubMed

    Boyle, Erin S; Neff-Mallon, Nathan A; Handali, Jonathan D; Wright, John C

    2014-05-01

    This work demonstrates the use of triply resonant sum frequency (TRSF) spectroscopy as a "resonance IR" analogue to resonance Raman spectroscopy. TRSF is a four-wave-mixing process where three lasers with independent frequencies interact coherently with a sample to generate an output at their triple summation frequency. The first two lasers are in the infrared and result in two vibrational excitations, while the third laser is visible and induces a two-quantum anti-Stokes resonance Raman transition. The signal intensity grows when the laser frequencies are all in resonance with coupled vibrational and electronic states. The method therefore provides electronic enhancement of IR-active vibrational modes. These modes may be buried beneath solvent in the IR spectrum and also be Raman-inactive and therefore inaccessible by other techniques. The method is presented on the centrosymmetric complex copper phthalocyanine tetrasulfonate. In this study, the two vibrational frequencies were scanned across ring-breathing modes, while the visible frequency was left in resonance with the copper phthalocyanine tetrasulfonate Q band, resulting in a two-dimensional infrared plot that also reveals coupling between vibrational states. TRSF has the potential to be a very useful probe of structurally similar biological motifs such as hemes, as well as synthetic transition-metal complexes. PMID:24707979

  18. Resonance Raman Study of an Anion Channelrhodopsin: Effects of Mutations near the Retinylidene Schiff Base.

    PubMed

    Yi, Adrian; Mamaeva, Natalia; Li, Hai; Spudich, John L; Rothschild, Kenneth J

    2016-04-26

    Optogenetics relies on the expression of specific microbial rhodopsins in the neuronal plasma membrane. Most notably, this includes channelrhodopsins, which when heterologously expressed in neurons function as light-gated cation channels. Recently, a new class of microbial rhodopsins, termed anion channel rhodopsins (ACRs), has been discovered. These proteins function as efficient light-activated channels strictly selective for anions. They exclude the flow of protons and other cations and cause hyperpolarization of the membrane potential in neurons by allowing the inward flow of chloride ions. In this study, confocal near-infrared resonance Raman spectroscopy (RRS) along with hydrogen/deuterium exchange, retinal analogue substitution, and site-directed mutagenesis were used to study the retinal structure as well as its interactions with the protein in the unphotolyzed state of an ACR from Guillardia theta (GtACR1). These measurements reveal that (i) the retinal chromophore exists as an all-trans configuration with a protonated Schiff base (PSB) very similar to that of bacteriorhodopsin (BR), (ii) the chromophore RRS spectrum is insensitive to changes in pH from 3 to 11, whereas above this pH the Schiff base (SB) is deprotonated, (iii) when Ser97, the homologue to Asp85 in BR, is replaced with a Glu, it remains in a neutral form (i.e., as a carboxylic acid) but is deprotonated at higher pH to form a blue-shifted species, (iv) Asp234, the homologue of the protonated retinylidene SB counterion Asp212 in BR, does not serve as the primary counteranion for the protonated SB, and (v) substitution of Glu68 with an Gln increases the pH at which SB deprotonation is observed. These results suggest that Glu68 and Asp234 located near the SB exist in a neutral state in unphotolyzed GtACR1 and indicate that other unidentified negative charges stabilize the protonated state of the GtACR1 SB. PMID:27039989

  19. Resonance Raman studies of substituent effects on the electronic structure of phenoxyl radicals

    SciTech Connect

    Tripathi, G.N.R.; Schuler, R.H.

    1988-09-08

    The resonance Raman spectra of para-substituted phenoxyl radicals (XC/sub 6/H/sub 4/O/center dot/; X = CH/sub 3/, F, Cl, Br, OCH/sub 3/, OH) observed by time-resolved techniques in aqueous medium, exhibit a wide variation in spectral features intermediate between phenoxyl and /rho/-benzosemiquinone anion radicals. The ..nu../sub 7a/ (CO stretch) vibration, which is strongly enhanced on Raman excitation in resonance with the electronic transition in the approx. 400-nm region, appears in a narrow frequency range 1511-1518 cm/sup /minus/1/, indicating that the CO bond in the ground electronic state of these radicals is very similar to that of phenoxyl (..nu../sub 7a/ at 1505 cm/sup /minus/1/). The relative intensities of the ..nu../sub 8a/ bands (CC stretch), observed in the 1552-1613-cm/sup /minus/1/ region, change dramatically with the electronic properties of the substituent group. This vibration, which is not apparent in the Raman spectrum of phenoxyl excited at 400 nm, is observed with an intensity comparable to the of the ..nu../sub 7a/ vibration in the /rho/-bromo, /rho/-methoxy, and /rho/-hydroxy derivatives. The Raman intensities show that the electronic structures in the excited states of the /rho/-methoxy and /rho/-fluoro-, and p-chloro-substituted radicals are essentially phenoxyl like, while the structures in p-methoxy and p-hydroxy derivatives approach that of /rho/-benzosemiquinone anion radical as a result of strong interaction of the substituent's p..pi.. electrons with the phenoxyl ..pi.. system. The excited state of /rho/-bromophenoxyl radical represents an important intermediate case. The resonance enhancement of the ..nu../sub 9a/ CH bending vibration, observed at approx. 1160 cm/sup /minus/1/, parallels that of the ..nu../sub 8a/ phenyl mode and provides an important diagnostic for assignment of the latter vibration.

  20. Auger resonant Raman spectroscopy used to study the angular distributions of the Xe 4d{sub 5/2} {yields} 6p decay spectrum

    SciTech Connect

    Langer, B.; Berrah, N.; Farhat, A.

    1997-04-01

    Auger resonant Raman spectroscopy is a powerful tool for studying the resonant Auger decay processes with a resolution narrower than the natural lifetime width of the initial inner-shell hole state. This effect has been used to analyze branching ratios of resonantly excited atoms and molecules. In this paper, the authors present results of a study of angular distributions of the spectator decay lines of Xe following 4d{sub 5/2}{r_arrow}6p excitation using the Auger resonant Raman effect and highly resolved photons from the Advanced Light Source (ALS).

  1. Resonance Raman study of the oxygenation cycle of optically trapped single red blood cells in a microfluidic system

    NASA Astrophysics Data System (ADS)

    Ramser, Kerstin; Logg, Katarina; Enger, Jonas; Goksor, Mattias; Kall, Mikael; Hanstorp, Dag

    2004-10-01

    The average environmental response of red blood cells (RBCs) is routinely measured in ensemble studies, but in such investigations valuable information on the single cell level is obscured. In order to elucidate this hidden information is is important to enable the selection of single cells with certain properties while subsequent dynamics triggered by environmental stimulation are recorded in real time. It is also desirable to manipulate and control the cells under phsyiological conditions. As shown here, this can be achieved by combining optical tweezers with a confocal Raman set-up equipped with a microfluidic system. A micro-Raman set-up is combined with an optical trap with separate optical paths, lasers and objectives, which enables the acquisition of resonance Raman profils of single RBCs. The microfluidic system, giving full control over the media surrounding the cell, consists of a pattern of channels and reservoirs produced by electron beam lithography and moulded in PDMS. Fresh Hepes buffer or buffer containing sodium dithionite are transported through the channels using electro-osmotic flow, while the direct Raman response of the single optically trapped RBC is registered in another reservoir in the middle of the channel. Thus, it is possible to monitor the oxygenation cycle in a single cell and to study photo-induced chemistry. This experimental set-up has high potential for monitoring the drug response or conformational changes caused by other environmental stimuli for many types of single functional cells since "in vivo" conditions can be created.

  2. Direct Observation of 4-Phenoxyphenylnitrenium Ion: A Transient Absorption and Transient Resonance Raman Study.

    PubMed

    Xue, Jiadan; Li, Yafang; Du, Lili; Du, Yong; Tang, Wenjian; Zheng, Xuming; Phillips, David Lee

    2015-11-19

    Femtosecond (fs) and nanosecond (ns) transient absorption (TA) and single pulse transient resonance Raman spectroscopic investigation of the intermediates after laser photolysis of 4-phenoxyphenyl azide in acetonitrile and mixed aqueous solution is reported. fs-TA results show that the singlet 4-phenoxyphenylnitrene was produced immediately after photolysis of the azide. Then, the singlet nitrene underwent intersystem crossing (ISC) and ring expansion to generate triplet nitrene and ketenimine in acetonitrile with t = 346 ps or protonation in mixed aqueous solution with t = 37 ps, respectively, a little slower than the counterparts of the methoxy one (108 and 5.4 ps for ISC and protonation processes, respectively). The transient Raman spectrum combined density functional theory (DFT) calculation predicting the structure and vibrational frequencies suggested that phenoxyphenylnitrenium ion has a comparable quinoidal character to that of methoxy- and ethoxy-phenylnitrenium ions. All of these results indicated that the phenoxy substitution has some impact on the reactivity of phenylnitrene but a slight influence on the structure of phenylnitrenium ion. PMID:26503835

  3. Absorption and resonance Raman study of the pyromellitic diahydride anion via density functional theory

    NASA Astrophysics Data System (ADS)

    Andruniow, T.; Pawlikowski, M.

    2000-05-01

    The electronic structure of the low-energy states of the pyromellitic diahydride (PMDA) anion is investigated in terms of the VWN (Vosco-Wilk-Nusair) the BP (Becke-Perdew) and the B3LYP density functional (DF) methods employed with 6-31G * basis sets. All the methods are shown to reproduce correctly the absorption and resonance Raman spectra in the region corresponding to the low-energy 1 2Au→1 2B3g transition. The discrepancies between the theory and experiment are attributed to a (weak) Dushinsky effect predominately due to a mixing of the ν3=1593 cm -1 and ν4=1342 cm -1 vibrations in the 1 2B3 g state of the PMDA radical.

  4. Structure, spectra and antioxidant action of ascorbic acid studied by density functional theory, Raman spectroscopic and nuclear magnetic resonance techniques

    NASA Astrophysics Data System (ADS)

    Singh, Gurpreet; Mohanty, B. P.; Saini, G. S. S.

    2016-02-01

    Structure, vibrational and nuclear magnetic resonance spectra, and antioxidant action of ascorbic acid towards hydroxyl radicals have been studied computationally and in vitro by ultraviolet-visible, nuclear magnetic resonance and vibrational spectroscopic techniques. Time dependant density functional theory calculations have been employed to specify various electronic transitions in ultraviolet-visible spectra. Observed chemical shifts and vibrational bands in nuclear magnetic resonance and vibrational spectra, respectively have been assigned with the help of calculations. Changes in the structure of ascorbic acid in aqueous phase have been examined computationally and experimentally by recording Raman spectra in aqueous medium. Theoretical calculations of the interaction between ascorbic acid molecule and hydroxyl radical predicted the formation of dehydroascorbic acid as first product, which has been confirmed by comparing its simulated spectra with the corresponding spectra of ascorbic acid in presence of hydrogen peroxide.

  5. Electron paramagnetic resonance, optical absorption and Raman spectral studies on a pyrite/chalcopyrite mineral

    NASA Astrophysics Data System (ADS)

    Udayabhaskar Reddy, G.; Seshamaheswaramma, K.; Nakamura, Yoshinobu; Lakshmi Reddy, S.; Frost, Ray L.; Endo, Tamio

    2012-10-01

    Pyrite and chalcopyrite mineral samples from Mangampet barite mine, Kadapa, Andhra Pradesh, India are used in the present study. XRD data indicate that the pyrite mineral has a face centered cubic lattice structure with lattice constant 5.4179 Å. Also it possesses an average particle size of 91.9 nm. An EPR study on the powdered samples confirms the presence of iron in pyrite and iron and Mn(II) in chalcopyrite. The optical absorption spectrum of chalcopyrite indicates presence of copper which is in a distorted octahedral environment. NIR results confirm the presence of water fundamentals and Raman spectrum reveals the presence of water and sulfate ions.

  6. Probing Nanoscale Pentacene Films by Resonant Raman Scattering

    NASA Astrophysics Data System (ADS)

    He, Rui; Dujovne, Irene; Chen, Liwei; Miao, Qian; Hirjibehedin, Cyrus F.; Pinczuk, Aron; Nuckolls, Colin; Kloc, Christian; Blanchet, Graciela B.

    2005-06-01

    Resonant enhancements of Raman scattering intensities offer the sensitivity required to study nanoscale pentacene films that reach into monolayer thickness. In the results reported here structural characterization of ultra-thin layers and of their fundamental optical properties are investigated by resonant Raman scattering from intra-molecular and inter-molecular vibrations. In this work Raman methods emerge as ideal tools for the study of physics and characterization of ultra-thin nanoscale films of molecular organic materials fabricated on diverse substrates of current and future devices.

  7. The study of near-resonance Raman scattering of AlInN/AlN/GaN heterostructure

    NASA Astrophysics Data System (ADS)

    Liu, Yanli; Yang, Lianhong; Chen, Dunjun; Zhang, Li; Lu, Hai; Zhang, Rong; Zheng, Youdou

    2015-07-01

    The visible and ultraviolet (UV) Raman scattering of an AlInN/AlN/GaN heterostructure were measured under z (x, _) z bar configuration at room temperature. Compared with the visible Raman spectrum, three new peaks at 609, 700, and 840 cm-1 occurred in the UV Raman spectrum and were verified to result from the resonance enhanced Raman effect. The near-resonance Raman scattering is stimulated by the electron transition process between the valence band and subband of triangular quantum well located at the interface of AlN/GaN because this transition process has a near equal energy with the 325 nm excitation light. According to the calculated dispersion relations of interface phonon modes in the AlInN/AlN/GaN heterostructure and the 2DEG-related resonance enhanced effect, these new Raman peaks were mainly attributed to the interface phonon modes and disorder-activated mode. The contributions from the bulk phonon modes of AlN and AlInN layers play a very minor role.

  8. Resonant Raman spectroscopy study of swift heavy ion irradiated MoS2

    NASA Astrophysics Data System (ADS)

    Guo, Hang; Sun, Youmei; Zhai, Pengfei; Zeng, Jian; Zhang, Shengxia; Hu, Peipei; Yao, Huijun; Duan, Jinglai; Hou, Mingdong; Liu, Jie

    2016-08-01

    Molybdenum disulphide (MoS2) crystal samples were irradiated by swift heavy ions (209Bi and 56Fe). Hillock-like latent tracks were observed on the surface of irradiated MoS2 by atomic force microscopy. The modifications of properties of irradiated MoS2 were investigated by resonant Raman spectroscopy and ultraviolet-visible spectroscopy (UV-Vis). A new peak (E1u2, ∼385.7 cm-1) occurs near the in-plane E2g1 peak (∼383.7 cm-1) after irradiation. The two peaks shift towards lower frequency and broaden due to structural defects and stress with increasing fluence. When irradiated with high fluence, two other new peaks appear at ∼ 190 and ∼ 230 cm-1. The peak at ∼230 cm-1 is disorder-induced LA(M) mode. The presence of this mode indicates defects induced by irradiation. The feature at ∼460 cm-1 is composed of 2LA(M) (∼458 cm-1) and A2u (∼466 cm-1) mode. With increasing fluence, the integrated intensity ratio between 2LA(M) and A2u increases. The relative enhancement of 2LA(M) mode is in agreement with the appearance of LA(M) mode, which both demonstrate structural disorder in irradiated MoS2. The ∼423-cm-1 peak shifts toward lower frequency due to the decrease in exciton energy of MoS2, and this was demonstrated by the results of UV-Vis spectra. The decrease in exciton energy could be due to introduction of defect levels into band gap.

  9. Resonance Raman spectroscopy and density functional theory study of the photodissociation dynamics of acetophenone in cyclohexane solution

    NASA Astrophysics Data System (ADS)

    Ma, Yufang; Pei, Kemei; Zheng, Xuming; Li, Haiyang

    2007-11-01

    Resonance Raman spectra were acquired for acetophenone using 228.7, 239.5, and 245.9 nm excitations in cyclohexane solution. The spectra display overtones of the benzene ring C-C stretch (1578 cm -1) and the carbonyl C dbnd O stretch (1671 cm -1) modes and their combination bands with other five vibrational modes. A preliminary resonance Raman intensity analysis was done and these results for acetophenone were compared to the those previously reported for 2-hydroxyacetophenone. The differences between the vibrational reorganizational energies for acetophenone relative to those of 2-hydroxyacetophenone were briefly discussed.

  10. Optically confined polarized resonance Raman studies in identifying crystalline orientation of sub-diffraction limited AlGaN nanostructure

    SciTech Connect

    Sivadasan, A. K. Patsha, Avinash; Dhara, Sandip

    2015-04-27

    An optical characterization tool of Raman spectroscopy with extremely weak scattering cross section tool is not popular to analyze scattered signal from a single nanostructure in the sub-diffraction regime. In this regard, plasmonic assisted characterization tools are only relevant in spectroscopic studies of nanoscale object in the sub-diffraction limit. We have reported polarized resonance Raman spectroscopic (RRS) studies with strong electron-phonon coupling to understand the crystalline orientation of a single AlGaN nanowire of diameter ∼100 nm. AlGaN nanowire is grown by chemical vapor deposition technique using the catalyst assisted vapor-liquid-solid process. The results are compared with the high resolution transmission electron microscopic analysis. As a matter of fact, optical confinement effect due to the dielectric contrast of nanowire with respect to that of surrounding media assisted with electron-phonon coupling of RRS is useful for the spectroscopic analysis in the sub-diffraction limit of 325 nm (λ/2N.A.) using an excitation wavelength (λ) of 325 nm and near ultraviolet 40× far field objective with a numerical aperture (N.A.) value of 0.50.

  11. Novel Raman resonance in ladder spin systems

    NASA Astrophysics Data System (ADS)

    Donkov, Alexander; Chubukov, Andrey

    2006-03-01

    We consider Raman intensity in spin S two-leg- spin-ladder, with the goal to understand recent experiments[1,2]. We argue that the Raman intensity has a pseudo-resonance peak whose width is very small at large S. The pseudo-resonance originates from the existence of a local minimum in the magnon excitation spectrum, and is located slightly below twice the magnon energy at the minimum. The physics behind the peak is surprisingly similar to that in the excitonic scenario for the neutron and Raman resonances in a d-wave superconductor. We also consider mid-infrared X-ray scattering in 2D systems and compare the results with recent measurements [3]. [1] A. Gozar et al, Phys. Rev. Lett. 87, 197202 (2001). [2] S. Sugai and M. Suzuki, Phys stat sol (b) 215, 653 (1999). [3] J. P. Hill, G Blumberg et al, [unpublished

  12. Dermal carotenoids as measured by resonance Raman spectroscopy as a biomarker of response to a fruit/vegetable intervention study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dermal carotenoid status may have utility as a biomarker for vegetable and fruit consumption. Resonance Raman spectroscopy (RRS) is a valid, non-invasive method to assess dermal carotenoids as a biomarker of usual vegetable and fruit intake, but has not been evaluated in response to a whole-diet in...

  13. In situ electron spin resonance and Raman spectroscopic studies of the electrochemical process of conducting polypyrrole films

    SciTech Connect

    Zhong, C.J.; Tian, Z.Q.; Tian, Z.W. )

    1990-03-08

    The electrochemical redox properties of conducting polypyrrole (PPy) films coated on electrodes are investigated in aqueous solutions by use of the in situ techniques of electron spin resonance (ESR) and Raman spectroscopy. Comparisons between the experimental in situ ESR data and a theoretical kinetic prediction on the basis of the polaron-bipolaron model are presented.

  14. Resonant Raman spectroscopy of twisted multilayer graphene.

    PubMed

    Wu, Jiang-Bin; Zhang, Xin; Ijäs, Mari; Han, Wen-Peng; Qiao, Xiao-Fen; Li, Xiao-Li; Jiang, De-Sheng; Ferrari, Andrea C; Tan, Ping-Heng

    2014-01-01

    Graphene and other two-dimensional crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientation have different optical and electronic properties. Probing and understanding the interface coupling is thus of primary importance for fundamental science and applications. Here we study twisted multilayer graphene flakes with multi-wavelength Raman spectroscopy. We find a significant intensity enhancement of the interlayer coupling modes (C peaks) due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. The interlayer coupling results in a Davydov splitting of the C peak in systems consisting of two equivalent graphene multilayers. This allows us to directly quantify the interlayer interaction, which is much smaller compared with Bernal-stacked interfaces. This paves the way to the use of Raman spectroscopy to uncover the interface coupling of two-dimensional hybrids and heterostructures. PMID:25382099

  15. Periodontitis diagnostics using resonance Raman spectroscopy on saliva

    NASA Astrophysics Data System (ADS)

    Gonchukov, S.; Sukhinina, A.; Bakhmutov, D.; Biryukova, T.; Tsvetkov, M.; Bagratashvily, V.

    2013-07-01

    In view of its wealth of molecular information, Raman spectroscopy has been the subject of active biomedical research. The aim of this work is Raman spectroscopy (RS) application for the determination of molecular biomarkers in saliva with the objective of early periodontitis detection. As was shown in our previous study, carotenoids contained in saliva can be molecular fingerprint information for the periodontitis level. It is shown here that the carotenoid RS lines at wavenumbers of 1156 and 1524 cm-1 can be easily detected and serve as reliable biomarkers of periodontitis using resonance Raman spectroscopy of dry saliva.

  16. Fano resonance of Li-doped KTa1−xNbxO3 single crystals studied by Raman scattering

    PubMed Central

    Rahaman, M. M.; Imai, T.; Sakamoto, T.; Tsukada, S.; Kojima, S.

    2016-01-01

    The enhancement of functionality of perovskite ferroelectrics by local structure is one of current interests. By the Li-doping to KTa1−xNbxO3 (KTN), the large piezoelectric and electro-optic effects were reported. In order to give new insights into the mechanism of doping, the microscopic origin of the Fano resonance induced by the local structure was investigated in 5%Li-doped KTN single crystals by Raman scattering. The coupling between the continuum states and the transverse optical phonon near 196 cm−1 (Slater mode) caused a Fano resonance. In the vicinity of the cubic-tetragonal phase transition temperature, TC-T = 31 °C, the almost disappearance of the Fano resonance and the remarkable change of the central peak (CP) intensity were observed upon heating. The local symmetry of the polar nanoregions (PNRs), which was responsible for the symmetry breaking in the cubic phase, was determined to E(x, y) symmetry by the angular dependence of Raman scattering. The electric field induced the significant change in the intensity of both CP and Fano resonance. From these experimental results, it is concluded that the origin of the Fano resonance in Li-doped KTN crystals is the coupling between polarization fluctuations of PNRs and the Slater mode, both belong to the E(x, y) symmetry. PMID:27049847

  17. Fano resonance of Li-doped KTa1-xNbxO3 single crystals studied by Raman scattering.

    PubMed

    Rahaman, M M; Imai, T; Sakamoto, T; Tsukada, S; Kojima, S

    2016-01-01

    The enhancement of functionality of perovskite ferroelectrics by local structure is one of current interests. By the Li-doping to KTa1-xNbxO3 (KTN), the large piezoelectric and electro-optic effects were reported. In order to give new insights into the mechanism of doping, the microscopic origin of the Fano resonance induced by the local structure was investigated in 5%Li-doped KTN single crystals by Raman scattering. The coupling between the continuum states and the transverse optical phonon near 196 cm(-1) (Slater mode) caused a Fano resonance. In the vicinity of the cubic-tetragonal phase transition temperature, TC-T = 31 °C, the almost disappearance of the Fano resonance and the remarkable change of the central peak (CP) intensity were observed upon heating. The local symmetry of the polar nanoregions (PNRs), which was responsible for the symmetry breaking in the cubic phase, was determined to E(x, y) symmetry by the angular dependence of Raman scattering. The electric field induced the significant change in the intensity of both CP and Fano resonance. From these experimental results, it is concluded that the origin of the Fano resonance in Li-doped KTN crystals is the coupling between polarization fluctuations of PNRs and the Slater mode, both belong to the E(x, y) symmetry. PMID:27049847

  18. Fano resonance of Li-doped KTa1‑xNbxO3 single crystals studied by Raman scattering

    NASA Astrophysics Data System (ADS)

    Rahaman, M. M.; Imai, T.; Sakamoto, T.; Tsukada, S.; Kojima, S.

    2016-04-01

    The enhancement of functionality of perovskite ferroelectrics by local structure is one of current interests. By the Li-doping to KTa1‑xNbxO3 (KTN), the large piezoelectric and electro-optic effects were reported. In order to give new insights into the mechanism of doping, the microscopic origin of the Fano resonance induced by the local structure was investigated in 5%Li-doped KTN single crystals by Raman scattering. The coupling between the continuum states and the transverse optical phonon near 196 cm‑1 (Slater mode) caused a Fano resonance. In the vicinity of the cubic-tetragonal phase transition temperature, TC-T = 31 °C, the almost disappearance of the Fano resonance and the remarkable change of the central peak (CP) intensity were observed upon heating. The local symmetry of the polar nanoregions (PNRs), which was responsible for the symmetry breaking in the cubic phase, was determined to E(x, y) symmetry by the angular dependence of Raman scattering. The electric field induced the significant change in the intensity of both CP and Fano resonance. From these experimental results, it is concluded that the origin of the Fano resonance in Li-doped KTN crystals is the coupling between polarization fluctuations of PNRs and the Slater mode, both belong to the E(x, y) symmetry.

  19. Resonant Raman scattering from silicon nanoparticles enhanced by magnetic response.

    PubMed

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

    2016-05-01

    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 a much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of the 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. PMID:27113352

  20. A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds of Scots pine ( Pinus sylvestris) wood . Part I: Lipophilic compounds

    NASA Astrophysics Data System (ADS)

    Nuopponen, M.; Willför, S.; Jääskeläinen, A.-S.; Sundberg, A.; Vuorinen, T.

    2004-11-01

    The wood resin in Scots pine ( Pinus sylvestris) stemwood and branch wood were studied using UV resonance Raman (UVRR) spectroscopy. UVRR spectra of the sapwood and heartwood hexane extracts, solid wood samples and model compounds (six resin acids, three fatty acids, a fatty acid ester, sitosterol and sitosterol acetate) were collected using excitation wavelengths of 229, 244 and 257 nm. In addition, visible Raman spectra of the fatty and resin acids were recorded. Resin compositions of heartwood and sapwood hexane extracts were determined using gas chromatography. Raman signals of both conjugated and isolated double bonds of all the model compounds were resonance enhanced by UV excitation. The oleophilic structures showed strong bands in the region of 1660-1630 cm -1. Distinct structures were enhanced depending on the excitation wavelength. The UVRR spectra of the hexane extracts showed characteristic bands for resin and fatty acids. It was possible to identify certain resin acids from the spectra. UV Raman spectra collected from the solid wood samples containing wood resin showed a band at ˜1650 cm -1 due to unsaturated resin components. The Raman signals from extractives in the resin rich branch wood sample gave even more strongly enhanced signals than the aromatic lignin.

  1. A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds of Scots pine (Pinus sylvestris) wood. Part I: lipophilic compounds.

    PubMed

    Nuopponen, M; Willför, S; Jääskeläinen, A-S; Sundberg, A; Vuorinen, T

    2004-11-01

    The wood resin in Scots pine (Pinus sylvestris) stemwood and branch wood were studied using UV resonance Raman (UVRR) spectroscopy. UVRR spectra of the sapwood and heartwood hexane extracts, solid wood samples and model compounds (six resin acids, three fatty acids, a fatty acid ester, sitosterol and sitosterol acetate) were collected using excitation wavelengths of 229, 244 and 257 nm. In addition, visible Raman spectra of the fatty and resin acids were recorded. Resin compositions of heartwood and sapwood hexane extracts were determined using gas chromatography. Raman signals of both conjugated and isolated double bonds of all the model compounds were resonance enhanced by UV excitation. The oleophilic structures showed strong bands in the region of 1660-1630 cm(-1). Distinct structures were enhanced depending on the excitation wavelength. The UVRR spectra of the hexane extracts showed characteristic bands for resin and fatty acids. It was possible to identify certain resin acids from the spectra. UV Raman spectra collected from the solid wood samples containing wood resin showed a band at approximately 1650 cm(-1) due to unsaturated resin components. The Raman signals from extractives in the resin rich branch wood sample gave even more strongly enhanced signals than the aromatic lignin. PMID:15477130

  2. Electronic resonances in broadband stimulated Raman spectroscopy

    PubMed Central

    Batignani, G.; Pontecorvo, E.; Giovannetti, G.; Ferrante, C.; Fumero, G.; Scopigno, T.

    2016-01-01

    Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field, and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process. PMID:26728791

  3. Electronic resonances in broadband stimulated Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Batignani, G.; Pontecorvo, E.; Giovannetti, G.; Ferrante, C.; Fumero, G.; Scopigno, T.

    2016-01-01

    Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field, and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process.

  4. X-ray absorption study of octafluorodirhenate(III): EXAFS structures and resonance raman spectroscopy of octahalodirhenates

    SciTech Connect

    Conradson, S.D.; Sattelberger, A.P.; Woodruff, W.H.

    1988-02-17

    The structure, bonding, spectroscopy, and photophysics of transition-metal complexes containing quadruple metal-metal bonds are subjects of intense and general interest. For both historic and fundamental reasons, the octahalodirhenate(III) ions have become the paradigms of this field. Extensive spectroscopic and photophysical studies exist for the entire Re/sub 2/X/sub 8//sup 2 -/ series (X = F, Cl, Br, and I). However, while excellent structural data exist for X = Cl and Br, the structures of Re/sub 2/Fe/sub 8//sup 2 -/ and Re/sub 2/I/sub 8//sup 2 -/ have not been determined. These structures are essential for complete understanding of the bonding and physical and chemical behavior in these systems. Toward this end, the authors report structural features of Re/sub 2/F/sub 8//sup 2 -/ determined by extended X-ray absorption fine structure (EXAFS) spectroscopy. They also report X-ray absorption near-edge spectra (XANES); resonance Raman (RR) spectra have been determined previously by others and subsequently by the authors. They find that in Re/sub 2/F/sub 8//sup 2 -/ the Re-Re distance is 2.20 Angstrom and the Re-F distance is 1.95 A. Both of these distances are unexpected considering the corresponding stretching frequencies in the RR spectra.

  5. Effective time-independent studies on resonance Raman spectroscopy of trans-stilbene including the Duschinsky effect

    NASA Astrophysics Data System (ADS)

    Lin, Na; Barone, Vincenzo; Cappelli, Chiara; Zhao, Xian; Ruud, Kenneth; Santoro, Fabrizio

    2013-07-01

    We simulate the resonance Raman spectra of trans-stilbene using a recently developed time-independent method that allows computations of the full two-dimensional spectrum as a function of the incident and scattered frequencies, including both the Franck-Condon and the Herzberg-Teller contributions. The potential energy surfaces (PESs) of the ground and resonant states are described in the harmonic approximation using density functional theory PBE0/6-31+G(d,p) calculations in gas phase and in cyclohexane. The simulated spectra are in good agreement with the experimental data [J. Chem. Phys. 83, 5000 (1985)] measured at four different excitation wavelengths, and allow us to unambiguously assign the main experimental bands. We perform an extensive comparison of the performance of four different vertical or adiabatic models for the PES of the resonant state, dissecting the effects of nuclear displacements and Duschinsky mixings on the spectra.

  6. Electron paramagnetic resonance and Raman spectroscopy studies on carbon-doped MgB{sub 2} superconductor nanomaterials

    SciTech Connect

    Bateni, Ali; Somer, Mehmet E-mail: msomer@ku.edu.tr; Erdem, Emre E-mail: msomer@ku.edu.tr; Repp, Sergej; Weber, Stefan; Acar, Selcuk; Kokal, Ilkin; Häßler, Wolfgang

    2015-04-21

    Undoped and carbon-doped magnesium diboride (MgB{sub 2}) samples were synthesized using two sets of mixtures prepared from the precursors, amorphous nanoboron, and as-received amorphous carbon-doped nanoboron. The microscopic defect structures of carbon-doped MgB{sub 2} samples were systematically investigated using X-ray powder diffraction, Raman and electron paramagnetic resonance spectroscopy. Mg vacancies and C-related dangling-bond active centers could be distinguished, and sp{sup 3}-hybridized carbon radicals were detected. A strong reduction in the critical temperature T{sub c} was observed due to defects and crystal distortion. The symmetry effect of the latter is also reflected on the vibrational modes in the Raman spectra.

  7. Resonant Raman scattering from silicon nanoparticles enhanced by magnetic response

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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 a much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of the 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.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 a much stronger effect on the scattering than electric modes of the same order. We demonstrate experimentally a 140-fold enhancement of the 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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07965a

  8. Light-Driven Reconfiguration of a Xanthophyll Violaxanthin in the Photosynthetic Pigment-Protein Complex LHCII: A Resonance Raman Study.

    PubMed

    Grudzinski, Wojciech; Janik, Ewa; Bednarska, Joanna; Welc, Renata; Zubik, Monika; Sowinski, Karol; Luchowski, Rafal; Gruszecki, Wieslaw I

    2016-05-19

    Resonance Raman analysis of the photosynthetic complex LHCII, immobilized in a polyacrylamide gel, reveals that one of the protein-bound xanthophylls, assigned as violaxanthin, undergoes light-induced molecular reconfiguration. The phototransformation is selectively observed in a trimeric structure of the complex and is associated with a pronounced twisting and a trans-cis molecular configuration change of the polyene chain of the carotenoid. Among several spectral effects accompanying the reconfiguration there are ones indicating a carotenoid triplet state. Possible physiological importance of the light-induced violaxanthin reconfiguration as a mechanism associated with making the pigment available for enzymatic deepoxidation in the xanthophyll cycle is discussed. PMID:27133785

  9. Excitons and exciton-phonon interactions in 2D MoS2 , WS2 and WSe2 studied by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Pimenta, Marcos; Del Corro, Elena; Carvalho, Bruno; Malard, Leandro; Alves, Juliana; Fantini, Cristiano; Terrones, Humberto; Elias, Ana Laura; Terrones, Mauricio

    The 2D materials exhibit a very strong exciton binding energy, and the exciton-phonon coupling plays an important role in their optical properties. Resonance Raman spectroscopy (RRS) is a very useful tool to provide information about excitons and their couplings with phonons. We will present in this work a RRS study of different samples of 2D transition metal dichalcogenides (MoS2, WS2 and WSe2) with one, two and three layers (1L, 2L, 3L) and bulk samples, using more than 30 different laser excitation lines covering the visible range. We have observed that all Raman features are enhanced by resonances with excitonic transitions. From the laser energy dependence of the Raman excitation profile (REP) we obtained the energies of the excitonic states and their dependence with the number of atomic layers.. In the case of MoS2, we observed that the electron-phonon coupling is symmetry dependent, and our results provide experimental evidence of the C exciton recently predicted theoretically. The RRS results WSe2 show that the Raman modes are enhanced by the excited excitonic states and we will present the dependence of the excited states energies on the number of layers.

  10. Theoretical studies of resonance enhanced stimulated raman scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor. Progress report

    SciTech Connect

    Lawandy, N.M.

    1986-10-01

    This work focused on understanding the effects of arbitrary transverse and longitudinal relaxation rates on the susceptibilities of coherently driven three-level systems. The approximation of a single relaxation rate often made in previous work is strongly invalidated by the variation in the spontaneous emission lifetime between various atomic level pairs in systems such as cesium. It is of great importance to the problem of nonlinear infrared generation to determine the dependence of both real and imaginary susceptibility on relaxation rates. The imaginary susceptibility on the pump transition determines the absorption of pump photons and the imaginary susceptibility on the laser transition determines the spectral dependence of the gain. This is of particular importance for pure Raman emission (i.e., absorption at linecenter of the gain transition) as it determines the tunability characteristics we are aiming to predict. The real susceptibility is important when cavities are used at the signal field as this will determine the loaded resonance of the Raman oscillator. Researchers show that in some cases which result from having different relaxation rates mode splitting may result, allowing more than one frequency to have the same Raman wavelength, possibly resulting in a temporal instability.

  11. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, N. M.

    1986-01-01

    This work focused on understanding the effects of arbitrary transverse and longitudinal relaxation rates on the susceptibilities of coherently driven three-level systems. The approximation of a single relaxation rate often made in previous work is strongly invalidated by the variation in the spontaneous emission lifetime between various atomic level pairs in systems such as cesium. It is of great importance to the problem of nonlinear infrared generation to determine the dependence of both real and imaginary susceptibility on relaxation rates. The imaginary susceptibility on the pump transition determines the absorption of pump photons and the imaginary susceptibility on the laser transition determines the spectral dependence of the gain. This is of particular importance for pure Raman emission (i.e., absorption at linecenter of the gain transition) as it determines the tunability characteristics we are aiming to predict. The real susceptibility is important when cavities are used at the signal field as this will determine the loaded resonance of the Raman oscillator. Researchers show that in some cases which result from having different relaxation rates mode splitting may result, allowing more than one frequency to have the same Raman wavelength, possibly resulting in a temporal instability.

  12. Resonance Raman study of the solvent dynamics for ultrafast charge transfer transition in 4-nitro-4'-dimethylamino-azobenzene

    NASA Astrophysics Data System (ADS)

    Biswas, Nandita; Umapathy, Siva

    2003-03-01

    Contribution of solvent reorganization energy is known to be significant for ultrafast charge transfer processes, when the solvent relaxation times are slower than the rate of charge transfer. In this paper, we show that from resonance Raman intensities of a charge transfer transition in combination with Heller's time-dependent wave packet approach and Brownian oscillator model, one can have a reasonable estimate for the different types of solvent (inertial as well as diffusive) and vibrational reorganization energies. Resonance Raman spectra have been recorded for 4-nitro-4'-dimethylamino-azobenzene (DA) that undergoes photoinduced charge transfer transition, in acetonitrile and benzonitrile. In the two solvents, the total solvent reorganization energy is partitioned into its inertial and diffusive components from the available information on their relaxation time scales. Thus, partitioning of the solvent reorganization energy reveals the importance of the extent of contribution of the two components to the charge transfer rates. The short time dynamics of DA in the two solvents is then examined from a priori knowledge of the ground state normal modes in order to convert the wave packet motion in dimensionless displacements to internal coordinates. The dynamics in DA infers that within 20 fs after photoexcitation from the ground to the charge transfer state, the excited state evolution occurs along N-O, N=N, C-N, and C-C stretching vibrations.

  13. Theoretical studies of resonance enhance stimulated raman scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor. Semiannual report

    SciTech Connect

    Lawandy, N.M.

    1986-01-01

    It is well known that the presence of a real atomic level which is nearly resonant with the pump field can greatly enhance the Raman emission cross section. In order to accurately calculate the Raman gain in systems where resonance enhancement plays a dominant role, expressions for the pump and signal susceptibilities must be derived. These expressions should be valid for arbitrary field strengths in order to allow for pump and signal saturation. In addition, the theory should allow for arbitrary longitudinal and transverse relaxation rates. This latter point is extremely vital for three level atomic systems such as the alkali earth metals since they do not have population reservoirs and can have widely varying spontaneous lifetimes on the three pertinent transitions. Moreover, the dephasing rates are strong functions of electron states and are therefore also different for the three coupled pairs of levels. These considerations are not as important when molecular systems are concerned since the large reservoir of rotational states serve to produce essentially equal longitudinal recovery rates for the population of the three levels. The three level system with three arbitrary longitudinal and transverse relaxation rates was solved. There is no need for setting either pair of rates equal and the expressions are valid for arbitrarily strong fields.

  14. Theoretical studies of Resonance Enhance Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, N. M.

    1986-01-01

    It is well known that the presence of a real atomic level which is nearly resonant with the pump field can greatly enhance the Raman emission cross section. In order to accurately calculate the Raman gain in systems where resonance enhancement plays a dominant role, expressions for the pump and signal susceptibilities must be derived. These expressions should be valid for arbitrary field strengths in order to allow for pump and signal saturation. In addition, the theory should allow for arbitrary longitudinal and transverse relaxation rates. This latter point is extremely vital for three level atomic systems such as the alkali earth metals since they do not have population reservoirs and can have widely varying spontaneous lifetimes on the three pertinent transitions. Moreover, the dephasing rates are strong functions of electron states and are therefore also different for the three coupled pairs of levels. These considerations are not as important when molecular systems are concerned since the large reservoir of rotational states serve to produce essentially equal longitudinal recovery rates for the population of the three levels. The three level system with three arbitrary longitudinal and transverse relaxation rates was solved. There is no need for setting either pair of rates equal and the expressions are valid for arbitrarily strong fields.

  15. Raman-assisted Rabi resonances in two-mode cavity QED

    SciTech Connect

    Gruenwald, P.; Singh, S. K.; Vogel, W.

    2011-06-15

    The dynamics of a vibronic system in a lossy two-mode cavity is studied, with the first mode being resonant to the electronic transition and the second one being nearly resonant due to Raman transitions. We derive analytical solutions for the dynamics of this system. For a properly chosen detuning of the second mode from the exact Raman resonance, we obtain conditions that are closely related to the phenomenon of Rabi resonance as it is well known in laser physics. Such resonances can be observed in the spontaneous emission spectra, where the spectrum of the second mode in the case of weak Raman coupling is enhanced substantially.

  16. Resonance electronic Raman scattering in rare earth crystals

    SciTech Connect

    Williams, G.M.

    1988-11-10

    The intensities of Raman scattering transitions between electronic energy levels of trivalent rare earth ions doped into transparent crystals were measured and compared to theory. A particle emphasis was placed on the examination of the effect of intermediate state resonances on the Raman scattering intensities. Two specific systems were studied: Ce/sup 3 +/(4f/sup 1/) in single crystals of LuPO/sub 4/ and Er/sup 3 +/(4f/sup 11/) in single crystals of ErPO/sub 4/. 134 refs., 92 figs., 33 tabs.

  17. Wavelength dependent resonance Raman band intensity of broadband stimulated Raman spectroscopy of malachite green in ethanol

    NASA Astrophysics Data System (ADS)

    Cen, Qiongyan; He, Yuhan; Xu, Mei; Wang, Jingjing; Wang, Zhaohui

    2015-03-01

    Resonance broadband stimulated Raman spectroscopy of malachite green in ethanol has been performed. With a tuning picosecond visible laser source and a broadband Raman probe, the Raman gain and loss spectra have been measured simultaneously. By scanning the Raman pump across the first absorption band of the molecule, we found that the resonant Raman bands could be only seen when the pump laser tuned in the range of the red edge of the S1←S0 transition. Dispersive lineshapes of resonant Raman bands have been observed in the Raman loss spectra, while the line shape is normal (same as spontaneous Raman) in the Raman gain spectra. Although, the resonant bands in the loss spectrum are usually stronger than that in the gain spectrum, the band intensities of both loss and gain linearly increase with the pump energy. The relative magnitude of each corresponding resonant band in the Raman loss and gain varies with the pump wavelength. Mode specified Raman excitation profiles have been obtained through broadband stimulated Raman measurement.

  18. Characterization and identification of contraband using UV resonant Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Lacey, Richard J.; Hayward, Ian P.; Sands, H. S.; Batchelder, David N.

    1997-02-01

    A range of explosives and narcotics have been examined using Raman spectroscopy with 244 nm excitation. This wavelength of excitation eliminates the fluorescence problems associated with excitation at visible wavelengths. Comparison with spectra obtained using visible excitation reveals that resonance Raman scattering is occurring. This results in simplified spectra, and enhanced Raman scattering efficiencies.

  19. Preventing Raman Lasing in High-Q WGM Resonators

    NASA Technical Reports Server (NTRS)

    Savchenkov, Anatoliy; Matsko, Andrey; Strekalov, Dmitry; Maleki, Lute

    2007-01-01

    A generic design has been conceived to suppress the Raman effect in whispering- gallery-mode (WGM) optical resonators that have high values of the resonance quality factor (Q). Although it is possible to exploit the Raman effect (even striving to maximize the Raman gain to obtain Raman lasing), the present innovation is intended to satisfy a need that arises in applications in which the Raman effect inhibits the realization of the full potential of WGM resonators as frequency-selection components. Heretofore, in such applications, it has been necessary to operate high-Q WGM resonators at unattractively low power levels to prevent Raman lasing. (The Raman-lasing thresholds of WGM optical resonators are very low and are approximately proportional to Q(sup -2)). Heretofore, two ways of preventing Raman lasting at high power levels have been known, but both entail significant disadvantages: A resonator can be designed so that the optical field is spread over a relatively large mode volume to bring the power density below the threshold. For any given combination of Q and power level, there is certain mode volume wherein Raman lasing does not start. Unfortunately, a resonator that has a large mode volume also has a high spectral density, which is undesirable in a typical photonic application. A resonator can be cooled to the temperature of liquid helium, where the Raman spectrum is narrower and, therefore, the Raman gain is lower. However, liquid-helium cooling is inconvenient. The present design overcomes these disadvantages, making it possible to operate a low-spectral-density (even a single-mode) WGM resonator at a relatively high power level at room temperature, without risk of Raman lasing.

  20. Resonance Raman spectroscopy utilizing tunable deep ultraviolet excitation for materials characterization

    NASA Astrophysics Data System (ADS)

    Chadwick, Christopher Todd

    Resonance Raman spectroscopy offers some key benefits over other spectroscopy methods. In one facet, resonance Raman provides a level of specificity not present in non-resonant Raman scattering. In another facet, resonance Raman can provide increased scattering cross-sections that rival those associated with the intensities of species fluorescence. These features provide mechanisms for improved trace species detection in current Raman remote sensing applications; as well as signal level enhancement in tiny volume regimes, such as those typical in near-field optical microscopy. This dissertation presents three main thrusts that are not well documented in the previous resonance Raman studies. We demonstrate fine resolution (approx 0:1nm) resonance tuning of the excitation wavelength corresponding to sharp absorption bands in liquid benzene and liquid toluene. The Raman spectra for these materials show an appreciable increase in scattering intensity of fundamental vibrational modes and show significant enhancements in scattering intensities for overtone and combination vibrational modes not observed with non-resonant excitation. Resonantly excited fundamental modes are observed to be enhanced by 3 to 5 orders of magnitude over non-resonant excitation; and several resonantly excited overtone modes are observed for both liquid benzene and liquid toluene. We have observed, that for liquid benzene and liquid toluene, the maximum Raman scattering intensity is realized when the excitation wavelength corresponds to that of the vapor phase absorption maximum, not the liquid phase absorption maximum as expected. We present a simple model of the time-dependent energy accumulation in the scattering volume that suggests that the scattering medium is a highly disorganized fluid. The observed Raman scattering intensity originates from this metastable fluid observed during the liquid-vapor phase transition. Using different concentration solutions of liquid benzene in heptane, we

  1. A combination of dynamic light scattering and polarized resonance Raman scattering applied in the study of Arenicola Marina extracellular hemoglobin

    NASA Astrophysics Data System (ADS)

    Jernshøj, K. D.; Hassing, S.; Olsen, L. F.

    2013-08-01

    Arenicola Marina extracellular hemoglobin (Hbl Hb) is considered to be a promising candidate as a blood substitute. To entangle some of the properties of extracellular giant hexagonal bilayer hemoglobin (Hbl Hb) of Arenicola Marina, we combined polarized resonance Raman scattering (532 nm excitation) with dynamic light scattering (DLS) (632.8 nm). An analysis of the depolarization ratio of selected a2g skeletal modes of the heme in native Hbl Hb and porcine Hb, shows that the distortion of the heme group away from its ideal fourfold symmetry is much smaller for heme groups bound in the Hbl Hb than for heme groups bound in porcine Hb. Using DLS, the average hydrodynamic diameter (⟨dh⟩) of Hbl Hb was measured at pH = 5, 7, 8, 9, and 10. At pH = 5 to 7, the Hbl Hb was found in its native form with ⟨dh⟩ equal to 24.2 nm, while at pH = 8 and 9, a dissociation process starts to take place resulting in ⟨dh⟩ = 9 nm. At pH = 10, only large aggregates of fragmented Hbl Hb with ⟨dh⟩ larger than 1000 nm was detected, however, a comparison of the DLS results with the polarized resonance Raman scattering (RRS) revealed that the coupling between the fragments did not involve direct interaction between the heme groups, but also that the local heme environment seems to be comparable in the aggregates and in the native Hbl Hb. By comparing the unpolarized RRS results obtained for erythrocytes (RBC) with those for Hbl Hb, led us to the important conclusion that Hbl Hb is much easier photolyzed than porcine RBC.

  2. UV-resonance Raman spectroscopy of amino acids

    NASA Astrophysics Data System (ADS)

    Höhl, Martin; Meinhardt-Wollweber, Merve; Schmitt, Heike; Lenarz, Thomas; Morgner, Uwe

    2016-03-01

    Resonant enhancement of Raman signals is a useful method to increase sensitivity in samples with low concentration such as biological tissue. The investigation of resonance profiles shows the optimal excitation wavelength and yields valuable information about the molecules themselves. However careful characterization and calibration of all experimental parameters affecting quantum yield is required in order to achieve comparability of the single spectra recorded. We present an experimental technique for measuring the resonance profiles of different amino acids. The absorption lines of these molecules are located in the ultraviolet (UV) wavelength range. One limitation for broadband measurement of resonance profiles is the limited availability of Raman filters in certain regions of the UV for blocking the Rayleigh scattered light. Here, a wavelength range from 244.8 nm to 266.0 nm was chosen. The profiles reveal the optimal wavelength for recording the Raman spectra of amino acids in aqueous solutions in this range. This study provides the basis for measurements on more complex molecules such as proteins in the human perilymph. The composition of this liquid in the inner ear is essential for hearing and cannot be analyzed non-invasively so far. The long term aim is to implement this technique as a fiber based endoscope for non-invasive measurements during surgeries (e. g. cochlear implants) making it available as a diagnostic tool for physicians. This project is embedded in the interdisciplinary cluster of excellence "Hearing for all" (H4A).

  3. Quantum lattice fluctuations in a 1-dimensional charge-density-wave material: Luminescence and resonance Raman studies of an MX solid

    SciTech Connect

    Long, F.H.; Love, S.P.; Swanson, B.I.

    1993-01-01

    Luminescence spectra, both emission and excitation, and the excitation dependence of the resonance Raman (RR) spectra were measured for a 1-dimensional charge-density-wave solid, [Pt(L)[sub 2]Cl[sub 2

  4. Resonance Raman based skin carotenoid measurements in newborns and infants

    PubMed Central

    Ermakov, Igor V.; Ermakova, Maia R.; Bernstein, Paul S.; Chan, Gary M.; Gellermann, Werner

    2014-01-01

    We describe Resonance Raman based skin carotenoid measurements in newborns and infants. Skin- and serum carotenoid levels correlate with high statistical significance in healthy newborns and infants, and with reduced accuracy also in prematurely born infants, who in general feature very low carotenoid levels and thin transparent skin giving rise to large background absorption effects. Skin carotenoid levels can be easily compared among subjects and/or tracked in longitudinal studies with the highly molecule-specific Raman method. It therefore holds promise as a rapid, non-invasive, carotenoid antioxidant assessment method for newborns and infants in the field of pediatrics. Photograph of an infant’s skin carotenoid measurement via Resonance Raman spectroscopy. The instrument’s fiber-coupled light delivery and collection module is held against the foot, exposing the heel skin to weak 488 nm laser light for 20 seconds. From spectral analysis of the Raman scattered light intensities, which occur in the green wavelength region, the carotenoid levels in the heel skin are obtained in a rapid, non-invasive, and painless fashion. PMID:23193015

  5. Resonant Raman scattering background in XRF spectra of binary samples

    NASA Astrophysics Data System (ADS)

    Sánchez, Héctor Jorge; Leani, Juan José

    2015-02-01

    In x-ray fluorescence analysis, spectra present singular characteristics produced by the different scattering processes. When atoms are irradiated with incident energy lower and close to an absorption edge, scattering peaks appear due to an inelastic process known as resonant Raman scattering. In this work we present theoretical calculations of the resonant Raman scattering contributions to the background of x-ray fluorescence spectra of binary samples of current technological or biological interest. On one hand, a binary alloy of Fe with traces of Mn (Mn: 0.01%, Fe: 99.99%) was studied because of its importance in the stainless steels industries. On the second hand a pure sample of Ti with V traces (Ti: 99%, V: 1%) was analyzed due to the current relevance in medical applications. In order to perform the calculations the Shiraiwa and Fujino's model was used to calculate characteristic intensities and scattering interactions. This model makes certain assumptions and approximations to achieve the calculations, especially in the case of the geometrical conditions and the incident and take-off beams. For the binary sample studied in this work and the considered experimental conditions, the calculations show that the resonant Raman scattering background is significant under the fluorescent peak, affects the symmetry of the peaks and, depending on the concentrations, overcomes the enhancements contributions (secondary fluorescence).

  6. Resonance Raman excitation profiles of lycopene

    NASA Astrophysics Data System (ADS)

    Hoskins, L. C.

    1981-01-01

    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.

  7. A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine ( Pinus sylvestris) wood . Part II. Hydrophilic compounds

    NASA Astrophysics Data System (ADS)

    Nuopponen, M.; Willför, S.; Jääskeläinen, A.-S.; Vuorinen, T.

    2004-11-01

    Hydrophilic extracts of Scots pine ( Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm -1. Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm -1. The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm -1. The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm -1) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.

  8. A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine (Pinus sylvestris) wood. Part II. Hydrophilic compounds.

    PubMed

    Nuopponen, M; Willför, S; Jääskeläinen, A-S; Vuorinen, T

    2004-11-01

    Hydrophilic extracts of Scots pine (Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm(-1). Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm(-1). The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm(-1). The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm(-1)) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin. PMID:15477131

  9. Double resonance Raman modes in monolayer and few-layer MoTe2

    NASA Astrophysics Data System (ADS)

    Guo, Huaihong; Yang, Teng; Yamamoto, Mahito; Zhou, Lin; Ishikawa, Ryo; Ueno, Keiji; Tsukagoshi, Kazuhito; Zhang, Zhidong; Dresselhaus, Mildred S.; Saito, Riichiro

    2015-05-01

    We study the second-order Raman process of mono- and few-layer MoTe2, by combining ab initio density functional perturbation calculations with experimental Raman spectroscopy using 532, 633, and 785 nm excitation lasers. The calculated electronic band structure and the density of states show that the resonance Raman process occurs at the M point in the Brillouin zone, where a strong optical absorption occurs due to a logarithmic Van Hove singularity of the electronic density of states. The double resonance Raman process with intervalley electron-phonon coupling connects two of the three inequivalent M points in the Brillouin zone, giving rise to second-order Raman peaks due to the M -point phonons. The calculated vibrational frequencies of the second-order Raman spectra agree with the observed laser-energy-dependent Raman shifts in the experiment.

  10. Time-resolved resonance Raman study of intermediates generated after photodissociation of wild-type and mutant co-myoglobins

    NASA Astrophysics Data System (ADS)

    Nakashima, Satoru; Kitagawa, Teizo; Olson, John S.

    1998-03-01

    Time-resolved resonance Raman (TR 3) spectroscopy was applied to elucidate transient structures of myoglobin (Mb) involved in its ligand binding. Pump/probe Raman measurements of the Fe-CO stretching bands ( νFe-CO) were carried out for various delay times (Δ t=-20 ns-1 ms with a time resolution of 7 ns) after laser photolysis of native and mutant COMb complexes. His64(E7) and Leu29(B10) were replaced with an aliphatic and aromatic residues. The static νFe-CO frequencies of the mutants depended strongly on the environments around the bound CO and correlated more with the hydropathy indices of the replaced residues than with their sizes. The kinetics of bimolecular CO recombination correlate with the static νFe-CO frequencies; a lower frequency generally results in faster rebinding. Despite these differences, all the proteins exhibited the shift of a porphyrin band from 370 to 379 cm -1 upon binding of CO and also a transient Raman band at ˜497 cm -1, which occurred before recovery of the original νFe-CO band. The latter frequency was unaffected by isotopically labeling the ligand with 13C 18O. The 497 cm -1 band was absent in the spectrum at Δ t=0 ns for all of the myoglobins examined except for the His64→Leu (H64L) mutant which shows the band immediately after photolysis. The 370 and 497 cm -1 bands are associated with the C β-C c-C d in-plane bending of the propionic side chains and the out-of-plane γ12 containing pyrrole swiveling and propionic bending motions, respectively. The 497 cm -1 transient band appears to reflect a deoxyheme intermediate in which the hydrogen bonding lattice between Arg45(CD3), His64(E7), the heme-6-propionate, and an external distal pocket water molecule is temporarily disrupted. This disruption allows larger movements of the propionate side chain, explaining intensity enhancement of the 497 cm -1 band. Recovery of the hydrogen bonding lattice dampens the movements of the propionate C β-C c-C d bond system and finally fixes

  11. UV resonance Raman sensing of pharmaceutical drugs in hollow fibers

    NASA Astrophysics Data System (ADS)

    Yan, D.; Popp, J.; Frosch, T.

    2014-05-01

    We report about the experimental combination of UV resonance Raman sensing (UV-RRS) and fiber enhanced Raman sensing (FERS) on pharmaceuticals. The results show that the chemical sensitivity is highly improved and at the same time the sample volume is reduced compared to conventional measurements. A hundreds-fold improvement of the limit of detection (LOD) has been achieved with the combination of resonance Raman enhancement and fiber enhancement. The enhanced Raman signal has a reliable linear relationship with the concentration of the analyte, and therefore shows great potential for quantitative analysis of pharmaceuticals.

  12. Far-infrared and resonance Raman spectroscopy and isotopic substitution studies of halogen-bridged platinum chain solids

    SciTech Connect

    Love, S.P.; Worl, L.A.; Donohoe, R.J.; Huckett, S.C.; Johnson, S.R.; Swanson, B.I.

    1992-12-31

    Here we our most recent results on the vibrational spectroscopy of the MX chain solids [Pt(en){sub 2}][Pt(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (X=Cl, Br or I, and en = C{sub 2}H{sub 8}N{sub 2}), referred to as PtX. Isotopic substitutions are used to clarify the nature of various vibrational modes. For Raman spectroscopy, fundamental phonon frequencies are determined, when possible, by excitation far below the band edge using a Ti:Sapphire laser, thus avoiding defect production, while photo-induced defects are studied specifically after intentional production.

  13. Heme Reactivity is Uncoupled from Quaternary Structure in Gel-encapsulated Hemoglobin: A Resonance Raman Spectroscopic Study

    PubMed Central

    Jones, Eric M.; Balakrishnan, Gurusamy; Spiro, Thomas G.

    2012-01-01

    Encapsulation of hemoglobin (Hb) in silica gel preserves structure and function, but greatly slows protein motion, thereby providing access to intermediates along the allosteric pathway that are inaccessible in solution. Resonance Raman (RR) spectroscopy with visible and ultraviolet laser excitation provides probes of heme reactivity and of key tertiary and quaternary contacts. These probes were monitored in gels after deoxygenation of oxyHb and after CO binding to deoxyHb, which intiate conformational change in the R-T and T-R directions, respectively. The spectra establish that quaternary structure change in the gel takes a week or more, but that the evolution of heme reactivity, as monitored by the Fe-histidine stretching vibration, νFeHis, is completed within two days, and is therefore uncoupled from the quaternary structure. Within each quaternary structure, the evolving νFeHis frequencies span the full range of values between those previously associated with the high- and low-affinity end states, R and T. This result supports the tertiary two-state (TTS) model, in which the Hb subunits can adopt high- and low-affinity tertiary structures, r and t, within each quaternary state. The spectra also reveal different tertiary pathways, involving the breaking and re-formation of E and F inter-helical contacts in the R-T direction but not the T-R direction. In the latter, tertiary motions are restricted by the T quaternary contacts. PMID:22263778

  14. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelength in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, Nabil M.

    1987-01-01

    The third phase of research will focus on the propagation and energy extraction of the pump and SERS beams in a variety of configurations including oscillator structures. In order to address these questions a numerical code capable of allowing for saturation and full transverse beam evolution is required. The method proposed is based on a discretized propagation energy extraction model which uses a Kirchoff integral propagator coupled to the three level Raman model already developed. The model will have the resolution required by diffraction limits and will use the previous density matrix results in the adiabatic following limit. Owing to its large computational requirements, such a code must be implemented on a vector array processor. One code on the Cyber is being tested by using previously understood two-level laser models as guidelines for interpreting the results. Two tests were implemented: the evolution of modes in a passive resonator and the evolution of a stable state of the adiabatically eliminated laser equations. These results show mode shapes and diffraction losses for the first case and relaxation oscillations for the second one. Finally, in order to clarify the computing methodology used to exploit the speed of the Cyber's computational speed, the time it takes to perform both of the computations previously mentioned to run on the Cyber and VAX 730 must be measured. Also included is a short description of the current laser model (CAVITY.FOR) and a flow chart of the test computations.

  15. Resonance Raman Spectroscopy of Armchair Single-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Haroz, Erik; Rice, William; Lu, Benjamin; Hauge, Robert; Magana, Donny; Doorn, Stephen; Nikolaev, Pasha; Arepalli, Sivaram; Kono, Junichiro

    2009-03-01

    We performed resonance Raman spectroscopy studies of metallic single-walled carbon nanotubes (SWNTs), including armchair SWNTs from (6,6) through (10,10). The measurements were carried out with excitation of 440-850 nm on aqueous ensemble samples of SWNTs enriched in metallic species. From this, we generated Raman excitation profiles (REPs) of the radial breathing mode and compare the REPs of armchairs and other metallic species. Additionally, we measured REPs of the G-band mode and observed how the Breit-Wigner-Fano line shape of the G^- peak evolves in peak position, width and intensity relative to the G^+ peak as different metallic nanotubes are excited. By combining these studies with absorption and photoluminescence excitation spectroscopy studies, we present a comprehensive examination of the optical signatures of metallic SWNTs.

  16. Radiolytic oxidation of 1,2,4-benzenetriol. An application of time-resolved resonance Raman spectroscopy to kinetic studies of reaction intermediates

    SciTech Connect

    Qin, L.; Tripathi, G.N.R.; Schuler, R.H.

    1987-03-26

    In acidic solution, 1,2,4-benzenetriol is rapidly oxidized by OH or N/sub 3/ to form a mixture of neutral 2,4- and 3,4-dihydroxyphenoxyl radicals. At higher pH these radicals deprotonate (pK/sub a/(1) = 4.75) to form the 2-hydroxy-p-benzosemiquinone radical anion which exhibits a prominent resonance Raman band at 1625 cm/sup -1/ attributable to the Wilson 8a ring stretching mode. In basic solutions this radical subsequently reacts with OH/sup -/ to form the radical dianion (pK/sub a/(2) = 8.85) in which the 8a band is shifted to an appreciably lower frequency (1587 cm/sup -1/). While the absorption spectra of these latter radicals are very similar and do not allow ready examination of their interconversion by absorption spectrophotometry, the difference between these 8a frequencies is sufficiently great that the Raman method can be used to examine the acid-base equilibrium between the two forms of the radical and to follow the deprotonation kinetics. It is shown that even at high pH the radical monoanion is initially formed on oxidation by N/sub 3/ and that deprotonation subsequently occurs by its reaction with base with a rate constant of (9.6 +/- 1.5) x 10/sup 9/ M/sup -1/ d/sup -1/. These studies illustrate very well the application of time-resolved resonance Raman spectroscopy as a complement to kinetic spectrophotometry in sorting out the details of secondary processes in pulse radiolysis studies.

  17. UV Resonant Raman Spectrometer with Multi-Line Laser Excitation

    NASA Technical Reports Server (NTRS)

    Lambert, James L.; Kohel, James M.; Kirby, James P.; Morookian, John Michael; Pelletier, Michael J.

    2013-01-01

    A Raman spectrometer employs two or more UV (ultraviolet) laser wavel engths to generate UV resonant Raman (UVRR) spectra in organic sampl es. Resonant Raman scattering results when the laser excitation is n ear an electronic transition of a molecule, and the enhancement of R aman signals can be several orders of magnitude. In addition, the Ra man cross-section is inversely proportional to the fourth power of t he wavelength, so the UV Raman emission is increased by another fact or of 16, or greater, over visible Raman emissions. The Raman-scatter ed light is collected using a high-resolution broadband spectrograph . Further suppression of the Rayleigh-scattered laser light is provi ded by custom UV notch filters.

  18. Resonance Raman Optical Activity of Single Walled Chiral Carbon Nanotubes.

    PubMed

    Nagy, Péter R; Koltai, János; Surján, Péter R; Kürti, Jenő; Szabados, Ágnes

    2016-07-21

    Resonance (vibrational) Raman Optical Activity (ROA) spectra of six chiral single-walled carbon nanotubes (SWCNTs) are studied by theoretical means. Calculations are performed imposing line group symmetry. Polarizability tensors, computed at the π-electron level, are differentiated with respect to DFT normal modes to generate spectral intensities. This computational protocol yields a ROA spectrum in good agreement with the only experiment on SWCNT, available at present. In addition to the conventional periodic electric dipole operator we introduce magnetic dipole and electric quadrupole operators, suitable for conventional k-space calculations. Consequences of the complex nature of the wave function on the scattering cross section are discussed in detail. The resonance phenomenon is accounted for by the short time approximation. Involvement of fundamental vibrations in the region of the intermediate frequency modes is found to be more notable in ROA than in Raman spectra. Calculations indicate exceptionally strong resonance enhancement of SWCNT ROA signals. Resonance ROA profile of the (6,5) tube shows an interesting sign change that may be exploited experimentally for SWCNT identification. PMID:27315548

  19. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency-doubled Alexandrite laser wavelength in cesium vapor

    NASA Technical Reports Server (NTRS)

    Lawandy, Nabil M.

    1987-01-01

    The solutions for the imaginary susceptibility of the Raman field transition with arbitrary relaxation rates and field strengths are examined for three different sets of relaxation rates. These rates correspond to: (1) Far Infrared (FIR) Raman lasers in the diabatic collision regime without consideration of coupled population decay in a closed system, (2) Raman FIR lasers in the diabatic collision regime with coupled population conserving decay, and (3) IR Raman gain in cesium vapor. The model is further expanded to include Doppler broadening and used to predict the peak gain as a function of detuning for a frequency doubled Alexandrite laser-pumped cesium vapor gain cell.

  20. Studies on adsorption of mono- and multi-chromophoric hemicyanine dyes on silver nanoparticles by surface-enhanced resonance raman and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Biswas, Nandita; Thomas, Susy; Kapoor, Sudhir; Mishra, Amaresh; Wategaonkar, Sanjay; Mukherjee, Tulsi

    2008-11-01

    Structural and vibrational properties of mono- and multichromophoric hemicyanine (HC) dyes in solution and adsorbed on silver-coated films have been investigated using optical absorption and resonance Raman scattering techniques, with interpretations aided by theoretical calculations. This is the first report on the Raman spectroscopic studies of multichromophoric HC derivatives. The structure of the monomer, N-propyl-4-(p-N,N-dimethylamino styryl)pyridinium bromide (HC3), and its charged and neutral silver complexes (HC3-Ag) in the ground electronic (S0) state were optimized using density functional calculations with the B3LYP method using the 6-31G* and LANL2DZ basis sets. The ground state structure of N-hexyl-4-(p-N,N-dimethylamino styryl)pyridinium bromide (HC6) and multichromophoric HC dyes were computed using the HF /6-31G* method. The negligible shift or broadening observed in the electronic absorption and resonance Raman spectra in solution with increasing size of the HC chromophore suggests that the excitations are localized within individual monomer units in bis and tetra chromophores. However, in the tris chromophore, considerable redshift and broadening were observed, indicating a significant electronic interaction between the nonbonded electrons of the N atom and the aromatic π-system that is supported by the calculated excitation energies using the time-dependent density functional theory method. The effect of HC dye concentration on the electronic absorption spectra of the silver-coated film showed significant broadening, which was attributed to the formation of H- and J-aggregates in addition to the formation of a metal-molecule complex. A considerable redshift along various vibrations observed in the surface-enhanced resonance Raman scattering (SERRS) spectra of the HC derivatives indicates that adsorption on the silver surface leads to a considerable interaction of the electron rich moiety of HC derivatives with the silver surface. The

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

    SciTech Connect

    Ouyang, Bing Xue, Jia-Dan Zheng, Xuming E-mail: zxm@zstu.edu.cn; Fang, Wei-Hai E-mail: fangwh@dnu.edu.cn

    2014-05-21

    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.

  2. Sensitive algorithm for multiple-excitation-wavelength resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Yellampalle, Balakishore; Wu, Hai-Shan; McCormick, William; Sluch, Mikhail; Martin, Robert; Ice, Robert; Lemoff, Brian E.

    2014-05-01

    Raman spectroscopy is a widely used spectroscopic technique with a number of applications. During the past few years, we explored the use of simultaneous multiple-excitation-wavelengths (MEW) in resonance Raman spectroscopy. This approach takes advantage of Raman band intensity variations across the Resonance Raman spectra obtained from two or more excitation wavelengths. Amplitude variations occur between corresponding Raman bands in Resonance Raman spectra due to complex interplay of resonant enhancement, self-absorption and laser penetration depth. We have developed a very sensitive algorithm to estimate concentration of an analyte from spectra obtained using the MEW technique. The algorithm uses correlations and least-square minimization approach to calculate an estimate for the concentration. For two or more excitation wavelengths, measured spectra were stacked in a two dimensional matrix. In a simple realization of the algorithm, we approximated peaks in the ideal library spectra as triangles. In this work, we present the performance of the algorithm with measurements obtained from a dual-excitation-wavelength Resonance Raman sensor. The novel sensor, developed at WVHTCF, detects explosives from a standoff distance. The algorithm was able to detect explosives with very high sensitivity even at signal-to-noise ratios as low as ~1.6. Receiver operating characteristics calculated using the algorithm showed a clear benefit in using the dual-excitation-wavelength technique over single-excitation-wavelength techniques. Variants of the algorithm that add more weight to amplitude variation information showed improved specificity to closely resembling spectra.

  3. Brain metastasis detection by resonant Raman optical biopsy method

    NASA Astrophysics Data System (ADS)

    Zhou, Yan; Liu, Cheng-hui; Cheng, Gangge; Zhou, Lixin; Zhang, Chunyuan; Pu, Yang; Li, Zhongwu; Liu, Yulong; Li, Qingbo; Wang, Wei; Alfano, Robert R.

    2014-03-01

    Resonant Raman (RR) spectroscopy provides an effective way to enhance Raman signal from particular bonds associated with key molecules due to changes on a molecular level. In this study, RR is used for detection of human brain metastases of five kinds of primary organs of lung, breast, kidney, rectal and orbital in ex-vivo. The RR spectra of brain metastases cancerous tissues were measured and compared with those of normal brain tissues and the corresponding primary cancer tissues. The differences of five types of brain metastases tissues in key bio-components of carotene, tryptophan, lactate, alanine and methyl/methylene group were investigated. The SVM-KNN classifier was used to categorize a set of RR spectra data of brain metastasis of lung cancerous tissues from normal brain tissue, yielding diagnostic sensitivity and specificity at 100% and 75%, respectively. The RR spectroscopy may provide new moleculebased optical probe tools for diagnosis and classification of brain metastatic of cancers.

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

    NASA Astrophysics Data System (ADS)

    Hoskins, L. C.

    1992-10-01

    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.

  5. Remote sensing of the atmosphere by resonance Raman LIDAR

    SciTech Connect

    Sedlacek, A.J.; Harder, D.; Leung, K.P.; Zuhoski, P.B. Jr.; Burr, D.; Chen, C.L.

    1994-12-01

    When in resonance, Raman scattering exhibits strong enhancement ranging from four to six orders of magnitude. This physical phenomenon has been applied to remote sensing of the Earth`s atmosphere. With a 16 inch Cassegrain telescope and spectrometer/ CCD-detector system, 70-150 ppm-m of SO{sub 2} in the atmosphere has been detected at a distance of 0.5 kilometer. This system can be used to detect/monitor chemical effluence in the atmosphere by their unique Raman fingerprints. Experimental result together with detailed resonance Raman and atmospheric laser propagation effects will be discussed.

  6. Resonant impulsive-stimulated Raman scattering on malachite green

    SciTech Connect

    Chesnoy, J.; Mokhtari, A.

    1988-10-01

    We have studied in the femtosecond regime the transient dynamics of dichroism (anisotropic absorption), birefringence, and frequency shift induced by an intense femtosecond pump beam in the dye malachite green in solution. Vibrational quantum beats were observed superimposed on the saturated absorption and dispersion signals and quantitatively explained in terms of impulsive-stimulated Raman scattering close to an electronic resonance. The selectivity for observation of the vibrations in the two electronic states is described for the different experimental schemes. We discuss the access to vibrational and electronic dynamics in both ground and excited electronic states and compare the possibilities to those of previous techniques.

  7. Deep ultraviolet Raman spectroscopy: A resonance-absorption trade-off illustrated by diluted liquid benzene

    NASA Astrophysics Data System (ADS)

    Chadwick, C. T.; Willitsford, A. H.; Philbrick, C. R.; Hallen, H. D.

    2015-12-01

    The magnitude of resonance Raman intensity, in terms of the real signal level measured on-resonance compared to the signal level measured off-resonance for the same sample, is investigated using a tunable laser source. Resonance Raman enhancements, occurring as the excitation energy is tuned through ultraviolet absorption lines, are used to examine the 1332 cm-1 vibrational mode of diamond and the 992 cm-1 ring-breathing mode of benzene. Competition between the wavelength dependent optical absorption and the magnitude of the resonance enhancement is studied using measured signal levels as a function of wavelength. Two system applications are identified where the resonance Raman significantly increases the real signal levels despite the presence of strong absorption: characterization of trace species in laser remote sensing and spectroscopy of the few molecules in the tiny working volumes of near-field optical microscopy.

  8. Application of resonance Raman LIDAR for chemical species identification

    SciTech Connect

    Chen, C.L.; Heglund, D.L.; Ray, M.D.; Harder, D.; Dobert, R.; Leung, K.P.; Wu, M.; Sedlacek, A.

    1997-07-01

    BNL has been developing a remote sensing technique for the detection of atmospheric pollutants based on the phenomenon of resonance Raman LIDAR that has also incorporated a number of new techniques/technologies designed to extend it`s performance envelope. When the excitation frequency approaches an allowed electronic transition of the molecule, an enormous enhancement of the inelastic scattering cross-section can occur, often up to 2 to 4 orders-of-magnitude, and is referred to as resonance Raman (RR), since the excitation frequency is in resonance with an allowed electronic transition. Exploitation of this enhancement along with new techniques such as pattern recognition algorithms to take advantage of the spectral fingerprint and a new laser frequency modulation technique designed to suppress broadband fluorescence, referred to as Frequency modulated Excitation Raman Spectroscopy (FreMERS) and recent developments in liquid edge filter technology, for suppression of the elastic channel, all help increase the overall performance of Raman LIDAR.

  9. Cold atom Raman spectrography using velocity-selective resonances.

    PubMed

    Fatemi, Fredrik K; Terraciano, Matthew L; Bashkansky, Mark; Dutton, Zachary

    2009-07-20

    We have studied velocity-selective resonances in the presence of a uniform magnetic field and shown how they can be used for rapid, single-shot assessment of the ground state magnetic sublevel spectrum in a cold atomic vapor. Cold atoms are released from a magneto-optical trap in the presence of a small bias magnetic field ( approximately 300 mG) and exposed to a laser field comprised of two phase-locked counterpropagating beams connecting the two ground state hyperfine manifolds. An image of the expanded cloud shows the velocity-selected resonances as distinct features, each corresponding to specific magnetic sublevel, in a direct, intuitive manner. We demonstrate the technique with both 87Rb and 85Rb, and show the utility of the technique by optically pumping into particular magnetic sublevels. The results are shown to agree with a theoretical model, and are compared to traditional Raman spectroscopy. PMID:19654701

  10. Multiphonon resonant Raman scattering in MoS{sub 2}

    SciTech Connect

    Gołasa, K. Grzeszczyk, M.; Wysmołek, A.; Babiński, A.; Leszczyński, P.; Faugeras, C.; Nicolet, A. A. L.; Potemski, M.

    2014-03-03

    Optical emission spectrum of a resonantly (λ = 632.8 nm) excited molybdenum disulfide (MoS{sub 2}) is studied at liquid helium temperature. More than 20 peaks in the energy range spanning up to 1400 cm{sup −1} from the laser line, which are related to multiphonon resonant Raman scattering processes, are observed. The attribution of the observed lines involving basic lattice vibrational modes of MoS{sub 2} and both the longitudinal (LA(M)) and the transverse (TA(M) and/or ZA(M)) acoustic phonons from the vicinity of the high-symmetry M point of the MoS{sub 2} Brillouin zone is proposed.

  11. Time-resolved resonance Raman spectroscopy of radiation-chemical processes. [Pulsed irradiation

    SciTech Connect

    Tripathi, G.N.R.

    1983-01-01

    A tunable pulsed laser Raman spectrometer for time resolved Raman studies of radiation-chemical processes is described. This apparatus utilizes the state of art optical multichannel detection and analysis techniques for data acquisition and electron pulse radiolysis for initiating the reactions. By using this technique the resonance Raman spectra of intermediates with absorption spectra in the 248-900 nm region, and mean lifetimes > 30 ns can be examined. This apparatus can be used to time resolve the vibrational spectral overlap between transients absorbing in the same region, and to follow their decay kinetics by monitoring the well resolved Raman peaks. For kinetic measurements at millisecond time scale, the Raman technique is preferable over optical absorption method where low frequency noise is quite bothersome. A time resolved Raman study of the pulse radiolytic oxidation of aqueous tetrafluorohydroquinone and p-methoxyphenol is briefly discussed. 15 references, 5 figures.

  12. Protonation of carbon single-walled nanotubes studied using 13C and 1H-13C cross polarization nuclear magnetic resonance and Raman spectroscopies.

    PubMed

    Engtrakul, Chaiwat; Davis, Mark F; Gennett, Thomas; Dillon, Anne C; Jones, Kim M; Heben, Michael J

    2005-12-14

    The reversible protonation of carbon single-walled nanotubes (SWNTs) in sulfuric acid and Nafion was investigated using solid-state nuclear magnetic resonance (NMR) and Raman spectroscopies. Magic-angle spinning (MAS) was used to obtain high-resolution 13C and 1H-13C cross polarization (CP) NMR spectra. The 13C NMR chemical shifts are reported for bulk SWNTs, H2SO4-treated SWNTs, SWNT-Nafion polymer composites, SWNT-AQ55 polymer composites, and SWNTs in contact with water. Protonation occurs without irreversible oxidation of the nanotube substrate via a charge-transfer process. This is the first report of a chemically induced change in a SWNT 13C resonance brought about by a reversible interaction with an acidic proton, providing additional evidence that carbon nanotubes behave as weak bases. Cross polarization was found to be a powerful technique for providing an additional contrast mechanism for studying nanotubes in contact with other chemical species. The CP studies confirmed polarization transfer from nearby protons to nanotube carbon atoms. The CP technique was also applied to investigate water adsorbed on carbon nanotube surfaces. Finally, the degree of bundling of the SWNTs in Nafion films was probed with the 1H-13C CP-MAS technique. PMID:16332107

  13. Investigation of anti-Stokes Raman processes at phonon-polariton resonance: from Raman oscillation, frequency upconversion to Raman amplification.

    PubMed

    Ding, Yujie J

    2015-03-01

    Raman oscillation, frequency upconversion, and Raman amplification can be achieved in a second-order nonlinear medium at the phonon-polariton resonance. By beating two optical fields, a second-order nonlinear polarization is generated inside the medium. Such a polarization induces a spatially uniform nonpropagating electric field at the beat frequency, which in turn mixes with the input optical field at the lower frequency to generate or amplify the anti-Stokes optical field. Raman oscillation can be efficiently reached for the copropagating configuration. In comparison, efficient frequency upconversion and large amplifications are achievable for the counterpropagating configuration. These Raman processes can be used to effectively remove transverse-optical phonons before decaying to lower-frequency phonons, achieve laser cooling, and significantly enhance coherent anti-Stokes Raman scattering. The counterpropagating configuration offers advantages for amplifying extremely weak signals. PMID:25723418

  14. Raman albedo and deep-UV resonance Raman signatures of explosives

    NASA Astrophysics Data System (ADS)

    Yellampalle, Balakishore; Lemoff, Brian E.

    2013-05-01

    Deep-ultraviolet resonance Raman spectroscopy (DUVRRS) is a promising approach to stand-off detection of explosive traces due to large Raman cross-section and background free signatures. In order to design an effective sensor, one must be able to estimate the signal level of the DUVRRS signature for solid-phase explosive residues. The conventional approach to signal estimation uses scattering cross-sections and molar absorptivity, measured on solutions of explosives dissolved in an optically-transparent solvent. Only recently have researchers started to measure solid-state cross-sections. For most solid-phase explosives and explosive mixtures, neither the DUV Raman scattering cross sections nor the optical absorption coefficient are known, and they are very difficult to separately measure. Therefore, for a typical solid explosive mixture, it is difficult to accurately estimate Raman signal strength using conventional approaches. To address this issue, we have developed a technique to measure the Raman scattering strength of optically-thick (opaque) materials, or "Raman Albedo", defined as the total power of Raman-scattered light per unit frequency per unit solid angle divided by the incident power of the excitation source. We have measured Raman Albedo signatures for a wide range of solid explosives at four different DUV excitation wavelengths. These results will be presented, and we will describe the use of Raman Albedo measurements in the design and current construction of a novel stand-off explosive sensor, based on dual-excitation-wavelength DUVRRS.

  15. Temperature dependence of resonance Raman spectra of carotenoids

    NASA Astrophysics Data System (ADS)

    Andreeva, A.; Apostolova, I.; Velitchkova, M.

    2011-04-01

    To understand the mechanism of the photoprotective and antioxidative functions of carotenoids, it is essential to have a profound knowledge of their excited electronic and vibronic states. In the present study we investigate the most powerful antioxidants: β-carotene and lutein by means of resonance Raman spectroscopy. The aim was to study in detail their Raman spectra in solution at room temperature and their changes as a function of temperature. To measure the spectra in their natural environment pyridine has been used as a solvent. It has been chosen because of its polarizability ( n = 1.5092) which is close to that of membrane lipids and proteins. The temperature dependence of the most intensive ν1 band in the range from 77 K to 295 K at 514.5 nm excitation has been obtained. It was found that in pyridine the C dbnd C stretching frequency, its intensity, line shape, and line width are very sensitive to the temperature (the sensitivity being different for the two studied carotenoids). The observed linear temperature dependence of the C dbnd C stretching frequency is explained by a mechanism involving changes of the vibronic coupling and the extent of π-electron delocalization. The different behavior of the temperature-induced broadening of the ν1 band and its intensity for the two studied carotenoids can be associated with the different nature of their solid matrices: glassy for β-carotene and crystalline-like for lutein, owing to their different chemical structures.

  16. Proliferation detection using a remote resonance Raman chemical sensor

    SciTech Connect

    Sedlacek, A.J.; Chen, C.L.; Dougherty, D.R.

    1993-08-01

    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.

  17. Resonance Raman spectra of. cap alpha. -copper phthalocyanine

    SciTech Connect

    Bovill, A.J.; McConnell, A.A.; Nimmo, J.A.; Smith, W.E.

    1986-02-13

    Raman spectra of ..cap alpha..-copper phthalocyanine (..cap alpha..-CuPc) were recorded at room temperature and at 10 K with excitation wavelengths between 457 and 714 nm. Resonance enhancement was greatest for modes for which the largest displacements were on either the inner five-membered ring of the isoindole groups or the inner macrocycle and consequently assignment of the bands to modes of the entire molecule was possible by comparison with nickel octaethylporphyrin. Four out of five bands resonant in the Q band region and preresonant near the B band absorption region are totally symmetric modes. B band preresonance occurs more strongly with high-frequency modes. At low temperatures, multimode interactions are reduced and profiles were obtained which can be compared with solution profiles of porphyrins. Both Q/sub x/ and Q/sub y/ 0-0 scattering can be identified and a helper mode is evident. A term enhancement predominates, with B/sub 1g/ and B/sub 2g/ modes enhanced because of a Jahn-Teller distortion of the excited state. The resonance studies, together with electronic absorption spectra and published theoretical studies, confirm that the Q band in ..cap alpha..-CuPc is largely due to an allowed ..pi..-..pi..* transition associated mainly with the macrocycle and inner five-membered rings of the isoindole groups. 25 references, 5 figures, 2 tables.

  18. Vibrational studies of reactive intermediates of aromatic amines. IV. Radical cation time-resolved resonance Raman investigation of N, N-dimethylaniline and N, N-diethylaniline derivatives

    NASA Astrophysics Data System (ADS)

    Poizat, O.; Guichard, V.; Buntinx, G.

    1989-05-01

    The radical cation time-resolved resonance Raman spectra of various isotopic derivatives of N, N-dimethylaniline (DMA), N, N-diethylaniline (DEA), N, N-dimethyl-p-toluidine (4MDMA) and 3, 5, N, N-tetramethylaniline (3,5DMDMA) are reported in the 300-1800 cm-1 range. Excitation was in the weak radical cation absorption around 480 nm. Complete vibrational assignments are proposed. The band activity and the changes in frequency with respect to the neutral molecules are consistent with a quinoidal-type conformation of the framework close to planarity. Stabilization of this conformation is observed when the phenyl ring contains methyl substituents. The analysis of the Raman enhancements suggests that the quinoidal character of the radical structure is significantly lowered in the resonant excited state. An obvious analogy is found between the spectra of DMA+ ṡ and of the biphenyl radical cation, which clearly indicates that (i) a nearly common chromophore structure characterizes these two radical cations and (ii) the distortion of this chromophore structure in the resonant excited state is comparable in both compounds, i.e., the biphenyl+ ṡ* ←biphenyl+ ṡ and DMA+ ṡ* ←DMA+ ṡ transitions are of similar nature. These results are consistent with structural previsions from simple molecular orbital considerations and a comprehensive interpretation of the Raman spectra is given in terms of HOMO population.

  19. Resonant enhancement of Raman scattering in metamaterials with hybrid electromagnetic and plasmonic resonances

    NASA Astrophysics Data System (ADS)

    Guddala, Sriram; Narayana Rao, D.; Ramakrishna, S. Anantha

    2016-06-01

    A tri-layer metamaterial perfect absorber of light, consisting of (Al/ZnS/Al) films with the top aluminum layer patterned as an array of circular disk nanoantennas, is investigated for resonantly enhancing Raman scattering from C60 fullerene molecules deposited on the metamaterial. The metamaterial is designed to have resonant bands due to plasmonic and electromagnetic resonances at the Raman pump frequency (725 nm) as well as Stokes emission bands. The Raman scattering from C60 on the metamaterial with resonantly matched bands is measured to be enhanced by an order of magnitude more than C60 on metamaterials with off-resonant absorption bands peaking at 1090 nm. The Raman pump is significantly enhanced due to the resonance with a propagating surface plasmon band, while the highly impedance-matched electromagnetic resonance is expected to couple out the Raman emission efficiently. The nature and hybridization of the plasmonic and electromagnetic resonances to form compound resonances are investigated by numerical simulations.

  20. Exploitation of resonance Raman spectroscopy as a remote chemical sensor

    SciTech Connect

    Sedlacek, A.J.; Chen, C.L.

    1995-08-01

    We have discussed recent experimental results using a resonance-Raman-based LIDAR system as a remote chemical sensor. This spectroscopy has the fundamental advantage that it is based on optical fingerprints that are insensitive to environmental perturbations. By taking advantage of resonance enhancement, which 6 orders-of-magnitude, can be as large as 4 to an increased sensing range for a given chemical concentration or lower detection limit for a given stand-off distance can be realized. The success discussed above can in part be traced back to the use of new state-of-the-art technologies which, only recently, have allowed the phenomenon of resonance-enhanced Raman spectroscopy to be fully exploited as a remote chemical sensor platform. Since many chemicals have electronic transitions in the UV/IS, it is expected that many will have pronounced resonance enhancements.

  1. Dual-excitation wavelength resonance Raman explosives detector

    NASA Astrophysics Data System (ADS)

    Yellampalle, Balakishore; Sluch, Mikhail; Wu, Hai-Shan; Martin, Robert; McCormick, William; Ice, Robert; Lemoff, Brian E.

    2013-05-01

    Deep-ultraviolet resonance Raman spectroscopy (DUVRRS) is a promising approach to stand-off detection of explosive traces due to: 1) resonant enhancement of Raman cross-section, 2) λ-4-cross-section enhancement, and 3) fluorescence and solar background free signatures. For trace detection, these signal enhancements more than offset the small penetration depth due to DUV absorption. A key challenge for stand-off sensors is to distinguish explosives, with high confidence, from a myriad of unknown background materials that may have interfering spectral peaks. To address this, we are developing a stand-off explosive sensor using DUVRRS with two simultaneous DUV excitation wavelengths. Due to complex interplay of resonant enhancement, self-absorption and laser penetration depth, significant amplitude variation is observed between corresponding Raman bands with different excitation wavelengths. These variations with excitation wavelength provide an orthogonal signature that complements the traditional Raman signature to improve specificity relative to single-excitation-wavelength techniques. As part of this effort, we are developing two novel CW DUV lasers, which have potential to be compact, and a compact dual-band high throughput DUV spectrometer, capable of simultaneous detection of Raman spectra in two spectral windows. We have also developed a highly sensitive algorithm for the detection of explosives under low signal-to-noise situations.

  2. Structural resonances in the Raman spectrum of glass microsphere

    NASA Astrophysics Data System (ADS)

    Wang, Ji-You; Xu, Xiao xuan; Zhang, Cun zhou

    2000-10-01

    Structural resonances have been found in the Raman spectrum of an optically levitated TiBa glass microsphere. The observed resonances could be assigned by using the well-known Lorenz-Mie Formalism. It was found that the diameter of the TiBa glass microsphere is 24.490micrometers , and the refractive index of TiBa glass is 1.895 at about 645nm.

  3. Resonant Raman and micro-Raman scattering from Si matrix with unburied beta-FeSi2 nanolayers.

    PubMed

    Marinova, M; Baleva, M; Zlateva, G

    2008-02-01

    Samples, representing Si matrix with nanolayers of the semiconducting beta-FeSi2 silicide are studied by Raman scattering. The unpolarized Raman spectra of the samples are measured in two different configurations. It is found that the characteristic beta-FeSi2 Raman modes are seen in the spectra, taken at incident angle of about 45 degrees , while only comparatively intensive broad feature is detected in a back-scattering geometry. The difference in the spectra is interpreted with the appearance of surface polariton modes of the optical phonons in the nanosized layers in near back-scattering geometry. The resonant Raman scattering is investigated at incident light angle of about 45 degrees and the energies of the interband transitions in the investigated energy range are determined. It is known that the resonant Raman scattering appears to be even more precise method for the determination of the interband transitions energies than the modulation spectroscopy. Thus we claim that the energies determined here are firstly determined with such a precision. PMID:18464405

  4. UV resonance Raman analysis of trishomocubane and diamondoid dimers

    SciTech Connect

    Meinke, Reinhard Thomsen, Christian; Maultzsch, Janina; Richter, Robert; Merli, Andrea; Fokin, Andrey A.; Koso, Tetyana V.; Schreiner, Peter R.; Rodionov, Vladimir N.

    2014-01-21

    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.

  5. Resonance Raman spectra of carotenoid molecules: influence of methyl substitutions.

    PubMed

    Macernis, Mindaugas; Galzerano, Denise; Sulskus, Juozas; Kish, Elizabeth; Kim, Young-Hun; Koo, Sangho; Valkunas, Leonas; Robert, Bruno

    2015-01-01

    We report here the resonance Raman spectra and the quantum chemical calculations of the Raman spectra for β-carotene and 13,13'-diphenyl-β-carotene. The first aim of this approach was to test the robustness of the method used for modeling β-carotene, and assess whether it could accurately predict the vibrational properties of derivatives in which conjugated substituents had been introduced. DFT calculations, using the B3LYP functional in combination with the 6-311G(d,p) basis set, were able to accurately predict the influence of two phenyl substituents connected to the β-carotene molecule, although these deeply perturb the vibrational modes. This experimentally validated modeling technique leads to a fine understanding of the origin of the carotenoid resonance Raman bands, which are widely used for assessing the properties of these molecules, and in particular in complex media, such as binding sites provided by biological macromolecules. PMID:25476500

  6. Raman Studies of Carbon Nanostructures

    NASA Astrophysics Data System (ADS)

    Jorio, Ado; Souza Filho, Antonio G.

    2016-07-01

    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.

  7. Raman spectroscopic studies of amorphous carbon and buckminsterfullerene

    SciTech Connect

    Sinha, K.

    1992-01-01

    Raman spectroscopic techniques have been applied to investigate a variety of carbon systems. Using resonance Raman spectroscopy as a probe for optical transitions in a system, a careful quantitative estimate of the Raman cross-section of graphite in the pre-resonance regime has been made. Raman and resonance Raman spectroscopy have been used to correlate the structural and electronic properties of amorphous carbon materials. The low optical gaps and e-2e spectroscopy measurements on evaporated carbon films suggests a structure close to graphite. Raman measurements, however, reveal a great amount of disorder in the material. This apparent contradiction has been resolved through the use of a phenomenological model for the electronic density of states for amorphous carbon systems. Raman spectroscopy has also been used to study the vibrational and the electronic properties of the recently discovered third allotrope of carbon, C[sub 60]. The vibrational modes of this molecule have been studied in great detail. The observed vibrational spectra confirms earlier work in this material. Furthermore, the mode frequencies have been found to be in reasonably good agreement with theoretical predictions. Resonance Raman studies of solid C[sub 60] and C[sub 60] dissolved in solvents has revealed, in the solid phase, the existence of optical transitions well below the symmetry allowed transitions for the isolated molecules. Loss of inversion symmetry in the solid state has been proposed to account for the resonance observed in the Raman excitation profile. Original Raman measurements on C[sub 60] revealed a strong peak at 1469 cm[sup [minus]1]. The peak was found to obey the correct selection rule for symmetric A[sub g] mode and was assigned to the [open quotes]pentagonal pinch[close quotes] mode of the molecule.

  8. Resonance Raman and far-infrared studies of isotopically disordered and mixed-halide halogen-bridged platinum chain solids

    SciTech Connect

    Love, S.P.; Worl, L.A.; Donohoe, R.J.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1992-12-31

    The MX chain solids [Pt(en){sub 2}][Pt(en){sub 2}X{sub 2}](CIO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), referred to as ``PtX,`` are used to explore some of the surprising spectral consequences of disorder in 1-D systems, first for pure PtCl, where the disorder arises from randomly distributed Cl isotopes, then for the more drastic case of the mixed-halide materials PtCl{sub 1minusx}Br{sub x}. Lattice dynamics and Peierls-Hubbard modelling are used to analyze the observed spectral behavior. In both cases, the complex structure seen in the Raman and IR spectra is found to arise from strongly localized vibrational modes residing on chain segments, defined by sequences of Cl isotopes for PtCl, and by sequences of Cl and Br for PtCl{sub 1minusx}Br{sub x}. 4 figs, 8 refs.

  9. Aggregation-Induced Resonance Raman Optical Activity (AIRROA): A New Mechanism for Chirality Enhancement.

    PubMed

    Zajac, Grzegorz; Kaczor, Agnieszka; Pallares Zazo, Ana; Mlynarski, Jacek; Dudek, Monika; Baranska, Malgorzata

    2016-05-01

    Raman optical activity (ROA) spectroscopy is hampered by low sensitivity, with limited possibilities for enhancing the signal. In the present study, we report a new mechanism whereby chirality is enhanced using the resonance resulting from supramolecular aggregation. We have named this mechanism aggregation-induced resonance Raman optical activity (AIRROA). As an example, we study J-aggregates of astaxanthin (AXT), which show strong absorption of circularly polarized light in the range of ROA excitation. The implications of aggregation-induced signal enhancement for chiroptical spectroscopy are discussed. PMID:27057926

  10. Investigation of the impact of fiber Bragg grating bandwidth on the efficiency of a Raman resonator

    NASA Astrophysics Data System (ADS)

    Henry, Leanne J.; Klopfer, Michael; Jain, Ravinder K.

    2015-03-01

    Significant spectral power leakage was found to occur around the high reflectivity fiber Bragg gratings (FBGs) defining a 1121 nm Raman resonator cavity comprised of PM 10/125 germanosilicate fiber. This cavity was part of a Raman system pumped with broad linewidth 1069 nm and seeded with narrow linewidth 1178 nm. The 1069 nm upon entering the resonator cavity was Raman converted to 1121 nm which then amplified the 1178 nm as it passed through the cavity. Spectral leakage of 1121 nm light from the resonator cavity resulted in sub-optimal amplification of 1178 nm which forced usage of longer resonator cavities having a decreased threshold for Stimulated Brillouin Scattering. Upon study of 1121 nm linewidth broadening as a function of resonator length for cavities employing 3 nm FBGs, differences in the percentage of 1121 nm power spectrally leaking past the output FBG as a function of the 1121 nm intracavity power propagating in the forward direction are not experimentally discernible for resonator cavities longer than 40 m. But, for cavity's shorter than 40 m, the percentage of 1121 nm power spectrally leaking past the output FBG decreased significantly for similar 1121 nm intracavity power levels. For all cavity lengths, a nearly linear relationship exists between percent 1121 nm power leakage and intracavity power levels. Also, cavities employing broader bandwidth FBGs experience less 1121 nm power leakage for similar 1121 nm intracavity power levels. Finally, modeling predictions of Raman system performance are greatly improved upon usage of experimentally derived effective FBG reflectivities.

  11. Characterization of the pigment xanthomonadin in the bacterial genus Xanthomonas using micro- and resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Paret, Mathews L.; Sharma, Shiv K.; Misra, Anupam K.; Acosta, Tayro; deSilva, Asoka S.; Vowell, Tomie; Alvarez, Anne M.

    2012-06-01

    We used micro- and resonance Raman spectroscopy with 785 nm and 514.5 nm laser excitation, respectively, to characterize a plant pathogenic bacteria, Xanthomonas axonopodis pv. dieffenbachiae D150. The bacterial genus Xathomonas is closely related to bacterial genus Stenotrophomonas that causes an infection in humans. This study has identified for the first time the unique Raman spectra of the carotenoid-like pigment xanthomonadin of the Xanthomonas strain. Xanthomonadin is a brominated aryl-polyene pigment molecule similar to carotenoids. Further studies were conducted using resonance Raman spectroscopy with 514.5 nm laser excitation on several strains of the bacterial genus Xanthomonas isolated from numerous plants from various geographical locations. The current study revealed that the Raman bands representing the vibrations (v1, v2, v3) of the polyene chain of xanthomonadin are 1003-1005 (v3), 1135-1138 (v2), and 1530 (v1). Overtone bands representing xanthomonadin were identified as 2264-2275 (2v2), and combinational bands at 2653-2662 (v1+ v2). The findings from this study validate our previous finding that the Raman fingerprints of xanthomonadin are unique for the genus Xanthomonas. This facilitates rapid identification (~5 minutes) of Xanthomonas spp. from bacterial culture plates. The xanthomonadin marker is different from Raman markers of many other bacterial genus including Agrobacterium, Bacillus, Clavibacter, Enterobacter, Erwinia, Microbacterium, Paenibacillus, and Ralstonia. This study also identified Xanthomonas spp. from bacterial strains isolated from a diseased wheat sample on a culture plate.

  12. Speciation of aqueous gold(III) chlorides from ultraviolet/visible absorption and Raman/resonance Raman spectroscopies

    SciTech Connect

    Peck, J.A.; Brown, G.E. Jr. ); Tait, C.D.; Swanson, B.I. )

    1991-03-01

    Gold(III) speciation in a one molar NaCl aqueous solution at ambient temperature and pressure was determined as a function of pH using ultraviolet/visible (UV/vis) absorption and Raman/resonance Raman (RR) spectroscopies. Gold concentrations in the solutions studies by UV/vis spectroscopy were {approximately}10{sup {minus}4} M whereas those studied by Raman spectroscopy were {approximately}10{sup {minus}2} M. Changes in the intensity and positions of ligand-to-metal charge transfer bands in the UV/vis spectra of the Au(III) chloride solutions with increasing pH are consistent with replacement of chloride by hydroxide ligands. Changes in the number, position, and intensity of Raman and RR spectra of the same solutions are also consistent with successive replacement of chloride by hydroxide ligands in the first coordination sphere of four-coordinated Au(III) with increasing pH. The Raman and UV/vis data are broadly consistent with earlier speciation predictions based on a variety of chemical measurements, but demonstrate that the mixed chloro-hydroxo complexes are more stable than predicted on the basis of theoretically estimated stability constants.

  13. Raman Scattering at Resonant or Near-Resonant Conditions: A Generalized Short-Time Approximation

    NASA Astrophysics Data System (ADS)

    Mohammed, Abdelsalam; Sun, Yu-Ping; Miao, Quan; Ågren, Hans; Gel'mukhanov, Faris

    2012-02-01

    We investigate the dynamics of resonant Raman scattering in the course of the frequency detuning. The dephasing in the time domain makes the scattering fast when the photon energy is tuned from the absorption resonance. This makes frequency detuning to act as a camera shutter with a regulated scattering duration and provides a practical tool of controlling the scattering time in ordinary stationary measurements. The theory is applied to resonant Raman spectra of a couple of few-mode model systems and to trans-1,3,5-hexatriene and guanine-cytosine (G-C) Watson-Crick base pairs (DNA) molecules. Besides some particular physical effects, the regime of fast scattering leads to a simplification of the spectrum as well as to the scattering theory itself. Strong overtones appear in the Raman spectra when the photon frequency is tuned in the resonant region, while in the mode of fast scattering, the overtones are gradually quenched when the photon frequency is tuned more than one vibrational quantum below the first absorption resonance. The detuning from the resonant region thus leads to a strong purification of the Raman spectrum from the contamination by higher overtones and soft modes and purifies the spectrum also in terms of avoidance of dissociation and interfering fluorescence decay of the resonant state. This makes frequency detuning a very useful practical tool in the analysis of the resonant Raman spectra of complex systems and considerably improves the prospects for using the Raman effect for detection of foreign substances at ultra-low concentrations.

  14. Raman resonance in iron-based superconductors: The magnetic scenario

    NASA Astrophysics Data System (ADS)

    Hinojosa, Alberto; Cai, Jiashen; Chubukov, Andrey V.

    2016-02-01

    We perform theoretical analysis of polarization-sensitive Raman spectroscopy on NaFe1 -xCoxAs , EuFe 2 As2 , SrFe2As2 , and Ba (Fe1 -xCox )2As2 , focusing on two features seen in the B1 g symmetry channel (in one Fe unit cell notation): the strong temperature dependence of the static, uniform Raman response in the normal state and the existence of a collective mode in the superconducting state. We show that both features can be explained by the coupling of fermions to pairs of magnetic fluctuations via the Aslamazov-Larkin process. We first analyze magnetically mediated Raman intensity at the leading two-loop order and then include interactions between pairs of magnetic fluctuations. We show that the full Raman intensity in the B1 g channel can be viewed as the result of the coupling of light to Ising-nematic susceptibility via Aslamazov-Larkin process. We argue that the singular temperature dependence in the normal state is the combination of the temperature dependencies of the Aslamazov-Larkin vertex and of Ising-nematic susceptibility. We discuss two scenario for the resonance below Tc. One is the resonance due to development of a pole in the fully renormalized Ising-nematic susceptibility. Another is orbital excitonic scenario, in which spin fluctuations generate attractive interaction between low-energy fermions.

  15. Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study.

    PubMed

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

    2015-10-01

    The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR(3)) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (μs). Interestingly, TR(3) spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ, assigned to nπ* and ππ* of which the ππ* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (∼2 ns) between the T(2)(1(3)nπ*) and T(1)(1(3)ππ*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents [ J. Chem. Phys. 2015 , 142 , 24305 ] suggest that the lowest nπ* and ππ* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism. PMID:26381591

  16. Resonant electronic Raman scattering: A BCS-like system

    NASA Astrophysics Data System (ADS)

    Rodrigues, Leonarde N.; Arantes, A.; Schüller, C.; Bell, M. J. V.; Anjos, V.

    2016-05-01

    In this paper we investigate the resonant intersubband Raman scattering of two-dimensional electron systems in GaAs-AlGaAs single quantum wells. Self-consistent calculations of the polarized and depolarized Raman cross sections show that the appearance of excitations at the unrenormalized single-particle energy are related to three factors: the extreme resonance regime, the existence of degeneracy in intersubband excitations of the electron gas, and, finally, degeneracy in the interactions between pairs of excitations. It is demonstrated that the physics that governs the problem is similar to the one that gives rise to the formation of the superconducting state in the BCS theory of normal metals. Comparison between experiment and theory shows an excellent agreement.

  17. Resonance Raman study of solvent dynamics on the spectral broadening and intramolecular charge transfer of a hemicyanine dye in aqueous solution

    NASA Astrophysics Data System (ADS)

    Cao, Xuan; McHale, Jeanne L.

    1998-08-01

    The spectroscopic properties of 4-[2-(4-dimethylaminophenyl)ethenyl]-1-methyl-pyridinium iodide (HR) in different solvents reveal the important effects of solvent dynamics on the spectral broadening and the intramolecular charge transfer of HR. In this article, Raman excitation profiles for 18 vibrational modes of HR are reported in aqueous solution at wavelengths that span the S0→S1 charge transfer transition. The absorption spectra, fluorescence spectra and resonance Raman profiles of HR are modeled using time-dependent wave packet theory and the Brownian oscillator solvent dephasing model. The solvent reorganization energy in the absorption process is much greater than that due to internal vibrational modes, and the solvent reorganization energy for the emission process is considerably smaller than that for the absorption process. The fluorescence spectrum is mainly broadened by the inhomogeneous Gaussian distribution of the electronic energy, perhaps due to internal rotations in the molecule. The results suggest similar polarity of the emission state and the ground state, and strong coupling between the torsional motion and solvent relaxation. The different dependence of the torsional potential on solvent polarity in the S0and S1 state is the cause of different absorption and fluorescence spectral width. In D2O, the absorption cross section of HR is slightly lower, and the absorption and fluorescence spectra are slightly narrower, than in H2O. The smaller absorption spectral linewidth and generally increased Raman cross sections in D2O are accounted for by smaller amplitude of solvent dephasing, perhaps due to the larger inertial moment and stronger hydrogen bonding in D2O compared to H2O. The magnitude and direction of the solvent isotope effect on Raman intensity varies with normal mode, suggesting that the solvent-induced dephasing is mode dependent. Vibrational modes which are strongly coupled to the electronic transition are most sensitive to the solvent

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

    PubMed

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

    2015-02-01

    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. PMID:25559740

  19. Peculiarities of the temperature dependence of electron spin resonance and Raman studies of Zn1-xNixO/NiO two-phase nanocomposites

    NASA Astrophysics Data System (ADS)

    Joshi, D. C.; Nayak, S.; Kumar, A.; Mohanta, A.; Pamu, D.; Thota, S.

    2016-02-01

    A meticulous investigation of electron-spin-resonance (ESR) and Raman spectroscopy of the two-phase nanocomposites of Zn1-xNixO/NiO is reported. The temperature variation of X-band ESR parameters viz., resonance field HR(T) and line-width ΔHPP(T) follows the power-law variation (δHR = (ΔHPP)n) of Nagata and Ishihara model, which was used to understand the orientation of statistical ensemble of particles with respect to a given direction of the anisotropy axis. This analysis yields the exponent "n" ≃ 2.13 and 2.85 for the composite system Zn1-xNixO/NiO and pure NiO suggesting the presence of partial and randomly oriented ellipsoidal nanocrystallites, respectively. The Raikher and Stepanov model has been employed to probe the role of amorphous Ni3+ clusters on the observed ESR spectra. Interestingly, after Ni substitution, a new zone boundary phonon mode was noticed at 129 cm-1 for all the samples, which is usually forbidden in the first-order Raman scattering for wurtzite ZnO. In addition to the 2M magnon mode, two extra modes appear at 558 and 900 cm-1 due to the increased volume fraction of NiO within the Zn1-xNixO matrix. A systematic correlation of the above results with a comparative analysis of their bulk counterpart has been presented.

  20. The effect of an anti-hydrogen bond on Fermi resonance: A Raman spectroscopic study of the Fermi doublet ν1-ν12 of liquid pyridine

    NASA Astrophysics Data System (ADS)

    Li, Dong-Fei; Gao, Shu-Qin; Sun, Cheng-Lin; Li, Zuo-Wei

    2012-08-01

    The effects of an anti-hydrogen bond on the ν1-ν12 Fermi resonance (FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, and pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode ν1 and triangle mode ν12 of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the ν1-ν12 Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν1-ν12 FR of pyridine. According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν1-ν12 FR of pyridine is given.

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

    NASA Astrophysics Data System (ADS)

    Wang, Zhong; Li, Yuee

    2015-09-01

    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.

  2. Resonance Raman spectroscopy of volatile organics -- Carbon tetrachloride

    SciTech Connect

    Barletta, R.E.; Veligdan, J.T.

    1994-09-01

    Volatile organic chemicals are a class of pollutants which are regulated at very low levels by the EPA. Consequently a need exists as a part of site remediation efforts within DOE to develop technologies which will allow for the in situ monitoring of these chemicals. Resonance Raman spectroscopy is a potential technique to accomplish this if the resonance enhancement is sufficiently high. Carbon tetrachloride was selected as a test case. Measurements under resonance conditions at 248 nm showed an enhancement factor of 2 {times} 10{sup 4}. Using this value an estimate of the sensitivity for both in situ and remote monitoring of CCl{sup 4} was made. It was concluded that resonance Raman could be used to detect these chemicals at levels of regulatory interest. Future effort directed towards the development of a suitable probe as well as a field-portable system would be desirable. Such effort could be directed towards the solution of a particular monitoring problem within a DOE waste remediation project. Once developed, however, it should be easily generalized to the analysis of other VOC`s in other environments.

  3. Study on Raman spectra of synthetic celluloses

    NASA Astrophysics Data System (ADS)

    Tong, Na; Zhu, Changjun; Zhang, Yixin

    2015-02-01

    Raman spectrometry was employed to study the characteristics of Raman spectra of aliphatic polyamide fiber and polyethylene terephthalate (PET), which were treated with sodium hydroxide, sulfuric acid and copper sulfate, respectively. Raman spectra under different conditions were obtained and the characteristics of the Raman spectra were analyzed. The results show that Raman peaks beyond 1200 cm-1 appear for aliphatic polyamide fiber processed by sodium hydroxide, while the Raman peaks beyond 1000 cm-1 disappear for aliphatic polyamide fiber processed by sulfuric acid. Raman peaks beyond 1750 cm-1 decrease for polyethylene terephthalate processed by sodium hydroxide, while Raman peaks beyond 1000 cm-1 disappear, except weak peaks around 3000 cm-1 , for polyethylene terephthalate processed by sulfuric acid. The variations of the Raman spectra are primarily related to the changes of chemical bonds and molecular structures.

  4. Resonance Raman Studies of the (His)(Cys)3 2Fe-2S Cluster of MitoNEET: Comparison to the (Cys)4 Mutant and Implications of the Effects of pH on the Labile Metal Center†

    PubMed Central

    Tirrell, Timothy F.; Paddock, Mark L.; Conlan, Andrea R.; Smoll, Eric J.; Nechushtai, Rachel; Jennings, Patricia A.; Kim, Judy E.

    2010-01-01

    MitoNEET is a 2Fe-2S outer mitochondrial membrane protein that was initially identified as a target for anti-diabetic drugs. It exhibits a novel protein fold, and in contrast to other 2Fe-2S proteins such as Rieske proteins and ferredoxins, the metal clusters in the mitoNEET homodimer are each coordinated by one histidine residue and three cysteine residues. The interaction of the ligating His87 residue with the 2Fe-2S moiety is especially significant because previous studies have shown that replacement with Cys in the H87C mutant stabilizes the cluster against release. Here, we report the resonance Raman spectra of this naturally occurring Fe2S2(His)(Cys)3 protein to assess local structural changes associated with cluster lability. Comparison of mitoNEET to its ferredoxin-like H87C mutant indicates that Raman peaks in the ~250–300 cm−1 region of mitoNEET are influenced by the Fe-His87 moiety. Systematic pH-dependent resonance Raman spectral changes were observed in this spectral region for native mitoNEET but not the H87C mutant. The ~250–300 cm−1 region of native mitoNEET is also sensitive to phosphate buffer. Thus, conditions that influence cluster release are shown here to concomitantly affect the resonance Raman spectrum in the region with Fe-His contribution. These results support the hypothesis that the Fe-N(His87) interaction is modulated within the physiological pH range, and this modulation may be critical to the function of mitoNEET. PMID:19388667

  5. ARTICLES: Stimulated Raman scattering in resonant nonequilibrium media

    NASA Astrophysics Data System (ADS)

    Khasanov, O. Kh

    1980-12-01

    An analysis is made of the propagation of a short coherent optical pulse in a three-level resonant medium with an essentially nonequidistant spectrum as a function of the degree of preexcitation of the medium. It is found that in addition to self-induced transparency and resonance scattering, stimulated Raman scattering (Stokes or anti-Stokes) should be observed under certain spatial phase-matching conditions. The area theorem is formulated for all radiation components. An analysis is made of the case of propagation of a resonant electromagnetic pulse of frequency ω in a system of three-level atoms having an equidistant spectrum. Under conditions of preexcitation of the medium at the frequency 2ω by longitudinal acoustic pulses, a scattered transverse acoustic wave at the frequency ω may be observed.

  6. Quantum lattice fluctuations in a 1-dimensional charge-density-wave material: Luminescence and resonance Raman studies of an MX solid

    SciTech Connect

    Long, F.H.; Love, S.P.; Swanson, B.I.

    1993-02-01

    Luminescence spectra, both emission and excitation, and the excitation dependence of the resonance Raman (RR) spectra were measured for a 1-dimensional charge-density-wave solid, [Pt(L){sub 2}Cl{sub 2}][Pt(L){sub 2}](ClO{sub 4}){sub 4} ; L=1, 2-diaminoethane. The luminescence experiments support the existence of tail states in the band gap region, which indicate the presence of disorder. In contrast, the RR measurements conclusively demonstrated that the effects of static structural disorder on the vibrational spectroscopy can be neglected. This apparently paradoxical result can be explained by considering the zero-point motion of the lattice. The experimental results are compared to recent theoretical models.

  7. Multidimensional resonance Raman spectroscopy by six-wave mixing in the deep UV.

    PubMed

    Molesky, Brian P; Giokas, Paul G; Guo, Zhenkun; Moran, Andrew M

    2014-09-21

    Two-dimensional (2D) resonance Raman spectroscopies hold great potential for uncovering photoinduced relaxation processes in molecules but are not yet widely applied because of technical challenges. Here, we describe a newly developed 2D resonance Raman experiment operational at the third-harmonic of a Titanium-Sapphire laser. High-sensitivity and rapid data acquisition are achieved by combining spectral interferometry with a background-free (six-pulse) laser beam geometry. The third-harmonic laser pulses are generated in a filament produced by the fundamental and second-harmonic pulses in neon gas at pressures up to 35 atm. The capabilities of the setup are demonstrated by probing ground-state wavepacket motions in triiodide. The information provided by the experiment is explored with two different representations of the signal. In one representation, Fourier transforms are carried out with respect to the two experimentally controlled delay times to obtain a 2D Raman spectrum. Further insights are derived in a second representation by dispersing the signal pulse in a spectrometer. It is shown that, as in traditional pump-probe experiments, the six-wave mixing signal spectrum encodes the wavepacket's position by way of the (time-evolving) emission frequency. Anharmonicity additionally induces dynamics in the vibrational resonance frequency. In all cases, the experimental signals are compared to model calculations based on a cumulant expansion approach. This study suggests that multi-dimensional resonance Raman spectroscopies conducted on systems with Franck-Condon active modes are fairly immune to many of the technical issues that challenge off-resonant 2D Raman spectroscopies (e.g., third-order cascades) and photon-echo experiments in the deep UV (e.g., coherence spikes). The development of higher-order nonlinear spectroscopies operational in the deep UV is motivated by studies of biological systems and elementary organic photochemistries. PMID:25240351

  8. Multidimensional resonance raman spectroscopy by six-wave mixing in the deep UV

    SciTech Connect

    Molesky, Brian P.; Giokas, Paul G.; Guo, Zhenkun; Moran, Andrew M.

    2014-09-21

    Two-dimensional (2D) resonance Raman spectroscopies hold great potential for uncovering photoinduced relaxation processes in molecules but are not yet widely applied because of technical challenges. Here, we describe a newly developed 2D resonance Raman experiment operational at the third-harmonic of a Titanium-Sapphire laser. High-sensitivity and rapid data acquisition are achieved by combining spectral interferometry with a background-free (six-pulse) laser beam geometry. The third-harmonic laser pulses are generated in a filament produced by the fundamental and second-harmonic pulses in neon gas at pressures up to 35 atm. The capabilities of the setup are demonstrated by probing ground-state wavepacket motions in triiodide. The information provided by the experiment is explored with two different representations of the signal. In one representation, Fourier transforms are carried out with respect to the two experimentally controlled delay times to obtain a 2D Raman spectrum. Further insights are derived in a second representation by dispersing the signal pulse in a spectrometer. It is shown that, as in traditional pump-probe experiments, the six-wave mixing signal spectrum encodes the wavepacket's position by way of the (time-evolving) emission frequency. Anharmonicity additionally induces dynamics in the vibrational resonance frequency. In all cases, the experimental signals are compared to model calculations based on a cumulant expansion approach. This study suggests that multi-dimensional resonance Raman spectroscopies conducted on systems with Franck-Condon active modes are fairly immune to many of the technical issues that challenge off-resonant 2D Raman spectroscopies (e.g., third-order cascades) and photon-echo experiments in the deep UV (e.g., coherence spikes). The development of higher-order nonlinear spectroscopies operational in the deep UV is motivated by studies of biological systems and elementary organic photochemistries.

  9. Real-Time Measurements of the Redox States of c-Type Cytochromes in Electroactive Biofilms: A Confocal Resonance Raman Microscopy Study

    PubMed Central

    Virdis, Bernardino; Millo, Diego; Donose, Bogdan C.; Batstone, Damien J.

    2014-01-01

    Confocal Resonance Raman Microscopy (CRRM) was used to probe variations of redox state of c-type cytochromes embedded in living mixed-culture electroactive biofilms exposed to different electrode polarizations, under potentiostatic and potentiodynamic conditions. In the absence of the metabolic substrate acetate, the redox state of cytochromes followed the application of reducing and oxidizing electrode potentials. Real-time monitoring of the redox state of cytochromes during cyclic voltammetry (CV) in a potential window where cytochromes reduction occurs, evidenced a measurable time delay between the oxidation of redox cofactors probed by CV at the electrode interface, and oxidation of distal cytochromes probed by CRRM. This delay was used to tentatively estimate the diffusivity of electrons through the biofilm. In the presence of acetate, the resonance Raman spectra of young (10 days, j = 208±49 µA cm−2) and mature (57 days, j = 267±73 µA cm−2) biofilms show that cytochromes remained oxidized homogeneously even at layers as far as 70 µm from the electrode, implying the existence of slow metabolic kinetics that do not result in the formation of a redox gradient inside the biofilm during anode respiration. However, old biofilms (80 days, j = 190±37 µA cm−2) with thickness above 100 µm were characterized by reduced catalytic activity compared to the previous developing stages. The cytochromes in these biofilm were mainly in the reduced redox state, showing that only aged mixed-culture biofilms accumulate electrons during anode respiration. These results differ substantially from recent observations in pure Geobacter sulfurreducens electroactive biofilms, in which accumulation of reduced cytochromes is already observed in thinner biofilms, thus suggesting different bottlenecks in current production for mixed-culture and G. sulfurreducens biofilms. PMID:24587123

  10. Experimental evaluation of the twofold electromagnetic enhancement theory of surface-enhanced resonance Raman scattering

    SciTech Connect

    Yoshida, Ken-ichi; Itoh, Tamitake; Biju, Vasudevanpillai; Ishikawa, Mitsuru; Ozaki, Yukihiro

    2009-02-15

    We examined an electromagnetic (EM) theory of surface-enhanced resonance Raman scattering (SERRS) using single Ag nanoaggregates. The SERRS-EM theory is characterized by twofold EM enhancement induced by the coupling of plasmon resonance with both excitation and emission of Raman scattering plus fluorescence. The total emission cross-section spectra of enhanced Raman scattering and enhanced fluorescence were calculated using the following parameters: the spectrum of enhancement factor induced by plasmon resonance, resonance Raman scattering overlapped with fluorescence, and excitation wavelengths. The calculations well agreed with experimental total emission cross-section spectra, thus providing strong indications that the SERRS-EM theory is quantitatively correct.

  11. Long-Lived Raman Resonance Amid Incoherence Above T_c

    NASA Astrophysics Data System (ADS)

    Klein, Miles V.

    1998-03-01

    Electronic Raman scattering from high and low energy excitations was studied as a function of temperature, hole doping, and energy of the incident photons in Bi_2Sr_2CaCu_2O8 ± δ superconductors. Short range antiferromagnetic correlations were found to persist when holes were doped into the insulating state, and excitations of the holes were found to be incoherent. Above the superconducting transition temperature Tc the system exhibits a sharp Raman resonance of B_1g symmetry and 75 meV energy with a pseudogap (PG) for electron-hole excitations below 75 meV.(G. Blumberg et al.), Science 278, 1427 (1997);

  12. Resonance Raman spectroscopic study of the interaction between Co(II)rrinoids and the ATP:corrinoid adenosyltransferase PduO from Lactobacillus reuteri.

    PubMed

    Park, Kiyoung; Mera, Paola E; Escalante-Semerena, Jorge C; Brunold, Thomas C

    2016-09-01

    The human-type ATP:corrinoid adenosyltransferase PduO from Lactobacillus reuteri (LrPduO) catalyzes the adenosylation of Co(II)rrinoids to generate adenosylcobalamin (AdoCbl) or adenosylcobinamide (AdoCbi(+)). This process requires the formation of "supernucleophilic" Co(I)rrinoid intermediates in the enzyme active site which are properly positioned to abstract the adeonsyl moiety from co-substrate ATP. Previous magnetic circular dichroism (MCD) spectroscopic and X-ray crystallographic analyses revealed that LrPduO achieves the thermodynamically challenging reduction of Co(II)rrinoids by displacing the axial ligand with a non-coordinating phenylalanine residue to produce a four-coordinate species. However, relatively little is currently known about the interaction between the tetradentate equatorial ligand of Co(II)rrinoids (the corrin ring) and the enzyme active site. To address this issue, we have collected resonance Raman (rR) data of Co(II)rrinoids free in solution and bound to the LrPduO active site. The relevant resonance-enhanced vibrational features of the free Co(II)rrinoids are assigned on the basis of rR intensity calculations using density functional theory to establish a suitable framework for interpreting rR spectral changes that occur upon Co(II)rrinoid binding to the LrPduO/ATP complex in terms of structural perturbations of the corrin ring. To complement our rR data, we have also obtained MCD spectra of Co(II)rrinoids bound to LrPduO complexed with the ATP analogue UTP. Collectively, our results provide compelling evidence that in the LrPduO active site, the corrin ring of Co(II)rrinoids is firmly locked in place by several amino acid side chains so as to facilitate the dissociation of the axial ligand. PMID:27383231

  13. Quantitative evaluation of proteins with bicinchoninic acid (BCA): resonance Raman and surface-enhanced resonance Raman scattering-based methods.

    PubMed

    Chen, Lei; Yu, Zhi; Lee, Youngju; Wang, Xu; Zhao, Bing; Jung, Young Mee

    2012-12-21

    A rapid and highly sensitive bicinchoninic acid (BCA) reagent-based protein quantitation tool was developed using competitive resonance Raman (RR) and surface-enhanced resonance Raman scattering (SERRS) methods. A chelation reaction between BCA and Cu(+), which is reduced by protein in an alkaline environment, is exploited to create a BCA-Cu(+) complex that has strong RR and SERRS activities. Using these methods, protein concentrations in solutions can be quantitatively measured at concentrations as low as 50 μg mL(-1) and 10 pg mL(-1). There are many advantages of using RR and SERRS-based assays. These assays exhibit a much wider linear concentration range and provide an additional one (RR method) to four (SERRS method) orders of magnitude increase in detection limits relative to UV-based methods. Protein-to-protein variation is determined using a reference to a standard curve at concentrations of BSA that exhibits excellent recoveries. These novel methods are extremely accurate in detecting total protein concentrations in solution. This improvement in protein detection sensitivity could yield advances in the biological sciences and medical diagnostic field and extend the applications of reagent-based protein assay techniques. PMID:23099478

  14. Theoretical studies of resonance enhanced stimulated raman scattering (RESRS) of frequency doubled Alexandrite laser wavelength in cesium vapor. Progress report, July-December 1987

    SciTech Connect

    Lawandy, N.M.

    1987-01-01

    The third phase of research will focus on the propagation and energy extraction of the pump and SERS beams in a variety of configurations including oscillator structures. In order to address these questions a numerical code capable of allowing for saturation and full transverse beam evolution is required. The method proposed is based on a discretized propagation energy extraction model which uses a Kirchoff integral propagator coupled to the three level Raman model already developed. The model will have the resolution required by diffraction limits and will use the previous density matrix results in the adiabatic following limit. Owing to its large computational requirements, such a code must be implemented on a vector array processor. One code on the Cyber is being tested by using previously understood two-level laser models as guidelines for interpreting the results. Two tests were implemented: the evolution of modes in a passive resonator and the evolution of a stable state of the adiabatically eliminated laser equations. These results show mode shapes and diffraction losses for the first case and relaxation oscillations for the second one. Finally, in order to clarify the computing methodology used to exploit the speed of the Cyber's computational speed, the time it takes to perform both of the computations previously mentioned to run on the Cyber and VAX 730 must be measured. Also included is a short description of the current laser model (CAVITY.FOR) and a flow chart of the test computations.

  15. The confinement induced resonance in spin-orbit coupled cold atoms with Raman coupling

    PubMed Central

    Zhang, Yi-Cai; Song, Shu-Wei; Liu, Wu-Ming

    2014-01-01

    The confinement induced resonance provides an indispensable tool for the realization of the low-dimensional strongly interacting quantum system. Here, we investigate the confinement induced resonance in spin-orbit coupled cold atoms with Raman coupling. We find that the quasi-bound levels induced by the spin-orbit coupling and Raman coupling result in the Feshbach-type resonances. For sufficiently large Raman coupling, the bound states in one dimension exist only for sufficiently strong attractive interaction. Furthermore, the bound states in quasi-one dimension exist only for sufficient large ratio of the length scale of confinement to three dimensional s-wave scattering length. The Raman coupling substantially changes the confinement-induced resonance position. We give a proposal to realize confinement induced resonance through increasing Raman coupling strength in experiments. PMID:24862314

  16. Resonance Raman Spectroscopy of Purple Membrane from Halobacterium Halobium.

    NASA Astrophysics Data System (ADS)

    Argade, Pramod Vasant

    Purple membrane from the halophilic bacteria, Halobacterium halobium, contains the protein, bacteriorhodopsin, which functions as a light transducing proton pump. Understanding the molecular mechanism underlying the functioning of bacteriorhodopsin is a key problem in membrane biophysics. After absorbing a photon, this protein cycles through a series of characteristic intermeidate states and pumps H('+) ions across the membrane. In this way, the energy of the absorbed photon is stored in the electrochemical potential gradient formed across the membrane. This energy is subsequently available for metabolism by the bacterium. Bacteriorhodopsin consists of a retinal chromophore (which is responsible for the purple color) bound to the protein, bacterioopsin, whose sequence is known and consists of 248 amino acid residues. There is evidence that conformational changes in the chromophore may contribute to the proton pumping action. Resonance Raman light scattering provides a selective tool to monitor the conformational changes in the chromophore during the proton pumping cycle. This dissertation consists of applying resonance Raman light scattering in conjunction with a variety of newly developed experimental techniques to gain information about the mode of action of bacteriorhodopsin. By selective isotopic labelling of (epsilon)-amino nitrogen of the lysine residues of the protein, the site of attachment of the chromophore with the protein was verified by in situ measurements. Also, a model proposing a secondary interaction of the chromophore with a lysine residue other than the binding site of the chromophore was tested using this method. Furthermore, by selective isotopic labelling of only a part of the protein the location of the lysine on the protein to which the chromophore is bound, was found by in situ measurements to be the fragment consisting of amino acid residues 72 through 248 of the protein. This is inconsistent with the previously reported binding site at

  17. Characterization of bundled and individual triple-walled carbon nanotubes by resonant Raman spectroscopy.

    PubMed

    Hirschmann, Thomas Ch; Araujo, Paulo T; Muramatsu, Hiroyuki; Zhang, Xu; Nielsch, Kornelius; Kim, Yoong Ahm; Dresselhaus, Mildred S

    2013-03-26

    The optical characterization of bundled and individual triple-walled carbon nanotubes was studied for the first time in detail by using resonant Raman spectroscopy. In our approach, the outer tube of a triple-walled carbon nanotube system protects the two inner tubes (or equivalently the inner double-walled carbon nanotube) from external environment interactions making them a partially isolated system. Following the spectral changes and line-widths of the radial breathing modes and G-band by performing laser energy dependent Raman spectroscopy, it is possible to extract important information as regards to the electronic and vibrational properties, tube diameters, wall-to-wall distances, radial breathing mode, and G-band resonance evolutions as well as high-curvature intertube interactions in isolated double- and triple-walled carbon nanotube systems. PMID:23311296

  18. Origin invariance in vibrational resonance Raman optical activity.

    PubMed

    Vidal, Luciano N; Egidi, Franco; Barone, Vincenzo; Cappelli, Chiara

    2015-05-01

    A theoretical investigation on the origin dependence of the vibronic polarizabilities, isotropic and anisotropic rotational invariants, and scattering cross sections in Resonance Raman Optical Activity (RROA) spectroscopy is presented. Expressions showing the origin dependence of these polarizabilities were written in the resonance regime using the Franck-Condon (FC) and Herzberg-Teller (HT) approximations for the electronic transition moments. Differently from the far-from-resonance scattering regime, where the origin dependent terms cancel out when the rotational invariants are calculated, RROA spectrum can exhibit some origin dependence even for eigenfunctions of the electronic Hamiltonian. At the FC level, the RROA spectrum is completely origin invariant if the polarizabilities are calculated using a single excited state or for a set of degenerate states. Otherwise, some origin effects can be observed in the spectrum. At the HT level, RROA spectrum is origin dependent even when the polarizabilities are evaluated from a single excited state but the origin effect is expected to be small in this case. Numerical calculations performed for (S)-methyloxirane, (2R,3R)-dimethyloxirane, and (R)-4-F-2-azetidinone at both FC and HT levels using the velocity representation of the electric dipole and quadrupole transition moments confirm the predictions of the theory and show the extent of origin effects and the effectiveness of suggested ways to remove them. PMID:25956084

  19. Origin invariance in vibrational resonance Raman optical activity

    NASA Astrophysics Data System (ADS)

    Vidal, Luciano N.; Egidi, Franco; Barone, Vincenzo; Cappelli, Chiara

    2015-05-01

    A theoretical investigation on the origin dependence of the vibronic polarizabilities, isotropic and anisotropic rotational invariants, and scattering cross sections in Resonance Raman Optical Activity (RROA) spectroscopy is presented. Expressions showing the origin dependence of these polarizabilities were written in the resonance regime using the Franck-Condon (FC) and Herzberg-Teller (HT) approximations for the electronic transition moments. Differently from the far-from-resonance scattering regime, where the origin dependent terms cancel out when the rotational invariants are calculated, RROA spectrum can exhibit some origin dependence even for eigenfunctions of the electronic Hamiltonian. At the FC level, the RROA spectrum is completely origin invariant if the polarizabilities are calculated using a single excited state or for a set of degenerate states. Otherwise, some origin effects can be observed in the spectrum. At the HT level, RROA spectrum is origin dependent even when the polarizabilities are evaluated from a single excited state but the origin effect is expected to be small in this case. Numerical calculations performed for (S)-methyloxirane, (2R,3R)-dimethyloxirane, and (R)-4-F-2-azetidinone at both FC and HT levels using the velocity representation of the electric dipole and quadrupole transition moments confirm the predictions of the theory and show the extent of origin effects and the effectiveness of suggested ways to remove them.

  20. Origin invariance in vibrational resonance Raman optical activity

    SciTech Connect

    Vidal, Luciano N. Cappelli, Chiara; Egidi, Franco; Barone, Vincenzo

    2015-05-07

    A theoretical investigation on the origin dependence of the vibronic polarizabilities, isotropic and anisotropic rotational invariants, and scattering cross sections in Resonance Raman Optical Activity (RROA) spectroscopy is presented. Expressions showing the origin dependence of these polarizabilities were written in the resonance regime using the Franck-Condon (FC) and Herzberg-Teller (HT) approximations for the electronic transition moments. Differently from the far-from-resonance scattering regime, where the origin dependent terms cancel out when the rotational invariants are calculated, RROA spectrum can exhibit some origin dependence even for eigenfunctions of the electronic Hamiltonian. At the FC level, the RROA spectrum is completely origin invariant if the polarizabilities are calculated using a single excited state or for a set of degenerate states. Otherwise, some origin effects can be observed in the spectrum. At the HT level, RROA spectrum is origin dependent even when the polarizabilities are evaluated from a single excited state but the origin effect is expected to be small in this case. Numerical calculations performed for (S)-methyloxirane, (2R,3R)-dimethyloxirane, and (R)-4-F-2-azetidinone at both FC and HT levels using the velocity representation of the electric dipole and quadrupole transition moments confirm the predictions of the theory and show the extent of origin effects and the effectiveness of suggested ways to remove them.

  1. Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency-doubled Alexandrite laser wavelength in cesium vapor. Progress report, January-June 1987

    SciTech Connect

    Lawandy, N.M.

    1987-01-01

    The solutions for the imaginary susceptibility of the Raman field transition with arbitrary relaxation rates and field strengths are examined for three different sets of relaxation rates. These rates correspond to: (1) Far Infrared (FIR) Raman lasers in the diabatic collision regime without consideration of coupled population decay in a closed system, (2) Raman FIR lasers in the diabatic collision regime with coupled population conserving decay, and (3) IR Raman gain in cesium vapor. The model is further expanded to include Doppler broadening and used to predict the peak gain as a function of detuning for a frequency doubled Alexandrite laser-pumped cesium vapor gain cell.

  2. Correlation between vibrational frequencies and hydrogen bonding states of the guanine ring studied by UV resonance Raman spectroscopy of 2'-deoxy-3',5'-bis(triisopropylsilyl)guanosine dissolved in various solvents

    NASA Astrophysics Data System (ADS)

    Toyama, Akira; Hamuara, Mutsuo; Takeuchi, Hideo

    1996-06-01

    Ultraviolet resonance Raman spectra of 2'-deoxy-3',5'-bis(triisopropylsilyl)guanosine (TPS-dGuo) were recorded in non-hydrogen bonding, proton acceptor, and proton donor/acceptor solvents. Raman spectral changes observed on going from inert to proton acceptor solvents were ascribed to the hydrogen bonding at the proton donor sites of the guanine ring (N1H and C2NH 2), and the spectral changes associated with the solvent change from proton acceptor to donor/acceptor were ascribed to the hydrogen bonding at the proton acceptor sites (N3, C6O, and N7). A Raman band appearing at 1624 cm -1 in inert solvents is assigned mainly to the NH 2 scissors mode and its frequency changes to ≈ 1640 cm -1 in acceptor solvents, reflecting the hydrogen bonding at C2NH 2. Another band at 1581 cm -1, arising largely from the N1H bend, shows an upshift of ≈ 10 cm -1 upon hydrogen bonding at either N1H or acceptor sites. Hydrogen bonding at the acceptor sites also produces frequency shifts of other Raman bands (at 1710, 1565, 1528, 1481, and 1154 cm -1 in 1,2-dichloroethane solution). Among the Raman bands listed above, the 1710 cm -1 band due to the C6O stretch decreases in frequency, whereas the others increase. The downshift of the C6O stretching frequency is correlated with the strength of hydrogen bonding at C6O. The frequency of the 1481 cm -1 band increases with a decrease of the C6O stretching frequency, indicating that the 1481 cm -1 band is also a marker of hydrogen bonding at C6O. This finding is in sharp contrast to the previously proposed correlation with the hydrogen bonding at N7. The 1565 cm -1 band is assigned to a vibration mainly involving the N1C2N3 linkage, and its frequency increases with increasing strength of the hydrogen bond at N3. Three bands around 1315, 1180, and 1030 cm -1, which are known to be sensitive to the ribose ring puckering and glycosidic bond orientation, also show small frequency changes upon hydrogen

  3. Manifestation of Structure of Electron Bands in Double-Resonant Raman Spectra of Single-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Stubrov, Yurii; Nikolenko, Andrii; Gubanov, Viktor; Strelchuk, Viktor

    2016-01-01

    Micro-Raman spectra of single-walled carbon nanotubes in the range of two-phonon 2D bands are investigated in detail. The fine structure of two-phonon 2D bands in the low-temperature Raman spectra of the mixture and individual single-walled carbon nanotubes is considered as the reflection of structure of their π-electron zones. The dispersion behavior of 2D band fine structure components in the resonant Raman spectra of single-walled carbon nanotube mixture is studied depending on the energy of excitating photons. The role of incoming and outgoing electron-phonon resonances in the formation of 2D band fine structure in Raman spectra of single-walled carbon nanotubes is analyzed. The similarity of dispersion behavior of 2D phonon bands in single-walled carbon nanotubes, one-layer graphene, and bulk graphite is discussed.

  4. Manifestation of Structure of Electron Bands in Double-Resonant Raman Spectra of Single-Walled Carbon Nanotubes.

    PubMed

    Stubrov, Yurii; Nikolenko, Andrii; Gubanov, Viktor; Strelchuk, Viktor

    2016-12-01

    Micro-Raman spectra of single-walled carbon nanotubes in the range of two-phonon 2D bands are investigated in detail. The fine structure of two-phonon 2D bands in the low-temperature Raman spectra of the mixture and individual single-walled carbon nanotubes is considered as the reflection of structure of their π-electron zones. The dispersion behavior of 2D band fine structure components in the resonant Raman spectra of single-walled carbon nanotube mixture is studied depending on the energy of excitating photons. The role of incoming and outgoing electron-phonon resonances in the formation of 2D band fine structure in Raman spectra of single-walled carbon nanotubes is analyzed. The similarity of dispersion behavior of 2D phonon bands in single-walled carbon nanotubes, one-layer graphene, and bulk graphite is discussed. PMID:26729220

  5. Intracavity CH4 Raman laser using negative-branch unstable resonator

    NASA Astrophysics Data System (ADS)

    Zhou, Dongjian; Guo, Jingwei; Zhou, Canhua; Liu, Jinbo; Liu, Dong; Jin, Yuqi

    2015-12-01

    An intracavity Q-switched Nd:YAG/CH4 Raman laser is realized based on the configuration of a negative-branch confocal unstable resonator. A numerical model of the bare resonator was introduced to simulate the fundamental transverse mode and calculate the loss of the fundamental resonator. With different magnifications of the fundamental resonator, the first Stokes output energy was presented as a function of the discharge voltage. The influence of the Stokes resonator on Raman conversion was analyzed. With a fundamental resonator magnification of 1.1, a maximum output energy of 58 mJ was obtained, and the corresponding photon conversion efficiency was 48%.

  6. η collective mode as A1 g Raman resonance in cuprate superconductors

    NASA Astrophysics Data System (ADS)

    Montiel, X.; Kloss, T.; Pépin, C.; Benhabib, S.; Gallais, Y.; Sacuto, A.

    2016-01-01

    We discuss the possible existence of a spin singlet excitation with charge ±2 (η mode) originating the A1 g Raman resonance in cuprate superconductors. This η mode relates the d -wave superconducting singlet pairing channel to a d -wave charge channel. We show that the η boson forms a particle-particle bound state below the 2 Δ threshold of the particle-hole continuum where Δ is the maximum d -wave gap. Within a generalized random phase approximation and Bethe-Salpeter approximation study, we find that this mode has energies similar to the resonance observed with inelastic neutron scattering below the superconducting (SC) coherent peak at 2 Δ in various SC cuprate compounds. We show that it is a very good candidate for the resonance observed in Raman scattering below the 2 Δ peak in the A1 g symmetry. Since the η mode sits in the S =0 channel, it may be observable via Raman, x-ray, or electron energy loss spectroscopy probes.

  7. Fluorescence and UV resonance Raman study of peptide-vesicle interactions of human cathelicidin LL-37 and its F6W and F17W mutants.

    PubMed

    Gable, Jonathan E; Schlamadinger, Diana E; Cogen, Anna L; Gallo, Richard L; Kim, Judy E

    2009-12-01

    LL-37 is a broad-spectrum human antimicrobial peptide in the cathelicidin family. Potency assays in the form of minimal inhibitory concentration and vesicle leakage indicate that the single-tryptophan mutants, F6W and F17W, are as effective at killing bacteria and disrupting membranes as the native, tryptophan-free LL-37 peptide. Steady-state fluorescence and UV resonance Raman spectroscopy of F6W and F17W reveal molecular details of these tryptophan residues. The local environment polarity, hydrogen bond strength of the indole N-H moiety, and rotational freedom decrease for both F6W and F17W in the presence of carbonate ions relative to in pure distilled water; these results are consistent with burial of the hydrophobic region of alpha-helical LL-37 in oligomeric cores induced in the presence of carbonate ions. Differences in the spectroscopic properties of the carbonate-induced alpha-helical forms of F6W and F17W reflect the presence of a local lysine residue near F6W that makes the microenvironment of F6W more polar than that of F17W. In the presence of lipid vesicles, the mutants undergo additional loss of environment polarity, hydrogen bond strength, and rotational freedom. Quenching experiments utilizing brominated lipids reveal that the tryptophan residues in both mutants are essentially equidistant from the bilayer center and that bromines closer to the bilayer center, in the 9,10 positions, quench fluorescence more efficiently than those closer to the headgroups (6,7 positions). These results support carpeting or toroidal pore mechanisms of membrane disruption by LL-37 and demonstrate that the combination of tryptophan mutants and sensitive spectroscopic tools may provide important molecular clues about antimicrobial action. PMID:19894716

  8. Pre-resonance Raman spectra of some simple gases. [sulfur oxides, hydrogen sulfide, and nitrogen oxides

    NASA Technical Reports Server (NTRS)

    Low, P. W.

    1974-01-01

    The pre-resonance Raman spectra of SO2, N2O, and H2S were investigated using the 4880 A, 4727 A, and 4579 A lines of the argon ion laser. Although these molecules have electronic absorption bands in the near ultraviolet, none exhibit any pre-resonance enhancement within our experimental error of + or - 10%. Possible explanations taking into account the current theories for resonance Raman are discussed.

  9. Third-order nonlinearities in molecular hydrogen - Two-photon resonance enhanced third-harmonic generation and Raman scattering

    NASA Technical Reports Server (NTRS)

    Pan, C.-L.; She, C.-Y.; Fairbank, W. M., Jr.; Billman, K. W.

    1977-01-01

    Effects of quantum mechanical interferences on third-order susceptibilities in molecules are studied. First principle calculations for molecular hydrogen are presented and shown to agree with results derived from experimental stimulated Raman gain and spontaneous Raman cross-section data. 10 percent third-harmonic conversion efficiency in H2 at 1 atm without phase matching should require a 150 MW per sq cm at 4.81 microns. As little as 5.9-MW power is sufficient when the beam is properly focused. Resonance Raman scattering (RRS) is proposed for experimentally investigating the interference effects, which tend to reduce the strength of third-order nonlinear susceptibilities.

  10. Vibro-conformational study of F2S(O)NCN: FTIR, pre-resonance Raman effect, force field and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Alvarez, R. M. S.; Cutin, E. H.; Mack, H.-G.; Sala, O.; Della Védova, C. O.

    1994-12-01

    The FTIR spectrum for vapour and the Raman spectrum for the liquid of difluorosulphenilimine cyanide (F2S(O)NCN) are presented. CS symmetry is suggested for the main conformer in the liquid phase. Vibrational assignments are made for all but the torsional fundamental mode. The symmetry force constants were calculated using an approximate value for the torsion. The study was complemented by theoretical calculations at various levels of sophistication. According to the ab initio methods (HF/3-21G*, HF/6-31G*, MP2/6-31G*) two stable conformations of the compound exist in the gas phase. The main form possesses CS symmetry (δ(OSNC) = 180°, trans), whilst for the less stable rotamer C1 symmetry (δ(OSNC) = 4 to 26°, near-cis) is predicted.

  11. Exploring the potential of Raman and resonance Raman spectroscopy for quantitative analysis of duplex DNA

    NASA Astrophysics Data System (ADS)

    Schulze, H. G.; Bass, A.; Addison, C.; Hughesman, C.; So, A. P.; Haynes, C. A.; Blades, M. W.; Turner, R. F. B.

    2005-09-01

    Advances in DNA microarray fabrication technologies, expanding probe libraries, and new bioinformatics methods and resources have firmly established array-based techniques as mainstream bioanalytical tools and the application space is proliferating rapidly. However, the capability of these tools to yield truly quantitative information remains limited, primarily due to problems inherent to the use of fluorescence imaging for reading the hybridized arrays. The obvious advantages of fluorescence are the unrivaled sensitivity and simplicity of the instrumentation. There are disadvantages of this approach, however, such as difficulties in achieving optimal labeling of targets and reproducible signals (due to quenching, resonance energy transfer, photobleaching effects, etc.) that undermine precision. We are exploring alternative approaches, based mainly on Raman and resonance Raman spectroscopy, that in principle permit direct analysis of structural differences between hybridized and unhybridized probes, thereby eliminating the need for labeling the target analytes. We report here on the status of efforts to evaluate the potential of these methods based on a combination of measured data and simulated experiments involving short (12-mer) ssDNA oligomer probes with varying degrees of hybridized target DNA. Preliminary results suggest that it may be possible to determine the fraction of duplex probes within a single register on a DNA microarray from 100% down to 10% (or possibly less) with a precision of +/-2 5%. Details of the methods used, their implementation, and their potential advantages and limitations are presented, along with discussion of the utility of using 2DCOS methods to emphasize small spectral changes sensitive to interstrand H bonding, backbone flexibility, hypochromicity due to base-stacking in duplex structures and solvation effects.

  12. Franck-Condon processes in pentacene monolayers revealed in resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    He, Rui; Tassi, Nancy G.; Blanchet, Graciela B.; Pinczuk, Aron

    2011-03-01

    Franck-Condon processes in pentacene monolayers are revealed in resonance Raman scattering from intramolecular vibrations. The Raman intensities from a totally symmetric vibrational mode display resonance enhancement double peaks when incident or scattered photon energies overlap the free exciton (FE) optical emission. The two resonances are of about equal strength. This remarkable symmetry in the resonance Raman profile suggests that Franck-Condon overlap integrals for the respective vibronic transitions have the same magnitude, which could be explained by the small displacement of potential energy curves along the configuration coordinate upon the FE excitation. The interference between scattering amplitudes in the Raman resonance reveals quantum coherence of the symmetry-split states (Davydov doublet) of the lowest intrinsic singlet exciton in pentacene monolayers.

  13. Near-field enhanced ultraviolet resonance Raman spectroscopy using aluminum bow-tie nano-antenna.

    PubMed

    Li, Ling; Fang Lim, Shuang; Puretzky, Alexander A; Riehn, Robert; Hallen, H D

    2012-09-10

    An aluminum bow-tie nano-antenna is combined with the resonance Raman effect in the deep ultraviolet to dramatically increase the sensitivity of Raman spectra to a small volume of material, such as benzene used here. We further demonstrate gradient-field Raman peaks for several strong infrared modes. We achieve a gain of [Formula: see text] in signal intensity from the near field enhancement due to the surface plasmon resonance in the aluminum nanostructure. The on-line resonance enhancement contributes another factor of several thousands, limited by the laser line width. Thus, an overall gain of hundreds of million is achieved. PMID:23066168

  14. Calculation of intensity of a resonant Raman effect by organic molecules

    NASA Astrophysics Data System (ADS)

    Schelokov, R. V.; Yatsishen, V. V.

    2006-03-01

    There is a set of definition methods of the molecular substances composition and molecules performances, but the most sensing and in too time not influencing an explored sample is the method of resonant Raman effect (resonant Raman scattering, RRS). In the present work we viewed RRS on one of the most toxic substances - monomethyihydrazine. Result of the done work became an electronic absorption spectrum, an oscillatory spectrum and spectra of a resonant Raman scattering monomethylhydrazine without taking into account and taking into account of an interference of bands.

  15. High-sensitivity pesticide detection using particle-enhanced resonant Raman scattering

    NASA Astrophysics Data System (ADS)

    Ranjan, Bikas; Saito, Yuika; Verma, Prabhat

    2016-03-01

    The use of pesticides in agriculture has raised concerns, as even a small residual of pesticide on food can be harmful. It is therefore of great importance to develop a robust technique to detect tiny amounts of pesticides. Although Raman spectroscopy is frequently used for chemical identification, it is not suitable for extremely low molecular concentrations. We propose a technique called particle-enhanced resonant Raman spectroscopy to detect extremely low concentrations of pesticides, where gold nanoparticles of desired plasmonic resonance are synthesized to match the resonance in Raman scattering. We successfully demonstrated the detection of extremely low amounts of pesticides on oranges.

  16. Resonance raman spectroscopy of an ultraviolet-sensitive insect rhodopsin

    SciTech Connect

    Pande, C.; Deng, H.; Rath, P.; Callender, R.H.; Schwemer, J.

    1987-11-17

    The authors present the first visual pigment resonance Raman spectra from the UV-sensitive eyes of an insect, Ascalaphus macaronius (owlfly). This pigment contains 11-cis-retinal as the chromophore. Raman data have been obtained for the acid metarhodopsin at 10/sup 0/C in both H/sub 2/O and D/sub 2/O. The C=N stretching mode at 1660 cm/sup -1/ in H/sub 2/O shifts to 1631 cm/sup -1/ upon deuteriation of the sample, clearly showing a protonated Schiff base linkage between the chromophore and the protein. The structure-sensitive fingerprint region shows similarities to the all-trans-protonated Schiff base of model retinal chromophores, as well as to the octopus acid metarhodopsin and bovine metarhodopsin I. Although spectra measured at -100/sup 0/C with 406.7-nm excitation, to enhance scattering from rhodopsin (lambda/sub max/ 345 nm), contain a significant contribution from a small amount of contaminants (cytochrome(s) and/or accessory pigment) in the sample, the C=N stretch at 1664 cm/sup -1/ suggests a protonated Schiff base linkage between the chromophore and the protein in rhodopsin as well. For comparison, this mode also appears at approx. 1660 cm/sup -1/ in both the vertebrate (bovine) and the invertebrate (octopus) rhodopsins. These data are particularly interesting since the absorption maximum of 345 nm for rhodopsin might be expected to originate from an unprotonated Schiff base linkage. That the Schiff base linkage in the owlfly rhodopsin, like in bovine and in octopus, is protonated suggests that a charged chromophore is essential to visual transduction.

  17. Study of virus by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Moor, K.; Kitamura, H.; Hashimoto, K.; Sawa, M.; Andriana, B. B.; Ohtani, K.; Yagura, T.; Sato, H.

    2013-02-01

    Problem of viruses is very actual for nowadays. Some viruses, which are responsible for human of all tumors, are about 15 %. Main purposes this study, early detection virus in live cell without labeling and in the real time by Raman spectroscopy. Micro Raman spectroscopy (mRs) is a technique that uses a Raman spectrometer to measure the spectra of microscopic samples. According to the Raman spectroscopy, it becomes possible to study the metabolites of a live cultured cell without labeling. We used mRs to detect the virus via HEK 293 cell line-infected adenovirus. We obtained raman specters of lives cells with viruses in 24 hours and 7 days after the infection. As the result, there is some biochemical changing after the treatment of cell with virus. One of biochemical alteration is at 1081 cm-1. For the clarification result, we use confocal fluorescent microscopy and transmission electron microscopy (TEM).

  18. Raman spectroscopy and polarization: Selected case studies

    NASA Astrophysics Data System (ADS)

    Ossikovski, Razvigor; Picardi, Gennaro; Ndong, Gérald; Chaigneau, Marc

    2012-10-01

    We show, through several selected case studies, the potential benefits that can be obtained by controlling the polarization states of the exciting and scattered radiations in a Raman scattering experiment. When coupled with polarization control, Raman spectroscopy is thus capable of providing extra information on the structural properties of the materials under investigation. The experimental examples presented in this work are taken from the area of both conventional, i.e., far-field, as well as from near-field Raman spectroscopy. They cover topics such as the stress tensor measurement in strained semiconductor structures, the vibration mode assignment in pentacene thin films and the Raman scattering tensor determination from near-field measurements on azobenzene monolayers. The basic theory necessary for modelling the far- and near-field polarized Raman responses is also given and the model efficiency is illustrated on the experimental data.

  19. Resonant Raman detectors for noninvasive assessment of carotenoid antioxidants in human tissue

    NASA Astrophysics Data System (ADS)

    Gellermann, Werner; Sharifzadeh, Mohsen; Ermakova, Maia R.; Ermakov, Igor V.; Bernstein, P. S.

    2003-07-01

    Carotenoid antioxidants form an important part of the human body's anti-oxidant system and are thought to play an important role in disease prevention. Studies have shown an inverse correlation between high dietary intake of carotenoids and risk of certain cancers, heart disease and degenerative diseases. For example, the carotenoids lutein and zeaxanthin, which are present in high concentrations in the human retina, are thought to prevent age-related macular degeneration, the leading cause of blindness in the elderly in the Western world. We have developed various clinical prototype instruments, based on resonance Raman spectroscopy, that are able to measure carotenoid levels directly in the tissue of interest. At present we use the Raman technology to quantify carotenoid levels in the human retina, in skin, and in the oral cavity. We use resonant excitation of the π-conjugated molecules in the visible wavelength range and detect the molecules' carbon-carbon stretch frequencies. The spectral properties of the various carotenoids can be explored to selectively measure in some cases individual carotenoid species linked ot the prevention of cancer, in human skin. The instrumentation involves home-built, compact, high-throughput Raman systems capable of measuring physiological carotenoid concentrations in human subjects rapidly and quantitatively. The instruments have been demonstrated for field use and screening of tissue carotenoid status in large populations. In Epidemiology, the technology holds promise as a novel, noninvasive and objective biomarker of fruit and vegetable uptake.

  20. Time-resolved resonance Raman study of the. delta. delta. * excited state of Re sub 2 Cl sub 8 sup 2 minus and Re sub 2 Br sub 8 sup 2 minus

    SciTech Connect

    Schoonover, J.R.; Dallinger, R.F.; Killough, P.M.; Sattelberger, A.P.; Woodruff, W.H. )

    1991-03-06

    Time-resolved resonance Raman (TR{sup 3}) spectra have been obtained for Re{sub 2}X{sub 8}{sup 2{minus}} (X = Cl, Br) in the A{sub 2u} ({delta}{delta}*) electronically excited state, at ambient temperature in solution. The Tr{sup 3} spectra exhibit Raman peaks that are assigned to the three symmetric vibrations of the excited state: the Re-Re stretch, Re-X stretch, and the Re-Re-X deformation. In addition, a depolarized peak attributed to an asymmetric X-Re-X bend is observed. Comparison of the TR{sub 3} results to single-crystal vibronic spectra reported by others clearly shows the effects of crystal constraints and observation time scale upon the strucutre of the {delta}{delta}* excited state. The TR{sup 3} data, obtained in solution on the nanosecond time scale, indicate that the excited state relaxes to a staggared molecular structure (D{sub 4} or D{sub 4d} symmetry). The vibronic data, obtained on single crystals under cryogenic conditions, are consistent with an eclipsed (D{sub 4h}) structure, similar to that of the ground state. A comparative TR{sup 3} study of quadruply bonded complexes, including both octahalodirhenate ions and Mo{sub 2}(PMe{sub 3}){sub 4}Cl{sub 4} (which is precluded by steric factors from significant torsional distorition about the metal-metal bond), was essential in elucidating the excited-state structures.

  1. Characterization of heavily B-doped polycrystalline diamond films using Raman spectroscopy and electron spin resonance

    NASA Astrophysics Data System (ADS)

    Gonon, P.; Gheeraert, E.; Deneuville, A.; Fontaine, F.; Abello, L.; Lucazeau, G.

    1995-12-01

    Heavily B-doped polycrystalline diamond films ([B]≳1019 cm-3) are studied by Raman spectroscopy and electron spin resonance. The formation of an impurity band is accompanied by a Fano-type interference for the one-phonon scattering. Bands at 1200 and 500 cm-1 are observed in Raman spectroscopy for concentrations above 1020 cm-3. They are related to maxima in the phonon density of states, and are ascribed to disordered regions or crystalline regions of very small size. The concentration of defects associated with the paramagnetic signal observed around g=2.0030 increases drastically above 1021 B cm-3. The Mott insulator-metal transition is accompanied by the presence of a new paramagnetic signal (g=2.0007 for 2×1020 B cm-3, g=1.9990 for 1021 B cm-3) ascribed to free holes in the impurity band.

  2. Simulations of resonant Raman response in bundles of semiconductor carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Roslyak, Oleksiy; Piryatinski, Andrei; Doorn, Stephen; Haroz, Erik; Telg, Hagen; Duque, Juan; Crochet, Jared; Simpson, J. R.; Hight Walker, A. R.; LANL Collaboration; Fordham Collaboration; NIST Collaboration

    This work is motivated by an experimental study of resonant Raman spectroscopy under E22 excitation, which shows a new, sharp feature associated with bundling in (6,5) semiconductor carbon nanotubes. In order to provide an insight into the experimental data, we model Raman excitation spectra using our modified discrete dipole approximation (DDA) method. The calculations account for the exciton states polarized along and across the nanotube axis that are characterized by a small energy splitting. Strong polarization of the nanotubes forming the bundle results in the exciton state mixing whose spectroscopic signatures such as peaks positions, line widths, and depolarization ratio are calculated and compared to the experiment. Furthermore, the effects of the energy and structural disorder, as well as structural defects within the bundle are also examined and compared with the experimental data.

  3. Intercalation between antitumor anthracyclines and DNA as probed by resonance and surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Smulevich, G.; Mantini, A. R.; Casu, M.; Marzocchi, M. P.

    1991-05-01

    The antiturnor anthracyclincs, idarubicin (IDA ), adrianiycin (ADM), epirubicin (EPI), carminomycin (CAR) and 1 1-deoxycarminornycin (DCM), whose siructural formula includes a substituted hydroxyanthraquirionc chrornophore and a sugar residue, form intercalation complexes with DNA. The stacking interaction between the chromophore and the base-pairs of DNA gives rise to noticeable ciTects on resonance Raman (RR) and surface-enhanced resonance Raman (SERRS) scattering as well as on the absorption (ABS), its second derivative (D2) and fluorescence emission (FEM) spectra.

  4. Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

    ERIC Educational Resources Information Center

    Schnitzer, Cheryl S.; Reim, Candace Lawson; Sirois, John J.; House, Paul G.

    2010-01-01

    Advanced chemistry students are introduced to surface-enhanced resonance Raman scattering (SERRS) by studying how sodium copper chlorophyllin (CuChl) adsorbs onto silver colloids (CuChl/Ag) as a function of pH. Using both SERRS and visible extinction spectroscopy, the extent of CuChl adsorption and colloidal aggregation are monitored. Initially at…

  5. Surface-enhanced resonance Raman scattering of hemoproteins and those in complicated biological systems.

    PubMed

    Kitahama, Yasutaka; Ozaki, Yukihiro

    2016-08-15

    In this review article, we discuss surface-enhanced resonance Raman scattering (SERRS) studies of hemeproteins such as myoglobin, hemoglobin, and cytochrome on various metal substrates; for example, colloidal silver nanoparticles coated with and without self-assembled monolayers (SAM), a roughened silver electrode protected with and without SAM, a sharp silver tip, and colloidal gold nanoparticles coated with and without SAM. Moreover, we classify the studies in terms of an excitation wavelength; namely, excitation at the B- (Soret) band, Q- (α and β) band, and in the near infrared (NIR) range. In the SERRS studies with B band excitation, it has been shown that the hemeprotein on a silver surface takes a non-native form through detachment from the heme pocket in the protein. With Q band excitation, on the other hand, the change in SERRS has been explained by the orientation of the hemeprotein on the surface. Even by excitation in the NIR range, the peak positions are consistent with the assignment of the major vibrational modes of heme despite there being no resonance Raman effect. Thus, the SERRS of hemeproteins is influenced by a resonance Raman effect, LSPR, and interactions with the metal surface such as structural changes, orientation, and selective adsorption. Moreover, we discuss how SERRS has been applied to complicated biological systems such as living cells containing hemeprotein. For mitochondria, a change of the oxidation-state was observed by the electron transport chain in the cell and at different positions. As an example of a biomedical application of SERRS, the sensitive detection of malaria is presented. PMID:27381192

  6. Application of time-resolved resonance Raman spectroscopy to intramolecular electron transfer

    SciTech Connect

    Schoonover, J.R.; Strouse, G.F.; Chen, P.; Bates, D.; Meyer, T.J. )

    1993-06-09

    Time-resolved resonance Raman spectroscopy has been applied for the first time to the study of intramolecular electron transfer in a chromophore-quencher complex, based on a metal-to-ligand charge-transfer (MLCT) excited state. These measurements allow for (1) the identification of redox sites that are reached following excitation and (2) the inferring of structural information in short-lived intermediates. This technique is a more sensitive probe than transient absorption as shown by its application to the redox-separated complex shown below involving a pyridinium acceptor and a phenothiazine donor.

  7. Resonant Raman scattering from a charge-density-wave system (TTF-TCNQ)

    NASA Astrophysics Data System (ADS)

    Eldridge, J. E.; Lin, Y.; Mayadunne, T. C.; Montgomery, L. K.; Kaganov, S.; Miebach, T.

    1998-02-01

    We report the observation of strong new lines in the resonant Raman scattering from a powder sample of TTF-TCNQ, as the temperature is lowered and the fluctuating charge-density-wave (CDW) occurs. The intensity of these lines increases with decreasing temperature. The new lines are assigned to normally infrared-active B 3u out-of-plane intramolecular distortion modes of TCNQ, in agreement with the results of an X-ray study which found that the CDW on the TCNQ chain involved such an out-of-plane distortion of the TCNQ molecule. The new lines are much weaker in TSeF-TCNQ.

  8. Resonant Raman scattering and luminescence in CuInS{sub 2} crystals

    SciTech Connect

    Wakita, K.; Hirooka, H.; Yasuda, S.; Fujita, F.; Yamamoto, N.

    1998-01-01

    Resonant Raman scattering and luminescence have been examined for CuInS{sub 2} crystals grown by the traveling heater method (THM) and the iodine vapor transport method (IT). Resonant Raman spectra of CuInS{sub 2} have been observed, and the spectra show seven single-phonon peaks and one two-phonon peak. Among them, three single-phonon modes have been found in the low-Raman-shift region because of resonant enhancement of phonon modes. The enhancement of these phonon modes is caused by incoming resonance mediated by bound excitons on the THM crystal, while it is attributed to outgoing resonance due to intermediate states of free excitons on the IT crystal. {copyright} {ital 1998 American Institute of Physics.}

  9. Intensity Ratio of Resonant Raman Modes for (n , m) Enriched Semiconducting Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Piao, Yanmei; Simpson, Jeffrey; Streit, Jason; Ao, Geyou; Fagan, Jeffrey; Hight Walker, Angela

    Relative intensities of resonant Raman spectral features, specifically the radial breathing mode (RBM) and G modes, of eleven, chirality-enriched, single-wall carbon nanotube (SWCNT) species were established under second-order optical transition excitation. The results demonstrate a significantly under-recognized complexity in the evaluation of Raman spectra for the assignment of (n , m) population distributions. Strong chiral angle and mod dependencies affect the intensity ratio of the RBM to G modes and can result in misleading interpretations. Furthermore, we report five additional values for chirality dependent G+ and G- Raman peak positions and intensities, supporting accuracy in literature values, and extending the available data to cover more of the small diameter regime by including the first (5,4) second-order, resonance Raman spectra. Together, the Raman spectral library is demonstrated to be sufficient for decoupling multiple species via a spectral fitting process, and enable fundamental characterization even in mixed chiral population samples.

  10. Raman Spectroscopy.

    ERIC Educational Resources Information Center

    Gerrard, Donald L.

    1984-01-01

    Reviews literature on Raman spectroscopy from late 1981 to late 1983. Topic areas include: instrumentation and sampling; liquids and solutions; gases and matrix isolation; biological molecules; polymers; high-temperature and high-pressure studies; Raman microscopy; thin films and surfaces; resonance-enhanced and surface-enhanced spectroscopy; and…

  11. Resonance Raman Probes for Organelle-Specific Labeling in Live Cells.

    PubMed

    Kuzmin, Andrey N; Pliss, Artem; Lim, Chang-Keun; Heo, Jeongyun; Kim, Sehoon; Rzhevskii, Alexander; Gu, Bobo; Yong, Ken-Tye; Wen, Shangchun; Prasad, Paras N

    2016-01-01

    Raman microspectroscopy provides for high-resolution non-invasive molecular analysis of biological samples and has a breakthrough potential for dissection of cellular molecular composition at a single organelle level. However, the potential of Raman microspectroscopy can be fully realized only when novel types of molecular probes distinguishable in the Raman spectroscopy modality are developed for labeling of specific cellular domains to guide spectrochemical spatial imaging. Here we report on the design of a next generation Raman probe, based on BlackBerry Quencher 650 compound, which provides unprecedentedly high signal intensity through the Resonance Raman (RR) enhancement mechanism. Remarkably, RR enhancement occurs with low-toxic red light, which is close to maximum transparency in the biological optical window. The utility of proposed RR probes was validated for targeting lysosomes in live cultured cells, which enabled identification and subsequent monitoring of dynamic changes in this organelle by Raman imaging. PMID:27339882

  12. Resonance Raman Probes for Organelle-Specific Labeling in Live Cells

    NASA Astrophysics Data System (ADS)

    Kuzmin, Andrey N.; Pliss, Artem; Lim, Chang-Keun; Heo, Jeongyun; Kim, Sehoon; Rzhevskii, Alexander; Gu, Bobo; Yong, Ken-Tye; Wen, Shangchun; Prasad, Paras N.

    2016-06-01

    Raman microspectroscopy provides for high-resolution non-invasive molecular analysis of biological samples and has a breakthrough potential for dissection of cellular molecular composition at a single organelle level. However, the potential of Raman microspectroscopy can be fully realized only when novel types of molecular probes distinguishable in the Raman spectroscopy modality are developed for labeling of specific cellular domains to guide spectrochemical spatial imaging. Here we report on the design of a next generation Raman probe, based on BlackBerry Quencher 650 compound, which provides unprecedentedly high signal intensity through the Resonance Raman (RR) enhancement mechanism. Remarkably, RR enhancement occurs with low-toxic red light, which is close to maximum transparency in the biological optical window. The utility of proposed RR probes was validated for targeting lysosomes in live cultured cells, which enabled identification and subsequent monitoring of dynamic changes in this organelle by Raman imaging.

  13. Resonance Raman Probes for Organelle-Specific Labeling in Live Cells

    PubMed Central

    Kuzmin, Andrey N.; Pliss, Artem; Lim, Chang-Keun; Heo, Jeongyun; Kim, Sehoon; Rzhevskii, Alexander; Gu, Bobo; Yong, Ken-Tye; Wen, Shangchun; Prasad, Paras N.

    2016-01-01

    Raman microspectroscopy provides for high-resolution non-invasive molecular analysis of biological samples and has a breakthrough potential for dissection of cellular molecular composition at a single organelle level. However, the potential of Raman microspectroscopy can be fully realized only when novel types of molecular probes distinguishable in the Raman spectroscopy modality are developed for labeling of specific cellular domains to guide spectrochemical spatial imaging. Here we report on the design of a next generation Raman probe, based on BlackBerry Quencher 650 compound, which provides unprecedentedly high signal intensity through the Resonance Raman (RR) enhancement mechanism. Remarkably, RR enhancement occurs with low-toxic red light, which is close to maximum transparency in the biological optical window. The utility of proposed RR probes was validated for targeting lysosomes in live cultured cells, which enabled identification and subsequent monitoring of dynamic changes in this organelle by Raman imaging. PMID:27339882

  14. Characterization of carotenoids in soil bacteria and investigation of their photodegradation by UVA radiation via resonance Raman spectroscopy.

    PubMed

    Kumar B N, Vinay; Kampe, Bernd; Rösch, Petra; Popp, Jürgen

    2015-07-01

    A soil habitat consists of an enormous number of pigmented bacteria with the pigments mainly composed of diverse carotenoids. Most of the pigmented bacteria in the top layer of the soil are photoprotected from exposure to huge amounts of UVA radiation on a daily basis by these carotenoids. The photostability of these carotenoids depends heavily on the presence of specific features like a carbonyl group or an ionone ring system on its overall structure. Resonance Raman spectroscopy is one of the most sensitive and powerful techniques to detect and characterize these carotenoids and also monitor processes associated with them in their native system at a single cell resolution. However, most of the resonance Raman profiles of carotenoids have very minute differences, thereby making it extremely difficult to confirm if these differences are attributed to the presence of different carotenoids or if it is a consequence of their interaction with other cellular components. In this study, we devised a method to overcome this problem by monitoring also the photodegradation of the carotenoids in question by UVA radiation wherein a differential photodegradation response will confirm the presence of different carotenoids irrespective of the proximities in their resonance Raman profiles. Using this method, the detection and characterization of carotenoids in pure cultures of five species of pigmented coccoid soil bacteria is achieved. We also shed light on the influence of the structure of the carotenoid on its photodegradation which can be exploited for use in the characterization of carotenoids via resonance Raman spectroscopy. PMID:26029748

  15. Investigating the phase-dependent photochemical reaction dynamics of chlorine dioxide using resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Hayes, Sophia C.; Wallace, Paul M.; Bolinger, Josh C.; Reid, Philip J.

    Recent progress in understanding the phase-dependent reactivity demonstrated by halooxides is outlined. Specifically, resonance Raman intensity analysis (RRIA) and time-resolved resonance Raman (TRRR) studies of chlorine dioxide (OClO) photochemistry in solution are presented. Using RRIA, it has been determined that the excited-state structural evolution that occurs along the asymmetric-stretch coordinate in the gas phase is restricted in solution. The absence of evolution along this coordinate results in the preservation of groundstate symmetry in the excited state. The role of symmetry in defining the reaction coordinate and the solvent-solute interactions responsible for modification of the excited-state potential energy surface are discussed. TRRR studies are presented which demonstrate that geminate recombination of the primary photoproducts resulting in the reformation of ground-state OClO is a central feature of OClO photochemistry in solution. These studies also demonstrate that a fraction of photoexcited OClO undergoes photoisomerization to form ClOO, with the ground-state thermal decomposition of this species resulting in Cl production on the subnanosecond timescale. Finally, time-resolved anti-Stokes experiments are presented which demonstrate that the OClO vibrational-relaxation dynamics are solvent dependent. The current picture of OClO photochemistry derived from these studies is discussed, and future directions for study are outlined.

  16. Raman spectroscopic studies on bacteria

    NASA Astrophysics Data System (ADS)

    Maquelin, Kees; Choo-Smith, Lin-P'ing; Endtz, Hubert P.; Bruining, Hajo A.; Puppels, Gerwin J.

    2000-11-01

    Routine clinical microbiological identification of pathogenic micro-organisms is largely based on nutritional and biochemical tests. Laboratory results can be presented to a clinician after 2 - 3 days for most clinically relevant micro- organisms. Most of this time is required to obtain pure cultures and enough biomass for the tests to be performed. In the case of severely ill patients, this unavoidable time delay associated with such identification procedures can be fatal. A novel identification method based on confocal Raman microspectroscopy will be presented. With this method it is possible to obtain Raman spectra directly from microbial microcolonies on the solid culture medium, which have developed after only 6 hours of culturing for most commonly encountered organisms. Not only does this technique enable rapid (same day) identifications, but also preserves the sample allowing it to be double-checked with traditional tests. This, combined with the speed and minimal sample handling indicate that confocal Raman microspectroscopy has much potential as a powerful new tool in clinical diagnostic microbiology.

  17. Exploring the Potential of Stable Isotope (Resonance) Raman Microspectroscopy and Surface-Enhanced Raman Scattering for the Analysis of Microorganisms at Single Cell Level.

    PubMed

    Kubryk, Patrick; Kölschbach, Janina S; Marozava, Sviatlana; Lueders, Tillmann; Meckenstock, Rainer U; Niessner, Reinhard; Ivleva, Natalia P

    2015-07-01

    Raman microspectroscopy is a prime tool to characterize the molecular and isotopic composition of microbial cells. However, low sensitivity and long acquisition times limit a broad applicability of the method in environmental analysis. In this study, we explore the potential, the applicability, and the limitations of stable isotope Raman microspectroscopy (SIRM), resonance SIRM, and SIRM in combination with surface-enhanced Raman scattering (SERS) for the characterization of single bacterial cells. The latter two techniques have the potential to significantly increase sensitivity and decrease measurement times in SIRM, but to date, there are no (SERS-SIRM) or only a limited number (resonance SIRM) of studies in environmental microbiology. The analyzed microorganisms were grown with substrates fully labeled with the stable isotopes (13)C or (2)H and compounds with natural abundance of atomic isotopes ((12)C 98.89% or (1)H 99.9844%, designated as (12)C or (1)H, respectively). Raman bands of bacterial cell compounds in stable isotope-labeled microorganisms exhibited a characteristic red-shift in the spectra. In particular, the sharp phenylalanine band was found to be an applicable marker band for SIRM analysis of the Deltaproteobacterium strain N47 growing anaerobically on (13)C-naphthalene. The study of G. metallireducens grown with (13)C- and (2)H-acetate showed that the information on the chromophore cytochrome c obtained by resonance SIRM at 532 nm excitation wavelength can be successfully complemented by whole-organism fingerprints of bacteria cells achieved by regular SIRM after photobleaching. Furthermore, we present here for the first time the reproducible SERS analysis of microbial cells labeled with stable isotopes. Escherichia coli strain DSM 1116 cultivated with (12)C- or (13)C-glucose was used as a model organism. Silver nanoparticles synthesized in situ were applied as SERS media. We observed a reproducible red-shift of an adenine-related marker band

  18. Raman Study of SWNT Under High Pressure

    NASA Astrophysics Data System (ADS)

    Venkateswaran, U.; Rao, A. M.; Richter, E.; Eklund, P. C.; Smalley, R. E.

    1998-03-01

    A gasketed Merrill-Bassett-type diamond anvil cell was used for high pressure Raman measurements at room temperature. A 4:1 methanol-ethanol mixture served as the pressure transmitting medium. The radial mode (denoted as R, occuring at 186 cm-1 at 1 bar) and tangential modes (designated T_1, T_2, and T_3, located, respectively, at 1550, 1567, and 1593 cm-1 at 1 bar) were recorded for several representative pressures. With increasing pressure, both the R and T modes shift to higher frequencies with gradual weakening of intensity and broadening of linewidth. The radial mode disappears around ~ 2 GPa whereas the tangential modes, albeit weak in intensity, persist until 5.2 GPa. The decrease in Raman intensity under pressure can be attributed to a loss of resonance, since the strong Raman signals observed at ambient pressure have been interpreted as due a resonance with the electronic bands [1]. The R and T mode frequencies are fit to quadratic function of pressure i.e., ω=ω(0)+aP+bP^2 where `a' represents the linear pressure shift of the mode frequency which is proportional to the mode Gruneisen parameter. The linear pressure coefficient for the R mode is found to be nearly twice that of the high frequency T mode. A. M. Rao et al., Science 275, 187, 1997

  19. Quantum dynamics and spectra of vibrational Raman-resonance fluorescence in a two-mode cavity

    NASA Astrophysics Data System (ADS)

    Ooi, C. H. Raymond; Sete, Eyob A.; Liu, W. M.

    2015-12-01

    We study the classically driven two-level system with its center-of-mass motion vibrating in a harmonic trap and coupled to the photons in a two-mode cavity. The first mode is resonant to the driving field and an electronic transition. The second mode is off-resonant, forming a vibrational-assisted Raman transition. Using an exact numerical method, we investigate the quantum dynamics of the light emitted by the atom and the cavity modes. We analyze and compare the corresponding atomic and intracavity photon spectra for a range of the driving laser field and the cavity coupling strengths. The results provide better understanding of the effects of the laser field and atom-cavity coupling strengths on quantum interference effects and photon blockade, particularly the Mollow's triplet and the Autler-Townes splitting in the good and bad cavity limits.

  20. High-resolution inverse Raman and resonant-wave-mixing spectroscopy

    SciTech Connect

    Rahn, L.A.

    1993-12-01

    These research activities consist of high-resolution inverse Raman spectroscopy (IRS) and resonant wave-mixing spectroscopy to support the development of nonlinear-optical techniques for temperature and concentration measurements in combustion research. Objectives of this work include development of spectral models of important molecular species needed to perform coherent anti-Stokes Raman spectroscopy (CARS) measurements and the investigation of new nonlinear-optical processes as potential diagnostic techniques. Some of the techniques being investigated include frequency-degenerate and nearly frequency-degenerate resonant four-wave-mixing (DFWM and NDFWM), and resonant multi-wave mixing (RMWM).

  1. Resonance Raman spectra of some radiolytically prepared halogen derivatives of para-benzosemiquinone radical anion

    SciTech Connect

    Tripathi, G.N.R.; Schuler, R.H.

    1982-03-01

    The resonance Raman spectra have been obtained on radiolytically and chemically prepared halogen derivatives (chloro-, bromo-, 2.5 dichloro-, tetra chloro-, and tetra bromo-) of p-benzosemiquinone radical anion. Excitation is in the moderately intense absorption band at 430--460 nm. All Raman spectra show a strongly resonance enhanced and polarized line corresponding to a vibrational frequency of 1590--1620 cm/sup -1/ which is assigned to the Wilson phenyl mode 8a (CC stretch). A number of weaker lines are also observed and their assignment discussed. The electronic transitions in resonance are identified as /sup 2/B/sub 3g/--/sup 2/B/sub 1u/ (in D/sub 2h/ point group) in view of the resonance Raman band intensities. This supports the assignment by Harada based on ASMO CI calculations which has recently been in dispute.

  2. Zeaxanthin ([3R,3'R]-beta, beta-carotene-3-3'diol) as a resonance Raman and visible absorption probe of membrane structure.

    PubMed Central

    Mendelsohn, R; Van Holten, R W

    1979-01-01

    When zeaxanthin ([3R,3R']-beta, beta-carotene-3,3'diol) is inserted into phospholipid dispersions and the latter heated through their gel-liquid crystal phase transitions, large changes are noted in the resonance Raman and absorption spectra of the carotenoid molecule. By analogy with the data of Carey and co-workers (J. Raman Spectrosc. 6:282) who studied the aggregation of zeaxanthin in acetone-water solutions, it is suggested that the carotenoid aggregates in the phospholipid gel state while forming a monomer in liquid crystal phases. The alterations in both the visible absorption and resonance Raman data have been used to monitor phospholipid phase behavior in dipalmitoylphosphatidylcholine and distearoylphosphatidylcholine, (DSPC) one-component systems and binary mixtures. The phase diagram obtained for the binary system, as constructed from visible absorption and resonance Raman data, is compared with that of Shimshick and McConnell (Biochemistry. 12:2351) obtained from electron spin resonance (ESR) studies. Although the agreement between absorption and ESR data is generally satisfactory, onset temperatures for phase separation at low DSPC mole fractions deduced from resonance Raman measurements are several degrees lower than those from the other methods. Nevertheless, the use of zeaxanthin as a resonance Raman and visible absorption probe behavior will be useful in some situations where ordinary Raman spectroscopic data cannot be obtained easily. The advantage of the resonance Raman approach is illustrated in a study of the phase behavior of a phospholipid extract of a cel- mutant of Neurospora crassa. A phase separation region is observed with onset and completion temperatures of -19 and -6 degrees C, respectively. PMID:162448

  3. Laser Raman Spectroscopy in studies of corrosion and electrocatalysis

    SciTech Connect

    Melendres, C.A.

    1988-01-01

    Laser Raman Spectroscopy (LRS) has become an important tool for the in-situ structural study of electrochemical systems and processes in recent years. Following a brief introduction of the experimental techniques involved in applying LRS to electrochemical systems, we survey the literature for examples of studies in the inhibition of electrode reactions by surface films (e.g., corrosion and passivation phenomena) as well as the acceleration of reactions by electro-sorbates (electrocatalysis). We deal mostly with both normal and resonance Raman effects on fairly thick surface films in contrast to surface-enhanced Raman investigations of monolayer adsorbates, which is covered in another lecture. Laser Raman spectroelectrochemical studies of corrosion and film formation on such metals as Pb, Ag, Fe, Ni, Co, Cr, Au, stainless steel, etc. in various solution conditions are discussed. Further extension of the technique to studies in high-temperature and high-pressure aqueous environments is demonstrated. Results of studies of the structure of corrosion inhibitors are also presented. As applications of the LRS technique in the area of electrocatalysis, we cite studies of the structure of transition metal macrocyclic compounds, i.e., phthalocyanines and porphyrins, used for catalysis of the oxygen reduction reaction. 104 refs., 20 figs.

  4. Carotenoid Analysis of Halophilic Archaea by Resonance Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Marshall, Craig P.; Leuko, Stefan; Coyle, Candace M.; Walter, Malcolm R.; Burns, Brendan P.; Neilan, Brett A.

    2007-08-01

    Recently, halite and sulfate evaporate rocks have been discovered on Mars by the NASA rovers, Spirit and Opportunity. It is reasonable to propose that halophilic microorganisms could have potentially flourished in these settings. If so, biomolecules found in microorganisms adapted to high salinity and basic pH environments on Earth may be reliable biomarkers for detecting life on Mars. Therefore, we investigated the potential of Resonance Raman (RR) spectroscopy to detect biomarkers derived from microorganisms adapted to hypersaline environments. RR spectra were acquired using 488.0 and 514.5 nm excitation from a variety of halophilic archaea, including Halobacterium salinarum NRC-1, Halococcus morrhuae, and Natrinema pallidum. It was clearly demonstrated that RR spectra enhance the chromophore carotenoid molecules in the cell membrane with respect to the various protein and lipid cellular components. RR spectra acquired from all halophilic archaea investigated contained major features at approximately 1000, 1152, and 1505 cm-1. The bands at 1505 cm-1 and 1152 cm-1 are due to in-phase C=C (ν1 ) and C-C stretching ( ν2 ) vibrations of the polyene chain in carotenoids. Additionally, in-plane rocking modes of CH3 groups attached to the polyene chain coupled with C-C bonds occur in the 1000 cm-1 region. We also investigated the RR spectral differences between bacterioruberin and bacteriorhodopsin as another potential biomarker for hypersaline environments. By comparison, the RR spectrum acquired from bacteriorhodopsin is much more complex and contains modes that can be divided into four groups: the C=C stretches (1600-1500 cm-1), the CCH in-plane rocks (1400-1250 cm-1), the C-C stretches (1250-1100 cm-1), and the hydrogen out-of-plane wags (1000-700 cm-1). RR spectroscopy was shown to be a useful tool for the analysis and remote in situ detection of carotenoids from halophilic archaea without the need for large sample sizes and complicated extractions, which are

  5. Double resonance surface enhanced Raman scattering substrates: an intuitive coupled oscillator model.

    PubMed

    Chu, Yizhuo; Wang, Dongxing; Zhu, Wenqi; Crozier, Kenneth B

    2011-08-01

    The strong coupling between localized surface plasmons and surface plasmon polaritons in a double resonance surface enhanced Raman scattering (SERS) substrate is described by a classical coupled oscillator model. The effects of the particle density, the particle size and the SiO2 spacer thickness on the coupling strength are experimentally investigated. We demonstrate that by tuning the geometrical parameters of the double resonance substrate, we can readily control the resonance frequencies and tailor the SERS enhancement spectrum. PMID:21934853

  6. Time-resolved resonance Raman observation of tetrafluoro-p-benzosemiquinone anion radical. [Pulse radiolysis

    SciTech Connect

    Tripathi, G.N.R.; Schuler, R.H.

    1983-08-04

    Time-resolved resonance Raman spectroscopy has been used to examine tetrafluoro-p-benzosemiquinone radical anion produced in the pulse radiolytic oxidation of tetrafluorohydroquinone in aqueous solution. This radical is much more reactive than p-benzosemiquinone and is observed to decay on the millisecond time scale in both Raman and pulse radiolytic experiments. For the Raman experiments excitation was on the red edge of the moderately strong absorption band of this radical at 430 nm. Two resonance-enhanced Raman bands are exhibited at 1556 and 1677 cm/sup -1/ and are assigned to the in-phase CO and symmetrical CC stretch vibrations. These frequencies are considerably higher than the corresponding values of 1435 and 1620 cm/sup -1/ observed in this radical's protonated counterpart. The relatively large increase in the CO stretch frequency, in particular, indicates that fluorination induces a substantial increase in the quinoid character of this radical. 3 figures, 1 table.

  7. Remote detection of trace effluents using Resonance Raman spectroscopy: Field results and evaluation

    SciTech Connect

    Sedlacek, A.J.; Chen, C.L.

    1995-10-01

    Resonance Raman spectroscopy (RRS) possesses many characteristics that are important for detecting, identifying and monitoring chemical effluents. Raman scattering is a coherent, inelastic, two-photon scattering process where an exciting photon of energy h{nu} promotes a molecule to a virtual level and the subsequently emitted photon is shifted in frequency in accordance with the rotational-vibrational structure of the irradiated species, thereby providing a unique fingerprint of the molecule. Under resonance enhancement, the Raman scattering cross-sections have been observed to increase up to 6 orders of magnitude above the normal scattering cross-sections, thereby providing the practical basis for a remote chemical sensor. Some of the other advantages that a Raman sensor possesses are: (1) very high selectivity (chemical specific fingerprints), (2) independence of the spectral fingerprint on 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 or solutions), (5) no absolute calibration is necessary because all Raman signals observed from a given species can be compared with the Raman signal for N{sub 2}, whose concentration is known very accurately, and (6) insensitivity of the Raman signature to environmental conditions (no quenching, or interference from water vapor). In this presentation, the technology of resonance Raman spectroscopy as applied to the detection of narcotics production activities will be presented along with some recent experimental results.

  8. Raman microspectroscopic study of oral buccal mucosa

    NASA Astrophysics Data System (ADS)

    Behl, Isha; Mamgain, Hitesh; Deshmukh, Atul; Kukreja, Lekha; Hole, Arti R.; Krishna, C. Murali

    2014-03-01

    Oral cancer is the most common cancer among Indian males, with 5-year- survival-rates of less than 50%. Efficacy of Raman spectroscopic methods in non-invasive and objective diagnosis of oral cancers and confounding factors has already been demonstrated. The present Raman microspectroscopic study was undertaken for in-depth and site-specific analysis of normal and tumor tissues. 10 normal and 10 tumors unstained sections from 20 tissues were accrued. Raman data of 160 x 60 μm and 140 x 140 μm in normal and tumor sections, respectively, were acquired using WITec alpha 300R equipped with 532 nm laser, 50X objective and 600 gr/mm grating. Spectral data were corrected for CCDresponse, background. First-derivitized and vector-normalized data were then subjected to K-mean cluster analysis to generate Raman maps and correlated with their respective histopathology. In normal sections, stratification among epithelial layers i.e. basal, intermediate, superficial was observed. Tumor, stromal and inflammatory regions were identified in case of tumor section. Extracted spectra of the pathologically annotated regions were subjected to Principal component analysis. Findings suggest that all three layers of normal epithelium can be differentiated against tumor cells. In epithelium, basal and superficial layers can be separated while intermediate layer show misclassifications. In tumors, discrimination of inflammatory regions from tumor cells and tumor-stroma regions were observed. Finding of the study indicate Raman mapping can lead to molecular level insights of normal and pathological states.

  9. Identifying or measuring selected substances or toxins in a subject using resonant raman signals

    NASA Technical Reports Server (NTRS)

    Lambert, James L. (Inventor); Borchert, Mark S. (Inventor)

    2005-01-01

    Methods and systems of the present invention identify the presence of and/or the concentration of a selected analyte in a subject by: (a) illuminating a selected region of the eye of a subject with an optical excitation beam, wherein the excitation beam wavelength is selected to generate a resonant Raman spectrum of the selected analyte with a signal strength that is at least 100 times greater than Raman spectrums generated by non-resonant wavelengths and/or relative to signals of normal constituents present in the selected region of the eye; (b) detecting a resonant Raman spectrum corresponding to the selected illuminated region of the eye; and (c) identifying the presence, absence and/or the concentration of the selected analyte in the subject based on said detecting step. The apparatus may also be configured to be able to obtain biometric data of the eye to identify (confirm the identity of) the subject.

  10. Resonance effects in the Raman scattering of monolayer and few-layer MoSe2

    NASA Astrophysics Data System (ADS)

    Soubelet, P.; Bruchhausen, A. E.; Fainstein, A.; Nogajewski, K.; Faugeras, C.

    2016-04-01

    Using resonant Raman scattering spectroscopy with 25 different laser lines, we describe the Raman scattering spectra of monolayer and multilayer 2H-molybdenum diselenide (MoSe2) as well as the different resonances affecting the most pronounced features. For high-energy phonons, both A - and E -symmetry type phonons present resonances with A and B excitons of MoSe2 together with a marked increase of intensity when exciting at higher energy, close to the C -exciton energy. We observe symmetry-dependent exciton-phonon coupling affecting mainly the low-energy rigid layer phonon modes. The shear mode for multilayer displays a pronounced resonance with the C exciton while the breathing mode has an intensity that grows with the excitation laser energy, indicating a resonance with electronic excitations at energies higher than that of the C exciton.

  11. State-by-state investigation of destructive interference in resonance Raman spectra of neutral tyrosine and the tyrosinate anion with the simplified sum-over-states approach.

    PubMed

    Cabalo, Jerry B; Saikin, Semion K; Emmons, Erik D; Rappoport, Dmitrij; Aspuru-Guzik, Alán

    2014-10-16

    UV resonance Raman scattering is uniquely sensitive to the molecular electronic structure as well as intermolecular interactions. To better understand the relationship between electronic structure and resonance Raman cross section, we carried out combined experimental and theoretical studies of neutral tyrosine and the tyrosinate anion. We studied the Raman cross sections of four vibrational modes as a function of excitation wavelength, and we analyzed them in terms of the contributions of the individual electronic states as well as of the Albrecht A and B terms. Our model, which is based on time-dependent density functional theory (TDDFT), reproduced the experimental resonance Raman spectra and Raman excitation profiles for both studied molecules with good agreement. We found that for the studied modes, the contributions of Albrecht's B terms in the Raman cross sections were important across the frequency range spanning the L(a,b) and B(a,b) electronic excitations in tyrosine and the tyrosinate anion. Furthermore, we demonstrated that interference with high-energy states had a significant impact and could not be neglected even when in resonance with a lower-energy state. The symmetry of the vibrational modes served as an indicator of the dominance of the A or B mechanisms. Excitation profiles calculated with a damping constant estimated from line widths of the electronic absorption bands had the best consistency with experimental results. PMID:25233377

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

    NASA Astrophysics Data System (ADS)

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

    1982-08-01

    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.

  13. Implantation effects on resonant Raman scattering in CdTe and Cd 0.23Hg 0.77Te

    NASA Astrophysics Data System (ADS)

    Ramsteiner, M.; Lusson, A.; Wagner, J.; Koidl, P.; Bruder, M.

    1990-04-01

    We have studied In + implanted CdTe and Cd 0.23Hg 0.77Te by resonant Raman scattering. The laser excitation was in resonance with the EO + Δ O band gap in CdTe or the E1 gap in Cd 0.23Hg 0.77Te. Under these conditions dipole forbidden but defect ind scattering by one longitudinal optical (LO) phonon as well as Fröhlich-induced two-LO phonon scattering is observed. In both cases scattering is found to be strongly affected by ion implantation. In + was implanted at an ion energy of 350 keV with doses ranging from 10 11 to 5×10 14 ions/cm 2. The intensity ratio of the one-LO phonon lines is found to be a quantitative measure of the implantation damage in CdTe and Cd 0.23Hg 0.77Te even for doses as low as 10 11 ions/cm 2. It is shown that the observed effects of implantation damage on resonant Raman scattering by LO phonons are due to a broadening and an energy shift of the corresponding resonances in the Raman scattering efficiency.

  14. Resonance Raman Spectroscopy of Extreme Nanowires and Other 1D Systems

    PubMed Central

    Smith, David C.; Spencer, Joseph H.; Sloan, Jeremy; McDonnell, Liam P.; Trewhitt, Harrison; Kashtiban, Reza J.; Faulques, Eric

    2016-01-01

    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

  15. Monitoring and trace detection of hazardous waste and toxic chemicals using resonance Raman spectroscopy

    SciTech Connect

    Sedlacek, A.J. III; Dougherty, D.R.; Chen, C.L.

    1993-04-01

    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.

  16. Monitoring and trace detection of hazardous waste and toxic chemicals using resonance Raman spectroscopy

    SciTech Connect

    Sedlacek, A.J. III; Dougherty, D.R.; Chen, C.L.

    1993-01-01

    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.

  17. Resonance Raman Spectroscopy of Extreme Nanowires and Other 1D Systems.

    PubMed

    Smith, David C; Spencer, Joseph H; Sloan, Jeremy; McDonnell, Liam P; Trewhitt, Harrison; Kashtiban, Reza J; Faulques, Eric

    2016-01-01

    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

  18. Synthesis of twisted bilayer graphene and studies of its low energy Raman modes

    NASA Astrophysics Data System (ADS)

    Chung, Ting Fung; He, Rui; Delaney, Conor; Keiser, Courtney; Jauregui, Luis A.; Shand, Paul M.; Chancey, C. C.; Wang, Yanan; Bao, Jiming; Chen, Yong P.

    2014-03-01

    We have synthesized bilayer graphene on copper foils with different twist angles and stacking orders using chemical vapor deposition. Raman spectroscopy has been used to study twisted bilayer graphene (tBLG) transferred on Si/SiO2 substrate, focusing on low frequency Raman modes below 200 cm-1. The modes are found in a small range of twist angle at which the G Raman peak is under resonance conditions with corresponding laser energy. The ~ 94 cm-1 mode (ZO'L) and ~ 160 cm-1 (ZO'H) modes (measured with a 532 nm laser) are assigned to the fundamental layer breathing vibration (ZO' mode) associated with different phonon wavenumbers, indicating different phonon scattering processes. We identify that the ZO'L mode shares the same resonance enhancement mechanism as G Raman mode arising from van Hove singularities (vHs) in the band structure of tBLG. The ZO'H mode was previously observed, related to the superlattice induced wavevector. The dependence of ZO'L mode frequency and line width on the twist angle can be understood by the double-resonance Raman scattering. We also observe another lower energy Raman mode at ~ 52 cm-1, whose origin is yet to be understood. We have also measured the doping dependence of Raman modes in tBLG. Our results probe the interlayer coupling and phonon dispersions in tBLG.

  19. Fourier-transform resonance Raman spectroscopy of intermediates of the phytochrome photocycle.

    PubMed

    Matysik, J; Hildebrandt, P; Schlamann, W; Braslavsky, S E; Schaffner, K

    1995-08-22

    The parent states of the 124-kDa phytochrome (phy A from Avena sativa) and intermediates of its photocycle were studied by low-temperature Fourier-transform resonance Raman spectroscopy. Spectra of the primary photoproducts I700 and lumi-F and of the thermal intermediate meta-F have been obtained for the first time. The spectra of the stable photochromic forms of photochrome, Pr and Pfr, presented in this work are significantly better in signal-to-noise ratio and resolution than previously published spectra, demonstrating the distinct advantages of our experimental approach. The high spectral quality allows for the identification of subtle details of the vibrational band pattern so that the resonance Raman spectra, which have been measured from samples in H2O and D2O, constitute a solid basis for the structural analysis of the various forms of phytochrome. Notwithstanding the current uncertainty in the vibrational assignment of many resonance Raman bands, the spectral changes of the tetrapyrrole chromophore can plausibly be interpreted in terms of conformational changes at two different methine bridges, i.e., torsions around two single bonds and the E/Z isomerization of a double bond. Within the framework of this interpretation, which is based on a vibrational analysis of biliverdin dimethyl ester (Smith, K. Matysik, J., Hlldebrandt, P., & Mark, F. (1993) J. Phys. Chem. 97, 11887-11900), a consistent model is proposed to describe the molecular events in the chromophore during the photocycle. The involvement of a proton transfer in the primary photoprocess of Pr can safely be ruled out. However, previous conclusions concerning the chromophore protonation in the individual states appear premature at the present state of the vibrational assignment. In particular, the attribution of a broad band at 1100 cm-1 to the N-H out-of-plane bending of the protonated pyrrolenin nitrogen (Hildebrandt, P., Hoffmann, A., Lindemann, P., Heibel, G., Braslavsky, S. E., Schaffner, K

  20. Resonance Raman Spectra of o-Safranin Dye, Free and Adsorbed on Silver Nanoparticles: Experiment and Density Functional Theory Calculation.

    PubMed

    Ricci, Marilena; Platania, Elena; Lofrumento, Cristiana; Castellucci, Emilio M; Becucci, Maurizio

    2016-07-14

    The properties of o-Safranin (SO) dye in the first electronic excited state were studied with combined experimental and theoretical methods. The electronic absorption spectra of SO molecules are measured in water solution and in the presence of silver nanoparticles. The normal Raman (NRS) and resonance Raman (RR) spectra of solid SO and the surface enhanced Raman (SERS) and surface enhanced resonance Raman (SE[R]RS) spectra of SO adsorbed on silver nanoparticles are measured at different excitation energies. The enhancement factors for selected vibrational bands of the RR, SERS, and SE[R]RS spectra of SO have been obtained with respect to the NRS spectra of the solid after a careful evaluation of the experimental conditions. The data furnished useful information on the excited electronic states and the interactions of SO with silver nanoparticles. The experimental results are discussed on the basis of DFT and TD-DFT calculations (B3LYP/6-311+G(d,p)) on the isolated SO molecule. PMID:27139691

  1. Elucidation of reactive wavepackets by two-dimensional resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Guo, Zhenkun; Molesky, Brian P.; Cheshire, Thomas P.; Moran, Andrew M.

    2015-09-01

    Traditional second-order kinetic theories fail to describe sub-picosecond photochemical reactions when solvation and vibrational dephasing undermine the assumption of equilibrium initial conditions. Four-wave mixing spectroscopies may reveal insights into such non-equilibrium processes but are limited by the single "population time" available in these types of experiments. Here, we use two-dimensional resonance Raman (2DRR) spectroscopy to expose correlations between coherent nuclear motions of the reactant and product in the photodissociation reaction of triiodide. It is shown that the transition of a nuclear wavepacket from the reactant (triiodide) to product (diiodide) states gives rise to a unique pattern of 2DRR resonances. Peaks associated with this coherent reaction mechanism are readily assigned, because they are isolated in particular quadrants of the 2DRR spectrum. A theoretical model in which the chemical reaction is treated as a vibronic coherence transfer transition from triiodide to diiodide reproduces the patterns of 2DRR resonances detected in experiments. These signal components reveal correlation between the nonequilibrium geometry of triiodide and the vibrational coherence frequency of diiodide. The 2DRR signatures of coherent reaction mechanisms established in this work may generalize to studies of ultrafast energy and charge transfer processes.

  2. Elucidation of reactive wavepackets by two-dimensional resonance Raman spectroscopy

    SciTech Connect

    Guo, Zhenkun; Molesky, Brian P.; Cheshire, Thomas P.; Moran, Andrew M.

    2015-09-28

    Traditional second-order kinetic theories fail to describe sub-picosecond photochemical reactions when solvation and vibrational dephasing undermine the assumption of equilibrium initial conditions. Four-wave mixing spectroscopies may reveal insights into such non-equilibrium processes but are limited by the single “population time” available in these types of experiments. Here, we use two-dimensional resonance Raman (2DRR) spectroscopy to expose correlations between coherent nuclear motions of the reactant and product in the photodissociation reaction of triiodide. It is shown that the transition of a nuclear wavepacket from the reactant (triiodide) to product (diiodide) states gives rise to a unique pattern of 2DRR resonances. Peaks associated with this coherent reaction mechanism are readily assigned, because they are isolated in particular quadrants of the 2DRR spectrum. A theoretical model in which the chemical reaction is treated as a vibronic coherence transfer transition from triiodide to diiodide reproduces the patterns of 2DRR resonances detected in experiments. These signal components reveal correlation between the nonequilibrium geometry of triiodide and the vibrational coherence frequency of diiodide. The 2DRR signatures of coherent reaction mechanisms established in this work may generalize to studies of ultrafast energy and charge transfer processes.

  3. Electronic Resonance Enhancement in Raman and CARS Spectroscopy: Surface Enhanced Scattering of Highly Fluorescent Molecules

    NASA Astrophysics Data System (ADS)

    Lawhead, Carlos; Ujj, Laszlo

    2015-03-01

    Surface enhanced Raman spectroscopy (SERS) is an extremely useful tool in increasing sensitivity of Raman spectroscopy; this technique significantly increases the signal from vibrational resonances which can overcome background fluoresces. Silver nanoparticles coated substrates and the silver nanoparticles in solution were used on a variety of fluorescent molecules in order to overcome sample complexities and measure the vibrational spectra. The possible enhancement of SERS using a coherent Raman (CARS) method was investigated, but enhancement factors due to Surface Enhanced CARS have yet to be verified. The instrument used was developed in the University of West Florida Physics Department utilized the second harmonic of a Nd:YAG laser to provide the excitation wavelength at 532 nm and is capable of both transmission and reflection Raman measurements. Special thanks to the UWF Office of Undergraduate Research.

  4. Phase-locking transition in Raman combs generated with whispering gallery mode resonators.

    PubMed

    Lin, Guoping; Chembo, Yanne K

    2016-08-15

    We investigate the mechanisms leading to phase locking in Raman optical frequency combs generated with ultrahigh Q crystalline whispering gallery mode disk resonators. We show that several regimes can be triggered depending on the pumping conditions, such as single-frequency Raman lasing, multimode operation involving more than one family of cavity eigenmodes, and Kerr-assisted Raman frequency comb generation. The phase locking and coherence of the combs are experimentally monitored through the measurement of beat signal spectra. These phase-locked combs, which feature high coherence and wide spectral spans, are obtained with pump powers in the range of a few tens of mW. In particular, Raman frequency combs with multiple free-spectral range spacings are reported, and the measured beat signal in the microwave domain features a 3 dB linewidth smaller than 50 Hz, thereby indicating phase locking. PMID:27519071

  5. Comparative study of the two-phonon Raman bands of silicene and graphene

    NASA Astrophysics Data System (ADS)

    Popov, Valentin N.; Lambin, Philippe

    2016-06-01

    We present a computational study of the two-phonon Raman spectra of silicene and graphene within a density-functional non-orthogonal tight-binding model. Due to the presence of linear bands close to the Fermi energy in the electronic structure of both structures, the Raman scattering by phonons is resonant. We find that the Raman spectra exhibit a crossover behavior for laser excitation close to the π-plasmon energy. This phenomenon is explained by the disappearance of certain paths for resonant Raman scattering and the appearance of other paths beyond this energy. Besides that, the electronic joint density of states (DOS) is divergent at this energy, which is reflected on the behavior of the Raman bands of the two structures in a qualitatively different way. Additionally, a number of Raman bands, originating from divergent phonon DOS at the M point and at points, inside the Brillouin zone, is also predicted. The calculated spectra for graphene are in excellent agreement with available experimental data. The obtained Raman bands can be used for structural characterization of silicene and graphene samples by Raman spectroscopy.

  6. Resonance Raman intensity analysis of ClNO(2) dissolved in methanol.

    PubMed

    Trimithioti, Marilena; Hayes, Sophia C

    2013-01-17

    Halogens such as chlorine are converted from halides, including ClNO(2), to reactive radicals by UV solar radiation. These radicals can affect ozone production and destruction in the stratosphere. Recently, it became clear that halogen radicals can also play a significant role in the chemistry of the troposphere. The photochemistry of ClNO(2) has been the subject of several studies in the gas and solid state that demonstrated a clear phase-dependent reactivity. Here, we report our initial studies of nitryl chloride in solution. Resonance Raman (RR) spectra of ClNO(2) dissolved in methanol after excitation within the 1(1)A(1)-2(1)A(1) absorption band (D band) in the region 200-240 nm are presented. RR intensity along the NO symmetric stretch coordinate (v(1)) at 1291 cm(-1) is observed at all excitation wavelengths, whereas limited intensity corresponding to the transition of the N-Cl symmetric stretch (v(3)) was only observed at 199.8 nm, whereas no intensity corresponding to the O-N-O symmetric bend (v(2)) was observed. Depolarization ratios and absolute resonance Raman cross sections for v(1) were obtained at several excitation wavelengths spanning the D band. Depolarization ratios were found to deviate significantly from 1/3, consistent with more than a single dipole-allowed electronic transition contributing to the scattering. RR intensity analysis (RRIA) reveals that two closely spaced excited electronic states contribute to the scattering, which are dissociative along the Cl-N coordinate. In this study the role the solvent environment plays in ClNO(2) state energetics and excited structural evolution along fundamental coordinates is discussed. PMID:23237473

  7. Surface-Enhanced Raman Scattering Using Silica Whispering-Gallery Mode Resonators

    NASA Technical Reports Server (NTRS)

    Anderson, Mark S.

    2013-01-01

    The motivation of this work was to have robust spectroscopic sensors for sensitive detection and chemical analysis of organic and molecular compounds. The solution is to use silica sphere optical resonators to provide surface-enhanced spectroscopic signal. Whispering-gallery mode (WGM) resonators made from silica microspheres were used for surface-enhanced Raman scattering (SERS) without coupling to a plasmonic mechanism. Large Raman signal enhancement is observed by exclusively using 5.08-micron silica spheres with 785-nm laser excitation. The advantage of this non-plasmonic approach is that the active substrate is chemically inert silica, thermally stable, and relatively simple to fabricate. The Raman signal enhancement is broadly applicable to a wide range of molecular functional groups including aliphatic hydrocarbons, siloxanes, and esters. Applications include trace organic analysis, particularly for in situ planetary instruments that require robust sensors with consistent response.

  8. Microsystem light source at 488 nm for shifted excitation resonance Raman difference spectroscopy.

    PubMed

    Maiwald, Martin; Schmidt, Heinar; Sumpf, Bernd; Güther, Reiner; Erbert, Götz; Kronfeldt, Heinz-Detlef; Tränkle, Günther

    2009-11-01

    A microsystem light source emitting at 488 nm was tested and applied as a light source for shifted excitation resonance Raman difference spectroscopy (SERRDS). A nonlinear frequency conversion using a distributed feedback (DFB) diode laser emission at 976 nm and a periodically poled lithium niobate (PPLN) waveguide crystal was realized on a micro-optical bench with a footprint of 25 mm x 5 mm. Joint temperature management via the microbench is used for wavelength tuning. Two emission lines at 487.61 nm and 487.91 nm are used for the SERRDS experiments. The Raman spectra of the test sample polystyrene demonstrate that a laser bandpass filter did not need to be implemented. Resonance Raman spectra of Tartrazine (FD&C Yellow 5, E 102) in distilled water are presented to demonstrate the suitability of this light source for SERRDS in, e.g., food safety control. PMID:19891837

  9. Pressure-induced depolarization and resonance in Raman scattering of single-crystalline boron carbide

    SciTech Connect

    Guo Junjie; Zhang Ling; Fujita, Takeshi; Chen Mingwei; Goto, Takashi

    2010-02-01

    We report polarized and resonant Raman scattering of single-crystal boron carbide (B{sub 4}C) at high pressures. Significant intensity enhancements of 270 and 1086 cm{sup -1} Raman bands of B{sub 4}C have been observed at quasihydrostatic pressures higher than approx20 GPa. The pressure-induced intensity change of the 1086 cm{sup -1} band is mainly due to the resonance between excitation energy and electronic transition, whereas the intensity change of 270 cm{sup -1} band is caused by the depolarization effect. Importantly, the first-order phase transition has not been found at high quasihydrostatic pressures and all the Raman intensity changes along with the corresponding high-pressure lattice distortion can be recovered during unloading.

  10. Raman spectroscopy of magneto-phonon resonances in graphene and graphite

    NASA Astrophysics Data System (ADS)

    Goler, Sarah; Yan, Jun; Pellegrini, Vittorio; Pinczuk, Aron

    2012-08-01

    The magneto-phonon resonance or MPR occurs in semiconductor materials when the energy spacing between Landau levels is continuously tuned to cross the energy of an optical phonon mode. MPRs have been largely explored in bulk semiconductors, in two-dimensional systems and in quantum dots. Recently there has been significant interest in the MPR interactions of the Dirac fermion magneto-excitons in graphene, and a rich splitting and anti-crossing phenomena of the even parity E2g long wavelength optical phonon mode have been theoretically proposed and experimentally observed. The MPR has been found to crucially depend on disorder in the graphene layer. This is a feature that creates new venues for the study of interplays between disorder and interactions in the atomic layers. We review here the fundamentals of MRP in graphene and the experimental Raman scattering works that have led to the observation of these phenomena in graphene and graphite.

  11. Characterizing millisecond intermediates in hemoproteins using rapid-freeze-quenched resonance Raman spectroscopy

    PubMed Central

    Matsumura, Hirotoshi; Moënne-Loccoz, Pierre

    2014-01-01

    Summary The combination of rapid-freeze-quenching (RFQ) technique and resonance Raman (RR) spectroscopy represents a unique tool to investigate the nature of short-lived intermediates formed during the enzymatic reaction of metalloproteins. Commercially available equipment allows trapping of intermediates within the millisecond to second timescale for low-temperature RR analysis and direct detection of metal-ligand vibrations and porphyrin skeletal vibrations in hemoproteins. This chapter briefly discusses previous RFQ-RR studies carried-out in our laboratory, and presents as a practical example protocols for the preparation of RFQ samples of the reaction of metmyoglobin with nitric oxide (NO) which requires anaerobic conditions. We also describe important controls and practical procedure for the analysis of these samples by low-temperature RR spectroscopy. PMID:24639256

  12. Nematic Resonance in the Raman Response of Iron-Based Superconductors.

    PubMed

    Gallais, Yann; Paul, Indranil; Chauvière, Ludivine; Schmalian, Jörg

    2016-01-01

    In a fully gapped superconductor the electronic Raman response has a pair-breaking peak at twice the superconducting gap Δ, if the Bogoliubov excitations are uncorrelated. Motivated by the iron based superconductors, we study how this peak is modified if the superconducting phase hosts a nematic-structural quantum critical point. We show that, upon approaching this point by tuning, e.g., doping, the growth of nematic correlations between the quasiparticles transforms the pair-breaking peak into a nematic resonance. The mode energy is below 2Δ, and stays finite at the quantum critical point, where its spectral weight is sharply enhanced. The latter is consistent with recent experiments on electron-doped iron based superconductors and provides direct evidence of nematic correlations in their superconducting phases. PMID:26799039

  13. Simulation of the resonance Raman spectra for 5-halogenated (F, Cl, and Br) uracils.

    PubMed

    Sun, Shuai; Brown, Alex

    2015-04-30

    The resonance Raman spectra of the 5-halogenated (F, Cl, and Br) uracils are simulated via the Herzberg-Teller (HT) short-time dynamics formalism. The gradient of the S1 excited state is computed at the CAMB3LYP/aug-cc-pVTZ level of theory in the conductor-like polarizable continuum model for water (C-PCM, H2O), based on the equilibrium geometry determined using PBE0/aug-cc-pVTZ in H2O (C-PCM). The simulated resonance Raman spectra show good agreement with the experimental spectra in terms of both peak positions and intensities. The differences between the resonance Raman spectra of the three 5-halogenated uracils, caused by the effect of halogen substitution, are examined in terms of ground-state normal-mode eigenvectors and excited-state Cartesian gradients, according to the HT formalism. The differences in the normal-mode eigenvectors and excited-state Cartesian gradients between 5-fluorouracil and 5-chlorouracil are used to interpret the dissimilarity between their resonance Raman spectra. Meanwhile, the similarity between the spectra of 5-chlorouracil and 5-bromouracil is explained by the correspondence between their normal modes and excited-state gradients. PMID:25856119

  14. Resonance Raman Spectroscopy of Beta-Carotene and Lycopene: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Hoskins, L. C.

    1984-01-01

    Discusses the theory of resonance Raman (RR) spectroscopy as it applies to beta-carotene and lycopene pigments (found in tomatoes and carrots, respectively). Also discusses an experiment which demonstrates the theoretical principles involved. The experiment has been tested over a three-year period and has received excellent acceptance by physical…

  15. Single- and few-layer WTe2 and their suspended nanostructures: Raman signatures and nanomechanical resonances

    NASA Astrophysics Data System (ADS)

    Lee, Jaesung; Ye, Fan; Wang, Zenghui; Yang, Rui; Hu, Jin; Mao, Zhiqiang; Wei, Jiang; Feng, Philip X.-L.

    2016-04-01

    Single crystal tungsten ditelluride (WTe2) has recently been discovered to exhibit non-saturating extreme magnetoresistance in bulk; it has also emerged as a new layered material from which atomic layer crystals can be extracted. While atomically thin WTe2 is attractive for its unique properties, little research has been conducted on single- and few-layer WTe2. Here we report the isolation of single- and few-layer WTe2, as well as the fabrication and characterization of the first WTe2 suspended nanostructures. We have observed new Raman signatures of single- and few-layer WTe2 that have been theoretically predicted but have not been reported to date, in both on-substrate and suspended WTe2 flakes. We have further probed the nanomechanical properties of suspended WTe2 structures by measuring their flexural resonances, and obtain a Young's modulus of EY ~ 80 GPa for the suspended WTe2 flakes. This study paves the way for future investigations and utilizations of the multiple new Raman fingerprints of single- and few-layer WTe2, and for explorations of mechanical control of WTe2 atomic layers.

  16. Rapid resonance Raman microspectroscopy to probe carbon dioxide fixation by single cells in microbial communities

    PubMed Central

    Li, Mengqiu; Canniffe, Daniel P; Jackson, Philip J; Davison, Paul A; FitzGerald, Simon; Dickman, Mark J; Burgess, J Grant; Hunter, C Neil; Huang, Wei E

    2012-01-01

    Photosynthetic microorganisms play crucial roles in aquatic ecosystems and are the major primary producers in global marine ecosystems. The discovery of new bacteria and microalgae that play key roles in CO2 fixation is hampered by the lack of methods to identify hitherto-unculturable microorganisms. To overcome this problem we studied single microbial cells using stable-isotope probing (SIP) together with resonance Raman (RR) microspectroscopy of carotenoids, the light-absorbing pigments present in most photosynthetic microorganisms. We show that fixation of 13CO2 into carotenoids produces a red shift in single-cell RR (SCRR) spectra and that this SCRR–SIP technique is sufficiently sensitive to detect as little as 10% of 13C incorporation. Mass spectrometry (MS) analysis of labelled cellular proteins verifies that the red shift in carotenoid SCRR spectra acts as a reporter of the 13C content of single cells. Millisecond Raman imaging of cells in mixed cultures and natural seawater samples was used to identify cells actively fixing CO2, demonstrating that the SCRR–SIP is a noninvasive method for the rapid and quantitative detection of CO2 fixation at the single cell level in a microbial community. The SCRR–SIP technique may provide a direct method for screening environmental samples, and could help to reveal the ecophysiology of hitherto-unculturable microorganisms, linking microbial species to their ecological function in the natural environment. PMID:22113377

  17. Single- and few-layer WTe2 and their suspended nanostructures: Raman signatures and nanomechanical resonances.

    PubMed

    Lee, Jaesung; Ye, Fan; Wang, Zenghui; Yang, Rui; Hu, Jin; Mao, Zhiqiang; Wei, Jiang; Feng, Philip X-L

    2016-04-14

    Single crystal tungsten ditelluride (WTe2) has recently been discovered to exhibit non-saturating extreme magnetoresistance in bulk; it has also emerged as a new layered material from which atomic layer crystals can be extracted. While atomically thin WTe2 is attractive for its unique properties, little research has been conducted on single- and few-layer WTe2. Here we report the isolation of single- and few-layer WTe2, as well as the fabrication and characterization of the first WTe2 suspended nanostructures. We have observed new Raman signatures of single- and few-layer WTe2 that have been theoretically predicted but have not been reported to date, in both on-substrate and suspended WTe2 flakes. We have further probed the nanomechanical properties of suspended WTe2 structures by measuring their flexural resonances, and obtain a Young's modulus of EY ≈ 80 GPa for the suspended WTe2 flakes. This study paves the way for future investigations and utilizations of the multiple new Raman fingerprints of single- and few-layer WTe2, and for explorations of mechanical control of WTe2 atomic layers. PMID:27030574

  18. Distinguishing Unfolding and Functional Conformational Transitions of Calmodulin Using Ultraviolet Resonance Raman Spectroscopy

    SciTech Connect

    Jones, Eric M.; Balakrishnan, G.; Squier, Thomas C.; Spiro, Thomas

    2014-06-14

    Calmodulin (CaM) is a ubiquitous moderator protein for calcium signaling in all eukaryotic cells. This small calcium-binding protein exhibits a broad range of structural transitions, including domain opening and folding-unfolding, that allow it to recognize a wide variety of binding partners in vivo. While the static structures of CaM associated with its various binding activities are fairly well known, it has been challenging to examine the dynamics of transition between these structures in real-time, due to a lack of suitable spectroscopic probes of CaM structure. In this paper, we examine the potential of ultraviolet resonance Raman (UVRR) spectroscopy for clarifying the nature of structural transitions in CaM. We find that the UVRR spectral change (with 229 nm excitation) due to thermal unfolding of CaM is qualitatively different from that associated with opening of the C-terminal domain in response to Ca2+ binding. This spectral difference is entirely due to differences in teritary contacts at the inter-domain tyrosine residue Tyr138, toward which other spectroscopic methods are not sensitive. We conclude that UVRR is ideally suited to identifying the different types of structural transitions in CaM and other proteins with conformation-sensitive tyrosine residues, opening a path to time-resolved studies of CaM dynamics using Raman spectroscopy.

  19. Resonance Raman and vibronic absorption spectra with Duschinsky rotation from a time-dependent perspective: Application to β-carotene

    NASA Astrophysics Data System (ADS)

    Banerjee, Shiladitya; Kröner, Dominik; Saalfrank, Peter

    2012-12-01

    The time-dependent approach to electronic spectroscopy, as popularized by Heller and co-workers in the 1980s, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption and resonance Raman spectra of β-carotene, with and without a solvent. Two-state models, the harmonic and the Condon approximations are used in order to do so. A new code has been developed which includes excited state displacements, vibrational frequency shifts, and Duschinsky rotation, i.e., mode mixing, for both non-adiabatic spectroscopies. It is shown that Duschinsky rotation has a pronounced effect on the resonance Raman spectra of β-carotene. In particular, it can explain a recently found anomalous behaviour of the so-called ν1 peak in resonance Raman spectra [N. Tschirner, M. Schenderlein, K. Brose, E. Schlodder, M. A. Mroginski, C. Thomsen, and P. Hildebrandt, Phys. Chem. Chem. Phys. 11, 11471 (2009)], 10.1039/b917341b, which shifts with the change in excitation wavelength.

  20. Hollow Au/Ag nanostars displaying broad plasmonic resonance and high surface-enhanced Raman sensitivity

    NASA Astrophysics Data System (ADS)

    Garcia-Leis, Adianez; Torreggiani, Armida; Garcia-Ramos, Jose Vicente; Sanchez-Cortes, Santiago

    2015-08-01

    Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars. The size, shape, and composition of Ag as well as their optical properties were studied by extinction spectroscopy, hyperspectral dark field microscopy, transmission and scanning electron microscopy (TEM and SEM), and energy dispersive X-ray spectroscopy (EDX). Finally, the surface-enhanced Raman scattering (SERS) activity of these HNS was investigated by using thioflavin T, a biomarker of the β-amyloid fibril formation, responsible for Alzheimer's disease. Lucigenin, a molecule displaying different SERS activities on Au and Ag, was also used to explore the presence of these metals on the NP surface. Thus, a relationship between the morphology, plasmon resonance and SERS activity of these new NPs was made.Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars

  1. Secondary and tertiary structure of the A-state of cytochrome c from resonance Raman spectroscopy.

    PubMed Central

    Jordan, T.; Eads, J. C.; Spiro, T. G.

    1995-01-01

    Ferricytochrome c can be converted to the partially folded A-state at pH 2.2 in the presence of 1.5 M NaCl. The structure of the A-state has been studied in comparison with the native and unfolded states, using resonance Raman spectroscopy with visible and ultraviolet excitation wavelengths. Spectra obtained with 200 nm excitation show a decrease in amide II intensity consistent with loss of structure for the 50s and 70s helices. The 230-nm spectra contain information on vibrational modes of the single Trp 59 side chain and the four tyrosine side chains (Tyr 48, 67, 74, and 97). The Trp 59 modes indicate that the side chain remains in a hydrophobic environment but loses its tertiary hydrogen bond and is rotationally disordered. The tyrosine modes Y8b and Y9a show disruption of tertiary hydrogen bonding for the Tyr 48, 67, and 74 side chains. The high-wavenumber region of the 406.7-nm resonance Raman spectrum reveals a mixed spin heme iron atom, which arises from axial coordination to His 18 and a water molecule. The low-frequency spectral region reports on heme distortions and indicates a reduced degree of interaction between the heme and the polypeptide chain. A structural model for the A-state is proposed in which a folded protein subdomain, consisting of the heme and the N-terminal, C-terminal, and 60s helices, is stabilized through nonbonding interactions between helices and with the heme. PMID:7613469

  2. Airborne Raman Lidar and its Applications for Atmospheric Process Studies

    NASA Astrophysics Data System (ADS)

    Wang, Zhien; Wechsler, Perry J.; Mahon, Nick; Wu, Decheng; Liu, Bo; Burkhart, Matthew; Glover, Brent; Kuestner, William; Welch, Wayne; Thomson, Andrew

    2016-06-01

    Although ground-base Raman lidars are widely used for atmospheric observations, the capabilities of airborne Raman lidar is not fully explored. Here we presented two recently developed airborne Raman lidar systems for the studies of atmospheric boundary layer process, aerosols, and clouds. The systems are briefly introduced. Observation examples are presented to illustrate the unique observational capabilities of airborne Raman lidar and their applications for atmospheric process studies.

  3. Heme Orientation of Cavity Mutant Hemoglobins (His F8 → Gly) in Either α or β Subunits: Circular Dichroism, (1) H NMR, and Resonance Raman Studies.

    PubMed

    Nagai, Masako; Nagai, Yukifumi; Aki, Yayoi; Sakurai, Hiroshi; Mizusawa, Naoki; Ogura, Takashi; Kitagawa, Teizo; Yamamoto, Yasuhiko; Nagatomo, Shigenori

    2016-08-01

    Native human adult hemoglobin (Hb A) has mostly normal orientation of heme, whereas recombinant Hb A (rHb A) expressed in E. coli contains both normal and reversed orientations of heme. Hb A with the normal heme exhibits positive circular dichroism (CD) bands at both the Soret and 260-nm regions, while rHb A with the reversed heme shows a negative Soret and decreased 260-nm CD bands. In order to examine involvement of the proximal histidine (His F8) of either α or β subunits in determining the heme orientation, we prepared two cavity mutant Hbs, rHb(αH87G) and rHb(βH92G), with substitution of glycine for His F8 in the presence of imidazole. CD spectra of both cavity mutant Hbs did not show a negative Soret band, but instead exhibited positive bands with strong intensity at the both Soret and 260-nm regions, suggesting that the reversed heme scarcely exists in the cavity mutant Hbs. We confirmed by (1) H NMR and resonance Raman (RR) spectroscopies that the cavity mutant Hbs have mainly the normal heme orientation in both the mutated and native subunits. These results indicate that the heme Fe-His F8 linkage in both α and β subunits influences the heme orientation, and that the heme orientation of one type of subunit is related to the heme orientation of the complementary subunits to be the same. The present study showed that CD and RR spectroscopies also provided powerful tools for the examination of the heme rotational disorder of Hb A, in addition to the usual (1) H NMR technique. Chirality 28:585-592, 2016. © 2016 Wiley Periodicals, Inc. PMID:27427792

  4. Intensity Ratio of Resonant Raman Modes for (n,m) Enriched Semiconducting Carbon Nanotubes.

    PubMed

    Piao, Yanmei; Simpson, Jeffrey R; Streit, Jason K; Ao, Geyou; Zheng, Ming; Fagan, Jeffrey A; Hight Walker, Angela R

    2016-05-24

    Relative intensities of resonant Raman spectral features, specifically the radial breathing mode (RBM) and G modes, of 11, chirality-enriched, single-wall carbon nanotube (SWCNT) species were established under second-order optical transition excitation. The results demonstrate an under-recognized complexity in the evaluation of Raman spectra for the assignment of (n,m) population distributions. Strong chiral angle and mod dependencies affect the intensity ratio of the RBM to G modes and can result in misleading interpretations. Furthermore, we report five additional (n,m) values for the chirality-dependent G(+) and G(-) Raman peak positions and intensity ratios; thereby extending the available data to cover more of the smaller diameter regime by including the (5,4) second-order, resonance Raman spectra. Together, the Raman spectral library is demonstrated to be sufficient for decoupling G peaks from multiple species via a spectral fitting process, and enables fundamental characterization even in mixed chiral population samples. PMID:27128733

  5. Time-gated pre-resonant femtosecond stimulated Raman spectroscopy of diethylthiatricarbocyanine iodide.

    PubMed

    Kim, Hyung Min; Kim, Hyunmin; Yang, Ilseung; Jin, Seung Min; Suh, Yung Doug

    2014-03-21

    We present time-gated femtosecond stimulated Raman spectroscopy (fSRS) under the pre-resonance Raman conditions of diethylthiatricarbocyanine (DTTC) iodide. A 'pseudo emission-free' condition is achieved by delivering the probe beam ahead of the pump beam. Regeneratively amplified pulse trains are employed to create an angle-geometry (non-collimated) mixing between the pump and probe beams, leading to highly sensitive measurement of the stimulated Raman gain. Time-integrated spectroscopy allows for a more quantitative distinction between the contributions of stimulated Raman scattering and stimulated emission. We successfully obtain a highly sensitive (signal-to-noise ratio >100) stimulated Raman spectrum under the optimized conditions, which compares favourably to results obtained using two-dimensional correlation spectroscopy (2DCOS). Given the optical pre-resonance of ∼0.1 eV, the background signals mostly originate from the stimulated emission of excited electrons and are significantly reduced by partial overlapping of the pump and probe beams; a genuine fSRS spectral profile is obtained for a temporal delay of ∼0.2 ps between the two beams. PMID:24496293

  6. Effect of atomic diffusion on the Raman-Ramsey coherent population trapping resonances

    NASA Astrophysics Data System (ADS)

    Kuchina, Elena; Mikhailov, Eugeniy E.; Novikova, Irina

    2016-04-01

    We experimentally investigated the characteristics of two-photon transmission resonances in Rb vapor cells with different amount of buffer gas under the conditions of steady-state coherent population trapping (CPT) and pulsed Raman-Ramsey (RR-) CPT interrogation scheme. We particularly focused on the influence of the Rb atoms diffusing in and out of the laser beam. We showed that this effect modifies the shape of both CPT and Raman-Ramsey resonances, as well as their projected performance for CPT clock applications. In particular we found that at moderate buffer gas pressures RR-CPT did not improved the projected atomic clock stability compare to the regular steady-state CPT resonance.

  7. Quantitative resonance Raman spectroscopy of N-acetylpyrrolidine in aqueous solution

    SciTech Connect

    Harhay, G.P.; Hudson, B.S. )

    1993-08-05

    The resonance Raman spectra of aqueous solutions of N-acetylpyrrolidine are determined at seven excitation frequencies from 40 660 to 53 130 cm[sup [minus]1] spanning the first strong absorption band which is broad and diffuse The resonance Raman spectra are dominated by the single amide II[prime]-like vibration at 1485 cm[sup [minus]1] and its overtones of up to five quanta. Absolute resonance Raman cross sections are determined for these fundamental and overtone transitions at each excitation wavelength by reference to an internal standard of sodium perchlorate. A quantitative analysis of these data and the broad absorption spectrum is made on the basis of a model for the electronic excitation that includes the effects of inhomogeneous broadening. The observation of only a single enhanced vibrational normal mode, with the assumption that there is no Duschinsky rotation upon electronic excitation, makes this a particularly simple case for detailed analysis. A reasonably good fit to the experimental data is obtained using standard assumptions of Lorentzian inhomogeneous broadening and A-term (Condom) Raman scattering. In this fitting procedure, the integrated absorption spectrum determines the transition dipole length. 43 refs., 4 figs., 2 tabs.

  8. Surface-enhanced Raman spectroscopic and surface plasmon resonance in situ study of self-assembly of 4-mercaptobenzoic acid on gold surface

    NASA Astrophysics Data System (ADS)

    Thi, Minh Do; Volka, Karel

    2010-07-01

    A feasibility study has been undertaken to assess the suitability of a commercially available SERS substrate for monitoring of self-assembling deposition process. Monolayer self-assembly of 4-mercaptobenzoic acid on SERS active substrate Klarite™ from absolute and acidified ethanol was studied and compared with deposition on SPR substrate from absolute ethanol. Changes in integral intensity of the phenyl bands at 1587 and 1076 cm -1 and ethanol band at 1451 cm -1 allow to follow structural changes in the monolayer. Stability of the monolayer assembled from acidified ethanol in contrast to the pure ethanol was demonstrated.

  9. Black phosphorus edges: a polarized Raman study

    NASA Astrophysics Data System (ADS)

    Ribeiro, H.; Villegas, C.; Bahamon, D.; Castro Neto, A.; de Souza, E.; Rocha, A.; Pimenta, M.; de Matos, C.

    Black phosphorus (BP) has been recently exfoliated down to few-layer thicknesses revealing numerous interesting features such as a tunable direct bandgap. Ever since, demonstrations of BP electronic devices have bloomed, as well as studies of the electric, optical, mechanical and thermal properties of its bulk and few-layer forms. However, the edges of BP crystals have, so far, been poorly characterized, even though the terminations of layered crystals are known to possess a range of interesting properties. In this work, the edges of exfoliated BP flakes are characterized by polarized confocal Raman spectroscopy. We will present experimental Raman spectra at zigzag and armchair edges, as well as density functional theory calculations that explain the peculiarities of the experimental data. Fapesp, INCT/Nanocarbono, Fapemig, CNPq, MackPesquisa, Grid-Unesp, CENAPAD-SP, and NRF.

  10. Krypton isotope analysis using near-resonant stimulated Raman spectroscopy

    SciTech Connect

    Whitehead, C.A.; Cannon, B.D.; Wacker, J.F.

    1994-12-01

    A method for measuring low relative abundances of {sup 85}Kr in one liter or less samples of air has been under development here at Pacific Northwest Laboratory. The goal of the Krypton Isotope Laser Analysis (KILA) method is to measure ratios of 10{sup {minus}10} or less of {sup 85}Kr to more abundant stable krypton. Mass spectrometry and beta counting are the main competing technologies used in rare-gas trace analysis and are limited in application by such factors as sample size, counting times, and selectivity. The use of high-resolution lasers to probe hyperfine levels to determine isotopic abundance has received much attention recently. In this study, we report our progress on identifying and implementing techniques for trace {sup 85}Kr analysis on small gas samples in a static cell as well as limitations on sensitivity and selectivity for the technique. High-resolution pulsed and cw lasers are employed in a laser-induced fluorescence technique that preserves the original sample. This technique, is based on resonant isotopic depletion spectroscopy (RIDS) in which one isotope is optically depleted while preserving the population of a less abundant isotope. The KILA method consists of three steps. In the first step, the 1s{sub 5} metastable level of krypton is populated via radiative cascade following two-photon excitation of the 2p{sub 6} energy level. Next, using RBDS, the stable krypton isotopes are optically depleted to the ground state through the 1s{sub 4} level with the bulk of the {sup 85}Kr population being preserved. Finally, the remaining metastable population is probed to determine {sup 85}Kr concentration. The experimental requirements for each of these steps are outlined below.

  11. Multi-wavelength Raman Spectroscopic Study of Silica-supported Vanadium Oxide Catalysts

    SciTech Connect

    Wu, Zili; Dai, Sheng; Overbury, Steven {Steve} H

    2010-01-01

    The molecular structure of silica-supported vanadium oxide (VOx) catalysts over wide range of surface VOx density (0.0002 8 V/nm2) has been investigated in detail under dehydrated condition by in situ multi-wavelength Raman spectroscopy (laser excitations at 244, 325, 442, 532, and 633 nm) and in situ UV-Vis diffuse reflectance spectroscopy. Resonance Raman scattering is clearly observed using 244 and 325-nm excitations while normal Raman scattering occurs using excitation at the three visible wavelengths. The observation of strong fundamentals, overtones and combinational bands due to selective resonance enhancement effect helps clarify assignments of some of the VOx Raman bands (920, 1032, and 1060 cm-1) whose assignments have been controversial. The resonance Raman spectra of dehydrated VOx/SiO2 show V=O band at smaller Raman shift than that in visible Raman spectra, an indication of the presence of two different surface VOx species on dehydrated SiO2 even at sub-monolayer VOx loading. Quantitative estimation shows that the two different monomeric VOx species coexist on silica surface from very low VOx loadings and transform to crystalline V2O5 at VOx loadings above monolayer. It is postulated that one of the two monomeric VOx species has pyramidal structure and the other is in partially hydroxylated pyramidal mode. The two VOx species show similar reduction-oxidation behavior and may both participate in redox reactions catalyzed by VOx/SiO2 catalysts. This study demonstrates the advantages of multi-wavelength Raman spectroscopy over conventional single-wavelength Raman spectroscopy in structural characterization of supported metal oxide catalysts.

  12. Raman study of opal at high pressure

    NASA Astrophysics Data System (ADS)

    Farfan, G.; Wang, S.; Mao, W. L.

    2011-12-01

    More commonly known for their beauty and lore as gemstones, opals are also intriguing geological materials which may have potential for materials science applications. Opal lacks a definite crystalline structure, and is composed of an amorphous packing of hydrated silica (SiO2) spheroids, which provides us with a unique nano-scaled mineraloid with properties unlike those of other amorphous materials like glass. Opals from different localities were studied at high pressure using a diamond anvil cell to apply pressure and Raman spectroscopy to look at changes in bonding as pressure was increased. We first tested different samples from Virgin Valley, NV, Spencer, ID, Juniper Ridge, OR, and Australia, which contain varying amounts of water at ambient conditions, using Raman spectroscopy to determine if they were opal-CT (semicrystalline cristobalite-trydimite volcanic origin) or opal-A (amorphous sedimentary origin). We then used x-ray diffraction and Raman spectroscopy in a diamond anvil cell to see how their bonding and structure changed under compression and to determine what effect water content had on their high pressure behavior. Comparison of our results on opal to other high pressure studies of amorphous materials like glass has implications from a geological and materials science standpoint.

  13. Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals

    NASA Astrophysics Data System (ADS)

    Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V.; Izquierdo-Roca, Victor; Fontane, Xavier; Volkova, Larisa V.; Arushanov, Ernest; Pérez-Rodríguez, Alejandro

    2016-01-01

    A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone-center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm-1 on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis.

  14. Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals

    PubMed Central

    Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V.; Izquierdo-Roca, Victor; Fontane, Xavier; Volkova, Larisa V.; Arushanov, Ernest; Pérez-Rodríguez, Alejandro

    2016-01-01

    A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone–center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm−1 on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis. PMID:26776727

  15. Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals.

    PubMed

    Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V; Izquierdo-Roca, Victor; Fontane, Xavier; Volkova, Larisa V; Arushanov, Ernest; Pérez-Rodríguez, Alejandro

    2016-01-01

    A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone-center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm(-1) on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis. PMID:26776727

  16. [Infrared and Raman spectra study on Tianhuang].

    PubMed

    Liu, Yun-gui; Chen, Tao

    2012-08-01

    The Tianhuang stones, from Shoushan in China, were studied by using X-ray powder diffractometry (XRD), infrared (IR) spectroscopy and Raman spectroscopy to obtain the spectra characterization. Wave numbers 3621, 3629 and 3631 cm(-1) in the IR spectra and 3626, 3627 and 3632 cm(-1) in the Raman spectra are the characteristic peaks of dickitic Tianhuang, nacritic Tianhuang and illitic Tianhuang, respectively. Raman spectra assigned to OH are in good agreement with the IR results at 3550 -3750 cm(-1). Dickitic Tianhuang includes ordered dickite and disordered dickite. Compared with ordered dickite, the band assigned to OH3 of disordered dickite shifts to low-frequency by 8 cm(-1) and the relative intensity becomes stronger. The disorder structure may relate to the high level of Fe. The IR absorption spectra of nacritic Tianhuang superimposes strong peaks of dickite, indicating that IR absorption bands of dickite are stronger than that of nacrite at 3550-3750 cm(-1). The main mineral composition of illitic Tianhuang is 2M(1), while illite Tianhuang contains a small amount of 1M. All these characters provide a theoretical basis for the scientific identification of Tianhuang. PMID:23156769

  17. Measurement of sex steroids and analogs with a fiber optic probe using pulsed ultraviolet resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Schulze, H. Georg; Greek, L. Shane; Blades, Michael W.; Bree, Alan V.; Gorzalka, Boris B.; Turner, Robin F. B.

    1997-05-01

    Resonance Raman spectroscopy, performed via an optical fiber probe, can be used in aqueous samples to detect a wide variety of chemical species in situ. It offers a potentially rapid, on-site alternative to the high performance chromatography/mass spectrometry methods currently considered definitive for the detection of sex steroids in human urine. As a first step in the development of a resonance Raman instrument for the rapid detection of sex steroids in biological samples, it had to be shown that these substances, their analogs, and the major components of human urine can be differentiated on the basis of their resonance Raman spectra. A fiber-optic linked Raman and tunable ultraviolet resonance Raman system was assembled with custom designed optical fiber probes. The ultraviolet absorption spectra of some sex steroids, analogs, and components of human urine were measured in order to determine feasible excitation light frequencies. We present here for the first time the UV resonance Raman spectra of these substances obtained via our novel fiber probes. These results indicate that some of the steroids tested can be differentiated from each other and from the major components of human urine on the basis of their resonance Raman spectra.

  18. Resonant Raman Scattering as a Probe of Intrinsic Defects in Gallium-Arsenide

    NASA Astrophysics Data System (ADS)

    Berg, Robert Scott

    This thesis presents a series of Raman scattering measurements performed on GaAs samples that have been irradiated with either high energy electrons or neutrons. The irradiation creates fairly high concentrations (10('17) - 10('18) cm(' -3)) of intrinsic defects. It is demonstrated that Raman scattering can give useful information about such defects. One important result of this work is the observation of new and relatively sharp peaks in the Raman spectra of the irradiated samples. These are attributed to vibrational modes of a specific point defect created by the irradiation. On the basis of annealing experiments it is concluded that one of thes modes is most likely associated with an As vacancy. The observed polarization dependence suggests that this can be a "breathing" vibration of the atoms surrounding the vacancy. In addition, experiments were performed that measured the lineshape of the enhancement of the Raman cross section of both the intrinsic and extrinsic modes near the band gap of GaAs using a tunable near infra-red laser. It was observed that the enhancement of the defect introduced modes was strong relative to the enhancement of the allowed TO phonon, which itself exhibits a strong enhancement. The observed enhancement lineshape can be explained by assuming that the scattering involving the defect induced modes occurs via a fourth order process. During this process quasi-momentum conservation is relaxed when electrons or holes scatter elastically from defects. On the basis of this model it is concluded that the strong resonant enhancement occurs when the vibrational modes involved have a component that is well localized around a defect. Thus resonant Raman scattering has greater sensitivity to motion within the first few lattice constants surrounding a point defect and is well suited to provide microscopic information about such defects. Another important conclusion is that the strong enhancement of the Raman cross section of the defect induced

  19. Raman spectroscopy study on the ν1-2ν2 Fermi resonance of liquid carbon disulfide in binary solutions: Effect of the weak hydrogen bond formation on the Fermi resonance

    NASA Astrophysics Data System (ADS)

    Li, DongFei; Sun, Shang; Sun, ChengLin; Jiang, XiuLan; Gao, ShuQin; Li, ZuoWei

    2012-10-01

    We have measured the Raman spectra of liquid CS2 at different volume concentrations in CHCl3 and CH2Cl2 solutions. With decreasing the volume concentration of CS2, a noticeable growth in the 2ν2 band frequency was observed, while the ν1 band location remained practically unchanged. This asymmetric wavenumber shift phenomenon of the Fermi doublet ν1 and 2ν2 of CS2 has been ascribed to weak, non-conventional hydrogen bonds formed between the CS2 and the solvent molecules. These weak hydrogen bonds were also responsible for significant decreases in the C-H bond symmetric stretching vibration band frequencies of CHCl3 and CH2Cl2. The values of the ν1-2ν2 FR parameters of CS2 in CH2Cl2 and CHCl3 at different volume concentrations were calculated according to the FR theory. The magnitude of the FR coupling coefficient W of CS2 increases upon dilution with CH2Cl2 and CHCl3, indicating that the vibrational anharmonicity is relatively sensitive to variations in the weak hydrogen bonding. Compared with the changing tendencies of Fermi coupling coefficient W of CS2 in CH2Cl2 and CHCl3 at different volume concentrations, we discussed the effect of the weak hydrogen bond formation on the FR and the asymmetric wavenumber shift phenomenon of the Fermi doublet ν1 and 2ν2 of CS2.

  20. Infrared resonance Raman, and excitation profile studies of Os/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/Cl/sub 2/ and Os/sub 2/(O/sub 2/CCD/sub 3/)/sub 4/Cl/sub 2/. The assignment of the osmium-osmium stretching vibration for a complex involving an osmium-osmium multiple bond

    SciTech Connect

    Clark, R.J.H.; Hempleman, A.J.; Tocher, D.A.

    1988-08-31

    Extensive Raman studies (1525-40 cm/sup /minus/1/) of Os/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/Cl/sub 2/ have led to the identification of the three strong bands, /nu//sub 1/, /nu//sub 2/, and /nu//sub 3/, at 229, 393, and 292 cm/sup /minus/1/ to the key skeletal stretching modes, /nu/(OsOs), /nu/(OsO), and /nu/(OsCl), respectively. Raman spectra of the complex at resonance with the intense electronic band at /lambda//sub max/ = 383 nm lead to the development of a six-membered overtone progression in /nu//sub 1/ as well as combination band progressions in /nu//sub 1/ based upon one quantum of either /nu//sub 2/ or /nu//sub 3/. This indicates that the principal structural change attendant upon excitation to the resonant state is along the OsOs coordinate. Fourier transform infrared spectra (3500-40 cm/sup /minus/1/) have also been obtained. Acetate deuteriation provides conclusive evidence for many of the infrared and Raman band assignments. The study provides the first firm identification of /nu/(OsOs) for a multiply bonded species.

  1. Excitons in one-phonon resonant Raman scattering: Fröhlich and interference effects

    NASA Astrophysics Data System (ADS)

    Cantarero, A.; Trallero-Giner, C.; Cardona, M.

    1989-12-01

    A theoretical model of resonant Raman scattering including excitons as intermediate states in the process is compared with recent experimental results in some III-V compound semiconductors where the Raman polarizability was obtained in absolute value for several scattering configurations. In particular, Fröhlich (F) interaction and its interference with the deformation potential (DP) one is analyzed in the E0+Δ0 critical point (CP) of GaAs at three different temperatures. Also the E0 and E0+Δ0 CP of GaP and E0+Δ0 of GaSb are analyzed. We show that the inclusion of impurity-induced forbidden LO-phonon Raman scattering is not necessary when excitonic effects are considered. The experimental data of GaAs corresponding to F interaction can be fitted by assuming a Fröhlich constant cF=0.14 eV Aṥ/2. Lifetime broadenings of 12 meV (10 K), 14 meV (100 K), and 28 meV (300 K) are deduced. The lifetime broadening of GaAs and GaSb at 100 K are taken from two-phonon Raman scattering spectra where the incoming and outgoing resonances are well defined. The general features in the comparison with the experiment is that the measured spectra corresponding to F interaction are well fitted; however, the theoretical interference is stronger than the measured one.

  2. Resonance Raman Scattering of Rhodamine 6G as Calculated Using Time-Dependent Density Functional Theory

    SciTech Connect

    Jensen, Lasse; Schatz, George C.

    2006-03-27

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. In this work, we present the first calculation of the resonance Raman scattering (RRS) spectrum of rhodamine 6G (R6G) which is a prototype molecule in surface-enhanced Raman scattering (SERS). The calculation is done using a recently developed time-dependent density functional theory (TDDFT) method, which uses a short-time approximation to evaluate the Raman scattering cross section. The normal Raman spectrum calculated with this method is in good agreement with experimental results. The calculated RRS spectrum shows qualitative agreement with SERS results at a wavelength that corresponds to excitation of the S1 state, but there are significant differences with the measured RRS spectrum at wavelengths that correspond to excitation of the vibronic sideband of S1. Although the agreement with the experiments is not perfect, the results provide insight into the RRS spectrum of R6G at wavelengths close to the absorption maximum where experiments are hindered due to strong fluorescence. The calculated resonance enhancements are found to be on the order of 105. This indicates that a surface enhancement factor of about 1010 would be required in SERS in order to achieve single-molecule detection of R6G.

  3. Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes.

    PubMed

    Wang, Chen; Angelella, Maria; Doyle, Samantha J; Lytwak, Lauren A; Rossky, Peter J; Holliday, Bradley J; Tauber, Michael J

    2015-09-17

    The characterization of triplet excited states is essential for research on organic photovoltaics and singlet fission. We report resonance Raman spectra of two triplet oligothiophenes with n-alkyl substituents, a tetramer and hexamer. The spectra of the triplets are more complex than the ground state, and we find that density functional theory calculations are a useful starting point for characterizing the bands. The spectra of triplet tetrathiophene and hexathiophene differ significantly from one another. This observation is consistent with a T1 excitation that is delocalized over at least five rings in long oligomers. Bands in the 500-800 cm(-1) region are greatly diminished for an aggregated sample of hexathiophene, likely caused by fast electronic dephasing. These experiments highlight the potential of resonance Raman spectroscopy to unequivocally detect and characterize triplets in thiophene materials. The vibrational spectra can also serve as rigorous standards for evaluating computational methods for excited-state molecules. PMID:26291623

  4. The Detection of Protein via ZnO Resonant Raman Scattering Signal

    NASA Astrophysics Data System (ADS)

    Shan, Guiye; Yang, Guoliang; Wang, Shuang; Liu, Yichun

    2008-03-01

    Detecting protein with high sensitivity and specificity is essential for disease diagnostics, drug screening and other application. Semiconductor nanoparticles show better properties than organic dye molecules when used as markers for optical measurements. We used ZnO nanoparticles as markers for detecting protein in resonant Raman scattering measurements. The highly sensitive detection of proteins was achieved by an antibody-based sandwich assay. A probe for the target protein was constructed by binding the ZnO/Au nanoparticles to a primary antibody by eletrostatic interaction between Au and the antibody. A secondary antibody, which could be specifically recognized by target protein, was attached to a solid surface. The ZnO/Au-antibody probe could specifically recognize and bind to the complex of the target protein and secondary antibody. Our measurements using the resonant Raman scattering signal of ZnO nanoparticles showed good selectivity and sensitivity for the target protein.

  5. Resonance Raman Spectroscopy of Single-Wall Carbon Nanotubes Separated via Aqueous Two-Phase Extraction

    NASA Astrophysics Data System (ADS)

    Simpson, J. R.; Fagan, J. A.; Hight Walker, A. R.

    2014-03-01

    We report Resonance Raman Spectroscopy (RRS) measurements of single-wall carbon nanotube (SWCNT) samples dispersed in aqueous solutions via surfactant wrapping and separated using aqueous two-phase extraction (ATPE) into chirality-enriched semiconducting and metallic SWCNT species. ATPE provides a rapid, robust, and remarkably tunable separation technique that allows isolation of high-purity, individual SWCNT chiralities via modification of the surfactant environment. We report RRS measurements of individual SWCNT species of various chiral index including, armchair and zigzag metals. Raman provides a powerful technique to quantify the metallic SWCNTs in ATPE fractions separated for metallicity. We measure Raman spectra over a wide range of excitation wavelengths from 457 nm to 850 nm using a series of discrete and continuously tunable laser sources coupled to a triple-grating spectrometer with a liquid-nitrogen-cooled detector. The spectra reveal Raman-active vibrational modes, including the low-frequency radial breathing mode (RBM) and higher-order modes. SWCNT chiral vectors are determined from the Raman spectra, specifically the RBM frequencies and corresponding energy excitation profiles, together with input from theoretical models.

  6. Resonance Raman Spectroscopy of Single-Wall Carbon Nanotubes Separated via Aqueous Two-Phase Extraction

    NASA Astrophysics Data System (ADS)

    Simpson, J. R.; Fagan, J. A.; Hight Walker, A. R.

    2015-03-01

    We report resonance Raman Spectroscopy measurements of single-wall carbon nanotube (SWCNT) samples dispersed in aqueous solutions via surfactant wrapping and separated using aqueous two-phase extraction (ATPE) into chirality-enriched semiconducting and metallic SWCNT species. ATPE provides a rapid, robust, and remarkably tunable separation technique that allows isolation of high-purity, individual SWCNT chiralities via modification of the surfactant environment. We report RRS measurements of individual SWCNT species of various chiral index including, semiconductors, armchair and zigzag metals. Raman provides a powerful technique to quantify the metallic SWCNTs in ATPE fractions separated for metallicity. We measure Raman spectra over a wide range of excitation wavelengths from (457 to 850) nm using a series of discrete and continuously tunable laser sources coupled to a triple-grating spectrometer. The spectra reveal Raman-active vibrational modes, including the low-frequency radial breathing mode (RBM) and higher-order modes. SWCNT chiral vectors are determined from Raman spectra, specifically the RBM frequencies and corresponding energy excitation profiles, together with input from theoretical models.

  7. Quantitative detection of astaxanthin and cantaxanthin in Atlantic salmon by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2006-02-01

    Two major carotenoids species found in salmonids muscle tissues are astaxanthin and cantaxanthin. They are taken up from fish food and are responsible for the attractive red-orange color of salmon filet. Since carotenoids are powerful antioxidants and biomarkers of nutrient consumption, they are thought to indicate fish health and resistance to diseases in fish farm environments. Therefore, a rapid, accurate, quantitative optical technique for measuring carotenoid content in salmon tissues is of economic interest. We demonstrate the possibility of using fast, selective, quantitative detection of astaxanthin and cantaxanthin in salmon muscle tissues, employing resonance Raman spectroscopy. Analyzing strong Raman signals originating from the carbon-carbon double bond stretch vibrations of the carotenoid molecules under blue laser excitation, we are able to characterize quantitatively the concentrations of carotenoids in salmon muscle tissue. To validate the technique, we compared Raman data with absorption measurements of carotenoid extracts in acetone. A close correspondence was observed in absorption spectra for tissue extract in acetone and a pure astaxanthin solution. Raman results show a linear dependence between Raman and absorption data. The proposed technique holds promise as a method of rapid screening of carotenoid levels in fish muscle tissues and may be attractive for the fish farm industry to assess the dietary status of salmon, risk for infective diseases, and product quality control.

  8. FTIR difference and resonance Raman spectroscopy of rhodopsins with applications to optogenetics

    NASA Astrophysics Data System (ADS)

    Saint Clair, Erica C.

    The major aim of this thesis is to investigate the molecular basis for the function of several types of rhodopsins with special emphasis on their application to the new field of optogenetics. Rhodopsins are transmembrane biophotonic proteins with 7 alpha-helices and a retinal chromophore. Studies included Archaerhodopsin 3 (AR3), a light driven proton pump similar to the extensively studied bacteriorhodopsin (BR); channelrhodopsins 1 and 2, light-activated ion channels; sensory rhodopsin II (SRII), a light-sensing protein that modulates phototaxis used in archaebacteria; and squid rhodopsins (sRho), the major photopigment in squid vision and a model for human melanopsin, which controls circadian rhythms. The primary techniques used in these studies were FTIR difference spectroscopy and resonance Raman spectroscopy. These techniques, in combination with site directed mutagenesis and other biochemical methodologies produced new knowledge regarding the structural changes of the retinal chromophore, the location and function of internal water molecules as well as specific amino acids and peptide backbone. Specialized techniques were developed that allowed rhodopsins to be studied in intact membrane environments and in some cases in vivo measurements were made on rhodopsin heterologously expressed in E. coli thus allowing the effects of interacting proteins and membrane potential to be investigated. Evidence was found that the local environment of one or more internal water molecules in SRII is altered by interaction with its cognate transducer, HtrII, and is also affected by the local lipid environment. In the case of AR3, many of the broad IR continuum absorption changes below 3000 cm -1, assigned to networks of water molecules involved in proton transport through cytoplasmic and extracellular portions in BR, were found to be very similar to BR. Bands assigned to water molecules near the Schiff base postulated to be involved in proton transport were, however, shifted

  9. Advances in fiber optic-based UV resonance Raman spectroscopy techniques for anatomical and physiological investigations

    NASA Astrophysics Data System (ADS)

    Schulze, H. Georg; Barbosa, Christopher J.; Greek, L. Shane; Turner, Robin F. B.; Haynes, C. A.; Klein, Karl-Friedrich; Blades, Michael W.

    1999-04-01

    UV resonance Raman spectroscopy (UVRRS) is becoming a very popular spectroscopic method for bioanalytical investigations due to its high sensitivity, lack of fluorescence, and suitability for use in aqueous solutions. We have made a number of technological advances, especially the development of fiber-optic-based technologies, which permit the performance of remote/in-situ UVRRS measurements. We will be reporting on improved optical fiber probes and demonstrate their benefits in performing UVRRS on neurotransmitters, saliva, and urine.

  10. Temperature evolution of the band gap in BiFeO3 traced by resonant Raman scattering

    NASA Astrophysics Data System (ADS)

    Weber, Mads Christof; Guennou, Mael; Toulouse, Constance; Cazayous, Maximilien; Gillet, Yannick; Gonze, Xavier; Kreisel, Jens

    2016-03-01

    Knowledge of the electronic band structure of multiferroic oxides, crucial for the understanding and tuning of photoinduced effects, remains very limited even in the model and thoroughly studied BiFeO3. Here, we investigate the electronic band structure of BiFeO3 using Raman scattering with twelve different excitation wavelengths ranging from the blue to the near infrared. We show that resonant Raman signatures can be assigned to direct and indirect electronic transitions, as well as in-gap electronic levels, most likely associated with oxygen vacancies. Their temperature evolution establishes that the remarkable and intriguing variation of the optical band gap can be related to the shrinking of an indirect electronic band gap, while the energies for direct electronic transitions remains nearly temperature independent.

  11. Pre-resonance-stimulated Raman scattering for water bilayer structure on laser-induced plasma bubble surface.

    PubMed

    Li, Zhanlong; Li, Hongdong; Fang, Wenhui; Wang, Shenghan; Sun, Chenglin; Li, Zuowei; Men, Zhiwei

    2015-07-15

    Pre-resonance-stimulated Raman scattering (PSRS) from water molecules in the air/water interfacial regions was studied when the laser-induced plasma bubble was generated at the interfaces. A characteristically lower Raman shift of OH-stretching vibrational modes of water molecules at around 3000  cm(-1) (370 meV) was observed, in which the mechanisms were possibly attributed to the strong hydrogen bond in a well-ordered water bilayer structure that was formed on a laser-induced plasma bubble surface. Simultaneously, the PSRS of ice Ih at about 3100  cm(-1) was obtained, which also belonged to the strong hydrogen bond effect in ice Ih structure. PMID:26176442

  12. Surface-enhanced resonance Raman scattering spectroscopy of photosystem II pigment-protein complexes

    SciTech Connect

    Picorel, R. Estacion Experimental Aula Dei, Zaragoza ); Chumanov, G.; Cotton, T.M. ); Montoya, G. ); Toon, S.; Seibert, M. )

    1994-06-09

    Three different photosystem II (PSII) pigment-protein complexes (D1-D2-Cyt b[sub 559]-CP47, D1-D2-Cyt b[sub 559], and CP47) isolated from spinach were studied by surface-enhanced resonance Raman scattering (SERRS) spectroscopy. Surface-enhanced Raman scattering (SERS) is a distance sensitive (on a 5-10-[angstrom] scale) spectroscopic tool that can be used to examine structural properties of large biological molecules. It is demonstrated here that SERS can also be used to determine organizational relationships between different pigment-protein complexes. Strong SERRS spectra from the above PSII complexes before and after treatment with sodium dithionite were obtained on roughened Ag electrodes and in citrate-reduced Ag colloids. The D1-D2-Cyt b[sub 559] complex adsorbs with the Cyt b[sub 559] heme close to the surface in the colloid, whereas the complex adsorbs differently on the Ag electrode due to the differing surface properties of the two types of substrates. An analysis of the SERRS spectra led to the following conclusions: CP47 binds next to Cyt b[sub 559] in the D1-D2-Cyt b[sub 559]-CP47 complex and covers the heme, the Cyt b[sub 559] heme is located closer to one side of the complex (the stromal side in the intact thylakoid membrane), and both Chl and [beta]-carotene molecules are located closer to the opposite side of the complex. 37 refs., 7 figs.

  13. Maximizing the electromagnetic and chemical resonances of surface-enhanced Raman scattering for nucleic acids.

    PubMed

    Freeman, Lindsay M; Pang, Lin; Fainman, Yeshaiahu

    2014-08-26

    Although surface-enhanced Raman spectroscopy (SERS) has previously been performed with nucleic acids, the measured intensities for each nucleic acid have varied significantly depending on the SERS substrate and excitation wavelength. We have demonstrated that the charge-transfer (CT) mechanism, also known as the chemical enhancement of SERS, is responsible for the discrepancies previously reported in literature. The electronic states of cytosine and guanine attached to silver atoms are computationally calculated and experimentally measured to be in the visible range, which leads to a resonance Raman effect at the corresponding maximum wavelengths. The resulting SERS measurements are in good agreement with the simulated values, in which cytosine-silver shows stronger enhancement at 532 nm and guanine-silver shows stronger enhancement at 785 nm. An atomic layer of aluminum oxide is deposited on substrates to prevent charge-transfer, and corresponding measurements show weaker Raman signals caused by the suppression of the chemical resonance. These findings suggest the optimal SERS signal can be achieved by tuning the excitation wavelength to match both the electromagnetic and chemical resonances, paving the way for future single molecule detection of nucleic acids other than adenine. PMID:25065837

  14. Solitons and frequency combs in silica microring resonators: Interplay of the Raman and higher-order dispersion effects

    NASA Astrophysics Data System (ADS)

    Milián, C.; Gorbach, A. V.; Taki, M.; Yulin, A. V.; Skryabin, D. V.

    2015-09-01

    The influence of Raman scattering and higher order dispersions on solitons and frequency comb generation in silica microring resonators is investigated. The Raman effect introduces a threshold value in the resonator quality factor above which the frequency-locked solitons cannot exist, and instead, a rich dynamics characterized by generation of self-frequency-shifting solitons and dispersive waves is observed. A mechanism for broadening the Cherenkov radiation through Hopf instability of the frequency-locked solitons is also reported.

  15. Resonance Raman spectra of the (2Fe-2S) clusters of the Rieske protein from thermus and phthalate dioxygenase from pseudomonas

    SciTech Connect

    Kuila, D.; Fee, J.A.; Schoonover, J.R.; Woodruff, W.H.

    1987-03-04

    In this paper a resonance Raman (RR) study of novel iron-sulfur-nitrogen clusters is described which provides evidence for an asymmetric distribution of Cys and N ligands on the cluster. The systems examined were Thermus Rieske protein (TRP) and phthalate dioxygenase (PDO) from Pseudomonas cepacia; the RR spectra of these proteins are compared to that of spinach ferredoxin (SFD).

  16. Study of spin-ordering and spin-reorientation transitions in hexagonal manganites through Raman spectroscopy

    PubMed Central

    Chen, Xiang-Bai; Hien, Nguyen Thi Minh; Han, Kiok; Nam, Ji-Yeon; Huyen, Nguyen Thi; Shin, Seong-Il; Wang, Xueyun; Cheong, S. W.; Lee, D.; Noh, T. W.; Sung, N. H.; Cho, B. K.; Yang, In-Sang

    2015-01-01

    Spin-wave (magnon) scattering, when clearly observed by Raman spectroscopy, can be simple and powerful for studying magnetic phase transitions. In this paper, we present how to observe magnon scattering clearly by Raman spectroscopy, then apply the Raman method to study spin-ordering and spin-reorientation transitions of hexagonal manganite single crystal and thin films and compare directly with the results of magnetization measurements. Our results show that by choosing strong resonance condition and appropriate polarization configuration, magnon scattering can be clearly observed, and the temperature dependence of magnon scattering can be simple and powerful quantity for investigating spin-ordering as well as spin-reorientation transitions. Especially, the Raman method would be very helpful for investigating the weak spin-reorientation transitions by selectively probing the magnons in the Mn3+ sublattices, while leaving out the strong effects of paramagnetic moments of the rare earth ions. PMID:26300075

  17. Study of spin-ordering and spin-reorientation transitions in hexagonal manganites through Raman spectroscopy.

    PubMed

    Chen, Xiang-Bai; Hien, Nguyen Thi Minh; Han, Kiok; Nam, Ji-Yeon; Huyen, Nguyen Thi; Shin, Seong-Il; Wang, Xueyun; Cheong, S W; Lee, D; Noh, T W; Sung, N H; Cho, B K; Yang, In-Sang

    2015-01-01

    Spin-wave (magnon) scattering, when clearly observed by Raman spectroscopy, can be simple and powerful for studying magnetic phase transitions. In this paper, we present how to observe magnon scattering clearly by Raman spectroscopy, then apply the Raman method to study spin-ordering and spin-reorientation transitions of hexagonal manganite single crystal and thin films and compare directly with the results of magnetization measurements. Our results show that by choosing strong resonance condition and appropriate polarization configuration, magnon scattering can be clearly observed, and the temperature dependence of magnon scattering can be simple and powerful quantity for investigating spin-ordering as well as spin-reorientation transitions. Especially, the Raman method would be very helpful for investigating the weak spin-reorientation transitions by selectively probing the magnons in the Mn(3+) sublattices, while leaving out the strong effects of paramagnetic moments of the rare earth ions. PMID:26300075

  18. Study of single walled carbon nanotube functionalization by means of surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Ceponkus, Justinas; Velicka, Martynas; Pucetaite, Milda; Sablinskas, Valdas

    2015-09-01

    Raman spectroscopy is known to provide information about the quality of the single walled carbon nanotubes (SWCNT). The information is based on the intensity ratio of D and G spectral modes and the frequency of RBM modes. However due to resonance nature of Raman spectrum of the nanotubes this method is not suitable to detect functionalization of the nanotubes. Surface enhanced Raman spectroscopy (SERS) is known to enhance the Raman bands up to fourteen orders of magnitude. Preferable adsorption sites for small silver nanoparticles are expected to be the functional groups of SWCNT; therefore SERS technique allows detecting small amounts of functional groups despite strong resonance Raman from backbone of SWCNT. In this study functionalized nanotubes were dispersed in silver colloid and dried on the standard silver plate for Raman measurements. Spectra of SWCNT without colloid in the spectral range between 50 and 1800 cm-1 exhibit only four main spectral features: G, D, and RBM modes between 200 and 400 cm-1. Spectra of SWCNT with the colloid exhibit several additional spectral bands which do not belong to the colloid. These bands attributed to vibrations of C-O, C-C and O-H from the functional groups and the carbon atom of the SWCNT attached to the corresponding group. The bands associated with the vibrations involving O atom is an indication that silver nanoparticles interact with the functional group attached to SWCNT.

  19. Surface-enhanced Raman scattering (SERS) study of anthocyanidins

    NASA Astrophysics Data System (ADS)

    Zaffino, Chiara; Russo, Bianca; Bruni, Silvia

    2015-10-01

    Anthocyanins are an important class of natural compounds responsible for the red, purple and blue colors in a large number of flowers, fruits and cereal grains. They are polyhydroxy- and polymethoxy-derivatives of 2-phenylbenzopyrylium (flavylium) salts, which are present in nature as glycosylated molecules. The aim of the present study is to assess the identification of anthocyanidins, i.e. anthocyanins without the glycosidic moiety, by means of surface-enhanced Raman spectroscopy (SERS), a very chemically-specific technique which is moreover sensitive to subtle changes in molecular structures. These features can lead to elect SERS, among the spectroscopic tools currently at disposal of scientists, as a technique of choice for the identification of anthocyanidins, since: (1) anthocyanidins structurally present the same benzopyrylium moiety and differentiate only for the substitution pattern on their phenyl ring, (2) different species are present in aqueous solution depending on the pH. It will be demonstrated that, while resonance Raman spectra of anthocyanidins are very similar to one another, SER spectra show greater differences, leading to a further step in the identification of such important compounds in diluted solutions by means of vibrational spectroscopy. Moreover, the dependence on the pH of the six most common anthocyanidins, i.e. cyanidin, delphinidin, pelargonidin, peonidin, malvidin and petunidin, is studied. To the best of the authors' knowledge, a complete SERS study of such important molecules is reported in the present work for the first time.

  20. Application of resonance Raman spectroscopy as a nuclear proliferation detection technology

    SciTech Connect

    Sedlacek, A.J. III; Chen, C.L.; Dougherty, D.R.

    1993-03-01

    Resonance Raman spectroscopy (RRS) potentially possesses many of the characteristics of an ideal verification technology. Some of these ideal traits are: very high selectivity and specificity to allow the deconvolution of a mixture of the chemicals of interest, high sensitivity in order to measure a species at trace levels, high reliability and long-term durability, applicability to a wide range of chemicals capability for sensing in a variety of environmental conditions, independence of the physical state of the chemical capability for quantitative analysis, and finally, but no less important capability for full signal development within seconds. In this presentation, the potential of RRS as a detection/identification technology for chemicals pertinent to nuclear materials production and processing will be assessed. A review of the basic principles behind this technique, both theoretical and experimental, will be discussed along with some recent results obtained in this laboratory. Raman scattering is a coherent, inelastic, two-photon scattering process where an exciting photon of energy hv promotes a molecule to a virtual level and the subsequently emitted photon is shifted in frequency in accordance with the rotational-vibrational structure of the irradiated species, therefore providing a unique fingerprint of the molecule. The enhancement of a Raman signal occurs when the excitation frequency is isoenergetic with an allowed electronic transition. Under resonance conditions, scattering cross-sections have been enhanced up to 6 orders of magnitude, thereby allowing the measurement of resonance Raman spectra from concentrations as dilute as 20 ppb for PAHs (with the potential of pptr). In detection/verification programs, this condition translates to increased sensitivity (ppm/ppb) and increased probing distance (m/km).

  1. Application of resonance Raman spectroscopy as a nuclear proliferation detection technology

    SciTech Connect

    Sedlacek, A.J. III; Chen, C.L.; Dougherty, D.R.

    1993-01-01

    Resonance Raman spectroscopy (RRS) potentially possesses many of the characteristics of an ideal verification technology. Some of these ideal traits are: very high selectivity and specificity to allow the deconvolution of a mixture of the chemicals of interest, high sensitivity in order to measure a species at trace levels, high reliability and long-term durability, applicability to a wide range of chemicals capability for sensing in a variety of environmental conditions, independence of the physical state of the chemical capability for quantitative analysis, and finally, but no less important capability for full signal development within seconds. In this presentation, the potential of RRS as a detection/identification technology for chemicals pertinent to nuclear materials production and processing will be assessed. A review of the basic principles behind this technique, both theoretical and experimental, will be discussed along with some recent results obtained in this laboratory. Raman scattering is a coherent, inelastic, two-photon scattering process where an exciting photon of energy hv promotes a molecule to a virtual level and the subsequently emitted photon is shifted in frequency in accordance with the rotational-vibrational structure of the irradiated species, therefore providing a unique fingerprint of the molecule. The enhancement of a Raman signal occurs when the excitation frequency is isoenergetic with an allowed electronic transition. Under resonance conditions, scattering cross-sections have been enhanced up to 6 orders of magnitude, thereby allowing the measurement of resonance Raman spectra from concentrations as dilute as 20 ppb for PAHs (with the potential of pptr). In detection/verification programs, this condition translates to increased sensitivity (ppm/ppb) and increased probing distance (m/km).

  2. Redox State of Cytochromes in Frozen Yeast Cells Probed by Resonance Raman Spectroscopy.

    PubMed

    Okotrub, Konstantin A; Surovtsev, Nikolay V

    2015-12-01

    Cryopreservation is a well-established technique used for the long-term storage of biological materials whose biological activity is effectively stopped under low temperatures (suspended animation). Since most biological methods do not work in a low-temperature frozen environment, the mechanism and details of the depression of cellular activity in the frozen state remain largely uncharacterized. In this work, we propose, to our knowledge, a new approach to study the downregulation of the redox activity of cytochromes b and c in freezing yeast cells in a contactless, label-free manner. Our approach is based on cytochrome photobleaching effects observed in the resonance Raman spectra of live cells. Photoinduced and native redox reactions that contributed to the photobleaching rate were studied over a wide temperature range (from -173 to +25 °C). We found that ice formation influences both the rate of cytochrome redox reactions and the balance between the reduced and oxidized cytochromes. We demonstrate that the temperature dependence of native redox reaction rates can be well described by the thermal activation law with an apparent energy of 32.5 kJ/mol, showing that the redox reaction rate is ∼10(15) times slower at liquid nitrogen temperature than at room temperature. PMID:26636934

  3. Resonance Raman spectroscopy as an in situ probe for monitoring catalytic events in a Ru-porphyrin mediated amination reaction.

    PubMed

    Zardi, Paolo; Gallo, Emma; Solan, Gregory A; Hudson, Andrew J

    2016-05-10

    Resonance Raman microspectroscopy has been widely used to study the structure and dynamics of porphyrins and metal complexes containing the porphyrin ligand. Here, we have demonstrated that the same technique can be adapted to examine the mechanism of a homogeneously-catalysed reaction mediated by a transition-metal-porphyrin complex. Previously it has been challenging to study this type of reaction using in situ spectroscopic monitoring due to the low stability of the reaction intermediates and elevated-temperature conditions. We have made a straightforward modification to the sample stage on a microscope for time-lapsed Raman microspectroscopy from reaction mixtures in these media. The allylic amination of unsaturated hydrocarbons by aryl azides, which can be catalysed by a ruthenium-porphyrin complex, has been used as an illustrative example of the methodology. The mechanism of this particular reaction has been studied previously using density-functional theory and kinetic approaches. The Raman measurements support the mechanism proposed in the earlier publications by providing the first experimental verification of a precursor reaction complex between the aryl azide and the ruthenium metal ion, and evidence for the formation of a mono-imido intermediate complex under conditions of high concentration of the reactant olefin. PMID:27070335

  4. Analysis of normal and diseased colon mucosa using ultraviolet resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Boustany, Nada N.; Manoharan, Ramasamy; Dasari, Ramachandra R.; Feld, Michael S.

    1996-04-01

    Ultraviolet resonance Raman (UVRR) spectroscopy was used to characterize normal and diseased colon mucosa in vitro. A tunable mode-locked Titanium:Sapphire laser operating at 76 MHz was used to irradiate normal and diseased colon tissue samples with 251 nm light generated from the third harmonic of the fundamental radiation. The Raman scattered light was collected and analyzed using a 1 meter spectrometer fitted with a UV coated, liquid nitrogen cooled CCD detector. The measured spectra show prominent bands that correspond to those of known tissue constituents including nucleic acids, aromatic amino acids and lipids. Using the Raman lineshapes measured from pure solutions of nucleotides, tryptophan, tyrosine, FAD, and from lipid-rich serosal fat, the colon spectra were modeled by a least square fitting algorithm whereby the colon spectra were assumed to be a linear combination of the pure biochemical lineshapes. The relative Raman scattering cross section of each biochemical was determined so that the relative concentration of each compound with respect to the others, could be extracted from a given tissue spectrum.

  5. Directly probing redox-linked quinones in photosystem II membrane fragments via UV resonance Raman scattering.

    PubMed

    Chen, Jun; Yao, Mingdong; Pagba, Cynthia V; Zheng, Yang; Fei, Liping; Feng, Zhaochi; Barry, Bridgette A

    2015-01-01

    In photosynthesis, photosystem II (PSII) harvests sunlight with bound pigments to oxidize water and reduce quinone to quinol, which serves as electron and proton mediators for solar-to-chemical energy conversion. At least two types of quinone cofactors in PSII are redox-linked: QA, and QB. Here, we for the first time apply 257-nm ultraviolet resonance Raman (UVRR) spectroscopy to acquire the molecular vibrations of plastoquinone (PQ) in PSII membranes. Owing to the resonance enhancement effect, the vibrational signal of PQ in PSII membranes is prominent. A strong band at 1661 cm(-1) is assigned to ring CC/CO symmetric stretch mode (ν8a mode) of PQ, and a weak band at 469 cm(-1) to ring stretch mode. By using a pump-probe difference UVRR method and a sample jet technique, the signals of QA and QB can be distinguished. A frequency difference of 1.4 cm(-1) in ν8a vibrational mode between QA and QB is observed, corresponding to ~86 mV redox potential difference imposed by their protein environment. In addition, there are other PQs in the PSII membranes. A negligible anharmonicity effect on their combination band at 2130 cm(-1) suggests that the 'other PQs' are situated in a hydrophobic environment. The detection of the 'other PQs' might be consistent with the view that another functional PQ cofactor (not QA or QB) exists in PSII. This UVRR approach will be useful to the study of quinone molecules in photosynthesis or other biological systems. PMID:25791219

  6. Resonance Raman scattering of perovskite-type relaxor ferroelectrics under nonambient conditions

    NASA Astrophysics Data System (ADS)

    de la Flor, G.; Wehber, M.; Rohrbeck, A.; Aroyo, M. I.; Bismayer, U.; Mihailova, B.

    2014-08-01

    Resonance Raman scattering (RRS) of two model perovskite-type (ABO3) relaxor compounds PbSc0.5Ta0.5O3 (PST) and PbSc0.5Nb0.5O3 (PSN) excited with a laser wavelength of 325 nm (3.8 eV) is studied at different temperatures and ambient pressure as well as at high pressures and room temperature (for PST). The origin of the observed RRS is reinspected by applying group-theory analysis of phonons compatible with symmetry-allowed electron transitions in cubic and possible polar and nonpolar rhombohedral ferroic structures. It is shown that the simultaneous enhancement of first- and second-order RRS generated by antisymmetric BO6 bending and stretching modes under resonance conditions when the photon energy is slightly above the energy gap Eg˜3.2eV results exclusively from spatial regions with coherent polar structural distortions. Upon cooling RRS appears in the vicinity of the characteristic temperature T*, and its total intensity significantly increases upon further temperature decrease. The predominate type of BO6 polarity changes from related to difference in B-O bonds to related to distorted O-B-O bond angles. At room temperature and high pressures RRS drops in intensity above the critical pressure of development of long-range antiphase octahedral tilting. However it persists up to 8.3 GPa, which is the highest pressure reached in the experiment, indicating that the high-pressure phase is polar due to the slight BO6 distortions accompanying the tilt order.

  7. Stimulated Stokes and Antistokes Raman Scattering in Microspherical Whispering Gallery Mode Resonators.

    PubMed

    Farnesi, Daniele; Berneschi, Simone; Cosi, Franco; Righini, Giancarlo C; Soria, Silvia; Nunzi Conti, Gualtiero

    2016-01-01

    Dielectric microspheres can confine light and sound for a length of time through high quality factor whispering gallery modes (WGM). Glass microspheres can be thought as a store of energy with a huge variety of applications: compact laser sources, highly sensitive biochemical sensors and nonlinear phenomena. A protocol for the fabrication of both the microspheres and coupling system is given. The couplers described here are tapered fibers. Efficient generation of nonlinear phenomena related to third order optical non-linear susceptibility Χ((3)) interactions in triply resonant silica microspheres is presented in this paper. The interactions here reported are: Stimulated Raman Scattering (SRS), and four wave mixing processes comprising Stimulated Anti-stokes Raman Scattering (SARS). A proof of the cavity-enhanced phenomenon is given by the lack of correlation among the pump, signal and idler: a resonant mode has to exist in order to obtain the pair of signal and idler. In the case of hyperparametric oscillations (four wave mixing and stimulated anti-stokes Raman scattering), the modes must fulfill the energy and momentum conservation and, last but not least, have a good spatial overlap. PMID:27078752

  8. Resonant raman scattering and dispersion of polar optical and acoustic phonons in hexagonal inn

    SciTech Connect

    Davydov, V. Yu. Klochikhin, A. A.; Smirnov, A. N.; Strashkova, I. Yu.; Krylov, A. S.; Lu Hai; Schaff, William J.; Lee, H.-M.; Hong, Y.-L.; Gwo, S.

    2010-02-15

    It is shown that a study of the dependence of impurity-related resonant first-order Raman scattering on the frequency of excitation light makes it possible to observe the dispersion of polar optical and acoustic branches of vibrational spectrum in hexagonal InN within a wide range of wave vectors. It is established that the wave vectors of excited phonons are uniquely related to the energy of excitation photon. Frequencies of longitudinal optical phonons E{sub 1}(LO) and A{sub 1}(LO) in hexagonal InN were measured in the range of excitation-photon energies from 2.81 to 1.17 eV and the frequencies of longitudinal acoustic phonons were measured in the range 2.81-1.83 eV of excitation-photon energies. The obtained dependences made it possible to extrapolate the dispersion of phonons A{sub 1}(LO) and E{sub 1}(LO) to as far as the point {Gamma} in the Brillouin zone and estimate the center-band energies of these phonons (these energies have not been uniquely determined so far).

  9. 13C Solid State Nuclear Magnetic Resonance and µ-Raman Spectroscopic Characterization of Sicilian Amber.

    PubMed

    Barone, Germana; Capitani, Donatella; Mazzoleni, Paolo; Proietti, Noemi; Raneri, Simona; Longobardo, Ugo; Di Tullio, Valeria

    2016-08-01

    (13)C cross-polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) and µ-Raman spectroscopy were applied to characterize Sicilian amber samples. The main goal of this work was to supply a complete study of simetite, highlighting discriminating criteria useful to distinguish Sicilian amber from fossil resins from other regions and laying the foundations for building a spectroscopic database of Sicilian amber. With this aim, a private collection of unrefined simetite samples and fossil resins from the Baltic region and Dominican Republic was analyzed. Overall, the obtained spectra permitted simetite to be distinguished from the other resins. In addition, principal component analysis (PCA) was applied to the spectroscopic data, allowing the clustering of simetite samples with respect to the Baltic and Dominican samples and to group the simetite samples in two sets, depending on their maturity. Finally, the analysis of loadings allowed for a better understanding of the spectral features that mainly influenced the discriminating characteristics of the investigated ambers. PMID:27340217

  10. Resonance Raman Spectroscopy for In-Situ Monitoring of Radiation Damage

    SciTech Connect

    Meents, A.; Owen, R. L.; Schneider, R.; Pradervand, C.; Schulze-Briese, C.; Murgida, D.; Hildebrandt, P.; Bohler, P

    2007-01-19

    Radiation induced damage of metal centres in proteins is a severe problem in X-ray structure determination. Photoreduction can lead to erroneous structural implications, and in the worst cases cause structure solution to fail. Resonance Raman (RR) spectroscopy is well suited in-situ monitoring of X-ray induced photoreduction. However the laser excitation needed for RR can itself cause photoreduction of the metal centres. In the present study myoglobin and rubredoxin crystals were used as model systems to assess the feasibility of using RR for this application. It is shown that at least 10-15 RR spectra per crystal can be recorded at low laser power before severe photoreduction occurs. Furthermore it is possible to collect good quality RR spectra from cryocooled protein crystals with exposure times of only a few seconds. Following extended laser illumination photoreduction is observed through the formation and decay of spectral bands as a function of dose. The experimental setup planned for integration into the SLS protein crystallography beamlines is also described. This setup should also prove to be very useful for other experimental techniques at synchrotrons where X-ray photoreduction is a problem e.g. X-ray absorption spectroscopy.

  11. Two-dimensional resonance Raman spectroscopy of oxygen- and water-ligated myoglobins

    NASA Astrophysics Data System (ADS)

    Molesky, Brian P.; Guo, Zhenkun; Cheshire, Thomas P.; Moran, Andrew M.

    2016-07-01

    Two-dimensional resonance Raman (2DRR) spectroscopy has recently been developed as a tool for studies of structural heterogeneity and photochemical dynamics in condensed phases. In this paper, 2DRR spectroscopy is used to investigate line broadening mechanisms of both oxygen- and water-ligated myoglobins. General signatures of anharmonicity and inhomogeneous line broadening are first established with model calculations to facilitate signal interpretation. It is shown that the present quasi-degenerate version of 2DRR spectroscopy is insensitive to anharmonicity, because signal generation is allowed for harmonic modes. Rather, the key information to be gained from 2DRR spectroscopy pertains to the line broadening mechanisms, which are fairly obvious by inspection of the data. 2DRR signals acquired for both heme protein systems reveal significant heterogeneity in the vibrational modes local to the heme's propionic acid side chains. These side chains are known to interact with solvent, because they protrude from the hydrophobic pocket that encloses the heme. Molecular dynamics simulations suggest that the heterogeneity detected in our 2DRR experiments reflects fluctuations in the geometries of the side chains. Knowledge of such thermal motions will be useful for understanding protein function (e.g., ligand binding) because the side chains are an effective "gateway" for the exchange of thermal energy between the heme and solvent.

  12. Raman spectroscopy of gliomas: an exploratory study

    NASA Astrophysics Data System (ADS)

    Shenoy, Mahesh; Hole, Arti R.; Shridhar, E.; Moiyadi, Aliasgar V.; Krishna, C. Murali

    2014-03-01

    Gliomas are extremely infiltrative type of brain cancers, the borders of which are difficult to locate. Gliomas largely consist of tumors of astrocytic or oligodendroglial lineage. Usually stereotactic surgery is performed to obtain tumor tissue sample. Complete excision of these tumors with preservation of uninvolved normal areas is important during brain tumor surgeries. The present study was undertaken to explore feasibility of classifying abnormal and normal glioma tissues with Raman spectroscopy (RS). RS is a nondestructive vibrational spectroscopic technique, which provides information about molecular composition, molecular structures and molecular interactions in tissue. Postoperated 33 (20-abnormal and 13-normal) gliomas tissue samples of different grades were collected under clinical supervision. Five micron section from tissue sample was used for confirmatory histopathological diagnosis while the remaining tissue was placed on CaF2 window and spectra were acquired using a fiberoptic-probe-coupled HE-785 Raman-spectrometer. Spectral acquisition parameters were laser power-80mW, integration-20s and averaged over 3 accumulations. Spectra were pre-processed and subjected to unsupervised Principal-Component Analysis (PCA) to identify trends of classification. Supervised PC-LDA (Principal-Component-Linear-Discriminant Analysis) was used to develop standard-models using spectra of 12 normal and abnormal specimens each. Leave-one-out crossvalidation yielded classification-efficiency of 90% and 80% for normal and abnormal conditions, respectively. Evaluation with an independent-test data-set comprising of 135 spectra of 9 samples provided sensitivity of 100% and specificity of 70%. Findings of this preliminary study may pave way for objective tumor margin assessment during brain surgery.

  13. Raman and AFM study of gamma irradiated plastic bottle sheets

    SciTech Connect

    Ali, Yasir; Kumar, Vijay; Dhaliwal, A. S.; Sonkawade, R. G.

    2013-02-05

    In this investigation, the effects of gamma irradiation on the structural properties of plastic bottle sheet are studied. The Plastic sheets were exposed with 1.25MeV {sup 60}Co gamma rays source at various dose levels within the range from 0-670 kGy. The induced modifications were followed by micro-Raman and atomic force microscopy (AFM). The Raman spectrum shows the decrease in Raman intensity and formation of unsaturated bonds with an increase in the gamma dose. AFM image displays rough surface morphology after irradiation. The detailed Raman analysis of plastic bottle sheets is presented here, and the results are correlated with the AFM observations.

  14. Raman and infrared spectroscopic study of turquoise minerals.

    PubMed

    Čejka, Jiří; Sejkora, Jiří; Macek, Ivo; Malíková, Radana; Wang, Lina; Scholz, Ricardo; Xi, Yunfei; Frost, Ray L

    2015-10-01

    Raman and infrared spectra of three well-defined turquoise samples, CuAl6(PO4)4(OH)8·4H2O, from Lavender Pit, Bisbee, Cochise county, Arizona; Kouroudaiko mine, Faleme river, Senegal and Lynch Station, Virginia were studied, interpreted and compared. Observed Raman and infrared bands were assigned to the stretching and bending vibrations of phosphate tetrahedra, water molecules and hydroxyl ions. Approximate O-H⋯O hydrogen bond lengths were inferred from the Raman and infrared spectra. No Raman and infrared bands attributable to the stretching and bending vibrations of (PO3OH)(2-) units were observed. PMID:25956330

  15. Raman and infrared spectroscopic study of turquoise minerals

    NASA Astrophysics Data System (ADS)

    Čejka, Jiří; Sejkora, Jiří; Macek, Ivo; Malíková, Radana; Wang, Lina; Scholz, Ricardo; Xi, Yunfei; Frost, Ray L.

    2015-10-01

    Raman and infrared spectra of three well-defined turquoise samples, CuAl6(PO4)4(OH)8·4H2O, from Lavender Pit, Bisbee, Cochise county, Arizona; Kouroudaiko mine, Faleme river, Senegal and Lynch Station, Virginia were studied, interpreted and compared. Observed Raman and infrared bands were assigned to the stretching and bending vibrations of phosphate tetrahedra, water molecules and hydroxyl ions. Approximate O-H⋯O hydrogen bond lengths were inferred from the Raman and infrared spectra. No Raman and infrared bands attributable to the stretching and bending vibrations of (PO3OH)2- units were observed.

  16. Remote-Raman spectroscopic study of minerals under supercritical CO2 relevant to Venus exploration.

    PubMed

    Sharma, Shiv K; Misra, Anupam K; Clegg, Samuel M; Barefield, James E; Wiens, Roger C; Acosta, Tayro E; Bates, David E

    2011-10-01

    The authors have utilized a recently developed compact Raman spectrometer equipped with an 85 mm focal length (f/1.8) Nikon camera lens and a custom mini-ICCD detector at the University of Hawaii for measuring remote Raman spectra of minerals under supercritical CO(2) (Venus chamber, ∼102 atm pressure and 423 K) excited with a pulsed 532 nm laser beam of 6 mJ/pulse and 10 Hz. These experiments demonstrate that by focusing a frequency-doubled 532 nm Nd:YAG pulsed laser beam with a 10× beam expander to a 1mm spot on minerals located at 2m inside a Venus chamber, it is possible to measure the remote Raman spectra of anhydrous sulfates, carbonates, and silicate minerals relevant to Venus exploration during daytime or nighttime with 10s integration time. The remote Raman spectra of gypsum, anhydrite, barite, dolomite and siderite contain fingerprint Raman lines along with the Fermi resonance doublet of CO(2). Raman spectra of gypsum revealed dehydration of the mineral with time under supercritical CO(2) at 423 K. Fingerprint Raman lines of olivine, diopside, wollastonite and α-quartz can easily be identified in the spectra of these respective minerals under supercritical CO(2). The results of the present study show that time-resolved remote Raman spectroscopy with a compact Raman spectrometer of moderate resolution equipped with a gated intensified CCD detector and low power laser source could be a potential tool for exploring Venus surface mineralogy both during daytime and nighttime from a lander. PMID:21333587

  17. Generating monomeric 5-coordinated microperoxidase-11 using carboxylic acid functionalized silver nanoparticles: A surface-enhanced resonance Raman scattering analysis.

    PubMed

    Kalaivani, Govindasamy; Sivanesan, Arumugam; Kannan, Ayyadurai; Sevvel, Ranganathan

    2016-10-01

    Microperoxidase-11 (MP-11), a heme undecapeptide obtained by proteolytic digestion of cytochrome c, resembles peroxidase enzyme when its heme center is 5-coordinated with a vacant sixth coordination site. However, MP-11 always tends to aggregate in both solution and on surface and eventually forms the 6-coordinated heme. Thus, the present study investigates the immobilization strategy of MP-11 on nanoparticle surface in order to generate monomeric 5-coordinated MP-11 and make them as an efficient biocatalyst. The powerful surface-enhanced resonance Raman scattering (SERRS) technique is being employed to attain the detailed structural information of the catalytic site i.e., the heme center. The localized surface plasmon resonance (LSPR) tuned and 6-mercaptohexanoic acid (MHA) functionalized silver nanoparticles (Ag@MHA NPs) are used as Raman signal amplifier. The outcome of the SERRS study unambiguously portrays the existence of monomeric 5-coordinated MP-11 on Ag@MHA NPs surface. Here, Ag@MHA NPs plays a dual role of providing a platform to create monomeric 5-coordinated MP-11 and to load large number of MP-11 due to its high surface to volume ratio. Further, the electrostatic interaction between Ag@MHA NPs and MP-11 leads to instantaneous SERRS signal enhancement with a Raman enhancement factor (EFSERS) of 2.36×10(6). Langmuir adsorption isotherm has been employed for the adsorption of MP-11 on Ag@MHA NPs surface, which provides the real surface coverage (ΓS(*)) and equilibrium constant (K) value of 1.54nm and 5×10(11)M(-1). Furthermore, the peroxidase activity of MP-11 has been demonstrated through electrocatalytic oxygen reduction reaction. PMID:27434160

  18. Monitoring LED-induced carotenoid increase in grapes by Transmission Resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Gonzálvez, Alicia G.; Martínez, Nerea L.; Telle, Helmut H.; Ureña, Ángel González

    2013-02-01

    Transmission Resonance Raman (TRR) spectroscopy combines increased signal-to-noise ratio with enhanced analytical sensibility. TRR was applied to directly monitor, without any sample preparation, the enhancement of β-carotene content in table grapes when they are irradiated by low power UV-LEDs. It was shown that, with respect to control samples, the carotenoid content in the grapes increased about five-fold, using UV-LED irradiation doses being two orders of magnitude lower than the maximum limit allowed by United States Food and Drug Administration. These promising results may pave the way for the development of easy, non-invasive techniques to improve food quality.

  19. Limiting effects on laser compression by resonant backward Raman scattering in modern experiments

    SciTech Connect

    Yampolsky, Nikolai A.; Fisch, Nathaniel J.

    2011-05-15

    Through resonant backward Raman scattering, the plasma wave mediates the energy transfer between long pump and short seed laser pulses. These mediations can result in pulse compression at extraordinarily high powers. However, both the overall efficiency of the energy transfer and the duration of the amplified pulse depend upon the persistence of the plasma wave excitation. At least with respect to the recent state-of-the-art experiments, it is possible to deduce that at present the experimentally realized efficiency of the amplifier is likely constrained mainly by two effects, namely, the pump chirp and the plasma wave wavebreaking.

  20. Physical origin of Davydov splitting and resonant Raman spectroscopy of Davydov components in multilayer MoTe2

    NASA Astrophysics Data System (ADS)

    Song, Q. J.; Tan, Q. H.; Zhang, X.; Wu, J. B.; Sheng, B. W.; Wan, Y.; Wang, X. Q.; Dai, L.; Tan, P. H.

    2016-03-01

    We systematically study the high-resolution and polarized Raman spectra of multilayer (ML) MoTe2 . The layer-breathing (LB) and shear (C) modes are observed in the ultralow-frequency region, which are used to quantitatively evaluate the interlayer coupling in ML MoTe2 based on the linear chain model, in which only the nearest interlayer coupling is considered. The Raman spectra on three different substrates verify the negligible substrate effect on the phonon frequencies of ML MoTe2 . Ten excitation energies are used to measure the high-frequency modes of N -layer MoTe2 (N L MoTe2 ; N is an integer). Under the resonant excitation condition, we observe N -dependent Davydov components in ML MoTe2 , originating from the Raman-active A1'(A1g 2) modes at ˜172 c m-1 . More than two Davydov components are observed in N L MoTe2 for N >4 by Raman spectroscopy. The N -dependent Davydov components are further investigated based on the symmetry analysis. A van der Waals model only considering the nearest interlayer coupling has been proposed to well understand the Davydov splitting of high-frequency A1'(A1g 2) modes. The different resonant profiles for the two Davydov components in 3L MoTe2 indicate that proper excitation energy of ˜1.8 -2.2 eV must be chosen to observe the Davydov splitting in ML MoTe2 . Our work presents a simple way to identify layer number of ultrathin MoTe2 flakes by the corresponding number and peak position of Davydov components. Our work also provides a direct evidence from Raman spectroscopy of how the nearest van der Waals interactions significantly affect the frequency of the high-frequency intralayer phonon modes in multilayer MoTe2 and expands the understanding on the lattice vibrations and interlayer coupling of transition metal dichalcogenides and other two-dimensional materials.

  1. Ultraviolet resonance Raman studies of hemoglobin quaternary structure using a tyrosine-α42 mutant: changes in the α1β2 subunit interface upon the T → R transition

    NASA Astrophysics Data System (ADS)

    Nagai, M.; Imai, K.; Kaminaka, S.; Mizutani, Y.; Kitagawa, T.

    1996-06-01

    Quaternary structure changes between T (tense) and R (relaxed) states of human hemoglobin A (Hb A) and its α42Tyr mutant, obtained through site-directed mutagenesis, were investigated by ultraviolet resonance Raman (UVRR) spectroscopy using 235-nm excitation. Raman excitation at 235 nm enabled us to detect bands of tryptophan (Trp) and tyrosine (Tyr) residues. The UVRR spectral contribution of α42Tyr, which is located in the "switch" region of the α1β2 interface and forms an H-bond with the carboxylate side chain of β99Asp only in the T state, was deduced for each of the deoxy-and CO-forms by subtracting the spectra of Hb αY42H from those of Hb A under a certain assumption. This suggested that α42Tyr is responsible for the frequency shifts of Y8a (1619 cm -1) and Y9a (1179 cm -1) of the Tyr RR bands of Hb A, but that other Tyr residues are involved in intensity changes. The ligand-induced intensity changes of Trp UVRR bands were similar for Hb A and Hb αY42H, indicating that the conformation changes of Trp residues of Hb A and Hb αY42H upon quaternary structure change are alike. In order to get an insight into implications of these changes of the Tyr UVRR bands of Hb A between the R and T states, UVRR spectra of tyrosine and p-cresol in various solvents were examined with 235-nm excitation. The UVRR spectrum of Tyr residues in Hb A was similar to that of tyrosine in an aqueous solution, but distinct from that of tyrosine crystalline powder. The ν8 a band of p-cresol was upshifted and intensified in H-bond-forming solvents, irrespective of the H-bond donor or acceptor, compared with that in a non-H-bonding solvent. Accordingly, the present results are compatible with the statement that the frequency shifts of Y8a and Y9a of Hb A upon the T → R transition are caused by the H-bond formation of α42Tyr in the T state.

  2. Surface-enhanced resonance Raman spectroscopy of iron-dopamine complexes

    NASA Astrophysics Data System (ADS)

    Kowalchyk, Will K.; Davis, Kevin L.; Morris, Michael D.

    1995-01-01

    Surface-enhanced resonance Raman spectroscopy (SERRS) at silver colloids is used to detect the catecholamines, 3-hydroxytyramine (dopamine) and 3,4-dihydroxyphenylacetic acid (DOPAC), in a modified Ringer's solution. Catecholamines form very strong complexes with iron(III) in solution ( Kf > 10 40) and exhibit a broad ligand-to-metal charge-transfer (LMCT) absorption in the visible (˜ 500 nm). Resonance enhancement is achieved by excitation at 532 nm from a frequency doubled Nd:YAG laser with high quality spectra attainable in 1 s. Maximum SERRS signal is observed when basic buffer is added to a dopamine sample containing 50 × 10 -6 M ferric ion. Dopamine concentrations in the nanomolar (resting level) range are obtained using this technique.

  3. Quantitative evaluation of blinking in surface enhanced resonance Raman scattering and fluorescence by electromagnetic mechanism

    NASA Astrophysics Data System (ADS)

    Itoh, Tamitake; Iga, Mitsuhiro; Tamaru, Hiroharu; Yoshida, Ken-ichi; Biju, Vasudevanpillai; Ishikawa, Mitsuru

    2012-01-01

    We analyze blinking in surface enhanced resonance Raman scattering (SERRS) and surface enhanced fluorescence (SEF) of rhodamine 6G molecules as intensity and spectral instability by electromagnetic (EM) mechanism. We find that irradiation of intense NIR laser pulses induces blinking in SERRS and SEF. Thanks to the finding, we systematically analyze SERRS and SEF from stable to unstable using single Ag nanoparticle (NP) dimers. The analysis reveals two physical insights into blinking as follows. (1) The intensity instability is inversely proportional to the enhancement factors of decay rate of molecules. The estimation using the proportionality suggests that separation of the molecules from Ag NP surfaces is several angstroms. (2) The spectral instability is induced by blueshifts in EM enhancement factors, which have spectral shapes similar to the plasmon resonance. This analysis provides us with a quantitative picture for intensity and spectral instability in SERRS and SEF within the framework of EM mechanism.

  4. Resonance Raman spectroscopy for human cancer detection of key molecules with clinical diagnosis

    NASA Astrophysics Data System (ADS)

    Zhou, Yan; Liu, Cheng-hui; Li, Jiyou; Zhou, Lixin; He, Jingsheng; Sun, Yi; Pu, Yang; Zhu, Ke; Liu, Yulong; Li, Qingbo; Cheng, Gangge; Alfano, Robert R.

    2013-03-01

    Resonance Raman (RR) has the potential to reveal the differences between cancerous and normal breast and brain tissues in vitro. This differences caused by the changes of specific biomolecules in the tissues were displayed in resonance enhanced of vibrational fingerprints. It observed that the changes of reduced collagen contents and the number of methyl may show the sub-methylation of DNA in cancer cells. Statistical theoretical models of Bayesian, principal component analysis (PCA) and support vector machine (SVM) were used for distinguishing cancer from normal based on the RR spectral data of breast and meninges tissues yielding the diagnostic sensitivity of 80% and 90.9%, and specificity of 100% and 100%, respectively. The results demonstrated that the RR spectroscopic technique could be applied as clinical optical pathology tool with a high accuracy and reliability.

  5. The peroxo intermediates in P450 catalysis: Characterization of Compound 0 by resonance Raman spectroscopy

    PubMed Central

    Denisov, Ilia G.; Mak, Piotr J.; Makris, Thomas M.; Sligar, Stephen G.; Kincaid, James R.

    2010-01-01

    Resonance Raman (RR) studies of intermediates generated by cryoreduction of the oxyferrous complex of the D251N mutant of cytochrome P450cam (CYP101) are reported. Owing to the fact that proton delivery to the active site is hindered in this mutant, the unprotonated peroxo-ferric intermediate is observed as the primary species after radiolytic reduction of the oxy-complex in frozen solutions at 77 K. Inasmuch as previous EPR and ENDOR studies have shown that annealing of this species to ~180 K results in protonation of the distal oxygen atom to form the hydroperoxo intermediate, this system has been exploited to permit direct RR interrogation of the changes in the Fe-O and O-O bonds caused by the reduction and subsequent protonation. Our results show that the ν(O-O) mode decreases from a “superoxo-like” frequency near ~1130 cm−1 to 792 cm−1 upon reduction. The latter frequency, as well as its lack of sensitivity to H/D exchange, is consistent with a heme-bound peroxide formulation. This species also exhibits a ν(Fe-O) mode, whose 553 cm−1 frequency is higher than that observed for the non-reduced oxy P450 precursor (537 cm−1), implying a strengthened Fe-O linkage upon reduction. Upon subsequent protonation, the resulting Fe-O-OH fragment exhibits a lowered ν(O-O) mode at 774 cm−1, while the ν(Fe-O) increases to 564 cm−1, both modes exhibiting downshifts upon H/D exchange, as expected for a hydroperoxo-ferric formulation. These experimental RR data are compared with those previously acquired for the wild-type protein and the shifts observed upon reduction and subsequent protonation are discussed with reference to theoretical predictions. PMID:18630867

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

    PubMed

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

    2016-12-01

    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. PMID:27314909

  7. Atypical Exciton-Phonon Interactions in WS2 and WSe2 Monolayers Revealed by Resonance Raman Spectroscopy.

    PubMed

    Del Corro, E; Botello-Méndez, A; Gillet, Y; Elias, A L; Terrones, H; Feng, S; Fantini, C; Rhodes, Daniel; Pradhan, N; Balicas, L; Gonze, X; Charlier, J-C; Terrones, M; Pimenta, M A

    2016-04-13

    Resonant Raman spectroscopy is a powerful tool for providing information about excitons and exciton-phonon coupling in two-dimensional materials. We present here resonant Raman experiments of single-layered WS2 and WSe2 using more than 25 laser lines. The Raman excitation profiles of both materials show unexpected differences. All Raman features of WS2 monolayers are enhanced by the first-optical excitations (with an asymmetric response for the spin-orbit related XA and XB excitons), whereas Raman bands of WSe2 are not enhanced at XA/B energies. Such an intriguing phenomenon is addressed by DFT calculations and by solving the Bethe-Salpeter equation. These two materials are very similar. They prefer the same crystal arrangement, and their electronic structure is akin, with comparable spin-orbit coupling. However, we reveal that WS2 and WSe2 exhibit quite different exciton-phonon interactions. In this sense, we demonstrate that the interaction between XC and XA excitons with phonons explains the different Raman responses of WS2 and WSe2, and the absence of Raman enhancement for the WSe2 modes at XA/B energies. These results reveal unusual exciton-phonon interactions and open new avenues for understanding the two-dimensional materials physics, where weak interactions play a key role coupling different degrees of freedom (spin, optic, and electronic). PMID:26998817

  8. Effects of ethanol, formaldehyde, and gentle heat fixation in confocal resonance Raman microscopy of purple nonsulfur bacteria.

    PubMed

    Kniggendorf, Ann-Kathrin; Gaul, Tobias William; Meinhardt-Wollweber, Merve

    2011-02-01

    Resonance Raman microscopy is well suited to examine living bacterial samples without further preparation. Therefore, comparatively little thought has been given to its compatibility with common fixation methods. However, fixation of cell samples is a very important tool in the microbiological sciences, allowing the preservation of samples in a specific condition for further examination, future measurements, transport, or later reference. We examined the effects of three common fixatives-ethanol, formaldehyde solution, and gentle heat--on the resonant Raman spectrum of three generic bacteria species, Rhodobacter sphaeroides DSM 158(T), Rhodopseudomonas palustris DSM 123(T), and Rhodospirillum rubrum DSM 467(T), holding carotenoid- and heme-chromophores in confocal Raman microscopy. In addition, we analyzed the effect of poly-L-lysine coating of microscope slides, widely used for mounting biological and medical samples, on subsequent confocal Raman measurements of native and fixed samples. The results indicate that ethanol is preferable to formaldehyde as fixative if applied for less than 24 h, whereas heat fixation has a strong, detrimental effect on the resonant Raman spectrum of bacteria. Formaldehyde fixation excels at fixation times above 24 h, but causes an overall reduction in signal intensity. Poly-L-lysine coating has no discernable effect on the Raman spectra of samples fixed with ethanol or heat, but it further decreases the signal intensity, especially at higher wavenumbers, in the spectra of samples fixed with formaldehyde. PMID:20544803

  9. Of microparticles and bacteria identification--(resonance) Raman micro-spectroscopy as a tool for biofilm analysis.

    PubMed

    Kniggendorf, Ann-Kathrin; Meinhardt-Wollweber, Merve

    2011-10-01

    Confocal resonance Raman microscopy is a powerful tool for the non-invasive analysis of complex biological aggregates without preparation and prior knowledge of the samples. We present the capabilities of confocal resonance Raman microscopy with a spatial resolution of 350 nm2×2.0 μm and excitation times of 1 s and less per recorded spectrum. Granules sampled from two sequencing batch reactors (SBR) for anaerobic ammonium oxidization (anammox) were regularly mapped in vivo for three months after SBR startup. Uncultured microorganisms and mineral particles were tracked throughout operation and identified in situ by their (resonance) Raman spectra. Co-existing microcolonies of Nitrosomonae formed the outer layer of anammox granules. Polymorph TiO2 microparticles were found embedded in the outer layer of granules overgrown with purple bacteria, indicating bacterial response to the variant toxicity of the mineral phase. PMID:21741670

  10. Magnetic field enriched surface enhanced resonance Raman spectroscopy for early malaria diagnosis

    NASA Astrophysics Data System (ADS)

    Yuen, Clement; Liu, Quan

    2012-01-01

    Hemozoin is a by-product of malaria infection in erythrocytes, which has been explored as a biomarker for early malaria diagnosis. We report magnetic field-enriched surface-enhanced resonance Raman spectroscopy (SERRS) of β--hematin crystals, which are the equivalent of hemozoin biocrystals in spectroscopic features, by using magnetic nanoparticles with iron oxide core and silver shell (Fe3O4@Ag). The external magnetic field enriches β--hematin crystals and enhances the binding between β--hematin crystals and magnetic nanoparticles, which provides further improvement in SERRS signals. The magnetic field-enriched SERRS signal of β--hematin crystals shows approximately five orders of magnitude enhancement in the resonance Raman signal, in comparison to about three orders of magnitude improvement in the SERRS signal without the influence of magnetic field. The improvement has led to a β--hematin detection limit at a concentration of 5 nM (roughly equivalent to 30 parasites/μl at the early stages of malaria infection), which demonstrates the potential of magnetic field-enriched SERRS technique in early malaria diagnosis.

  11. Low-Cost Resonant Cavity Raman Gas Probe for Multi-Gas Detection

    NASA Astrophysics Data System (ADS)

    Thorstensen, J.; Haugholt, K. H.; Ferber, A.; Bakke, K. A. H.; Tschudi, J.

    2014-12-01

    Raman based gas sensing can be attractive in several industrial applications, due to its multi-gas sensing capabilities and its ability to detect O_2 and N_2. In this article, we have built a Raman gas probe, based on low-cost components, which has shown an estimated detection limit of 0.5 % for 30 second measurements of N_2 and O_2. While this detection limit is higher than that of commercially available equipment, our estimated component cost is approximately one tenth of the price of commercially available equipment. The use of a resonant Fabry-Pérot cavity increases the scattered signal, and hence the sensitivity, by a factor of 50. The cavity is kept in resonance using a piezo-actuated mirror and a photodiode in a feedback loop. The system described in this article was made with minimum-cost components to demonstrate the low-cost principle. However, it is possible to decrease the detection limit using a higher-powered (but still low-cost) laser and improving the collection optics. By applying these improvements, the detection limit and estimated measurement precision will be sufficient for e.g. the monitoring of input gases in combustion processes, such as e.g. (bio-)gas power plants. In these processes, knowledge about gas compositions with 0.1 % (absolute) precision can help regulate and optimize process conditions. The system has the potential to provide a low-cost, industrial Raman sensor that is optimized for specific gas-detection applications.

  12. Resonance Raman frequencies and core size for low- and high-spin nickel porphyrins

    SciTech Connect

    Kim, D.; Su, Y.O.; Spiro, T.G.

    1986-10-22

    Resonance Raman (RR) spectra are reported with B- and Q-band excitation for nickel(II) complexes of octaethylporphyrin (OEP), protoporphyrin IX dimethyl ester (PP), and meso-tetraphenylporphine (TPP) in methylene chloride (4-coordinate, low spin) and piperidine (pip) (6-coordinate, high spin). The large core size expansion accompanying the formation of the 6-coordinate species (1.96-2.04 A) is reflected in large decreases, up to 40 cm/sup -1/ in the positions of high-frequency porphyrin skeletal modes. For NiOEP and NiPP, these are in near-quantitative accord with the core size correlations obtained previously for iron porphyrin complexes, although certain deviations due to differential coupling with the vinyl modes of protoporphyrin are noted. Contributions of a minority 5-coordinate complex to the RR spectrum of NiTPP in piperidine, previously noted on the basis of photolysis effects, are evaluated quantitatively from titration data. Formation of a monopiperidine adduct, detected previously via a RR study of NiTPP(pip)/sub 2/ photolysis, is examined for nickel meso-tetrakis(p-cyanophenyl)porphine. Equilibrium constants for successive addition of piperidine ligands, K/sub 1/ = 0.4 and K/sub 2/ = 2.5 M/sup -1/, are evaluated from optical titration data, and the absorptivities of the 5- and 6-coordinate species are found to be nearly the same, consistent with both having a high-spin configuration. The frequency of the 5-coordinate nu/sub 4/ RR band is likewise found to be much closer to the 6-coordinate than to the 4-coordinate frequency.

  13. Raman spectroscopy

    SciTech Connect

    Gerrard, D.L.; Bowley, H.J.

    1986-04-01

    The period of this review is from late 1983 to late 1985. During this time over 5000 papers have appeared in the scientific literature dealing with many applications of Raman spectroscopy and extending its use to several new areas of study. As in the previous review in this series most of the applications relevant to solids are covered in one or other of the ten categories, which are the same as those used previously. However, aspects relating to solids which are not covered elsewhere include general reviews and the specific field of semiconductors. This is an area of great current interest in terms of Raman spectroscopy and the characterization of semiconductor materials and surfaces has been reported. Raman scattering also provides a new probe for the elucidation of structural properties of microcrystalline silicon and resonance Raman scattering in silicon at elevated temperatures has been studied. Many studies on carbon have also appeared in the literature including that of the various types of carbon, the use of Raman scattering to investigate disorder and crystallite formation in annealed carbon, in situ studies of intercalation kinetics, structural aspects of cokes and coals, and instrumentation for coal gasification. Raman spectroscopy has been applied to such diverse systems as organic crystals, the determination of modifications in layered crystals, the detection of explosives on silica gel or carbon, diagnostics of heterogeneous chemical processes, and a study of tungsten-halogen bulbs. Laser Raman spectroscopy has also been coupled with liquid chromatography and phase-resolved background suppression has been used to enhance Raman spectra. 397 references.

  14. Raman spectroscopic studies of disordered ferroelectric oxides

    NASA Astrophysics Data System (ADS)

    Savvinov, Alexey A.

    Relaxational properties of compositionally disordered AB03 perovskite oxides were studied. These oxides are the prototypical soft ferroelectric (FE) mode systems, and their interesting dipolar relaxational properties are determined by their long, strongly temperature-dependent correlation lengths for the dipolar interactions. The simple cases involve dilute chemical substitutions in the incipient ferroelectrics KTaO3 and SrTiO3, which exhibit relatively weak, low-temperature Debye-type relaxations. More complicated dipolar interactions are seen in B-site disordered Nb-doped KTaO3, which exhibits glass-like relaxor and relaxor-to-ferroelectric crossover behaviors at low temperatures. Finally, there is a class of more complex perovskites represented by PMN, PZN-PT and the PLT that exhibit strong, high-temperature relaxor and/or ferroelectric properties. The renewed interest in the KTa1-xNbxO (KTN) mixed perovskite materials, especially in high quality thin films, is connected with their remarkable dielectric properties in the dilute compositions. Off-center Nb ions in the highly polarizable KTaO3 lattice provide a drastic increase in the dielectric peak, up to 20 times in comparison with the pure KTaO3 and KNbO3. The effects of the substrate and the symmetry-breaking defects on their vibration spectra were studied by micro-Raman spectroscopy. An anomalous residual intensity of the forbidden first-order scattering modes in the cubic paraelectric phase of the KTN films was connected with the formation of polar microregions even far above the bulk Tc. On the whole, the KTN film behavior shows the existence of specific defects enhancing the perovskite unit cell in the film so that the activity of off-center Nb ions increases in producing larger electric dipoles and extending the precursor phase above Tc. In diluted compositions with low Nb concentrations KTN materials exhibit formation of polar nano regions and relaxor like behavior. This behavior is analogous with

  15. Combined dielectric and plasmon resonance for giant enhancement of Raman scattering

    NASA Astrophysics Data System (ADS)

    Kukushkin, V. I.; Grishina, Ya. V.; Egorov, S. V.; Solov'ev, V. V.; Kukushkin, I. V.

    2016-04-01

    Combined dielectric/metal resonators for colossal enhancement of inelastic light scattering are developed and their properties are investigated. It is shown that a record enhancement factor of 2 × 108 can be obtained using these structures. The dielectric resonators are fabricated on Si/SiO2 substrates where periodic arrays of square 10- to 200-nm-high dielectric pillars are produced via electron-beam lithography and plasma etching. The lateral size a of the pillars varies between 50 and 1500 nm, and their period in the array is 2 a. To make a combined dielectric/metal resonator, a nanostructured layer of silver is deposited onto the fabricated periodic dielectric structure by thermal evaporation. It is established that, for a fixed height of the dielectric pillars, the Raman scattering enhancement factor experiences pronounced oscillations as a function of the period (and size) of the pillars. It is shown that these oscillations are determined by the modes of the dielectric resonator and governed by the relation between the excitation laser wavelength and the planar size of the dielectric pillars.

  16. Raman scattering studies of pollutant systems.

    NASA Technical Reports Server (NTRS)

    Schwiesow, R. L.

    1971-01-01

    Results and techniques for laboratory measurements of Raman scattering cross sections and depolarization ratios of atmospheric gases as a function of the incident photon energy are discussed. Referred to N2, the cross section of H2O changes by a factor of 2 as the incident photon energy is changed by 5%. Less striking results are obtained for SO2, NO and other atmospheric gases. Tentative results are given for spectral features of scattering from polluted air-water interfaces. Raman lidar is assessed as a potentially useful aid in remote sensing of atmospheric and water-borne pollution distributions at least in near-source concentrations.

  17. Raman structural studies of the nickel electrode

    NASA Technical Reports Server (NTRS)

    Cornilsen, Bahne C.

    1994-01-01

    The objectives of this investigation have been to define the structures of charged active mass, discharged active mass, and related precursor materials (alpha-phases), with the purpose of better understanding the chemical and electrochemical reactions, including failure mechanisms and cobalt incorporation, so that the nickel electrode may be improved. Although our primary tool has been Raman spectroscopy, the structural conclusions drawn from the Raman data have been supported and augmented by three other analysis methods: infrared spectroscopy, powder X-ray Diffraction (XRD), and x-ray absorption spectroscopy (in particular EXAFS, Extended X-ray Absorption Fine Structure spectroscopy).

  18. Single-molecular surface-enhanced resonance Raman scattering as a quantitative probe of local electromagnetic field: The case of strong coupling between plasmonic and excitonic resonance

    NASA Astrophysics Data System (ADS)

    Itoh, Tamitake; Yamamoto, Yuko S.; Tamaru, Hiroharu; Biju, Vasudevanpillai; Wakida, Shin-ichi; Ozaki, Yukihiro

    2014-05-01

    We investigate electromagnetic coupling between plasmonic and molecular electronic resonances using single-molecular surface-enhanced resonance Raman scattering (SERRS) from single silver nanoparticle dimers. When dimers exhibit SERRS activity, their elastic light scattering spectra show two lines, which are temporally closing toward each other. The higher energy line eventually disappears at the time of SERRS quenching. A coupled-oscillator model composed of plasmonic and molecular electronic resonances consistently reproduces the above interesting results by decreasing coupling energy, indicating that SERRS can be a quantitative probe for strong coupling between the two resonances.

  19. Vibrational techniques applied to photosynthesis: Resonance Raman and fluorescence line-narrowing.

    PubMed

    Gall, Andrew; Pascal, Andrew A; Robert, Bruno

    2015-01-01

    Resonance Raman spectroscopy may yield precise information on the conformation of, and the interactions assumed by, the chromophores involved in the first steps of the photosynthetic process. Selectivity is achieved via resonance with the absorption transition of the chromophore of interest. Fluorescence line-narrowing spectroscopy is a complementary technique, in that it provides the same level of information (structure, conformation, interactions), but in this case for the emitting pigment(s) only (whether isolated or in an ensemble of interacting chromophores). The selectivity provided by these vibrational techniques allows for the analysis of pigment molecules not only when they are isolated in solvents, but also when embedded in soluble or membrane proteins and even, as shown recently, in vivo. They can be used, for instance, to relate the electronic properties of these pigment molecules to their structure and/or the physical properties of their environment. These techniques are even able to follow subtle changes in chromophore conformation associated with regulatory processes. After a short introduction to the physical principles that govern resonance Raman and fluorescence line-narrowing spectroscopies, the information content of the vibrational spectra of chlorophyll and carotenoid molecules is described in this article, together with the experiments which helped in determining which structural parameter(s) each vibrational band is sensitive to. A selection of applications is then presented, in order to illustrate how these techniques have been used in the field of photosynthesis, and what type of information has been obtained. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. PMID:25268562

  20. A comparative study of Raman enhancement in capillaries

    NASA Astrophysics Data System (ADS)

    Eftekhari, Fatemeh; Irizar, Juan; Hulbert, Laila; Helmy, Amr S.

    2011-06-01

    This work reports on the comparative studies of Raman enhancement in liquid core waveguides (LCWs). The theoretical considerations that describe Raman enhancement in LCWs is adapted to analyze and compare the performance of hollow core photonic crystal fibers (HCPCFs) to conventional Teflon capillary tubes. The optical losses in both platforms are measured and used to predict their performance for different lengths. The results show that for an optimal waveguide length, two orders of magnitude enhancement in the Raman signal can be achieved for aqueous solutions using HCPCFs. This length, however, cannot be achieved using normal capillary effects. By integrating the interface of the fluidic pump and the HCPCF into a microfluidic chip, we are able to control fluid transport and fill longer lengths of HCPCFs regardless of the viscosity of the sample. The long-term stability and reproducibility of Raman spectra attained through this platform are demonstrated for naphthalenethiol, which is a well-studied organic compound. Using the HCPCF platform, the detection limit of normal Raman scattering in the range of micro-molars has been achieved. In addition to the higher signal-to-noise ratio of the Raman signal from the HCPCF-platform, more Raman modes of naphthalenethiol are revealed using this platform.

  1. The first photoexcitation step of ruthenium-based models for artificial photosynthesis highlighted by resonance Raman spectroscopy.

    PubMed

    Herrmann, Carmen; Neugebauer, Johannes; Presselt, Martin; Uhlemann, Ute; Schmitt, Michael; Rau, Sven; Popp, Jürgen; Reiher, Markus

    2007-05-31

    Ruthenium-polypyridine and related complexes play an important role as models for light-harvesting antenna systems to be employed in artificial photosynthesis. In this theoretical and experimental work, the first photoexcitation step of a tetranuclear [Ru2Pd2] complex composed of two ruthenium-bipyridyl subunits and two palladium-based fragments, {[(tbbpy)2Ru(tmbi)]2[Pd(allyl)]2}2+ (tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine, tmbi = 5,6,5',6'-tetramethyl-2,2'-bibenzimidazolate), is investigated by means of experimental and theoretical resonance Raman spectroscopy. The calculated spectra, which were obtained within the short-time approximation combined with time-dependent density functional theory (TDDFT), reproduce the experimental spectrum with excellent agreement. We also compared calculations on off-resonance Raman spectra, for which a completely different theoretical approach has to be used, to experimental ones and again found very good agreement. The [Ru2Pd2] complex represents the probably largest system for which a quantum chemical frequency analysis and a calculation of conventional Raman as well as resonance Raman spectra with reasonable basis sets have been performed. A comparison between the resonance Raman spectra of the [Ru2Pd2] complex and its mononuclear [Ru] building block [(tbbpy)2Ru(tmbi)]2+ and a normal-mode analysis reveal that the [Ru2Pd2] resonance Raman spectrum is composed uniquely from peaks arising from the [Ru] fragment. This observation and an analysis of the Kohn-Sham orbitals mainly involved in the initial electronic excitation in the TDDFT description of the [Ru2Pd2] system support the hypothesis that the initial photoexcitation step of [Ru2Pd2] is a charge-transfer excitation from the ruthenium atoms to the adjacent butyl-2,2'-bipyridine ligands. PMID:17489631

  2. Measurement of nitric oxide concentrations in flames by using electronic-resonance-enhanced coherent anti-Stokes Raman scattering.

    PubMed

    Kulatilaka, Waruna D; Chai, Ning; Naik, Sameer V; Laurendeau, Normand M; Lucht, Robert P; Kuehner, Joel P; Roy, Sukesh; Gord, James R

    2006-11-15

    We have measured nitric oxide (NO) concentrations in flames by using electronic-resonance-enhanced coherent anti-Stokes Raman spectroscopy (ERE-CARS). Visible pump and Stokes beams were tuned to a Q-branch vibrational Raman resonance of NO. A UV probe beam was tuned into resonance with specific rotational transitions in the (v"=1,v'=0) vibrational band in the A(2)Sigma(+)-X(2)Pi electronic transition, thus providing a substantial electronic-resonance enhancement of the resulting CARS signal. NO concentrations were measured at levels down to 50 parts in 10(6) in H(2)/air flames at atmospheric pressure. NO was also detected in heavily sooting C(2)H(2)/air flames at atmospheric pressure with minimal background interference. PMID:17072422

  3. A theoretical simulation of the resonant Raman spectroscopy of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes.

    PubMed

    Franklin-Mergarejo, Ricardo; Rubayo-Soneira, Jesús; Halberstadt, Nadine; Janda, Kenneth C; Apkarian, V Ara

    2016-02-01

    The resonant Raman spectra of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes have been studied in the framework of a 2-dimensional model previously used in the simulation of their UV-visible absorption spectra using time-dependent techniques. In addition to the vibrational progression along the dihalogen mode, a progression is observed along the intermolecular mode and its combination with the intramolecular one. The relative intensity of the inter to intramolecular vibrational progressions is about 15% for H2O⋯Cl2 and 33% for H2O⋯Br2. These results make resonant Raman spectra a potential tool for detecting the presence of halogen bonded complexes in condensed phase media such as clathrates and ice. PMID:26851921

  4. Resonant Two-Magnon Raman Scattering in Cuprate Antiferromagnetic Insulators and Superconductors.

    NASA Astrophysics Data System (ADS)

    Blumberg, G.; Abbamonte, P.; Klein, M. V.

    1996-03-01

    We present results of low-temperature two-magnon resonance Raman excitation profile measurements for single layer Sr_2CuO_2Cl2 and bilayer YBa_2Cu_3O6 + δ antiferromagnets over the excitation region from 1.65 to 3.05 eV. These data reveal composite structure of the B_1g two-magnon line shape peaked at ~ 2.7J and ~ 4J and strong nonmonotonic dependence of the scattering intensity on excitation energy. Resonant magnetic scattering contributes also to A_1g and B_2g channels. We analyze these data using the triple resonance theory of Chubukov and Frenkel(A. Chubukov and D. Frenkel, Phys. Rev. Lett.74), 3057 (1995). and deduce information about magnetic interaction (J and J_⊥) and band parameters (NN hopping t and charge transfer gap 2Δ) in these antiferromagnets.(G. Blumberg et. al.), Preprint cond-mat/9511080. The ~ 3J spin superexchange excitation persists upon hole doping and is present in superconductors, proving the universality of the short wavelength magnetic excitations in the cuprate superconducting metals and the parent antiferromagnetic insulators.(G. Blumberg et. al.), Phys. Rev. B 49, 13 295 (1994).

  5. Amplification of ultra-short laser pulses via resonant backward Raman amplification in plasma

    NASA Astrophysics Data System (ADS)

    Mishra, S. K.; Andreev, A.

    2016-08-01

    In this paper, we have examined the possibility of using resonant backward Raman amplification (BRA) as an efficient mechanism in amplifying the low intensity ultra-short ( ≤ fs ) pulses using plasma as intermediate amplifying medium; such pulses are anticipated to get produced in the form of the secondary sources at ALPS (Attosecond Light Pulse Source) center of ELI (Extreme Light Infrastructure). In preliminary assessment of the scheme, the analytical expressions for the pump/seed laser pulses and plasma characteristic features are obtained which concisely describe the parameter regime of resonant BRA applicability in achieving significant amplification. The consistency of the scheme in the context of ELI-ALPS sources has been validated through particle in cell (PIC) simulations. The peak intensity of the amplified seed pulse predicted via simulation results is found in reasonable agreement with the analytical estimates. Utilizing these analytical expressions as a basis in perspective of ELI-ALPS parameter access, a specific example displaying the key plasma and laser parameters for amplifying weak seed pulse has been configured; the limitations and conceivable remedies in resonant BRA implementation have also been highlighted.

  6. Plasmon-resonant Raman spectroscopy in metallic nanoparticles: Surface-enhanced scattering by electronic excitations

    NASA Astrophysics Data System (ADS)

    Carles, R.; Bayle, M.; Benzo, P.; Benassayag, G.; Bonafos, C.; Cacciato, G.; Privitera, V.

    2015-11-01

    Since the discovery of surface-enhanced Raman scattering (SERS) 40 years ago, the origin of the "background" that is systematically observed in SERS spectra has remained questionable. To deeply analyze this phenomenon, plasmon-resonant Raman scattering was recorded under specific experimental conditions on a panel of composite multilayer samples containing noble metal (Ag and Au) nanoparticles. Stokes, anti-Stokes, and wide, including very low, frequency ranges have been explored. The effects of temperature, size (in the nm range), embedding medium (SiO2, Si3N4, or TiO2) or ligands have been successively analyzed. Both lattice (Lamb modes and bulk phonons) and electron (plasmon mode and electron-hole excitations) dynamics have been investigated. This work confirms that in Ag-based nanoplasmonics composite layers, only Raman scattering by single-particle electronic excitations accounts for the background. This latter appears as an intrinsic phenomenon independently of the presence of molecules on the metallic surface. Its spectral shape is well described by revisiting a model developed in the 1990s for analyzing electron scattering in dirty metals, and used later in superconductors. The gs factor, that determines the effective mean-free path of free carriers, is evaluated, gsexpt=0.33 ±0.04 , in good agreement with a recent evaluation based on time-dependent local density approximation gstheor=0.32 . Confinement and interface roughness effects at the nanometer range thus appear crucial to understand and control SERS enhancement and more generally plasmon-enhanced processes on metallic surfaces.

  7. Raman-resonance-enhanced composite nonlinearity of air-guided modes in hollow photonic-crystal fibers.

    PubMed

    Fedotov, Il'ya V; Fedotov, Andrei B; Zheltikov, Aleksei M

    2006-09-01

    Coherent anti-Stokes Raman scattering (CARS) is used to measure relations between the resonant (Raman) and nonresonant (Kerr-type) optical nonlinearities of air-guided modes in a hollow-core photonic-crystal fiber (PCF). We demonstrate that, due to its interference nature, CARS provides a convenient tool for measuring the contribution of the fiber cladding to the total nonlinearity sensed by air-guided modes in hollow PCFs. On a Raman resonance with molecular vibrations in the gas that fills the fiber core, a two-color laser field is shown to induce optical nonlinearities that are several orders of magnitude higher than the nonresonant Kerr-type nonlinearities typical of air-guided PCF modes. PMID:16902633

  8. Formation of high-valent iron-oxo species in superoxide reductase: characterization by resonance Raman spectroscopy.

    PubMed

    Bonnot, Florence; Tremey, Emilie; von Stetten, David; Rat, Stéphanie; Duval, Simon; Carpentier, Philippe; Clemancey, Martin; Desbois, Alain; Nivière, Vincent

    2014-06-01

    Superoxide reductase (SOR), a non-heme mononuclear iron protein that is involved in superoxide detoxification in microorganisms, can be used as an unprecedented model to study the mechanisms of O2 activation and of the formation of high-valent iron-oxo species in metalloenzymes. By using resonance Raman spectroscopy, it was shown that the mutation of two residues in the second coordination sphere of the SOR iron active site, K48 and I118, led to the formation of a high-valent iron-oxo species when the mutant proteins were reacted with H2O2. These data demonstrate that these residues in the second coordination sphere tightly control the evolution and the cleavage of the O-O bond of the ferric iron hydroperoxide intermediate that is formed in the SOR active site. PMID:24777646

  9. Status of miniature integrated UV resonance fluorescence and Raman sensors for detection and identification of biochemical warfare agents

    NASA Astrophysics Data System (ADS)

    Hug, William F.; Bhartia, Rohit; Taspin, Alexandre; Lane, Arthur; Conrad, Pamela; Sijapati, Kripa; Reid, Ray D.

    2005-11-01

    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.

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

    SciTech Connect

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

    2013-12-10

    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.

  11. Interface Coupling in Twisted Multilayer Graphene by Resonant Raman Spectroscopy of Layer Breathing Modes.

    PubMed

    Wu, Jiang-Bin; Hu, Zhi-Xin; Zhang, Xin; Han, Wen-Peng; Lu, Yan; Shi, Wei; Qiao, Xiao-Fen; Ijiäs, Mari; Milana, Silvia; Ji, Wei; Ferrari, Andrea C; Tan, Ping-Heng

    2015-07-28

    Raman spectroscopy is the prime nondestructive characterization tool for graphene and related layered materials. The shear (C) and layer breathing modes (LBMs) are due to relative motions of the planes, either perpendicular or parallel to their normal. This allows one to directly probe the interlayer interactions in multilayer samples. Graphene and other two-dimensional (2d) crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientations have different optical and electronic properties. In twisted multilayer graphene there is a significant enhancement of the C modes due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. Here we show that this applies also to the LBMs, which can be now directly measured at room temperature. We find that twisting has a small effect on LBMs, quite different from the case of the C modes. This implies that the periodicity mismatch between two twisted layers mostly affects shear interactions. Our work shows that ultralow-frequency Raman spectroscopy is an ideal tool to uncover the interface coupling of 2d hybrids and heterostructures. PMID:26062640

  12. Lignin Radicals in the Plant Cell Wall Probed by Kerr-Gated Resonance Raman Spectroscopy

    PubMed Central

    Barsberg, Søren; Matousek, Pavel; Towrie, Mike; Jørgensen, Henning; Felby, Claus

    2006-01-01

    Lignin radicals are crucial intermediates for lignin biosynthesis in the cell wall of vascular plants. In this work they were for the first time, to our knowledge, selectively observed in wood cell walls by laser-based Kerr-gated resonance Raman spectroscopy, and the observations were supported by density functional theory prediction of their vibrational properties. For dry wood cells a lignin radical Raman band is observed at 1570 cm−1 irrespective of species. For wet beech cells they were generated in situ and observed at 1606 cm−1. DFT/B3LYP/6-31+G(d) modeling results support that in beech they are formed from syringyl (S) phenolic moieties and in spruce from guaiacyl (G) phenolic moieties. The observed lignin radical band is predicted as G is ∼1597 cm−1 and S is ∼1599 cm−1, respectively, and is assigned the (Wilson notation) ν8a phenyl ring mode. The RR band probes lignin radical properties, e.g., spin density distribution, and these respond to charge polarization or hydrogen bonding to proximate water molecules. These observations can be crucial for an understanding of the factors that control cell wall structure during biosynthesis of vascular plants and demonstrate the unique potential of RR spectroscopy of lignin radicals. PMID:16443659

  13. Raman and fluorescence characteristics of resonant inelastic X-ray scattering from doped superconducting cuprates

    DOE PAGESBeta

    Huang, H. Y.; Jia, C. J.; Chen, Z. Y.; Wohlfeld, K.; Moritz, B.; Devereaux, T. P.; Wu, W. B.; Okamoto, J.; Lee, W. S.; Hashimoto, M.; et al

    2016-01-22

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O8+δ. Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast,more » the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors.« less

  14. Raman and fluorescence characteristics of resonant inelastic X-ray scattering from doped superconducting cuprates

    PubMed Central

    Huang, H. Y.; Jia, C. J.; Chen, Z. Y.; Wohlfeld, K.; Moritz, B.; Devereaux, T. P.; Wu, W. B.; Okamoto, J.; Lee, W. S.; Hashimoto, M.; He, Y.; Shen, Z. X.; Yoshida, Y.; Eisaki, H.; Mou, C. Y.; Chen, C. T.; Huang, D. J.

    2016-01-01

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O8+δ. Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast, the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors. PMID:26794437

  15. Raman and fluorescence characteristics of resonant inelastic X-ray scattering from doped superconducting cuprates

    NASA Astrophysics Data System (ADS)

    Huang, H. Y.; Jia, C. J.; Chen, Z. Y.; Wohlfeld, K.; Moritz, B.; Devereaux, T. P.; Wu, W. B.; Okamoto, J.; Lee, W. S.; Hashimoto, M.; He, Y.; Shen, Z. X.; Yoshida, Y.; Eisaki, H.; Mou, C. Y.; Chen, C. T.; Huang, D. J.

    2016-01-01

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O8+δ. Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast, the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors.

  16. Photoreductive titration of the resonance Raman spectra of cytochrome oxidase in whole mitochondria.

    PubMed

    Adar, F; Erecińska, M

    1979-05-01

    A photoreductive titration of the resonance Raman (RR) spectra of cytochrome c oxidase in whole mitochondria was recorded by exploiting the preferential enhancement of the Raman signals of reduced cytochrome oxidase excited at 441.6 nm. When the sample was cooled to about--10 degrees C, it was possible to slow down the photoreductive effect of the laser and to record RR spectra at various states of reduction. Compared to the earliest recorded scan (most oxidized), the dithionite-reduced sample shows the appearance of new bands at 216, 363, 560, and 1665 cm-1. At intermediate stages of photoreduction, the 216- and 560-cm-1 bands appear before the 363- and 1665-cm-1 bands; photoreduction induces full intensity in the former bands, whereas the latter bands are photoreduced to 50% of the dithionite-reduced intensity. The relative intensities of a doublet at 1609--1623 cm-1 are affected by reduction: the band at 1609 cm-1 is weaker in the earlier scans; in later scans this band has grown to equal intensity with the 1623-cm-1 band. We conclude that this reductive titration of the RR spectrum of cytochrome c oxidase reflects three states in its reduction. The behavior of the doublet at 1609--1623 cm-1 suggests that the two hemes are nonequivalent but interacting. The band at 216 cm-1 may be indicative of an iron-copper interaction that is affected by the presence of external ligands. PMID:219887

  17. Solvent effects on the resonance Raman and electronic absorption spectra of bacteriochlorophyll a cation radical

    SciTech Connect

    Misono, Yasuhito; Itoh, Koichi; Limanatara, Leenawaty; Koyama, Yasushi

    1996-02-08

    Resonance Raman and electronic absorption spectra of bacteriocholrophyll a cation radical (BChl a{sup .+}) were recorded in 14 different kinds of solvents. The frequency of the ring-breathing Raman band of BChl a{sup .+} was in the region of 1596-1599 cm{sup -1} in solvents forming the pentacoordinated state in neutral bacteriochlorophyll a (BChl a), while it was in the region of 1584-1588 cm{sup -1} in solvents forming the hexacoordinated state. BChl a{sup .+} exhibited a key absorption band in the regions 546-554 and 557-563 nm in the above penta- and hexa-coordinating solvents. Therefore, it has been concluded that the penta- and hexa-coordinated states are retained even after conversion of BChl a into BChl a{sup .+} (one-electron oxidization). Application of this rule to the case of 2-propanol solution showed transformation from the penta- to the hexa-coordinated state upon one-electron oxidation in this particular solution. The coordination states of BChl a{sup .+} could be correlated with the donor number(DN) and the Taft parameters, {Beta} and {pi}{sup *}, of the solvent: The hexacoordinated state was formed in solvents with DN >= 18 or {Beta} > 0.5 showing higher electron donating power, while the pentacoordinated state was formed in solvents with {pi}{sup *} > 0.65 showing higher dielectric stabilization. 27 refs., 8 figs., 3 tabs.

  18. Resonance-Raman-scattering spectroscopy for the halogen-molecular-ion centers in alkali halides

    NASA Astrophysics Data System (ADS)

    Suzuki, T.; Tanimura, K.; Itoh, N.

    1993-10-01

    We have measured the Raman scattering in resonance with the bonding-to-antibonding transitions of two types of dihalogen-molecular-ion centers in alkali halides, the VK and H centers; the molecular ion occupies two adjacent halogen sites in the former and a single halogen site in the latter. It is found that the stretching-vibration frequency of the molecular ion is higher by more than 30% for the H center than for the VK center. The hardening is ascribed to the bond tightening due to the Madelung potential. Although the Raman line due to the stretching vibration consists of a single line in most alkali halides, two closely lying lines are observed for the H centers in alkali halides with small alkali-metal to halogen radius ratio and also for the VK center in NaCl. The paired-line structure is ascribed to the coupling of the stretching vibration of the halogen molecular ion with the lattice.

  19. Raman and fluorescence characteristics of resonant inelastic X-ray scattering from doped superconducting cuprates.

    PubMed

    Huang, H Y; Jia, C J; Chen, Z Y; Wohlfeld, K; Moritz, B; Devereaux, T P; Wu, W B; Okamoto, J; Lee, W S; Hashimoto, M; He, Y; Shen, Z X; Yoshida, Y; Eisaki, H; Mou, C Y; Chen, C T; Huang, D J

    2016-01-01

    Measurements of spin excitations are essential for an understanding of spin-mediated pairing for superconductivity; and resonant inelastic X-ray scattering (RIXS) provides a considerable opportunity to probe high-energy spin excitations. However, whether RIXS correctly measures the collective spin excitations of doped superconducting cuprates remains under debate. Here we demonstrate distinct Raman- and fluorescence-like RIXS excitations of Bi1.5Pb0.6Sr1.54CaCu2O(8+δ). Combining photon-energy and momentum dependent RIXS measurements with theoretical calculations using exact diagonalization provides conclusive evidence that the Raman-like RIXS excitations correspond to collective spin excitations, which are magnons in the undoped Mott insulators and evolve into paramagnons in doped superconducting compounds. In contrast, the fluorescence-like shifts are due primarily to the continuum of particle-hole excitations in the charge channel. Our results show that under the proper experimental conditions RIXS indeed can be used to probe paramagnons in doped high-Tc cuprate superconductors. PMID:26794437

  20. [Laser Raman Spectroscopy and Its Application in Gas Hydrate Studies].

    PubMed

    Fu, Juan; Wu, Neng-you; Lu, Hai-long; Wu, Dai-dai; Su, Qiu-cheng

    2015-11-01

    Gas hydrates are important potential energy resources. Microstructural characterization of gas hydrate can provide information to study the mechanism of gas hydrate formation and to support the exploitation and application of gas hydrate technology. This article systemly introduces the basic principle of laser Raman spectroscopy and summarizes its application in gas hydrate studies. Based on Raman results, not only can the information about gas composition and structural type be deduced, but also the occupancies of large and small cages and even hydration number can be calculated from the relative intensities of Raman peaks. By using the in-situ analytical technology, laser Raman specstropy can be applied to characterize the formation and decomposition processes of gas hydrate at microscale, for example the enclathration and leaving of gas molecules into/from its cages, to monitor the changes in gas concentration and gas solubility during hydrate formation and decomposition, and to identify phase changes in the study system. Laser Raman in-situ analytical technology has also been used in determination of hydrate structure and understanding its changing process under the conditions of ultra high pressure. Deep-sea in-situ Raman spectrometer can be employed for the in-situ analysis of the structures of natural gas hydrate and their formation environment. Raman imaging technology can be applied to specify the characteristics of crystallization and gas distribution over hydrate surface. With the development of laser Raman technology and its combination with other instruments, it will become more powerful and play a more significant role in the microscopic study of gas hydrate. PMID:26978895

  1. Simulations of Two-dimensional Infrared and Stimulated Resonance Raman Spectra of Photoactive Yellow Protein

    PubMed Central

    Preketes, Nicholas K; Biggs, Jason D; Ren, Hao; Andricioaei, Ioan; Mukamel, Shaul

    2012-01-01

    We present simulations of one and two-dimensional infrared (2DIR) and stimulated resonance Raman (SRR) spectra of the dark state (pG) and early red-shifted intermediate (pR) of photoactive yellow protein (PYP). Shifts in the amide I and Glu46 COOH stretching bands distinguish between pG and pR in the IR absorption and 2DIR spectra. The one-dimensional SRR spectra are similar to the spontaneous RR spectra. The two-dimensional SRR spectra show large changes in cross peaks involving the C=O stretch of the two species and are more sensitive to the chromophore structure than 2DIR spectra. PMID:24244064

  2. Intense chirality induction in nitrile solvents by a helquat dye monitored by near resonance Raman scattering.

    PubMed

    Šebestík, Jaroslav; Teplý, Filip; Císařová, Ivana; Vávra, Jan; Koval, Dušan; Bouř, Petr

    2016-05-01

    Chirality induction phenomena attract attention because of their relevance to intermolecular interactions encountered in living matter. Usually, such effects are weak. However, enantiomers of a [6]helquat dye were found to induce exceptionally strong chirality in several achiral solvents containing nitrile groups. This effect was observable as an intense Raman optical activity (ROA) induced in acetonitrile, acetonitrile-d3, and liquid hydrogen cyanide solvents. The observation was verified by measurement of both helquat enantiomers which provided mirror image ROA spectra. Theoretical analysis indicated that the 532 nm laser excitation light was in a near resonance with electronic transitions of the dye, which made the effect observable in very dilute solutions (1 : 200 000 helquat to nitrile ratio) and thus the phenomenon can be generally useful in analytical chemistry. PMID:27087537

  3. Freely designable optical frequency conversion in Raman-resonant four-wave-mixing process.

    PubMed

    Zheng, Jian; Katsuragawa, Masayuki

    2015-01-01

    Nonlinear optical processes are governed by the relative-phase relationships among the relevant electromagnetic fields in these processes. In this Report, we describe the physics of arbitrary manipulation of Raman-resonant four-wave-mixing process by artificial control of relative phases. As a typical example, we show freely designable optical-frequency conversions to extreme spectral regions, mid-infrared and vacuum-ultraviolet, with near-unity quantum efficiencies. Furthermore, we show that such optical-frequency conversions can be realized by using a surprisingly simple technology where transparent plates are placed in a nonlinear optical medium and their positions and thicknesses are adjusted precisely. In a numerical simulation assuming practically applicable parameters in detail, we demonstrate a single-frequency tunable laser that covers the whole vacuum-ultraviolet spectral range of 120 to 200 nm. PMID:25748023

  4. Operational electrochemical stability of thiophene-thiazole copolymers probed by resonant Raman spectroscopy

    SciTech Connect

    Wade, Jessica; Wood, Sebastian; Kim, Ji-Seon; Beatrup, Daniel; Hurhangee, Michael; McCulloch, Iain; Durrant, James R.; Bronstein, Hugo

    2015-06-28

    We report on the electrochemical stability of hole polarons in three conjugated polymers probed by resonant Raman spectroscopy. The materials considered are all isostructural to poly(3-hexyl)thiophene, where thiazole units have been included to systematically deepen the energy level of the highest occupied molecular orbital (HOMO). We demonstrate that increasing the thiazole content planarizes the main conjugated backbone of the polymer and improves the electrochemical stability in the ground state. However, these more planar thiazole containing polymers are increasingly susceptible to electrochemical degradation in the polaronic excited state. We identify the degradation mechanism, which targets the C=N bond in the thiazole units and results in disruption of the main polymer backbone conjugation. The introduction of thiazole units to deepen the HOMO energy level and increase the conjugated backbone planarity can be beneficial for the performance of certain optoelectronic devices, but the reduced electrochemical stability of the hole polaron may compromise their operational stability.

  5. Solvent effects on the resonance Raman spectra of bacteriochlorophyll a cation radical

    NASA Astrophysics Data System (ADS)

    Misono, Yasuhito; Nishizawa, Ei-ichi; Limantara, Leenawaty; Koyama, Yasushi; Itoh, Koichi

    1995-04-01

    Resonance Raman (RR) spectra were measured for the cation radical of bacteriochlorophyll a in acetone, methanol, dichloromethane and mixed solvents of acetone and methanol. The ring-breathing (C a-C m stretching) frequency of the radical (abbreviated as vr+) was observed at 1601 cm -1 in acetone (forming a penta-coordinated monomer), at 1587 cm -1 in a methanol (forming a hexa-coordinated monomer) and at 1600 cm -1 in dichloromethane (forming a penta-coordinated aggregate). The RR spectrum of the radical in dichloromethane is almost identical to the transient RR spectrum ascribed to 'the aggregated T 1 species of Bchl a' formed in the particular solvent by Nishizawa, Limantara, Nanjou, Nagae, Kakuno and Koyama, indicating that their interpretation needs to be revised.

  6. Subpicosecond resonance Raman spectra of the early intermediates in the photocycle of bacteriorhodopsin

    PubMed Central

    van den Berg, R.; Du-Jeon-Jang; Bitting, Herbert C.; El-Sayed, M. A.

    1990-01-01

    The resonance Raman spectra are presented for the species formed during the photocycle of bacteriorhodopsin (bR) on a timescale of 800-900 fs. In the ethylenic stretch region two intermediates were found with frequencies of 1,510 and 1,518 cm-1, corresponding to species with optical absorption maxima at 660 and 625 nm, respectively. This leads to the assignment of the 1,518 cm-1 band to the J625 intermediate. In the fingerprint region, the appearance of a vibration at 1,195 cm-1 strongly suggests that the isomerization indeed has taken place in a time less than the pulsewidth of our laser. This supports the previous proposals made on the basis of the optical spectra. The spectra are compared with those observed in tens of picoseconds up to nanoseconds. PMID:19431759

  7. Rapid analysis of malachite green and leucomalachite green in fish muscles with surface-enhanced resonance Raman scattering.

    PubMed

    Zhang, Yuanyuan; Yu, Wansong; Pei, Lu; Lai, Keqiang; Rasco, Barbara A; Huang, Yiqun

    2015-02-15

    Surface-enhanced resonance Raman scattering (SERRS) coupled with gold nanospheres was applied for rapid analysis of the hazardous substances malachite green (MG) and leucomalachite green (LMG) in fish muscle tissues. The lowest concentration of MG that could be detected was 0.5ngmL(-1) with high linear correlation (R(2)=0.970-0.998) between MG concentration and intensities of characteristic Raman peaks. A simplified sample preparation method taking less than 1h for recovering MG and LMG in fish fillets was developed for SERRS analysis, and 4-8 samples could be handled in parallel. MG and LMG could be detected in extracts of tilapia fish fillets at as low as 2ngg(-1) with SERRS and a simple principle component analysis method. For six other fish species, the lowest detectable concentration of MG ranged from 1ngg(-1) to 10ngg(-1). This study provides a new sensitive approach for the detection of trace amounts of the prohibited drugs MG and LMG in muscle food, which has the potential for rapidly screening a large number of samples. PMID:25236201

  8. Near-IR resonance Raman spectroscopy of archaerhodopsin 3: effects of transmembrane potential.

    PubMed

    Saint Clair, Erica C; Ogren, John I; Mamaev, Sergey; Russano, Daniel; Kralj, Joel M; Rothschild, Kenneth J

    2012-12-20

    Archaerhodopsin 3 (AR3) is a light driven proton pump from Halorubrum sodomense that has been used as a genetically targetable neuronal silencer and an effective fluorescent sensor of transmembrane potential. Unlike the more extensively studied bacteriorhodopsin (BR) from Halobacterium salinarum, AR3 readily incorporates into the plasma membrane of both E. coli and mammalian cells. Here, we used near-IR resonance Raman confocal microscopy to study the effects of pH and membrane potential on the AR3 retinal chromophore structure. Measurements were performed both on AR3 reconstituted into E. coli polar lipids and in vivo in E. coli expressing AR3 in the absence and presence of a negative transmembrane potential. The retinal chromophore structure of AR3 is in an all-trans configuration almost identical to BR over the entire pH range from 3 to 11. Small changes are detected in the retinal ethylenic stretching frequency and Schiff Base (SB) hydrogen bonding strength relative to BR which may be related to a different water structure near the SB. In the case of the AR3 mutant D95N, at neutral pH an all-trans retinal O-like species (O(all-trans)) is found. At higher pH a second 13-cis retinal N-like species (N(13-cis)) is detected which is attributed to a slowly decaying intermediate in the red-light photocycle of D95N. However, the amount of N(13-cis) detected is less in E. coli cells but is restored upon addition of carbonyl cyanide m-chlorophenyl hydrazone (CCCP) or sonication, both of which dissipate the normal negative membrane potential. We postulate that these changes are due to the effect of membrane potential on the N(13-cis) to M(13-cis) levels accumulated in the D95N red-light photocycle and on a molecular level by the effects of the electric field on the protonation/deprotonation of the cytoplasmic accessible SB. This mechanism also provides a possible explanation for the observed fluorescence dependence of AR3 and other microbial rhodopsins on transmembrane

  9. Near-IR Resonance Raman Spectroscopy of Archaerhodopsin 3: Effects of Transmembrane Potential

    PubMed Central

    Saint Clair, Erica C.; Ogren, John I.; Mamaev, Sergey; Russano, Daniel; Kralj, Joel M.; Rothschild, Kenneth J.

    2013-01-01

    Archaerhodopsin 3 (AR3) is a light driven proton pump from Halorubrum sodomense that has been used as a genetically targetable neuronal silencer and an effective fluorescent sensor of transmembrane potential. Unlike the more extensively studied bacteriorhodopsin (BR) from Halobacterium salinarum, AR3 readily incorporates into the plasma membrane of both E. coli and mammalian cells. Here, we used near-IR resonance Raman confocal microscopy to study the effects of pH and membrane potential on the AR3 retinal chromophore structure. Measurements were performed both on AR3 reconstituted into E. coli polar lipids and in vivo in E. coli expressing AR3 in the absence and presence of a negative transmembrane potential. The retinal chromophore structure of AR3 is in an all-trans configuration almost identical to BR over the entire pH range from 3–11. Small changes are detected in the retinal ethylenic stretching frequency and Schiff Base (SB) hydrogen bonding strength relative to BR which may be related to a different water structure near the SB. In the case of the AR3 mutant D95N, at neutral pH an all-trans retinal O-like species (Oall-trans) is found. At higher pH a second 13-cis retinal N-like species (N13-cis) is detected which is attributed to a slowly decaying intermediate in the red-light photocycle of D95N. However, the amount of N13-cis detected is less in E. coli cells but is restored upon addition of carbonyl cyanide m-chlorophenyl hydrazone (CCCP) or sonication, both of which dissipate the normal negative membrane potential. We postulate that these changes are due to the effect of membrane potential on the N13-cis to M13-cis levels accumulated in the D95N red-light photocycle and on a molecular level by the effects of the electric field on the protonation/deprotonation of the cytoplasmic accessible SB. This mechanism also provides a possible explanation for the observed fluorescence dependence of AR3 and other microbial rhodopsins on transmembrane potential

  10. Resonance Raman Structural Evidence that the Cis-to-Trans Isomerization in Rhodopsin Occurs in Femtoseconds

    PubMed Central

    Kim, Judy E.; McCamant, David W.; Zhu, Leyun; Mathies, Richard A.

    2005-01-01

    Picosecond time-resolved resonance Raman spectroscopy is used to probe the structural changes of rhodopsin's retinal chromophore as the cis-to-trans isomerization reaction occurs that initiates vision. Room-temperature resonance Raman spectra of rhodopsin's photoproduct with time delays from −0.7 to 20.8 ps are measured using 2.2 ps, 480 nm pump and 1.5 ps, 600 nm probe pulses. Hydrogen-out-of-plane (HOOP) modes at 852, 871, and 919 cm−1, fingerprint peaks at 1272, 1236, 1211, and 1166 cm−1, and a broad red-shifted ethylenic band at 1530 cm−1 are present at the earliest positive pump−probe time delay of 0.8 ps, indicating that the chromophore is already in a strained, all-trans configuration. Kinetic analyses of both the HOOP and ethylenic regions of the photoproduct spectra reveal that these features grow in with fast (∼ 200 fs) and slow (∼ 2–3 ps) components. These data provide the first structural evidence that photorhodopsin has a thermally unrelaxed, torsionally strained all-trans chromophore within ∼1 ps, and possibly within 200 fs, of photon absorption. Following this ultrafast product formation, the all-trans chromophore cools and conformationally relaxes within a few picoseconds to form bathorhodopsin. This cooling process is revealed as an ethylenic frequency blue-shift of 6 cm−1 (τ ∼ 3.5 ps) as well as an ethylenic width narrowing (τ ∼ 2 ps). The ultrafast production of photorhodopsin is likely accompanied by an impulsively driven, localized protein response. More delocalized protein modes are unable to relax on this ultrafast time scale enabling the chromophore-protein complex to store the large amounts of photon energy (30–35 kcal/mol) that are subsequently used to drive activating protein conformational changes. PMID:16755302

  11. Deformations of the Heme Group of Different Ferrocytochrome c Proteins Probed by Resonance Raman Spectroscopy

    SciTech Connect

    Hagarman, Andrew; Schweitzer-Stenner, Reinhard; Wallace, Carmichael; Laberge, Monique

    2008-11-14

    We measured the low-frequency polarized resonance Raman spectra of horse heart, chicken, and yeast(C102T) ferrocytochromes c with Soret excitation. We examined the out-of-plane deformations of the heme groups by determining the relative intensities and depolarization ratios of a variety of out-of-plane and in-plane Raman active bands. Analysis of relative Raman intensities shows differences in non-planarity of the heme groups of yeast(C102T), horse heart and chicken cytochrome c. Cytochrome c has been shown to have a dominant ruffling (B{sub 1u}) deformation by means of normal coordinate structural decomposition (NSD) analysis of the heme group in crystal structures. The presence and intensity of B{sub 1u} modes, {gamma}{sub 10}-{gamma}{sub 12}, support the indication of ruffling being the major contribution to the non-planar deformations in cytochrome c. Other types of non-planar deformations like doming (A{sub 2U}) and waving (E{sub g}) can be deduced from the Raman activity of {gamma}{sub 5} (A{sub 2u}), {gamma}{sub 21} and {gamma}{sub 22} (E{sub g}). The depolarization ratios of {gamma}{sub 5}, {gamma}{sub 10}, {gamma}{sub 11} and {gamma}{sub 12} are larger than 0.125, indicating the presence of other deformations such as saddling (B{sub 2u}) and propellering (A{sub 1u}), which is again in agreement with the crystal structures of horse heart and yeast ferrocytochrome c. An analysis of the intensities and depolarization ratios of out-of-plane modes revealed that ruffling is comparable in yeast and horse heart cytochrome c, saddling is larger and doming as well as propellering are lower in yeast cytochrome c. With respect to doming and ruffling our results contradict values obtained from the NSD analysis of the corresponding crystal structures. With respect to saddling, our data are in agreement with the crystal structure. The NSD analysis of heme structures resulting from MD simulations did not correlate very well with the spectroscopically obtained results

  12. Low energy electronic excitations and fano resonance in K doped C 60 from Raman scattering excited at 1.16 eV

    NASA Astrophysics Data System (ADS)

    Danieli, R.; Denisov, V. N.; Ruani, G.; Zamboni, R.; Taliani, C.; Zakhidov, A. A.; Ugawa, A.; Imaeda, K.; Yakushi, K.; Inokuchi, H.; Kikuchi, K.; Ikemoto, I.; Suzuki, S.; Achiba, Y.

    1992-01-01

    We present a Raman scattering study of pristine and K doped C 60 at various doping levels by exciting in the near-IR at 1.16 eV. The normal metallic state of K 3C 60 is characterized by a broad scattering background and by the resonance of low energy phonons in the range of 250-500 cm -1. We assign the broad background to an electronic Raman scattering due to low energy electronic excitations. This spectral feature is indicative of an anomalous normal state behaviour and is similar to the case of high temperature ceramic superconductors. In the overdoped K 6C 60 the squashing mode at 278 cm -1 shows a Fano resonance with the electronic scattering associated with localized electronic excitations which are characteristic of isolated regions of K 3C 60 into the matrix of K 6C 60 as a result of inhomogeneous doping. The Fano resonance indicates a specific electron-phonon coupling of this Jahn-Teller mode with low energy excitations and suggests that the symmetry of this electronic excitation is h g (i.e. the same of the coupled phonon mode). We discuss the nature of the anomalous electronic Raman scattering in terms of scattering from low energy excitations involving a low lying singlet band resulting from electron correlation and/or dynamical J-T distortion caused by the squashing mode.

  13. Magnetic-bead-based sub-femtomolar immunoassay using resonant Raman scattering signals of ZnS nanoparticles.

    PubMed

    Ding, Yadan; Cong, Tie; Chu, Xueying; Jia, Yan; Hong, Xia; Liu, Yichun

    2016-07-01

    Highly sensitive, specific, and selective immunoassays are of great significance for not only clinical diagnostics but also food safety, environmental monitoring, and so on. Enzyme-linked immunosorbent assays and fluorescence-based and electrochemical immunoassays are important intensively investigated immunoassay techniques. However, they might suffer from low sensitivity or false-positive results. In this work, a simple, reliable, and ultrasensitive magnetic-bead-based immunoassay was performed using biofunctionalized ZnS semiconductor nanocrystals as resonant Raman probes. The resonant Raman scattering of ZnS nanocrystals displays evenly spaced multi-phonon resonant Raman lines with narrow bandwidths and has strong resistance to environmental variation due to the nature of the electron-phonon interaction, thus rendering reliable signal readout in the immunoassays. The superparamagnetic Fe3O4 nanoparticles facilitated greatly the separation, purification, and concentration processes. It is beneficial for both reducing the labor intensity and amplifying the detection signals. The immobilization of antibodies on the surface of magnetic beads, the preparation of resonant Raman probes, and the immunological recognition between the antibody and analyte all occurred in the liquid phase, which minimized the diffusion barriers and boundary layer constraints. All these factors contributed to the ultralow detection limit of human IgG, which was determined to be about 0.5 fM (∼0.08 pg/ml). It is nearly the highest sensitivity obtained for IgG detection. This work shall facilitate the design of nanoplatforms for ultrasensitive detections of proteins, DNAs, bacteria, explosives, and so on. Graphical abstract An ultrasensitive magnetic-bead-based immunoassay was performed using multi-phonon resonant Raman lines of ZnS nanoparticles as detection signals. PMID:27173389

  14. FT-Raman spectroscopy study of human breast tissue

    NASA Astrophysics Data System (ADS)

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

    2004-07-01

    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.

  15. [Study on the treatment turquoise using Raman spectroscopy].

    PubMed

    Chen, Quan-li; Yuan, Xin-qiang; Chen, Jing-zhong; Qi, Li-jian

    2010-07-01

    Due to a variety of the enhancement and treatment turquoises discovered in gem markets, the identification of turquoise is becoming more and more difficult. By using laser Raman spectroscopy analysis, the characteristics of Raman spectra of the pressed and filled turquoises were studied. The results show that laser Raman spectroscopy is an effective technique to identify the enhancement and treatment turquoises and the natural ones, moreover, it's a non-destructive testing method. The Raman spectra of the enhancement and treatment turquoises are resulted mainly from the vibrational mode and frequency of water, hydroxyl units, PO4 tetrahedron and CH2 units. Besides, they have the characteristic Raman spectra peaks at 2,937, 2,883 and 1,451 cm(-1) which are attributed to the stretching vibration and the bending vibration of CH2, respectively. These characteristic Raman vibration bands, it will help to distinguish the natural turquoises and the treatment ones. The study provides a new train of thought on the rapid, accurate, and non-destructive identification of turquoise. PMID:20827971

  16. From molecular fragments to crystals: a UV Raman spectroscopic study on the mechanism of Fe-ZSM-5 synthesis.

    PubMed

    Fan, Fengtao; Sun, Keju; Feng, Zhaochi; Xia, Haian; Han, Bo; Lian, Yuxiang; Ying, Pinliang; Li, Can

    2009-01-01

    The nucleation process of iron-exchanged zeolite Fe-ZSM-5, from the assembly of distorted tetrahedrally coordinated iron species and silicate rings in the precursor to the final Fe-ZSM-5 crystals, as well as variations in the coordination environment of iron, were studied by UV resonance Raman spectroscopy and complementary techniques.The entire sequence of crystallization events of Fe-ZSM-5 was monitored by UV Raman spectroscopy in combination with HRTEM, UV/Vis spectroscopy, X-ray diffraction patterns, and periodic DFT calculations. Fe-ZSM-5 was synthesized by an organic-free method to avoid signal interference from the organic template in Raman spectra. Framework iron atoms with resonance Raman bands at 516, 1115, and 1165 cm(-1), and a Raman band at 1016 cm(-1) are detected for Fe-ZSM-5. In the early stage of Fe-ZSM-5 synthesis, the precursor contains iron atoms in distorted tetrahedral coordination and five- and six-membered silicate rings. Nucleation by aggregation of the precursor species was monitored by UV Raman spectroscopy based on the resonance Raman effect, and confirmed by periodic DFT calculations. Evolution of iron species on the surface and in the bulk phase was monitored by UV Raman spectroscopy with excitation at 244 and 325 nm, as well as HRTEM. Nucleation takes place first in the core of the amorphous particles, and crystalline nuclei with Fe-ZSM-5 structure are formed in the core by consuming the amorphous shell. Finally the amorphous particles are completely transformed into Fe-ZSM-5 crystals. PMID:19197930

  17. Phononic Molecules Studied by Raman Scattering

    SciTech Connect

    Lanzillotti-Kimura, N. D.; Fainstein, A.; Jusserand, B.; Lemaitre, A.

    2010-01-04

    An acoustic nanocavity can confine phonons in such a way that they act like electrons in an atom. By combining two of these phononic-atoms, it is possible to form a phononic 'molecule', with acoustic modes that are similar to the electronic states in a hydrogen molecule. We report Raman scattering experiments performed in a monolithic structure formed by a phononic molecule embedded in an optical cavity. The acoustic mode splitting becomes evident through both the amplification and change of selection rules induced by the optical cavity confinement. The results are in perfect agreement with photoelastic model simulations.

  18. Coherent Raman Studies of Shocked Liquids

    NASA Astrophysics Data System (ADS)

    McGrane, Shawn; Brown, Kathryn; Dang, Nhan; Bolme, Cynthia; Moore, David

    2013-06-01

    Transient vibrational spectroscopies offer the potential to directly observe time dependent shock induced chemical reaction kinetics. We report recent experiments that couple a hybrid picosecond/femtosecond coherent anti-Stokes Raman spectroscopy (CARS) diagnostic with our tabletop ultrafast laser driven shock platform. Initial results on liquids shocked to 20 GPa suggest that sub-picosecond dephasing at high pressure and temperature may limit the application of this nonresonant background free version of CARS. Initial results using interferometric CARS to increase sensitivity and overcome these limitations will be presented.

  19. Surface origin and control of resonance Raman scattering and surface band gap in indium nitride

    NASA Astrophysics Data System (ADS)

    Alarcón-Lladó, Esther; Brazzini, Tommaso; Ager, Joel W.

    2016-06-01

    Resonance Raman scattering measurements were performed on indium nitride thin films under conditions where the surface electron concentration was controlled by an electrolyte gate. As the surface condition is tuned from electron depletion to accumulation, the spectral feature at the expected position of the (E 1, A 1) longitudinal optical (LO) near 590 cm‑1 shifts to lower frequency. The shift is reversibly controlled with the applied gate potential, which clearly demonstrates the surface origin of this feature. The result is interpreted within the framework of a Martin double resonance, where the surface functions as a planar defect, allowing the scattering of long wavevector phonons. The allowed wavevector range, and hence the frequency, is modulated by the electron accumulation due to band gap narrowing. A surface band gap reduction of over 500 meV is estimated for the conditions of maximum electron accumulation. Under conditions of electron depletion, the full InN bandgap (E g  =  0.65 eV) is expected at the surface. The drastic change in the surface band gap is expected to influence the transport properties of devices which utilize the surface electron accumulation layer.

  20. Excited-state structure and isomerization dynamics of the retinal chromophore in rhodopsin from resonance Raman intensities.

    PubMed Central

    Loppnow, G R; Mathies, R A

    1988-01-01

    Resonance Raman excitation profiles have been measured for the bovine visual pigment rhodopsin using excitation wavelengths ranging from 457.9 to 647.1 nm. A complete Franck-Condon analysis of the absorption spectrum and resonance Raman excitation profiles has been performed using an excited-state, time-dependent wavepacket propagation technique. This has enabled us to determine the change in geometry upon electronic excitation of rhodopsin's 11-cis-retinal protonated Schiff base chromophore along 25 normal coordinates. Intense low-frequency Raman lines are observed at 98, 135, 249, 336, and 461 cm-1 whose intensities provide quantitative, mode-specific information about the excited-state torsional deformations that lead to isomerization. The dominant contribution to the width of the absorption band in rhodopsin results from Franck-Condon progressions in the 1,549 cm-1 ethylenic normal mode. The lack of vibronic structure in the absorption spectrum is shown to be caused by extensive progressions in low-frequency torsional modes and a large homogeneous linewidth (170 cm-1 half-width) together with thermal population of low-frequency modes and inhomogeneous site distribution effects. The resonance Raman cross-sections of rhodopsin are unusually weak because the excited-state wavepacket moves rapidly (approximately 35 fs) and permanently away from the Franck-Condon geometry along skeletal stretching and torsional coordinates. PMID:3416032

  1. Brillouin and Raman Scattering Study of Ethylene Glycol Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Seshimo, Y.; Ike, Y.; Kojima, S.

    2008-02-01

    We studied the cluster structure of ethylene glycol aqueous solutions by Brillouin and Raman scattering. We measured the ultrasonic sound velocity of the sample by Brillouin scattering. From the concentration dependence of the sound velocity, we studied the cluster structure in the solution. We showed that the number of H2O molecule neighboring a EG molecule becomes a little higher with increasing temperature and the intermolecular interaction between EG and H2O molecules weakened with increasing temperature. In Raman scattering study, We studied the hydrogen bond in the solution using the OD stretching band. We revealed that the strength of the hydrogen bond is independent of the EG concentration.

  2. Raman spectroscopic study of leptospiral glycolipoprotein

    NASA Astrophysics Data System (ADS)

    Bao, PeiDi; Bao, Lang; Huang, TianQuan; Liu, XinMing

    1998-04-01

    The Raman scattering spectra of two different samples of Leptospiral Glycoipoprotein (GLP-1 and GLP-2) which have different toxic effects have been obtained and investigated. Leptospirosis is one of the most harmful zoonosis. It is a serious public health issue in some area of Sichusan province. The two samples offer different structural informations of GLP molecules, it would be important to find the difference in contents, structures and the amino acid side - chains environment of the molecules between the two samples of GLP for understanding the different toxic effects. The intense Am I at 1651 cm-1 and weak Am III at 1283 cm-1 show that GLP-1 has a predominantly (alpha) -helix secondary structure. The intense Am I at 1674 cm-1 and intense Am III at 1246 cm-1 show that the conformation of GLP-2 has a high content of (Beta) - sheet and a low content of random - coil secondary structure. Strong Raman scattering occurs in the range 920- 980 cm-1, belong to the C-COO vibration and the stretching of the peptide backbone. The molecules of GLP-1 has trans-gauche-trans configuration of the C-S-S-C-C linkage and the molecules of GLP-2 has trans-gauche-gauche configuration of the C-C-S-S-C-C linkage. The intensity ratio of the two tyrosine liens at 830 cm-1 and 850 cm-1 is 1.1 and 1.23, indicate their tyrosine reduces environment respectively. Other side-chain environment in the two samples were discussed.

  3. A triple-resonance Raman chip for simultaneous enhancement of Stokes and anti-Stokes lines utilizing both localized and non-localized plasmonic resonance

    NASA Astrophysics Data System (ADS)

    Lin, Jiao; Zhang, Yuan; Lee, El-Hang; He, Sailing

    2015-10-01

    In this paper we report a triple-resonance surface-enhanced Raman scattering (SERS) chip that is able to provide simultaneous field enhancement for both the Stokes and anti-Stokes lines. The structure consists of an array of periodic gold bowties placed on the surface of a uniform gold film. It can support two localized surface plasmonic resonances (LSPRs): an electric dipole binding resonance (EDBR) and a magnetic dipole resonance (MDR). A third field enhancement peak is obtained by utilizing the strong interaction between the non-localized surface plasmonic resonance (non-localized SPR) and the LSPR, which greatly raises the field enhancement for the non-localized SPR. In addition, a gold strip-line resonator is incorporated to further enhance the local field intensity. Consequently, the field enhancement of the three peaks are all increased. Compared with the same structure without strip, the periodic bowtie-strip compound structure on gold film can gain as much as ∼22.8 times and ∼3.6 times larger Raman intensity enhancement simultaneously for both the Stokes and anti-Stokes lines.

  4. Raman spectroscopic study of Lactarius spores (Russulales, Fungi).

    PubMed

    De Gussem, Kris; Vandenabeele, Peter; Verbeken, Annemieke; Moens, Luc

    2005-10-01

    Fungi are important organisms in ecosystems, in industrial and pharmaceutical production and are valuable food sources as well. Classical identification is often time-consuming and specialistic. In this study, Raman spectroscopy is applied to the analysis of fungal spores of Lactarius, an economically and ecologically important genus of Basidiomycota. Raman spectra of spores of Lactarius controversus Pers.: Fr., Lactarius lacunarum (Romagn.) ex Hora, Lactarius quieticolor Romagn. and Lactarius quietus (Fr.: Fr.) Fr. are reported for the first time. The spectra of these species show large similarity. These spectra are studied and compared with the Raman spectra of reference substances known to occur in macrofungi, including saccharides, lipids and some minor compounds that may serve as specific biomarkers (adenine, ergosterol and glycine). Most Raman bands could be attributed to specific components. In agreement with the biological role of fungal spores, high amounts of lipids were observed, the main fatty acid being oleate. In addition to different types of lipids and phospholipids, the polysaccharides chitin and amylopectin could be detected as well. The presence of trehalose is not equivocally shown, due to overlapping bands. Raman band positions are reported for the observed bands of the different species and reference products. PMID:16165029

  5. Raman spectroscopic study of Lactarius spores (Russulales, Fungi)

    NASA Astrophysics Data System (ADS)

    De Gussem, Kris; Vandenabeele, Peter; Verbeken, Annemieke; Moens, Luc

    2005-10-01

    Fungi are important organisms in ecosystems, in industrial and pharmaceutical production and are valuable food sources as well. Classical identification is often time-consuming and specialistic. In this study, Raman spectroscopy is applied to the analysis of fungal spores of Lactarius, an economically and ecologically important genus of Basidiomycota. Raman spectra of spores of Lactarius controversus Pers.: Fr., Lactarius lacunarum (Romagn.) ex Hora, Lactarius quieticolor Romagn. and Lactarius quietus (Fr.: Fr.) Fr. are reported for the first time. The spectra of these species show large similarity. These spectra are studied and compared with the Raman spectra of reference substances known to occur in macrofungi, including saccharides, lipids and some minor compounds that may serve as specific biomarkers (adenine, ergosterol and glycine). Most Raman bands could be attributed to specific components. In agreement with the biological role of fungal spores, high amounts of lipids were observed, the main fatty acid being oleate. In addition to different types of lipids and phospholipids, the polysaccharides chitin and amylopectin could be detected as well. The presence of trehalose is not equivocally shown, due to overlapping bands. Raman band positions are reported for the observed bands of the different species and reference products.

  6. Resonance Raman mapping as a tool to monitor and manipulate Si nanocrystals in Si-SiO{sub 2} nanocomposite

    SciTech Connect

    Rani, Ekta; Ingale, Alka A.; Chaturvedi, A.; Joshi, M. P.; Kukreja, L. M.

    2015-10-19

    Specially designed laser heating experiment along with Raman mapping on Si-SiO{sub 2} nanocomposites elucidates the contribution of core and surface/interface in the intermediate frequency range (511–514 cm{sup −1}) Si phonons. The contribution of core to surface/interface increases with the size of Si nanocrystal, which itself increases on laser irradiation. Further, it is found that resonance Raman is crucial to the observance of surface/interface phonons and wavelength dependent Raman mapping can be corroborated with band edges observed in absorption spectra. This understanding can be gainfully used to manipulate and characterize Si-SiO{sub 2} nanocomposite, simultaneously for photovoltaic device applications.

  7. Structural characterization of titania by X-ray diffraction, photoacoustic, Raman spectroscopy and electron paramagnetic resonance spectroscopy.

    PubMed

    Kadam, R M; Rajeswari, B; Sengupta, Arijit; Achary, S N; Kshirsagar, R J; Natarajan, V

    2015-02-25

    A titania mineral (obtained from East coast, Orissa, India) was investigated by X-ray diffraction (XRD), photoacoustic spectroscopy (PAS), Raman and Electron Paramagnetic Resonance (EPR) studies. XRD studies indicated the presence of rutile (91%) and anatase (9%) phases in the mineral. Raman investigation supported this information. Both rutile and anatase phases have tetragonal structure (rutile: space group P4(2)/mnm, a=4.5946(1) Å, c=2.9597(1) Å, V=62.48(1) (Å)(3), Z=2; anatase: space group I4(1)/amd, 3.7848(2) Å, 9.5098(11) Å, V=136.22(2) (Å)(3), Z=4). The deconvoluted PAS spectrum showed nine peaks around 335, 370, 415,485, 555, 605, 659, 690,730 and 785 nm and according to the ligand field theory, these peaks were attributed to the presence of V(4+), Cr(3+), Mn(4+) and Fe(3+) species. EPR studies revealed the presence of transition metal ions V(4+)(d(1)), Cr(3+)(d(3)), Mn(4+)(d(3)) and Fe(3+)(d(5)) at Ti(4+) sites. The EPR spectra are characterized by very large crystal filed splitting (D term) and orthorhombic distortion term (E term) for multiple electron system (s>1) suggesting that the transition metal ions substitute the Ti(4+) in the lattice which is situated in distorted octahedral coordination of oxygen. The possible reasons for observation of unusually large D and E term in the EPR spectra of transition metal ions (S=3/2 and 5/2) are discussed. PMID:25233027

  8. Structural characterization of titania by X-ray diffraction, photoacoustic, Raman spectroscopy and electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Kadam, R. M.; Rajeswari, B.; Sengupta, Arijit; Achary, S. N.; Kshirsagar, R. J.; Natarajan, V.

    2015-02-01

    A titania mineral (obtained from East coast, Orissa, India) was investigated by X-ray diffraction (XRD), photoacoustic spectroscopy (PAS), Raman and Electron Paramagnetic Resonance (EPR) studies. XRD studies indicated the presence of rutile (91%) and anatase (9%) phases in the mineral. Raman investigation supported this information. Both rutile and anatase phases have tetragonal structure (rutile: space group P42/mnm, a = 4.5946(1) Å, c = 2.9597(1) Å, V = 62.48(1) (Å)3, Z = 2; anatase: space group I41/amd, 3.7848(2) Å, 9.5098(11) Å, V = 136.22(2) (Å)3, Z = 4). The deconvoluted PAS spectrum showed nine peaks around 335, 370, 415,485, 555, 605, 659, 690,730 and 785 nm and according to the ligand field theory, these peaks were attributed to the presence of V4+, Cr3+, Mn4+ and Fe3+ species. EPR studies revealed the presence of transition metal ions V4+(d1), Cr3+(d3), Mn4+(d3) and Fe3+(d5) at Ti4+ sites. The EPR spectra are characterized by very large crystal filed splitting (D term) and orthorhombic distortion term (E term) for multiple electron system (s > 1) suggesting that the transition metal ions substitute the Ti4+ in the lattice which is situated in distorted octahedral coordination of oxygen. The possible reasons for observation of unusually large D and E term in the EPR spectra of transition metal ions (S = 3/2 and 5/2) are discussed.

  9. Detailed evaluation of the performance of microfluidic T mixers using fluorescence and ultraviolet resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Masca, Sergiu I.; Rodriguez-Mendieta, Iñigo R.; Friel, Claire T.; Radford, Sheena E.; Smith, D. Alastair

    2006-05-01

    A reliable device that produces efficient mixing with a short dead time has enormous utility in the kinetic analysis of biochemical and chemical processes. We have designed two different T mixers that use moderate flow rates (0.2-0.4ml/s), can monitor reactions up to several milliseconds, and achieve mixing times as low as 20μs. The two mixers are easy to build and dismantle, reliable, and can perform hundreds of experiments without blocking. The first mixer comprises a stainless steel block, containing a microchannel, glued to a quartz cuvette, containing a 200×200μm2 observation channel defining a conventional T mixer. The reactions are monitored by imaging the length of the observation channel onto a charge-coupled device camera. In the second mixer the entire T (200×200μm2 internal cross section) is contained within a 40-mm-long quartz cuvette. We have adopted a novel approach to controlling the entrance channel bore by inserting a stainless steel wire in order to increase the linear speed of the impinging fluids. Using a dye to visualize the flow profile inside the second T mixer, it was shown that in this T geometry segregation of the reactants is observed in the junction between the inlet channels and the observation channel (T junction) and mixing occurs entirely in the observation channel. We thoroughly tested the two mixers through several kinetic reactions using both fluorescence and ultraviolet resonance Raman spectroscopy measurements. We show that both mixers provide efficient mixing with nominal dead times (using 1:10 v /v dilution), calculated using the quenching of the fluorescence of N-acetyl-L-tryptophanamide by N-bromosuccinimide, of 200±20 and 100±10μs, for each mixer, respectively. However, the ability to monitor within the inlet channels and the entire observation channel of the second mixer shows that this standard approach to estimating the dead time is artifactual, since it relies on assuming a constant flow speed throughout the

  10. Application of Raman spectroscopy technology to studying Sudan I

    NASA Astrophysics Data System (ADS)

    Li, Gang; Zhang, Guoping; Chen, Chen

    2006-06-01

    Being an industrial dye, the Sudan I may have a toxic effect after oral intake on the body, and has recently been shown to cause cancer in rats, mice and rabbits. Because China and some other countries have detected the Sudan I in samples of the hot chilli powder and the chilli products, it is necessary to study the characteristics of this dye. As one kind of molecule scattering spectroscopy, Raman spectroscopy is characterized by the frequency excursion caused by interactions of molecules and photons. The frequency excursion reflects the margin between certain two vibrational or rotational energy states, and shows the information of the molecule. Because Raman spectroscopy can provides quick, easy, reproducible, and non-destructive analysis, both qualitative and quantitative, with no sample preparation required, Raman spectroscopy has been a particularly promising technique for analyzing the characteristics and structures of molecules, especially organic ones. Now, it has a broad application in biological, chemical, environmental and industrial applications. This paper firstly introduces Sudan I dye and the Raman spectroscopy technology, and then describes its application to the Sudan I. Secondly, the fingerprint spectra of the Sudan I are respectively assigned and analyzed in detail. Finally, the conclusion that the Raman spectroscopy technology is a powerful tool to determine the Sudan I is drawn.

  11. Mapping of Low-Frequency Raman Modes in CVD-Grown Transition Metal Dichalcogenides: Layer Number, Stacking Orientation and Resonant Effects.

    PubMed

    O'Brien, Maria; McEvoy, Niall; Hanlon, Damien; Hallam, Toby; Coleman, Jonathan N; Duesberg, Georg S

    2016-01-01

    Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterization of mono- and few-layered TMDs which is complementary to well-established (high-frequency) Raman and photoluminescence spectroscopy. This study presents a major stepping stone in fundamental understanding of layered materials as mapping the low-frequency modes allows the quality, symmetry, stacking configuration and layer number of 2D materials to be probed over large areas. In addition, we report on anomalous resonance effects in the low-frequency region of the WS2 Raman spectrum. PMID:26766208

  12. Mapping of Low-Frequency Raman Modes in CVD-Grown Transition Metal Dichalcogenides: Layer Number, Stacking Orientation and Resonant Effects

    NASA Astrophysics Data System (ADS)

    O'Brien, Maria; McEvoy, Niall; Hanlon, Damien; Hallam, Toby; Coleman, Jonathan N.; Duesberg, Georg S.

    2016-01-01

    Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterization of mono- and few-layered TMDs which is complementary to well-established (high-frequency) Raman and photoluminescence spectroscopy. This study presents a major stepping stone in fundamental understanding of layered materials as mapping the low-frequency modes allows the quality, symmetry, stacking configuration and layer number of 2D materials to be probed over large areas. In addition, we report on anomalous resonance effects in the low-frequency region of the WS2 Raman spectrum.

  13. Mapping of Low-Frequency Raman Modes in CVD-Grown Transition Metal Dichalcogenides: Layer Number, Stacking Orientation and Resonant Effects

    PubMed Central

    O’Brien, Maria; McEvoy, Niall; Hanlon, Damien; Hallam, Toby; Coleman, Jonathan N.; Duesberg, Georg S.

    2016-01-01

    Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterization of mono- and few-layered TMDs which is complementary to well-established (high-frequency) Raman and photoluminescence spectroscopy. This study presents a major stepping stone in fundamental understanding of layered materials as mapping the low-frequency modes allows the quality, symmetry, stacking configuration and layer number of 2D materials to be probed over large areas. In addition, we report on anomalous resonance effects in the low-frequency region of the WS2 Raman spectrum. PMID:26766208

  14. Resonance-Enhanced Raman Scattering of Ring-Involved Vibrational Modes in the (1)B(2u) Absorption Band of Benzene, Including the Kekule Vibrational Modes ν(9) and ν(10).

    PubMed

    Willitsford, Adam H; Chadwick, C Todd; Kurtz, Stewart; Philbrick, C Russell; Hallen, Hans

    2016-02-01

    Resonance Raman spectroscopy provides much stronger Raman signal levels than its off-resonant counterpart and adds selectivity by excitation tuning. Raman preresonance of benzene has been well studied. On-resonance studies, especially at phonon-allowed absorptions, have received less attention. In this case, we observe resonance of many of the vibration modes associated motion of the carbons in the ring while tuning over the (1)B2u absorption, including the related ν9 (CC stretch Herzberg notation, ν14 Wilson notation) and ν10 (CH-parallel bend Herzberg notation, ν15 Wilson notation) vibrational modes along with the ν2 (CC-stretch or ring-breathing Herzberg notation, ν1 Wilson notation) mode and multiples of the ν18 (CCC-parallel bend Herzberg notation, ν6 Wilson notation) vibrational mode. The ring-breathing mode is found to mix with the b2u modes creating higher frequency composites. Through the use of an optical parametric oscillator (OPO) to tune through the (1)B2u absorption band of liquid benzene, a stiffening (increase in energy) of the vibrational modes is observed as the excitation wavelength nears the (1)B2u absorption peak of the isolated molecule (vapor) phase. The strongest resonance amplitude observed is in the 2 × ν18 (e2g) mode, with nearly twice the intensity of the ring-breathing mode, ν2. Several overtones and combination modes, especially with ν2 (a1g), are also observed to resonate. Raman resonances on phonon-allowed excitations are narrow and permit the measurement of vibrations not Raman-active in the ground state. PMID:26731431

  15. Electronic and resonance Raman spectra of [Au2(CS3)2]2-. Spectroscopic properties of a "short" Au(I)-Au(I) bond.

    PubMed

    Cheng, E C; Leung, K H; Miskowski, V M; Yam, V W; Phillips, D L

    The anion [Au2(CS3)2]2- has an unusually short Au-Au distance (2.80 A) for a binuclear Au(I) complex. We report detailed Raman studies of the nBu4N+ salt of this complex, including FT-Raman of the solid and UV/vis resonance Raman of dimethyl sulfoxide solutions. All five totally symmetric vibrations of the anion have been located and assigned. A band at delta nu = 125 cm-1 is assigned to nu (Au2). The visible-region electronic absorption bands (384 (epsilon 30,680) and 472 nm (epsilon 610 M-1 cm-1)) are attributable to CS3(2-) localized transitions, as confirmed by the dominance of nu sym(C-Sexo) (delta nu = 951 cm-1) in RR spectra measured in this region. An absorption band at 314 nm (22,250 M-1 cm-1) is assigned as the metal-metal 1(d sigma*-->p sigma) transition, largely because nu sym(C-Sexo) is not strongly enhanced in RR involving this band. Observation of the expected strong resonance enhancement of nu (Au2) was precluded as a result of masking by intense solvent Rayleigh scattering in the UV. PMID:11196834

  16. Resonance Raman imaging as a tool to assess the atmospheric pollution level: carotenoids in Lecanoraceae lichens as bioindicators.

    PubMed

    Ibarrondo, I; Prieto-Taboada, N; Martínez-Arkarazo, I; Madariaga, J M

    2016-04-01

    Raman spectroscopy differentiation of carotenoids has traditionally been based on the ν 1 position (C = C stretching vibrations in the polyene chain) in the 1500-1600 cm(-1) range, using a 785 nm excitation laser. However, when the number of conjugated double bonds is similar, as in the cases of zeaxanthin and β-carotene, this distinction is still ambiguous due to the closeness of the Raman bands. This work shows the Raman results, obtained in resonance conditions using a 514 mm laser, on Lecanora campestris and Lecanora atra species, which can be used to differentiate and consequently characterize carotenoids. The presence of the carotenoid found in Lecanoraceae lichens has been demonstrated to depend on the atmospheric pollution level of the environment they inhabit. Astaxanthin, a superb antioxidant, appears as the principal xanthophyll in highly polluted sites, usually together with the UV screening pigment scytonemin; zeaxanthin is the major carotenoid in medium polluted environments, while β-carotene is the major carotenoid in cleaner environments. Based on these observations, an indirect classification of the stress suffered in a given environment can be assessed by simply analysing the carotenoid content in the Lecanoraceae lichens by using resonance Raman imaging. PMID:26620863

  17. A Raman Study of the Origin of Oxygen Defects in Hexagonal Manganite Thin Films

    NASA Astrophysics Data System (ADS)

    Chen, Xiang-Bai; Hien Nguyen Thi, Minh; Yang, In-Sang; Lee, Daesu; Noh, Tae-Won

    2012-12-01

    Oxygen defects are usually unavoidable when synthesizing oxide thin films. We study the origin of the oxygen defects in hexagonal manganite HoMnO3 epitaxial thin films through Raman scattering spectroscopy. Our results show that the oxygen defects in hexagonal HoMnO3 thin films have distinct effects on different phonon modes and on magnon scattering. Our analyses indicate that the oxygen defects in hexagonal HoMnO3 thin films mainly originate from the basal O3 and/or O4 oxygen vacancies. Furthermore, our analyses of oxygen defects predict that the Mn 3d orbitals would be more strongly hybridized with the apical O1 and/or O2 2p orbitals than the basal O3 and/or O4 2p orbitals. This prediction is consistent with our resonant Raman scattering study and earlier first-principle calculations of the electronic structures of hexagonal manganites.

  18. Raman spectroscopic study of plasma-treated salmon DNA

    SciTech Connect

    Lee, Geon Joon; Kim, Yong Hee; Choi, Eun Ha; Kwon, Young-Wan

    2013-01-14

    In this research, we studied the effect of plasma treatment on the optical/structural properties of the deoxyribonucleic acid (DNA) extracted from salmon sperm. DNA-cetyltrimethylammonium (CTMA) films were obtained by complexation of DNA with CTMA. Circular dichroism (CD) and Raman spectra indicated that DNA retained its double helical structure in the solid film. The Raman spectra exhibited several vibration modes corresponding to the nuclear bases and the deoxyribose-phosphate backbones of the DNA, as well as the alkylchains of CTMA. Dielectric-barrier-discharge (DBD) plasma treatment induced structural modification and damage to the DNA, as observed by changes in the ultraviolet-visible absorption, CD, and Raman spectra. The optical emission spectra of the DBD plasma confirmed that DNA modification was induced by plasma ions such as reactive oxygen species and reactive nitrogen species.

  19. Two Stereoisomers of Spheroidene in the Rhodobacter sphaeroides R26 Reaction Center: A DFT Analysis of Resonance Raman Spectra

    PubMed Central

    Wirtz, A. C.; van Hemert, M. C.; Lugtenburg, J.; Frank, H. A.; Groenen, E. J. J.

    2007-01-01

    From a theoretical analysis of the resonance Raman spectra of 19 isotopomers of spheroidene reconstituted into the reaction center (RC) of Rhodobacter sphaeroides R26, we conclude that the carotenoid in the RC occurs in two configurations. The normal mode underlying the resonance Raman transition at 1239 cm−1, characteristic for spheroidene in the RC, has been identified and found to uniquely refer to the cis nature of the 15,15′ carbon-carbon double bond. Detailed analysis of the isotope-induced shifts of transitions in the 1500–1550 cm−1 region proves that, besides the 15,15′-cis configuration, spheroidene in the RC adopts another cis-configuration, most likely the 13,14-cis configuration. PMID:17617552

  20. Raman Tensors and their application in structural studies of biological systems

    PubMed Central

    Tsuboi, Masamichi; Benevides, James M.; Thomas, George J.

    2009-01-01

    The Raman scattering of a molecule is generated by interactions of its electrons with incident light. The electric vector of the Raman scattered light is related to the electric vector of the incident light through a characteristic Raman tensor. A unique Raman tensor exists for each Raman-active molecular vibrational mode. In the case of biologically important macromolecules Raman tensors have been determined for a few hundred vibrational Raman bands. These include proteins and their amino acid constituents, as well as nucleic acids (DNA and RNA) and their nucleotide constituents. In this review Raman tensors for 39 representative vibrational Raman bands of biological molecules are considered. We present details of the Raman tensor determinations and discuss their application in structural studies of filamentous bacteriophages (fd, Pf1, Pf3 and PH75), fowl feather rachis and eyespots of the protists, Chlamydomonas and Euglena. PMID:19282645

  1. Raman and Brillouin scattering studies of bulk 2H-WSe2.

    PubMed

    Akintola, K; Andrews, G T; Curnoe, S H; Koehler, M R; Keppens, V

    2015-10-01

    Raman and Brillouin spectroscopy were used to probe optic and acoustic phonons in bulk 2H-WSe2. Raman spectra collected under different polarization conditions allowed assignment of spectral peaks to various first- and second-order processes. In contrast to some previous studies, a Raman peak at  ∼259 cm(-1)was found not to be due to the A(1g) mode but to a second-order process involving phonons at either the M or K point of the Brillouin zone. Resonance effects due to excitons were also observed in the Raman spectra. Brillouin spectra of 2H-WSe2 contain a single peak doublet arising from a Rayleigh surface mode propagating with a velocity of [Formula: see text] m s(-1). This value is comparable to that estimated from Density Functional Theory calculations and also to those for the transition metal diselenides 2H-TaSe2 and 2H-NbSe2. Unlike these two materials, however, peaks arising from scattering via the elasto-optic mechanism were not observed in Brillouin spectra of WSe2 despite its lower opacity. PMID:26381161

  2. Raman structural studies of the nickel electrode

    NASA Technical Reports Server (NTRS)

    Cornilsen, B. C.

    1985-01-01

    Raman spectroscopy is sensitive to empirically controlled nickel electrode structural variations, and has unique potential for structural characterization of these materials. How the structure relates to electrochemical properties is examined so that the latter can be more completely understood, controlled, and optimized. Electrodes were impregnated and cycled, and cyclic voltammetry is being used for electrochemical characterization. Structural variation was observed which has escaped detection using other methods. Structural changes are induced by: (1) cobalt doping, (2) the state of change or discharge, (3) the preparation conditions and type of buffer used, and (4) the formation process. Charged active mass has an NiOOH-type structure, agreeing with X-ray diffraction results. Discharged active mass, however, is not isostructural with beta-Ni(OH)2. Chemically prepared alpha phases are not isostructural either. A disordered structural model, containing point defects, is proposed for the cycled materials. This model explains K(+) incorporation. Band assignments were made and spectra interpreted for beta-Ni(OH)2, electrochemical NiOOH and chemically precipitated NiOOH.

  3. Polarized micro-Raman spectroscopy study of pentacene thin films

    NASA Astrophysics Data System (ADS)

    Stenger, Ingrid; Frigout, Alexandre; Tondelier, Denis; Geffroy, Bernard; Ossikovski, Razvigor; Bonnassieux, Yvan

    2009-03-01

    We report on polarized micro-Raman spectroscopy study of two pentacene thin films exhibiting different microstructures: a well-ordered sample and a more disordered one. We have investigated the frequency range of the intramolecular C-H bending modes in the plane of the pentacene molecule and proposed an interpretation of the Raman spectra. The use of symmetry properties of the two intramolecular (uncoupled) modes allowed us to unambiguously identify it among the five main contributions observed in this spectral range. The three other modes were assumed to be resulting from molecular coupling effect owing to their different behavior upon the samples microstructure.

  4. Raman spectroscopic studies of carbon in extra-terrestrial materials

    NASA Technical Reports Server (NTRS)

    Macklin, John; Brownlee, Donald; Chang, Sherwood; Bunch, Ted

    1990-01-01

    The measurements obtained here indicate ways in which micro-Raman spectroscopy can be used to elucidate structural characteristics and distribution of carbon in meteorites and interplanetary dust particles (IDPs). Existing information about structurally significant aspects of Raman measurements of graphite is combined with structurally relevant findings from the present micro-Raman studies of carbons prepared by carbonization of polyvinylidine chloride (PVDC) at various temperatures and natural material, as well as several acid residues from the Allende and Murchison meteorites in order to establish new spectra-structure relationships. Structural features of many of the materials in this study have been measured by x ray analysis and electron microscopy: thus, their structural differences can be directly correlated with differences in the Raman spectra. The spectral parameters consequently affirmed as indicators of structure are used as a measure of structure in materials that have unknown carbon structure, especially IDPs. The unique applicability of micro-Raman spectroscopy is realized not only in the ability to conveniently measure spectra of micron-size IDPs, but also micro-sized parts of an inhomogeneous material. Microcrystalline graphite is known to give Raman spectra that differ dependent on crystallite size (see e.g., Lespade, et. al., 1984, or Nemanich and Solin, 1979). The spectral changes that accompany decreasing particle size include increase in the ratio (R) of the intensity of the band near 1350 cm(-1) (D band) to that of the band near 1600 cm(-1) (G band) increase in the half width of the D band (wD) increase in the frequency maximum of the G band and increase in the half-width (wG) of the 2nd order band near 2700 cm(-1) (G) band.

  5. E{sub 1} Gap of Wurtzite InAs Single Nanowires Measured by Means of Resonant Raman Spectroscopy

    SciTech Connect

    Moeller, M.; Lima, M. M. Jr. de; Cantarero, A.; Dacal, L. C. O.; Iikawa, F.; Chiaramonte, T.; Cotta, M. A.

    2011-12-23

    Indium arsenide nanowires were synthesized with an intermixing of wurtzite and zincblende structure by chemical beam epitaxy with the vapor-liquid-solid mechanism. Resonant Raman spectroscopy of the transverse optical phonon mode at 215 cm{sup -1} reveals an E{sub 1} gap of 2.47 eV which is assigned to the electronic band gap at the A point in the indium arsenide wurtzite phase.

  6. Multiple-order resonant Raman scattering of the localized molecular rose center in BaF 2

    NASA Astrophysics Data System (ADS)

    Deyhimi, Farzad; Bill, Hans

    1983-11-01

    The rose center in BaF 2 is investigated by resonant Raman scattering. The spectra obtained at liquid-helium temperature show multiple order and combination bands of the internal local modes (up to the sixth order), and associated side bands of the lattice. The temperature dependence of the linewidth of the local-mode transitions has been investigated and is explained as being due to anharmonic coupling to the lattice.

  7. Generation of multi-hundred petawatt pulses by resonant Raman amplification in plasma

    NASA Astrophysics Data System (ADS)

    Wu, Zhaohui; Zuo, Yanlei; Su, Jingqin; Liu, Lanqin; Zhang, Zhimeng; Li, Zhilin; Jiao, Zhihong; Wei, Xiaofeng

    2015-03-01

    Backward Raman amplification (BRA) in plasma has been proposed to produce overcritical high-power laser pulses. In this paper, an application based on CPA and BRA is promoted to generate multi-hundred petawatt laser pulses. The compression of short-wavelength (around 351 nm) and picosecond pulses has been proposed for high output intensity and short plasma length. This principle was employed in an application and a scheme is demonstrated using a full-kinetic particle-in-cell (PIC) code. The PIC code is also used to optimize key parameters in the resonant interaction. According to the simulated result using optimized parameters, the output seed fluence is amplified to 6.5 kJ/cm2 and the full-width at half-maximum duration is compressed to 13 fs, showing an energy transfer over 60%. Extending the result to the multidimensional case, a total energy of 3.9 kJ and a laser power of 300 PW are achievable, in a 0.6 cm2 interaction spot. This result is helpful for the improvement of high-energy density physics.

  8. Time-resolved resonance raman spectra of polypyridyl complexes of ruthenium(II)

    SciTech Connect

    Kumar, C.V.; Barton, J.K.; Turro, N.J.; Gould, I.R.

    1987-05-06

    Time-resolved resonance Raman (TR/sup 3/) spectroscopy has recently evolved as a powerful tool for the investigation of the dynamics and structures of a variety of reactive intermediates, electronic excited states, biological systems, and enzyme-substrate complexes. In this communication, the authors report the TR/sup 3/ spectra of three ruthenium complexes of special importance because of three ruthenium complexes of special importance because of their binding ability to nucleic acids, because of their success as chiral probes that recognize the conformations and helicity of nucleic acids, and because of their potential to serve as models for the interaction of metal ions with nucleic acids. They report here the results of TR/sup 3/ and transient absorption experiments which demonstrate that the excited states of three Ru(II) complexes, tris(2,2'-bipyridyl)ruthenium(II) dichloride (I), tris(1,20-phenanthroline)-ruthenium(II) dichloride (II), and tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) dichloride (III), are indeed localized on the ligand.

  9. Asymmetric resonance Raman excitation profiles and violation of the Condon approximation in single-wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Doorn, Stephen; Duque, Juan; Telg, Hagen; Chen, Hang; Swan, Anna; Haroz, Erik; Kono, Junichiro; Tu, Xiaomin; Zheng, Ming

    2012-02-01

    DNA wrapping-based ion exchange chromatography and density gradient ultracentrifugation provide nanotube samples highly enriched in single chiralities. We present resonance Raman excitation profiles for the G-band of several single chirality semiconducting and metallic species. The expected incoming and outgoing resonance peaks are observed in the profiles, but contrary to long-held assumptions, the outgoing resonance is always significantly weaker than the ingoing resonance peak. This strong asymmetry in the profiles arises from a violation of the Condon approximation [1]. Results will be discussed in the context of theoretical models that suggest significant coordinate dependence in the transition dipole (non-Condon effects). The generality of the behavior across semiconducting and metallic types, nanotube family, phonon mode, and Eii will be demonstrated. [4pt] [1] J. Duque et. al., ACS Nano, 5, 5233 (2011).

  10. Doubly resonant Raman electron paramagnetic transitions of Cr{sup 3+} in ruby (Al{sub 2}O{sub 3}:Cr{sup 3+}).

    SciTech Connect

    Lu, X.; Venugopalan, S.; Kim, H.; Grimsditch, M.; Rodriguez, S.; Ramdas, A. K.; Materials Science Division; Purdue Univ.; State Univ. of New York at Binghamton; Sogang Univ.

    2009-06-01

    We report the Raman electron paramagnetic resonance (EPR) of Cr{sup 3+} in ruby (Al{sub 2}O{sub 3}:Cr{sup 3+}) in the {sup 4}A{sub 2} (ground) and E{sup -} (excited) states of its well-known R{sub 1} emission line. Using tunable dye laser excitation within the range of the Zeeman components of R{sub 1}, we observe highly selective doubly resonant enhancements of the Raman EPR lines. The double resonances confirm the assignments of the Raman EPR lines, and they underscore the simultaneous occurrence of both 'in resonance' and 'out resonance' as visualized in the Kramers-Heisenberg quantum-mechanical picture of inelastic light scattering. The g factors of the {sup 4}A{sub 2} and E{sup -} states are consistent with the observed magnetic field dependence of the Raman EPR shifts. Through the interplay of Raman effect and the sharp Zeeman components of R{sub 1}, the results provide clear insights into the underlying microscopic mechanism of these resonant Raman EPR spectra of ruby.

  11. [Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

    SciTech Connect

    Eyring, E.M.

    1992-01-01

    The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd[sup 3+] + L(ligand), [RuL[sub 5]H[sub 2]O][sup 2+], laser flash photolysis of Mo(CO)[sub 6] + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd[sup 3+] ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO)[sub 6]-2,2'-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

  12. [Laser flash photolysis, EPR and Raman studies of liquids at elevated pressures

    SciTech Connect

    Eyring, E.M.

    1992-10-01

    The proposed research will solve a number of analytical chemical problems in solutions with measurement techniques that benefit from the use of elevated hydrostatic pressures: stopped-flow spectrophotometry (Gd{sup 3+} + L(ligand), [RuL{sub 5}H{sub 2}O]{sup 2+}, laser flash photolysis of Mo(CO){sub 6} + L, flash photolysis of binuclear metalloproteins), EPR spectroscopy (Gd{sup 3+} ion-exchanged into ETS-10 and ETAS-10 molecular sieves), laser flash photolysis kinetic studies of Mo(CO){sub 6}-2,2`-bipyridine, and electrochemical studies of metalloporphyrins using resonance Raman spectroscopy.

  13. Single molecule surface enhanced resonance Raman scattering (SERRS) of the enhanced green fluorescent protein (EGFP)

    NASA Astrophysics Data System (ADS)

    Hofkens, Johan; De Schryver, Frans C.; Cotlet, Mircea; Habuchi, Satoshi

    2004-06-01

    One of the most intriguing findings in single molecule spectroscopy (SMS) is the observation of Raman spectra of individual molecules, despite the small cross section of the transitions involved. The observation of the spectra can be explained by the surface enhanced Raman scattering (SERRS) effect. At the single-molecule level, the SERRS-spectra recorded as a function of time reveal inhomogeneous behaviour such as on/off blinking, spectral diffusion, intensity fluctuations of vibrational line, and even splitting of some lines within the spectrum of one molecule. Single-molecule SERRS (SM-SERRS) spectroscopy opens up exciting opportunities in the field of biophysics and biomedical spectroscopy. The first example of single protein SERRS was performed on hemoglobin. However, the possibility of extracting the heme group by silver sols can not be excluded. Here we report on SM-SERRS spectra of enhanced green fluorescent protein (EGFP) in which the chromophore is kept in the protein. The time series of SM-SERRS spectra suggest the conversion of the EGFP chromophore between the deprotonated and the protonated form. Autocorrelation analysis of SM-SERRS trajectory reveals the presence of fast dynamics taking place in the protein. Our findings show the potential of the technique to study structural dynamics of protein molecules.

  14. Resonance Raman characterization of different forms of ground-state 8-bromo-7-hydroxyquinoline caged acetate in aqueous solutions.

    PubMed

    An, Hui-Ying; Ma, Chensheng; Nganga, Jameil L; Zhu, Yue; Dore, Timothy M; Phillips, David Lee

    2009-03-26

    The 8-bromo-7-hydroxyquinolinyl group (BHQ) is a derivative of 7-hydroxyquinoline (7-HQ) and BHQ molecules coexisting as different forms in aqueous solution. Absorption and resonance Raman spectroscopic methods were used to examine 8-bromo-7-hydroxyquinoline protected acetate (BHQ-OAc) in acetonitrile (MeCN), H(2)O/MeCN (60:40, v/v, pH 6 approximately 7), and NaOH-H(2)O/MeCN (60:40, v/v, pH 11 approximately 12) to obtain a better characterization of the forms of the ground-state species of BHQ-OAc in aqueous solutions and to examine their properties. The absorption spectra of BHQ-OAc in water show no absorption bands of the tautomeric species unlike the strong band at about 400 nm observed for the tautomeric form in 7-HQ aqueous solution. The resonance Raman spectra in conjunction with Raman spectra predicted from density functional theory (DFT) calculations reveal the observation of a double Raman band system characteristic of the neutral form (the nominal C=C ring stretching, C-N stretching, and O-H bending modes at 1564 and 1607 cm(-1)) and a single Raman band diagnostic of the enol-deprotonated anionic form (the nominal C=C ring, C-N, and C-O(-) stretching modes in the 1593 cm(-1) region). These results suggest that the neutral form of BHQ-OAc is the major species in neutral aqueous solution. There is a modest increase in the amount of the anionic form and a big decrease in the amount of the tautomeric form of the molecules for BHQ-OAc compared to 7-HQ in neutral aqueous solution. The presence of the 8-bromo group and/or competitive hydrogen bonding that hinder the formation and transfer process of a BHQ-OAc-water cyclic complex may be responsible for this large substituent effect. PMID:19296708

  15. Comparison of high-resolution ultrasonic resonator technology and Raman spectroscopy as novel process analytical tools for drug quantification in self-emulsifying drug delivery systems.

    PubMed

    Stillhart, Cordula; Kuentz, Martin

    2012-02-01

    Self-emulsifying drug delivery systems (SEDDS) are complex mixtures in which drug quantification can become a challenging task. Thus, a general need exists for novel analytical methods and a particular interest lies in techniques with the potential for process monitoring. This article compares Raman spectroscopy with high-resolution ultrasonic resonator technology (URT) for drug quantification in SEDDS. The model drugs fenofibrate, indomethacin, and probucol were quantitatively assayed in different self-emulsifying formulations. We measured ultrasound velocity and attenuation in the bulk formulation containing drug at different concentrations. The formulations were also studied by Raman spectroscopy. We used both, an in-line immersion probe for the bulk formulation and a multi-fiber sensor for measuring through hard-gelatin capsules that were filled with SEDDS. Each method was assessed by calculating the relative standard error of prediction (RSEP) as well as the limit of quantification (LOQ) and the mean recovery. Raman spectroscopy led to excellent calibration models for the bulk formulation as well as the capsules. The RSEP depended on the SEDDS type with values of 1.5-3.8%, while LOQ was between 0.04 and 0.35% (w/w) for drug quantification in the bulk. Similarly, the analysis of the capsules led to RSEP of 1.9-6.5% and LOQ of 0.01-0.41% (w/w). On the other hand, ultrasound attenuation resulted in RSEP of 2.3-4.4% and LOQ of 0.1-0.6% (w/w). Moreover, ultrasound velocity provided an interesting analytical response in cases where the drug strongly affected the density or compressibility of the SEDDS. We conclude that ultrasonic resonator technology and Raman spectroscopy constitute suitable methods for drug quantification in SEDDS, which is promising for their use as process analytical technologies. PMID:22079118

  16. Raman spectroscopy and immunohistochemistry for schwannoma characterization: a case study

    NASA Astrophysics Data System (ADS)

    Neto, Lazaro P. M.; das Chagas, Maurilio J.; Carvalho, Luis Felipe C. S.; Ferreira, Isabelle; dos Santos, Laurita; Haddad, Marcelo; Loddi, Vinicius; Martin, Airton A.

    2016-03-01

    The schwannomas is a tumour of the tissue that covers nerves, called the nerve sheath. Schwannomas are often benign tumors of the Schwan cells, which are the principal glia of the peripheral nervous system (PNS). Preoperative diagnosis of this lesion usually is difficult, therefore, new techniques are being studied as pre surgical evaluation. Among these, Raman spectroscopy, that enables the biochemical identification of the tissue analyzed by their optical properties, may be used as a tool for schwannomas diagnosis. The aim of this study was to discriminate between normal nervous tissue and schwannoma through the confocal Raman spectroscopy and Raman optical fiber-based techniques combined with immunohistochemical analysis. Twenty spectra were analyzed from a normal nerve tissue sample (10) and schwannoma (10) by Holospec f / 1.8 (Kayser Optical Systems) coupled to an optical fiber with a 785nm laser line source. The data were pre-processed and vector normalized. The average analysis and standard deviation was performed associated with cluster analysis. AML, 1A4, CD34, Desmin and S-100 protein markers were used for immunohistochemical analysis. Immunohistochemical analysis was positive only for protein S-100 marker which confirmed the neural schwanomma originality. The immunohistochemistry analysis were important to determine the source of the injury, whereas Raman spectroscopy were able to differentiated tissues types indicating important biochemical changes between normal and benign neoplasia.

  17. Effects of Cation Disordering in Magnesium Aluminate Spinel on the Rectangular Parallelepiped Resonance and Raman Measurements of Vibrational Spectra

    NASA Astrophysics Data System (ADS)

    Cynn, Hyunchae

    The effects of cation disordering of a natural MgAl_2O_4^inel on acoustic and optic vibration were measured for the first time using the rectangular parallelepiped resonance method and Raman measurements. In the resonant frequency measurements of a natural spinel at high temperatures over the temperature range 298 to 1068 K, a discontinuous increase in the measured acoustic resonant vibrations of the lower harmonic modes and a discontinuous decrease in the measured acoustic resonant vibrations of the higher harmonic modes were observed at around 1000 K. Similar differences among the resonant frequencies were also observed at ambient conditions between a less disordered spinel and the highly disordered states of a natural spinel. In the Raman measurements of the same natural spinel over the temperature range 298 to 1424 K, plots of the Raman vibrational frequencies of the external and internal vibrational modes versus temperature change slopes at around 1000 K. These two measurements clearly indicate that a major change occurred at 1000 K, which I label as a transition temperature. I interpret the change that occurred around 1000 K as the onset of cation disordering in the natural spinel. The interpretation is consistent with the following observations: (1) an abrupt decrease in oxygen positional parameter in an x-ray single crystal structure analysis of a synthetic spinel between 873 and 973 K; (2) a discontinuous decrease of linear thermal expansion coefficients in a synthetic spinel at 933 K by dilatometry, and (3) a discontinuous decrease of the unit cell parameter of a natural spinel at around 1073 K by x-ray diffraction. The adiabatic elastic moduli found here for the natural spinel are different from results which have been previously reported by others, however, the moduli of a disordered natural spinel are similar to those previously reported for synthetic spinels. These observations demonstrate that cation disordering of a spinel clearly affects the

  18. Doping of C70 fullerene peapods with lithium vapor: Raman spectroscopic and Raman spectroelectrochemical studies.

    PubMed

    Kalbáč, Martin; Vales, Vaclav; Kavan, Ladislav; Dunsch, Lothar

    2014-12-01

    Raman spectroscopy and in situ Raman spectroelectrochemistry were applied to study the lithium vapor doping of C70@SWCNTs (peapods). A strong degree of doping was proved by the vanishing of the single walled carbon nanotubes (SWCNT's) radial breathing mode (RBM) and by the attenuation of the tangential (TG) band intensity. In contrast to potassium vapor doping, the strong downshift of the frequency of the TG band has not been observed for Li-doping. The Li vapor treated peapods remained partly doped even if they were exposed to humid air. This has been reflected by a reduced intensity of the nanotube and the fullerene modes and by the change of the shape of the RBM band as compared to that of the undoped sample. The modes of the intratubular fullerene were almost unresolved after the contact of the Li-doped sample with water. A lithium insertion into the interior of a peapod and its strong interaction with the intratubular fullerene is suggested to be responsible for the air-insensitive residual doping. This residual doping was studied by spectroelectrochemical measurements. The TG band of the Li doped peapods is partly upshifted during the anodic doping, which points to the different state of C70@SWCNTs and C60@SWCNTs studied previously. PMID:25397777

  19. Resonant surface-enhanced Raman scattering by optical phonons in a monolayer of CdSe nanocrystals on Au nanocluster arrays

    NASA Astrophysics Data System (ADS)

    Milekhin, Alexander G.; Sveshnikova, Larisa L.; Duda, Tatyana A.; Rodyakina, Ekaterina E.; Dzhagan, Volodymyr M.; Sheremet, Evgeniya; Gordan, Ovidiu D.; Himcinschi, Cameliu; Latyshev, Alexander V.; Zahn, Dietrich R. T.

    2016-05-01

    Here we present the results on an investigation of resonant Stokes and anti- Stokes surface-enhanced Raman scattering (SERS) by optical phonons in colloidal CdSe nanocrystals (NCs) homogeneously deposited on arrays of Au nanoclusters using the Langmuir-Blodgett technology. The thickness of deposited NCs, determined by transmission and scanning electron microscopy, amounts to approximately 1 monolayer. Special attention is paid to the determination of the localized surface plasmon resonance (LSPR) energy in the arrays of Au nanoclusters as a function of the nanocluster size by means of micro-ellipsometry. SERS by optical phonons in CdSe NCs shows a significant enhancement factor with a maximal value of 2 × 103 which depends resonantly on the Au nanocluster size and thus on the LSPR energy. The deposition of CdSe NCs on the arrays of Au nanocluster dimers enabled us to study the polarization dependence of SERS. It was found that a maximal SERS signal is observed for the light polarization along the dimer axis. Finally, SERS by optical phonons was observed for CdSe NCs deposited on the structures with a single Au dimer. A difference of the LO phonon energy is observed for CdSe NCs on different single dimers. This effect is explained as the confinement-induced shift which depends on the CdSe nanocrystal size and indicates quasi-single NC Raman spectra being obtained.

  20. Microanalysis of organic pigments and glazes in polychrome works of art by surface-enhanced resonance Raman scattering

    PubMed Central

    Leona, Marco

    2009-01-01

    Scientific studies of works of art are usually limited by severe sampling restrictions. The identification of organic colorants, a class of compounds relevant for attribution and provenance studies, is further complicated by the low concentrations at which these compounds are used and by the interference of the protein-, gum-, or oil-binding media present in pigment and glaze samples. Surface-enhanced resonance Raman scattering (SERRS) was successfully used to identify natural organic colorants in archaeological objects, polychrome sculptures, and paintings from samples smaller than 25 μm in diameter. The key factors in achieving the necessary sensitivity were a highly active stabilized silver colloid, obtained by the reproducible microwave-supported reduction of silver sulfate with glucose and sodium citrate, and a non-extractive hydrolysis sample treatment procedure that maximizes dye adsorption on the colloid. Among the examples presented are the earliest so far found occurrence of madder lake (in a 4,000 years old Egyptian object dating to the Middle Kingdom period), and the earliest known occurrence in Europe of the South Asian dyestuff lac (in the Morgan Madonna, a 12th century polychrome sculpture from Auvergne, France). PMID:19667181

  1. Raman spectroscopic study of ancient South African domestic clay pottery.

    PubMed

    Legodi, M A; de Waal, D

    2007-01-01

    The technique of Raman spectroscopy was used to examine the composition of ancient African domestic clay pottery of South African origin. One sample from each of four archaeological sites including Rooiwal, Lydenburg, Makahane and Graskop was studied. Normal dispersive Raman spectroscopy was found to be the most effective analytical technique in this study. XRF, XRD and FT-IR spectroscopy were used as complementary techniques. All representative samples contained common features, which were characterised by kaolin (Al2Si2O5(OH)5), illite (KAl4(Si7AlO20)(OH)4), feldspar (K- and NaAlSi3O8), quartz (alpha-SiO2), hematite (alpha-Fe2O3), montmorillonite (Mg3(Si,Al)4(OH)2 x 4.5 5H(2)O[Mg]0.35), and calcium silicate (CaSiO3). Gypsum (CaSO4 x 2H2O) and calcium carbonates (most likely calcite, CaCO3) were detected by Raman spectroscopy in Lydenburg, Makahane and Graskop shards. Amorphous carbon (with accompanying phosphates) was observed in the Raman spectra of Lydenburg, Rooiwal and Makahane shards, while rutile (TiO(2)) appeared only in Makahane shard. The Raman spectra of Lydenburg and Rooiwal shards further showed the presence of anhydrite (CaSO4). The results showed that South African potters used a mixture of clays as raw materials. The firing temperature for most samples did not exceed 800 degrees C, which suggests the use of open fire. The reddish brown and grayish black colours were likely due to hematite and amorphous carbon, respectively. PMID:16839805

  2. Molecular vibrational dynamics in polyvinyl alcohol studied by femtosecond coherent anti-stokes Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Kozai, T.; Yamashita, S.; Hirochi, K.; Miyagawa, H.; Tsurumachi, N.; Koshiba, S.; Nakanishi, S.; Itoh, H.

    2012-11-01

    We have performed femtosecond time-resolved coherent anti-stokes Raman spectroscopy (CARS) to study the vibrational dynamics in polyvinyl alcohol (PVA) film. We observed femtosecond coherent vibrational relaxation and CARS signal beats in PVA at room temperature. We found that the coherent vibrational relaxation of anti-symmetric CH2 stretching modes in PVA is faster than that of symmetric modes, probably due to faster vibrational energy transfer. The coherent vibrational relaxation of OH stretching modes was observed to be slower than that of CH2 modes, because OH stretching modes have less resonant energy transfer rate compared to CH2 modes.

  3. A copper(II) complex with a Cu-S₈ bond. Attenuated total reflectance, electron paramagnetic resonance, resonance Raman and atoms-in-molecule calculations.

    PubMed

    Shee, Nirmal K; Adekunle, Florence A O; Verma, Ravi; Kumar, Devesh; Datta, Dipankar

    2015-12-01

    Green [Cu(1,10-phenanthroline)2OH2](ClO4)2 (1) reacts with yellow elemental sulfur at room temperature in methanol to yield turquoise blue [Cu(1,10-phenanthro-line)2(S8)](ClO4)2 (2). A comparative study of the EPR spectra of 1 and 2 in solid state and in methanol glass indicates that the S8 unit in 2 is bound to the metal. High level DFT calculations show that the cation in 2 is five coordinate, distorted square pyramidal with S8 occupying the apical position. The crucial Cu(II)-S bond is around 2.9Å. Such long Cu(II)-S bonds occur in oxidized plastocyanin where it is considered to be bonding. Presence of a weak Cu-S8 bond is revealed in the resonance Raman spectra of 2. Satisfactory matching of the calculated and experimental IR spectra vindicates the theoretically derived structure of the cation in 2. PMID:26125988

  4. Possibility of VOx/SiO2 Complexes Speciation: Comparative Multi-wavelength Raman and DR UV-vis Study

    NASA Astrophysics Data System (ADS)

    Bulánek, Roman; Čičmanec, Pavel; Setnička, Michal

    Raman spectroscopy is one of the very often used spectroscopic methods for characterization of vanadium surface species. However, Raman spectra of VOx-silica systems are more complex and interpretation is more difficult in comparison with other supports (like Al2O3, ZrO2, TiO2 or Nb2O5) because there is strong vibrational coupling between the vanadia species and the silica support. Therefore, assignment and interpretation of some vibrational bands is still subject of controversy. This fact results in incongruity of suggested molecular structure and population of individual vanadium surface complexes. In this contribution, we present systematic comparative study of diffuse reflectance UV-vis spectra and Raman spectra excited by 325 and 514.5 nm lasers obtained on set of dehydrated vanadium modifed hexagonal mesoporous silica (VOx-HMS) samples with vanadium loading from 2 up to 12 wt. %. We prove that changes in population of oligomeric and monomeric VOx species in individual samples are not manifested by significant changes in the character of Raman signals. On the other hand it is evident that with increasing of vanadium loadings the UV-vis spectra show systematic changes. Raman spectroscopy is useful characterization technique for detection presence of very small amount of V2O5 microcrystallites, especially if suitable wavelength of laser is used for remarkable resonant enhancement of Raman intensity of its bands (e.g. 514.5 nm).

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

    SciTech Connect

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

    1981-12-16

    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. Back-bonding in ruthenium porphyrins as monitored by Resonance Raman spectroscopy

    SciTech Connect

    Kim, D.; Su, Y.O.; Spiro, T.G.

    1986-10-22

    Resonance Raman spectra are reported for Ru/sup II/ complexes of octaethylporphyrin (OEP) and tetraphenylporphine (TPP) with pyridine, methanol, and CO axial ligands, using both B- and Q-band excitation. For Ru/sup II/ OEP(CO)(MeOH) the porphyrin skeletal mode frequencies above 1370 cm/sup -1/ agree remarkably well with the values calculated on the basis of the porphyrin core size by using parameters derived earlier for iron protoporphyrin complexes. These frequencies shift both positively and negatively when the CO is replaced by pyridine due to ..pi..-back-donation from Ru to the porphyrin ..pi.. orbitals. The shift pattern is the same as that observed for the bis(imidazole) adduct of iron(II) protoporphyrin, relative to the core size predictions, and the extent of the shifts is very similar in the two cases. Thus, ..pi..-back-bonding to the porphyrin appears to be quantitatively similar for Ru/sup II/ and Fe/sup II/. ..pi..-Back-bonding shifts are also reported for Ru/sup II/TPP(py)/sub 2/. For Ru/sup II/OEP(CO)(py) the Ru-CO stretching, Ru-C-O bending, and C-O stretching modes are observed at 513, 578, and 1930 cm/sup -1/. For Fe/sup II/ porphyrins, the M-CO and C-O frequencies are somewhat lower and higher, respectively, implying greater back-donation to the bound CO for Ru/sup II/ than for Fe/sup II/.

  7. Localized surface plasmon resonance immunoassay and verification using surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Yonzon, Chanda R.; Zhang, Xiaoyu; Van Duyne, Richard P.

    2003-11-01

    This work exploits the localized surface plasmon resonance (LSPR) spectroscopy of noble metal nanoparticles to achieve sensitive and selective detection of biological analytes. Noble metal nanoparticles exhibit an LSPR that is strongly dependent on their size, shape, material, and the local dielectric environment. The LSPR is also responsible for the intense signals observed in surface-enhanced Raman scattering (SERS). Ag nanoparticles fabricated using the nanosphere lithography (NSL) technique exploits this LSPR sensitivity as a signal transduction method in biosensing applications. The current work implements LSPR biosensing for the anti dinitrophenyl (antiDNP) immunoassay system. Upon forming the 2,4 dinitrobenzoic acid/antiDNP complex, this system shows a large LSPR shift of 44 nm when exposed to antiDNP concentration of 1.5 x 10-6 M. In addition, due to the unique molecular characteristics of the functional groups on the biosensor, it can also be characterized using SERS. First, the nanoparticles are functionalized with a mixed self-assembled monolayer (SAM) comprised of 2:1 octanethiol and 11-amino undecanethiol. The SAM is exposed to 2,4-dinitrobenzoic acid with the 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC) coupling reagent. Finally, the 2,4-dinitrophenyl terminated SAM is exposed to various concentration of antiDNP. LSPR shifts indicate the occurrence of a binding event. SER spectra confirm binding of 2,4 dinitrobenzoic acid with amine-terminated SAM. This LSPR/SERS biosensing method can be generalized to a myriad of biologically relevant systems.

  8. Resonance Raman microscopy in combination with partial dark-field microscopy lights up a new path in malaria diagnostics.

    PubMed

    Wood, Bayden R; Hermelink, Antje; Lasch, Peter; Bambery, Keith R; Webster, Grant T; Khiavi, Mehdi Asghari; Cooke, Brian M; Deed, Samantha; Naumann, Dieter; McNaughton, Don

    2009-06-01

    Our goal is to produce a rapid and accurate diagnostic tool for malaria using resonance Raman spectroscopy to detect small inclusions of haemozoin in Plasmodium falciparum infected red blood cells. In pursuit of this aim we serendipitously discovered a partial dark-field effect generated by our experimental setup, which helps identify in thick blood films potential parasites that are normally difficult to see with conventional bright-field microscopy. The haemozoin deposits 'light up' and these can be selectively targeted with the Raman microscope to confirm the presence or absence of haemozoin by the strong 1569 cm(-1) band, which is a marker for haemozoin. With newly developed imaging Raman microscopes incorporating ultra-sensitive rapid readout CCDs it is possible to obtain spectra with a good signal-to-noise ratio in 1 second. Moreover, images from a smear of potentially infected cells can be recorded and analysed with multivariate methods. The reconstructed images show what appear to be sub-micron-inclusions of haemozoin in some cells indicating that the technique has potential to identify low pigmented forms of the parasite including early trophozoite-stage infected cells. Further work is required to unambiguously confirm the presence of such forms through systematic staining but the results are indeed promising and may lead to the development of a new Raman-based malaria diagnostic. PMID:19475137

  9. Resonant surface enhancement of Raman scattering of Ag nanoparticles on silicon substrates fabricated by dc sputtering

    SciTech Connect

    Fang Yingcui; Li Xiaxi; Blinn, Kevin; Mahmoud, Mahmoud A.; Liu Meilin

    2012-09-15

    Ag nanoparticles (AgNPs) were deposited onto silicon substrates by direct current (dc) magnetron sputtering. The influences of sputtering power and sputtering time on the AgNP film morphology were studied using atomic force microscopy. The particle size was successfully tuned from 19 nm to 53 nm by varying the sputtering time at a dc power of 10 W. When Rhodamine 6 G (R6G) was used as the probe molecule, the AgNP films showed significant surface enhanced Raman scattering effect. In particular, it is found that larger particles show stronger enhancement for lower concentrations of R6G while smaller particles display stronger enhancement for higher concentrations of R6G.

  10. Strong dependence of surface plasmon resonance and surface enhanced Raman scattering on the composition of Au-Fe nanoalloys.

    PubMed

    Amendola, Vincenzo; Scaramuzza, Stefano; Agnoli, Stefano; Polizzi, Stefano; Meneghetti, Moreno

    2014-01-01

    Nanoalloys of noble metals with transition metals are crucial components for the integration of plasmonics with magnetic and catalytic properties, as well as for the production of low-cost photonic devices. However, due to synthetic challenges in the realization of nanoscale solid solutions of noble metals and transition metals, very little is known about the composition dependence of plasmonic response in nanoalloys. Here we demonstrate for the first time that the elemental composition of Au-Fe nanoalloys obtained by laser ablation in liquid solution can be tuned by varying the liquid environment. Due to surface passivation and reaction with thiolated ligands, the nanoalloys obtained by our synthetic protocol are structurally and colloidally stable. Hence, we studied the dependence of the surface plasmon resonance (SPR) on the iron fraction and, for the first time, we observed surface enhanced Raman scattering (SERS) in Au-Fe nanoalloys. SPR and SERS performances are strongly affected by the iron content and are investigated using analytical and numerical models. By demonstrating the strong modification of plasmonic properties on the composition, our results provide important insights into the exploitation of Au-Fe nanoalloys in photonics, nanomedicine, magneto-plasmonic and plasmon-enhanced catalysis. Moreover, our findings show that several other plasmonic materials exist beyond gold and silver nanostructures. PMID:24309909

  11. Quantum-mechanical analysis of the intensity distribution in spectra of resonant Raman scattering spectra of aqueous solutions of tyrosine

    NASA Astrophysics Data System (ADS)

    Burova, T. G.; Shcherbakov, R. S.

    2016-05-01

    Quantum-mechanical calculations of the intensity distribution in the resonant Raman scattering spectra of aqueous solutions of tyrosine excited by laser radiation with wavelengths of 244, 229, 218, 200, and 193 nm, as well as in the nonresonant Raman scattering spectrum excited at a wavelength of 488 nm, are performed. Satisfactory agreement is achieved between the calculation results and the experimental data. It is shown that the changes in the intensity distribution observed in the spectra with a change in the excitation wavelength from 244 to 193 nm correlate with the determined changes in the contribution made by excited electronic states into the scattering tensor components. It is noted that it is necessary to take into account the Herzberg-Teller effect and that the number of excited electronic states taken into account considerably affects the calculated relative intensities of lines. The possibility of existence of several tyrosine conformers in aqueous solution at room temperature is shown.

  12. Resonance Raman spectroscopy can detect structural changes in haemozoin (malaria pigment) following incubation with chloroquine in infected erythrocytes.

    PubMed

    Webster, Grant T; Tilley, Leann; Deed, Samantha; McNaughton, Don; Wood, Bayden R

    2008-04-01

    Resonance Raman spectroscopy was applied to monitor the effects of chloroquine (CQ) treatment on cultures of Plasmodium falciparum trophozoites. A number of bands assigned to A(1g) and B(1g) modes characteristic of the haemozoin aggregate are reduced in intensity in the CQ-treated cells, however, no bands from the CQ are observed. The intensity changes are attributed to intermolecular drug binding of the CQ in a sandwich type complex between ferriprotoporphyrin IX (FePPIX) dimer units. It is postulated that the CQ binds via pi-pi interactions between adjacent and orientated porphyrins thereby disrupting the haemozoin aggregate and reducing excitonic interactions between adjacent haems. The results show the potential of Raman microscopy as a screening tool for FePPIX:drug interactions in live cells. PMID:18325340

  13. Raman studies of low-dimensional conductors and superconductors

    NASA Astrophysics Data System (ADS)

    Lin, Yuankun

    Using a Fourier Raman spectrometer equipped with an infrared laser, together with cryogenics, three types of materials have been investigated as a function of temperature in this thesis. The first is the investigation of organic materials including kappa-(BEDT-TTF)2Cu(NCS)2 (T c = 10.4 K), kappa-(BEDT-TTF)2Cu(N(CN)2)Br (Tc = 11.6 K), alphat-(BEDT-TTF) 2I3 (Tc = 8 K) and beta-(BEDT-TTF) 2AuI2 (Tc = 5 K) which become superconductors at low temperature. The second is the study of the first organic conductor TTF-TCNQ which behaves in exactly the opposite way by becoming an insulator at low temperature. The third is the study of the strontium-doped lanthanum copper oxide superconductors with higher transition temperature. For BEDT-TTF based organic superconductors, the electron-phonon coupling is very strong. The frequencies and intensities of three strongest features (nu3 (Ag), nu9 (A g) and nu60 (B3g) modes) in the Raman spectra have been analyzed as a function of temperature. The frequencies of some modes are observed to soften in the temperature range where antiferromagnetic spin fluctuations have been observed, providing evidence of interactions between the phonons and the magnetism. The nu3 g (B3g) mode is observed to be very unusual in many ways, such as having an inverse isotope frequency shift. Below Tc this mode exhibits an increase of 2.2 cm -1in kappa-(BEDT-TTF)2Cu(N(CN)2)Br (T c = 11.6 K) and a decrease of 1.7 cm-1in alpha t-(BEDT-TTF)2I3 (Tc = 8 K). This is the highest frequency phonon in any material to be affected by superconductivity. For TTF-TCNQ, many new lines are observed at temperatures below 150 K as the fluctuating charge-densitywave occurs. The intensity of these lines increases with decreasing temperature. These new lines are assigned according to the deuterium-isotope frequency shifts. In the fluctuating charge-density-wave phase the Frohlich electron-phonon interaction is the probable cause of the appearance of Raman-forbidden scattering

  14. Polarized resonance Raman spectroscopy of single-wall carbon nanotubes within a polymer under strain

    NASA Astrophysics Data System (ADS)

    Frogley, M. D.; Zhao, Q.; Wagner, H. D.

    2002-03-01

    The D* Raman band of single-wall carbon nanotubes aligned by shear flow in a polymer matrix has been measured as a function of tensile strain. The Raman intensity varies with the optical polarization direction, an effect which is used here to assess the degree of tube alignment. The strain dependence of the Raman shift depends strongly on the nanotube orientation and the polarization direction. We show that, using polarized light, unoriented nanotubes can be used as strain sensors so that no tube alignment is necessary and the strain can be measured in all directions in a single sample.

  15. Davydov Splitting and Excitonic Resonance Effects in Raman Spectra of Few-Layer MoSe2.

    PubMed

    Kim, Kangwon; Lee, Jae-Ung; Nam, Dahyun; Cheong, Hyeonsik

    2016-08-23

    Raman spectra of few-layer MoSe2 were measured with eight excitation energies. New peaks that appear only near resonance with various exciton states are analyzed, and the modes are assigned. The resonance profiles of the Raman peaks reflect the joint density of states for optical transitions, but the symmetry of the exciton wave functions leads to selective enhancement of the A1g mode at the A exciton energy and the shear mode at the C exciton energy. We also find Davydov splitting of intralayer A1g, E1g, and A2u modes due to interlayer interaction for some excitation energies near resonances. Furthermore, by fitting the spectral positions of interlayer shear and breathing modes and Davydov splitting of intralayer modes to a linear chain model, we extract the strength of the interlayer interaction. We find that the second-nearest-neighbor interlayer interaction amounts to about 30% of the nearest-neighbor interaction for both in-plane and out-of-plane vibrations. PMID:27479147

  16. Magnetic immunoassay for cancer biomarker detection based on surface-enhanced resonance Raman scattering from coupled plasmonic nanostructures.

    PubMed

    Rong, Zhen; Wang, Chongwen; Wang, Junfeng; Wang, Donggen; Xiao, Rui; Wang, Shengqi

    2016-10-15

    A surface-enhanced resonance Raman scattering (SERRS) sensor was developed for the ultrasensitive detection of cancer biomarkers. Capture antibody-coated silver shell magnetic nanoparticles (Fe3O4@Ag MNPs) were utilized as the CEA enrichment platform and the SERRS signal amplification substrate. Gold nanorods (AuNRs) were coated with a thin silver shell to be in resonance with the resonant Raman dye diethylthiatricarbocyanine iodide (DTTC) and the excitation wavelength at 785nm. The silver-coated AuNRs (Au@Ag NRs) were then modified with detection antibody as the SERRS tags. Sandwich immune complexes formed in the presence of the target biomarker carcinoembryonic antigen (CEA), and this formation induced the plasmonic coupling between the Au@Ag NRs and Fe3O4@Ag MNPs. The SERRS signal of DTTC molecules located in the coupled plasmonic nanostructures was significantly enhanced. As a result, the proposed SERRS sensor was able to detect CEA with a low limit of detection of 4.75fg/mL and a wide dynamic linear range from 10fg/mL to 100ng/mL. The sensor provides a novel SERRS strategy for trace analyte detection and has a potential for clinical applications. PMID:27149164

  17. Study of atmospheric aerosol processing using confocal Raman microspectroscopy

    NASA Astrophysics Data System (ADS)

    Laskina, O.; Grassian, V. H.

    2012-12-01

    Aerosols undergo aging and heterogeneous chemistry as they are transported through the atmosphere. This leads to changes in their properties and their effects on climate, biogeochemistry and human health. Chemical imaging of individual particles may be used to directly investigate the heterogeneity of composition within atmospheric aerosol particles. Single-particle Raman microspectroscopy is a powerful method for chemical imaging and non-destructive physico-chemical characterization of aerosol particles. In this study we investigate the effect of chemical processing on the distribution of chemical species in single particles of mineral dust aerosol using Raman spectral imaging. Raman mapping was used to show the distribution of humic substances and organic acids on some major components of mineral dust (quartz, clays and calcium carbonate). It was shown that humic materials form coating on the surface of particles, whereas interactions of calcium carbonate with organic acids (oxalic and acetic acids) lead to reactions that cause a heterogeneous distribution of components within the reacted particle. Additionally, in a newly designed flow system aerosol can be equilibrated at different relative humidities to study hygroscopicity and phase transitions within these particles. These types of studies are important as the distribution of species in a single particle determines its reactivity, water uptake, and optical properties and thus defines its impact on climate and environment.

  18. IR, Raman, SERS and DFT study of amoxicillin

    NASA Astrophysics Data System (ADS)

    Bebu, Andreea; Szabó, László; Leopold, Nicolae; Berindean, Cătălin; David, Leontin

    2011-05-01

    In this work a joint experimental and theoretical study on amoxicillin is reported. The molecular vibrations of amoxicillin were investigated by FTIR, FT-Raman and SERS spectroscopies. In parallel, quantum chemical calculations based on density functional theory (DFT) were used to determine the geometrical, energetic and vibrational characteristics of the molecule with particular emphasis put on the interaction and adsorption geometry of the molecule to the silver colloidal surface. The SERS spectrum of amoxicillin was recorded using a 532 nm laser line and hydroxylamine reduced silver colloid as SERS substrate. FTIR, FT-Raman and SERS spectra of amoxicillin were assigned based on DFT calculations with the hybrid B3LYP exchange-correlation functional, coupled with the standard 6-31G(d) basis set. The calculated molecular electrostatic potential (MEP) was used in conjunction with SERS data to predict the adsorption geometry of the molecule on the silver surface.

  19. DSC and Raman studies of silver borotellurite glasses

    NASA Astrophysics Data System (ADS)

    Kaur, Amandeep; Khanna, Atul; Gonzàlez, Fernando

    2016-05-01

    Silver borotellurite glasses of composition: xAg2O-yB2O3-(100-x-y)TeO2 (x=20-mol%, y = 0, 10, 20 and 30-mol%) were prepared and characterized by density, X-ray diffraction (XRD), differential scanning calorimetry, and Raman spectroscopy. XRD confirmed the amorphous structure of all samples. Density of glasses decreases while the glass transition temperature increases with increase in B2O3 content from 10 to 30-mol%. Raman study shows that coordination number of Te with oxygen decreases steadily from 3.42 to 3.18 on adding B2O3 due to the transformation of TeO4 into TeO3 units.

  20. Raman and infrared spectroscopic study of kamphaugite-(Y)

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; López, Andrés; Scholz, Ricardo

    2015-05-01

    We have studied the carbonate mineral kamphaugite-(Y)(CaY(CO3)2(OH)·H2O), a mineral which contains yttrium and specific rare earth elements. Chemical analysis shows the presence of Ca, Y and C. Back scattering SEM appears to indicate a single pure phase. The vibrational spectroscopy of kamphaugite-(Y) was obtained using a combination of Raman and infrared spectroscopy. Two distinct Raman bands observed at 1078 and 1088 cm-1 provide evidence for the non-equivalence of the carbonate anion in the kamphaugite-(Y) structure. Such a concept is supported by the number of bands assigned to the carbonate antisymmetric stretching mode. Multiple bands in the ν4 region offers further support for the non-equivalence of carbonate anions in the structure. Vibrational spectroscopy enables aspects of the structure of the mineral kamphaugite-(Y) to be assessed.

  1. Raman spectroscopic study of "The Malatesta": a Renaissance painting?

    PubMed

    Edwards, Howell G M; Vandenabeele, Peter; Benoy, Timothy J

    2015-02-25

    Raman spectroscopic analysis of the pigments on an Italian painting described as a "Full Length Portrait of a Gentleman", known also as the "Malatesta", and attributed to the Renaissance period has established that these are consistent with the historical research provenance undertaken earlier. Evidence is found for the early 19th Century addition of chrome yellow to highlighted yellow ochre areas in comparison with a similar painting executed in 1801 by Sir Thomas Lawrence of John Kemble in the role of Hamlet, Prince of Denmark. The Raman data are novel in that no analytical studies have previously been made on this painting and reinforces the procedure whereby scientific analyses are accompanied by parallel historical research. PMID:25194320

  2. [Raman and EDXRF Study on Overglaze Decorations of Jingdezhen Ceramics].

    PubMed

    Wu, Juan; Zhang, Mao-lin; Wu, Jun-ming; Li, Qi-jiang; Cao, Jian-wen; Li, Qing-hui; Zhao, Hong-xia

    2015-05-01

    Overglaze decoration porcelain is an important category of ancient Chinese ceramics, which has significant artistic value and scientific value. Nondestructive analysis methods such as Raman spectroscopy and EDXRF were used to analyze the overglaze decorations on the Jingdezhen ceramic samples of Yuan, Ming and Qing Dynasty. The recipe and color mechanism of the overglaze pigments were discussed according to the chemical composition and phase composition analysis. The study found that dark red overglaze decorations of ancient Honglvcai, Wucai and famille rose in Jingdezhen are colored by hematite, yellow color is lead tin yellow, carmine decoration is colored by gold less than 0. 1 % in concentration, and green decorations are colored by bivalent copper ion. The result also indicates that the effective combination of Raman spectroscopy and EDXRF can play an important role in the deep research on ceramic artifacts, especially for the overglaze decoration pigments which are interveined each other. PMID:26415441

  3. The study of interaction between graphene and metals by Raman spectroscopy

    SciTech Connect

    Wang, W. X.; Liang, S. H.; Yu, T.; Han, X. F.; Li, D. H.; Li, Y. B.

    2011-04-01

    Different metal films (Co, Ni, Au, and Ag) were deposited on graphene and the interactions between these metals and graphene were studied by Raman spectroscopy. The Raman peaks were shifted after the deposition of metal films. The electron doping of graphene with cobalt contacts and the hole doping with the nickel contacts are the main reasons for Raman peak shift. However, for gold contacts and silver contacts with graphene, strain effect dominates Raman peak shift instead of charge transfer.

  4. Pump probe based Raman spectroscopic studies of PTFE under laser driven shock compression

    NASA Astrophysics Data System (ADS)

    Rastogi, Vinay; Rao, Usha; Chaurasia, S.; Mishra, A. K.; Poswal, H. K.; Deo, M. N.; Sharma, S. M.

    2016-05-01

    High pressure spontaneous Raman spectroscopic studies of poly tetra fluro ethylene (PTFE) have been carried out under laser driven shock compression in confinement geometry target. The Raman modes under shock compression as a function of pressure were measured and compared with the corresponding Raman modes in static pressure experiments. Our results indicate that PTFE undergoes transition to phase III across this pressure.

  5. Preresonance Raman spectroscopic studies on retinoid binding proteins: RBP, CRBP-I and CRALBP

    NASA Astrophysics Data System (ADS)

    Ju, Zhongmo

    1997-07-01

    The nature of the binding interactions between retinoid and many retinoid binding proteins is not well understood. Three such proteins: Retinol Binding Protein (RBP), Cellular Retinol Binding Protein-I (CRBP-I) and Cellular Retinaldehyde Bingding Protein (CRALBP) have been isolated, complexed with all-trans and 11-cis retinal respectively, and probed using pre-resonance and difference Raman spectroscopy. In the study of RBP, we have measured the pre-presonance Raman spectra of retinal, retinoic acid and retinol in dilute CCl4 solutions and when bound to bovine-serum RBP. The comparison reveals that the binding interaction does not involve any specific interactions of the terminal group and the polyene chain with a particular protein residue. The data indicate hydrogen bonding of bound retinal's head group oxygen to water, as well as some torsional angle change of its polyene chain upon binding. The pre-resonance Raman spectrum of all-trans retinal complexed with CRBP-I has also been obtained, displaying a spectral shift in the position of the retinal carbonyl band that is typical of hydrogen bonding effects. This carbonyl red shift has been compared to hydrogen bonding interactions between the all-trans retinal carbonyl and a series of phenol derivatives, varying in proton donating ability by FT-IR spectroscopy, allowing quantitation of the hydrogen bond enthalpy. To characterize the bonding between CRALBP and the carbonyl of 11-cis retinal, a difference Raman experiment was performed using protein complexes with native 11-cis retinal and 11-cis retinal isotopically labeled with 13C at the 15 position. The difference spectrum has been compared to solution Raman spectra of 11-cis retinaldehyde, Schiff Base and Protonated Schiff Base in order to evaluate the retinoid CRALBP link. The results point to a possibility either Schiff Base or H-bond as the linkage between CRALBP and 11-cis retinal. Future isotopic labeling study of CRALBP complexed with 18O-edited 11-cis

  6. Study of antibacterial mechanism of graphene oxide using Raman spectroscopy

    PubMed Central

    Nanda, Sitansu Sekhar; Yi, Dong Kee; Kim, Kwangmeyung

    2016-01-01

    Graphene oxide (GO) is extensively proposed as an effective antibacterial agent in commercial product packaging and for various biomedical applications. However, the antibacterial mode of action of GO is yet hypothetical and unclear. Here we developed a new and sensitive fingerprint approach to study the antibacterial activity of GO and underlying mechanism, using Raman spectroscopy. Spectroscopic signatures obtained from biomolecules such as Adenine and proteins from bacterial cultures with different concentrations of GO, allowed us to probe the antibacterial activity of GO with its mechanism at the molecular level. Escherichia coli (E. coli) and Enterococcus faecalis (E. faecalis) were used as model micro-organisms for all the experiments performed. The observation of higher intensity Raman peaks from Adenine and proteins in GO treated E. coli and E. faecalis; correlated with induced death, confirmed by Scanning electron Microscopy (SEM) and Biological Atomic Force Microscopy (Bio-AFM). Our findings open the way for future investigations of the antibacterial properties of different nanomaterial/GO composites using Raman spectroscopy. PMID:27324288

  7. Raman study of supported molybdenum disulfide single layers

    NASA Astrophysics Data System (ADS)

    Durrer, William; Manciu, Felicia; Afanasiev, Pavel; Berhault, Gilles; Chianelli, Russell

    2008-10-01

    Owing to the increasing demand for clean transportation fuels, highly dispersed single layer transition metal sulfides such as MoS2-based catalysts play an important role in catalytic processes for upgrading and removing sulfur from heavy petroleum feed. In its crystalline bulk form, MoS2 is chemically rather inactive due to a strong tendency to form highly stacked layers, but, when dispersed as single-layer nanoclusters on a support, the MoS2 becomes catalytically active in the hydrogenolysis of sulphur and nitrogen from organic compounds (hydrotreating catalysis). In the present studies alumina-supported MoS2 samples were analyzed by confocal Raman spectroscopy. Evidence of peaks at 152 cm-1, 234 cm-1, and 336 cm-1, normally not seen in the Raman spectrum of the standard bulk crystal, confirms the formation of single layers of MoS2. Furthermore, the presence of the 383 cm-1 Raman line suggests the trigonal prismatic coordination of the formed MoS2 single layers. Depending on the sample preparation method, a restacking of MoS2 layers is also observed, mainly for ex-thiomolybdate samples sulfided at 550 C.

  8. Raman spectroscopy study of calcium oxalate extracted from cacti stems.

    PubMed

    Frausto-Reyes, Claudio; Loza-Cornejo, Sofia; Terrazas, Teresa; Terrazas, Tania; Miranda-Beltrán, María de la Luz; Aparicio-Fernández, Xóchitl; López-Macías, Brenda M; Morales-Martínez, Sandra E; Ortiz-Morales, Martín

    2014-01-01

    To find markers that distinguish the different Cactaceae species, by using near infrared Raman spectroscopy and scanning electron microscopy, we studied the occurrence, in the stem, of solid deposits in five Cactaceae species (Coryphantha clavata, Ferocactus latispinus, Opuntia ficus-indica, O. robusta, and O. strepthacantha) collected from their natural habitats from a region of México. The deposits in the tissues usually occurred as spheroidal aggregates, druses, or prismatic crystals. From the Raman spectra, the crystals were identified either as calcium oxalate monohydrate (CaC2O4·H2O) or calcium oxalate dihydrate (CaC2O4·2H2O). Opuntia species (subfamily Opuntioideae) showed the presence of CaC2O4·H2O, and the deposition of CaC2O4·2H2O was present in C. clavata and F. latispinus (subfamily Cactoideae, Cacteae tribe). As a punctual technique, Raman spectroscopy seems to be a useful tool to identify crystal composition. In addition to allowing the analysis of crystal morphology, this spectroscopic technique can be used to identify Cactaceae species and their chemotaxonomy. PMID:25280368

  9. HPLC assisted Raman spectroscopic studies on bladder cancer

    NASA Astrophysics Data System (ADS)

    Zha, W. L.; Cheng, Y.; Yu, W.; Zhang, X. B.; Shen, A. G.; Hu, J. M.

    2015-04-01

    We applied confocal Raman spectroscopy to investigate 12 normal bladder tissues and 30 tumor tissues, and then depicted the spectral differences between the normal and the tumor tissues and the potential canceration mechanism with the aid of the high-performance liquid chromatographic (HPLC) technique. Normal tissues were demonstrated to contain higher tryptophan, cholesterol and lipid content, while bladder tumor tissues were rich in nucleic acids, collagen and carotenoids. In particular, β-carotene, one of the major types of carotenoids, was found through HPLC analysis of the extract of bladder tissues. The statistical software SPSS was applied to classify the spectra of the two types of tissues according to their differences. The sensitivity and specificity of 96.7 and 66.7% were obtained, respectively. In addition, different layers of the bladder wall including mucosa (lumps), muscle and adipose bladder tissue were analyzed by Raman mapping technique in response to previous Raman studies of bladder tissues. All of these will play an important role as a directive tool for the future diagnosis of bladder cancer in vivo.

  10. Raman spectroscopic studies of the cure of dicyclopentadiene (DCPD)

    NASA Astrophysics Data System (ADS)

    Barnes, S. E.; Brown, E. C.; Corrigan, N.; Coates, P. D.; Harkin-Jones, E.; Edwards, H. G. M.

    2005-10-01

    The cure of polydicyclopentadiene conducted by ring-opening metathesis polymerisation in the presence of a Grubbs catalyst was studied using non-invasive Raman spectroscopy. The spectra of the monomer precursor and polymerised product were fully characterised and all stages of polymerisation monitored. Because of the monomer's high reactivity, the cure process is adaptable to reaction injection moulding and reactive rotational moulding. The viscosity of the dicyclopentadiene undergoes a rapid change at the beginning of the polymerisation process and it is critical that the induction time of the viscosity increase is determined and controlled for successful manufacturing. The results from this work show non-invasive Raman spectroscopic monitoring to be an effective method for monitoring the degree of cure, paving the way for possible implementation of the technique as a method of real-time analysis for control and optimisation during reactive processing. Agreement is shown between Raman measurements and ultrasonic time of flight data acquired during the initial induction period of the curing process.

  11. Raman study of phonon dynamics in PMN crystal

    NASA Astrophysics Data System (ADS)

    Svitelskiy, O.; Toulouse, J.; Ye, Z.-G.

    2002-03-01

    PMN is a model system for lead relaxors.Despite much effort,the origin of the relaxor behavior remains a puzzle.Difficulties arise from the coexistence of several phases at the same temperature.We have carried out a new detailed Raman study of PMN in a wide temperature range of 100-1000K.The entire acquired spectra have been analyzed using multiple peak decomposition.A comparison with neutron scattering data[1] suggests that strong Raman line at 45 cm_-1 is dominated by scattering from a distribution of TA phonons near the zone boundary.The fine structure of the line can be explained by interaction with TO1 and LA phonons.Lowering the temperature leads to the gradual appearance of the rhombohedral phase and to the growth and splitting of lines associated with it (as in KTN[2]): TO2,TO3,TO4.None of the lines exhibit a characteristic ferroelectric behavior.No Raman analogue of the neutron scattering waterfall[3] have been observed Thanks for support to DOE#DE-FG02-00ER45842 1.A.Naberezhnov et al,Eur.Phys.J.B11,13(1999) 3.P.DiAntonio et al,Phys.Rev.B,47,5629(1993) 2.P.Gehring et al.,accepted to PRL

  12. A novel extremophile strategy studied by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Edwards, Howell G. M.

    2007-12-01

    A case is made for the classification of the colonisation by Dirina massiliensis forma sorediata of pigments on ancient wall-paintings as extremophilic behaviour. The lichen encrustations studied using FT-Raman spectroscopy have yielded important molecular information which has assisted in the identification of the survival strategy of the organism in the presence of significant levels of heavy metal toxins. The production of a carotenoid, probably astaxanthin, at the surface of the lichen thalli is identified from its characteristic biomolecular signatures in the Raman spectrum, whereas the presence of calcium oxalate dihydrate (weddellite) has been identified at both the upper and lower surfaces of the thalli and in core samples taken from depths of up to 10 mm through the encrustation into the rock substrate. The latter observation explains the significant disintegrative biodeteriorative effect of the colonisation upon the integrity of the wall-paintings and can be used to direct conservatorial and preservation efforts of the art work. A surprising result proved to be the absence of Raman spectroscopic evidence for the complexation of the metal pigments by the oxalic acid produced by the metabolic action of the organisms, unlike several cases that have been reported in the literature.

  13. Study of antibacterial mechanism of graphene oxide using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Nanda, Sitansu Sekhar; Yi, Dong Kee; Kim, Kwangmeyung

    2016-06-01

    Graphene oxide (GO) is extensively proposed as an effective antibacterial agent in commercial product packaging and for various biomedical applications. However, the antibacterial mode of action of GO is yet hypothetical and unclear. Here we developed a new and sensitive fingerprint approach to study the antibacterial activity of GO and underlying mechanism, using Raman spectroscopy. Spectroscopic signatures obtained from biomolecules such as Adenine and proteins from bacterial cultures with different concentrations of GO, allowed us to probe the antibacterial activity of GO with its mechanism at the molecular level. Escherichia coli (E. coli) and Enterococcus faecalis (E. faecalis) were used as model micro-organisms for all the experiments performed. The observation of higher intensity Raman peaks from Adenine and proteins in GO treated E. coli and E. faecalis; correlated with induced death, confirmed by Scanning electron Microscopy (SEM) and Biological Atomic Force Microscopy (Bio-AFM). Our findings open the way for future investigations of the antibacterial properties of different nanomaterial/GO composites using Raman spectroscopy.

  14. Study of antibacterial mechanism of graphene oxide using Raman spectroscopy.

    PubMed

    Nanda, Sitansu Sekhar; Yi, Dong Kee; Kim, Kwangmeyung

    2016-01-01

    Graphene oxide (GO) is extensively proposed as an effective antibacterial agent in commercial product packaging and for various biomedical applications. However, the antibacterial mode of action of GO is yet hypothetical and unclear. Here we developed a new and sensitive fingerprint approach to study the antibacterial activity of GO and underlying mechanism, using Raman spectroscopy. Spectroscopic signatures obtained from biomolecules such as Adenine and proteins from bacterial cultures with different concentrations of GO, allowed us to probe the antibacterial activity of GO with its mechanism at the molecular level. Escherichia coli (E. coli) and Enterococcus faecalis (E. faecalis) were used as model micro-organisms for all the experiments performed. The observation of higher intensity Raman peaks from Adenine and proteins in GO treated E. coli and E. faecalis; correlated with induced death, confirmed by Scanning electron Microscopy (SEM) and Biological Atomic Force Microscopy (Bio-AFM). Our findings open the way for future investigations of the antibacterial properties of different nanomaterial/GO composites using Raman spectroscopy. PMID:27324288

  15. Docking Prediction of a Water Soluble Porphyrin and Tubulin Assisted with Resonance Raman and Vibrational Mode Analysis

    NASA Astrophysics Data System (ADS)

    McMicken, Brady; Brancaleon, Lorenzo; Thomas, Robert; Parker, James

    2015-03-01

    The ability to modify protein conformation by controlling its partial unfolding may have practical applications such as diminishing its function or blocking its activity. One method used to induce partial unfolding of a protein involves the use of a photosensitizer non-covalently bound to a protein that triggers photochemical reactions upon irradiation leading to protein conformational changes. We are investigating the photoinduced conformational changes of tubulin mediated by a bound water-soluble porphyrin that acts as a photosensitizer. Analysis of how tubulin conformational changes affect its function including polymeric assembly forming microtubules is of interest to uncover the mechanism responsible for the structural change. Our approach to better understand the conformational change, we first plan to discover the binding location between the porphyrin and protein. Use of vibrational mode analysis using density functional theory and resonance Raman experiments targeting the porphyrin molecule will be used to correlate Raman peaks with vibrational modes. The relative intensities of the porphyrin bound to tubulin can be used to calculate the equilibrium geometry observed from Raman spectra. These data will provide the relative distortion of the porphyrin when bound to tubulin, which will subsequently be used in docking simulations to find the most likely binding configuration.

  16. Tiny peaks vs mega backgrounds: a general spectroscopic method with applications in resonant Raman scattering and atmospheric absorptions.

    PubMed

    Auguié, Baptiste; Reigue, Antoine; Le Ru, Eric C; Etchegoin, Pablo G

    2012-09-18

    A simple method using standard spectrometers with charge-coupled device (CCD) detectors is described to routinely measure background-corrected spectra in situations where the signal is composed of weak spectral features (such as Raman peaks or absorption lines) engulfed in a much stronger (by as much as ∼10(5)) broad background. The principle of the method is to subtract the dominant fixed-structure noise and obtain a shot-noise limited spectrum. The final noise level can therefore be reduced as desired by sufficient integration time. The method requires multiple shifts of the diffraction gratings to extract the pixel-dependent noise structure, which is then used as a flat-field correction. An original peak-retrieval procedure is proposed, demonstrating accurate determination of peak lineshapes and linewidths and robustness on practical examples where conventional methods would not be applicable. Examples are discussed to illustrate the potential of the technique to perform routine resonant Raman measurements of fluorescent dyes with high quantum yield, using conventional Raman systems. The method can equally be applied to other situations where small features are masked by a broad overwhelming background. An explicit example is given with the measurement of weak absorption lines in atmospheric gases. PMID:22894881

  17. Optical pathology of human brain metastasis of lung cancer using combined resonance Raman and spatial frequency spectroscopies

    NASA Astrophysics Data System (ADS)

    Zhou, Yan; Liu, Cheng-hui; Pu, Yang; Cheng, Gangge; Zhou, Lixin; Chen, Jun; Zhu, Ke; Alfano, Robert R.

    2016-03-01

    Raman spectroscopy has become widely used for diagnostic purpose of breast, lung and brain cancers. This report introduced a new approach based on spatial frequency spectra analysis of the underlying tissue structure at different stages of brain tumor. Combined spatial frequency spectroscopy (SFS), Resonance Raman (RR) spectroscopic method is used to discriminate human brain metastasis of lung cancer from normal tissues for the first time. A total number of thirty-one label-free micrographic images of normal and metastatic brain cancer tissues obtained from a confocal micro- Raman spectroscopic system synchronously with examined RR spectra of the corresponding samples were collected from the identical site of tissue. The difference of the randomness of tissue structures between the micrograph images of metastatic brain tumor tissues and normal tissues can be recognized by analyzing spatial frequency. By fitting the distribution of the spatial frequency spectra of human brain tissues as a Gaussian function, the standard deviation, σ, can be obtained, which was used to generate a criterion to differentiate human brain cancerous tissues from the normal ones using Support Vector Machine (SVM) classifier. This SFS-SVM analysis on micrograph images presents good results with sensitivity (85%), specificity (75%) in comparison with gold standard reports of pathology and immunology. The dual-modal advantages of SFS combined with RR spectroscopy method may open a new way in the neuropathology applications.

  18. Multi-wavelength Raman spectroscopy study of supported vanadia catalysts: Structure identification and quantification

    SciTech Connect

    Wu, Zili

    2014-10-20

    Revealing the structure of supported metal oxide catalysts is a prerequisite for establishing the structure - catalysis relationship. Among a variety of characterization techniques, multi-wavelength Raman spectroscopy, combining resonance Raman and non-resonance Raman with different excitation wavelengths, has recently emerged as a particularly powerful tool in not only identifying but also quantifying the structure of supported metal oxide clusters. In our review, we make use of two supported vanadia systems, VOx/SiO2 and VOx/CeO2, as examples to showcase how one can employ this technique to investigate the heterogeneous structure of active oxide clusters and to understand the complex interaction between the oxide clusters and the support. Moreover, the qualitative and quantitative structural information gained from the multi-wavelength Raman spectroscopy can be utilized to provide fundamental insights for designing more efficient supported metal oxide catalysts.

  19. Multi-wavelength Raman spectroscopy study of supported vanadia catalysts: Structure identification and quantification

    DOE PAGESBeta

    Wu, Zili

    2014-10-20

    Revealing the structure of supported metal oxide catalysts is a prerequisite for establishing the structure - catalysis relationship. Among a variety of characterization techniques, multi-wavelength Raman spectroscopy, combining resonance Raman and non-resonance Raman with different excitation wavelengths, has recently emerged as a particularly powerful tool in not only identifying but also quantifying the structure of supported metal oxide clusters. In our review, we make use of two supported vanadia systems, VOx/SiO2 and VOx/CeO2, as examples to showcase how one can employ this technique to investigate the heterogeneous structure of active oxide clusters and to understand the complex interaction between themore » oxide clusters and the support. Moreover, the qualitative and quantitative structural information gained from the multi-wavelength Raman spectroscopy can be utilized to provide fundamental insights for designing more efficient supported metal oxide catalysts.« less

  20. Skin carotenoid status measured by resonance Raman spectroscopy as a biomarker of fruit and vegetable intake in preschool children

    PubMed Central

    Scarmo, S; Henebery, K; Peracchio, H; Cartmel, B; Lin, H; Ermakov, IV; Gellermann, W; Bernstein, PS; Duffy, VB; Mayne, ST

    2012-01-01

    BACKGROUND/OBJECTIVE Dietary assessment in children is difficult, suggesting a need to develop more objective biomarkers of intake. Resonance Raman spectroscopy (RRS) is a non-invasive, validated method of measuring carotenoid status in skin as a biomarker of fruit/vegetable intake. The purpose of this study was to examine the feasibility of using RRS in preschool children, to describe inter-individual variability in skin carotenoid status and to identify factors associated with the biomarker in this population. SUBJECTS/METHODS We conducted a cross-sectional study of 381 economically disadvantaged preschoolers in urban centers in Connecticut (USA). In all, 85.5% were black non-Hispanic or Hispanic/Latino, and 14.1% were obese and 16.9% were overweight by age- and sex-specific body mass index (BMI) percentiles. Children had their skin carotenoid status assessed by RRS in the palm of the hand. Fruit/vegetable consumption was assessed by a brief parent/guardian-completed food frequency screener and a liking survey. RESULTS We observed inter-individual variation in RRS values that was nearly normally distributed. In multiple regression analysis, higher carotenoid status, measured by RRS, was positively associated with fruit/vegetable consumption (P =0.02) and fruit/vegetable preference (P<0.01). Lower carotenoid status was observed among younger children, those participating in the US Supplemental Nutrition Assistance Program, and those with greater adiposity (P<0.05 for all). CONCLUSIONS We observed wide variability in skin carotenoid status in a population of young children, as assessed by RRS. Parent-reported fruit/vegetable intake and several demographic factors were significantly associated with RRS-measured skin carotenoid status. We recommend further development of this biomarker in children, including evaluating response to controlled interventions. PMID:22434053

  1. Strong dependence of surface plasmon resonance and surface enhanced Raman scattering on the composition of Au-Fe nanoalloys

    NASA Astrophysics Data System (ADS)

    Amendola, Vincenzo; Scaramuzza, Stefano; Agnoli, Stefano; Polizzi, Stefano; Meneghetti, Moreno

    2014-01-01

    Nanoalloys of noble metals with transition metals are crucial components for the integration of plasmonics with magnetic and catalytic properties, as well as for the production of low-cost photonic devices. However, due to synthetic challenges in the realization of nanoscale solid solutions of noble metals and transition metals, very little is known about the composition dependence of plasmonic response in nanoalloys. Here we demonstrate for the first time that the elemental composition of Au-Fe nanoalloys obtained by laser ablation in liquid solution can be tuned by varying the liquid environment. Due to surface passivation and reaction with thiolated ligands, the nanoalloys obtained by our synthetic protocol are structurally and colloidally stable. Hence, we studied the dependence of the surface plasmon resonance (SPR) on the iron fraction and, for the first time, we observed surface enhanced Raman scattering (SERS) in Au-Fe nanoalloys. SPR and SERS performances are strongly affected by the iron content and are investigated using analytical and numerical models. By demonstrating the strong modification of plasmonic properties on the composition, our results provide important insights into the exploitation of Au-Fe nanoalloys in photonics, nanomedicine, magneto-plasmonic and plasmon-enhanced catalysis. Moreover, our findings show that several other plasmonic materials exist beyond gold and silver nanostructures.Nanoalloys of noble metals with transition metals are crucial components for the integration of plasmonics with magnetic and catalytic properties, as well as for the production of low-cost photonic devices. However, due to synthetic challenges in the realization of nanoscale solid solutions of noble metals and transition metals, very little is known about the composition dependence of plasmonic response in nanoalloys. Here we demonstrate for the first time that the elemental composition of Au-Fe nanoalloys obtained by laser ablation in liquid solution can

  2. SNAKE DEPLORIZING RESONANCE STUDY IN RHIC

    SciTech Connect

    BAI,M.; CAMERON, P.; LUCCIO, A.; HUANG, H.; PITISYN, V.; ET AL.

    2007-06-25

    Snake depolarizing resonances due to the imperfect cancellation of the accumulated perturbations on the spin precession between snakes were observed at the Relativistic Heavy Ion Collider (RHIC). During the RHIC 2005 and 2006 polarized proton runs, we mapped out the spectrum of odd order snake resonance at Q{sub y} = 7/10. Here, Q, is the beam vertical betatron tune. We also studied the beam polarization after crossing the 7/10th resonance as a function of resonance crossing rate. This paper reports the measured resonance spectrum as well as the results of resonance crossing.

  3. Dynamical rate theory of enzymatic reactions and triple-resonant coherent anti-Stokes Raman scattering microspectroscopy

    NASA Astrophysics Data System (ADS)

    Min, Wei

    Chapters 2-7 focus on physical enzymology. Despite its long history, recent single-molecule spectroscopy, among many others techniques, has generated new quantitative data that reveal unobserved features of protein dynamics and enzyme catalysis at unprecedented levels. Much of these are beyond the classic framework of transition state theory and Michalis-Menten (MM) enzyme kinetics. Due to the complexity of the problem, theoretical developments in this area have much lagged behind experiments. After an initial experimental characterization on single-molecule protein conformational fluctuations, we then develop a dynamical rate theory for enzyme catalyzed chemical reactions, from a statistical mechanics approach. Towards this goal, we formulate a two-dimensional (2D) multi-surface free energy description of the entire catalytic process that explicitly combines the concept of "fluctuating enzymes" with the MM enzyme kinetics. The outcome of this framework has two folds. On the rate theory side, going much beyond transition state theory, it connects conformational fluctuations to catalysis, allows for the interplay between energetics (e.g. Haldane's stain energy) and dynamics (e.g. Koshland's induced fit), and predicts the time dependence of single-enzyme catalysis. On the enzyme kinetics side, it gives mechanistic and unified understanding of MM and non-MM (both positive and negative cooperativity) kinetics of monomeric enzymes, in term of non-equilibrium steady state cycle on the 2D free energy surface. Chapters 8-11 present the principle and application of a new ultra-sensitive nonlinear optical microspectroscopy, femtosecond (fs) triple-resonant coherent anti-Stokes Raman scattering (CARS), in which the amplitude and phase of input fs laser pulses are optimally shaped to be in triple resonant with the molecular electronic and vibrational transitions to generate a coherent nonlinear signal beam at a new color with a highest possible efficiency. This technique

  4. Excited-state transient of vanadyl uroporphyrin I detected by resonance Raman spectroscopy

    SciTech Connect

    Alden, R.G.; Sparks, L.D.; Ondrias, M.R. ); Crawford, B.A.; Shelnutt, J.A. )

    1990-02-22

    Transient Raman spectroscopy has been used to investigate excited states of vanadyl uroporphyrin I (VOUroP) in both monomeric and dimeric forms. Uroporphyrins are water-soluble porphyrins with propionic and acetic acid groups substituted at the {beta}-pyrrole carbon positions. Monomeric VOUroP in aqueous solution is known to be six-coordinate with a ligand trans to the oxo ligand. Upon dimerization, the sixth ligand site is inaccessible, and a five-coordinate species is observed. At high laser fluence, an excited-state transient is formed in the monomeric species. Raman spectra of this species are most consistent with an {sup 2}A{sub 1u} (a{sub 1u}({pi}) {yields} d{sub xy}) charge-transfer state. In contrast, dimeric VOUroP shows little evidence of an excited state in the transient Raman spectra during a 10-ns laser pulse.

  5. Resonance Raman spectroscopy of 2H-labelled spheroidenes in petroleum ether and in the Rhodobacter sphaeroides reaction centre.

    PubMed

    Kok, P; Köhler, J; Groenen, E J; Gebhard, R; van der Hoef, I; Lugtenburg, J; Farhoosh, R; Frank, H A

    1997-03-01

    As a step towards the structural analysis of the carotenoid spheroidene in the Rhodobacter sphaeroides reaction centre, we present the resonance Raman spectra of 14-2H, 15-2H, 15'-2H, 14'-2H, 14,15'-2H2 and 15-15'-2H2 spheroidenes in petroleum ether and, except for 14,15'-2H2 spheroidene, in the Rb. sphaeroides R26 reaction center (RC). Analysis of the spectral changes upon isotopic substitution allows a qualitative assignment of most of the vibrational bands to be made. For the all-trans spheroidenes in solution the resonance enhancement of the Raman bands is determined by the participation of carbon carbon stretching modes in the centre of the conjugated chain, the C9 to C15' region. For the RC-bound 15,15'-cis spheroidenes, enhancement is determined by the participation of carbon-carbon stretching modes in the centre of the molecule, the C13 to C13' region. Comparison of the spectra in solution and in the RC reveals evidence for an out-of-plane distortion of the RC-bound spheroidene in the central C14 to C14' region of the carotenoid. The characteristic 1240 cm-1 band in the spectrum of the RC-bound spheroidene has been assigned to a normal mode that contains the coupled C12-C13 and C13'-C12' stretch vibrations. PMID:9177038

  6. Theory of dynamic absorption spectroscopy of nonstationary states. 4. Application to 12-fs resonant impulsive Raman spectroscopy of bacteriorhodopsin

    SciTech Connect

    Pollard, W.T.; Peteanu, L.A.; Mathies, R.A.

    1992-07-23

    A time-dependent theory for femtosecond dynamic absorption spectroscopy is used to describe the creation and observation of molecular ground-state vibrational coherence through the resonance impulsive stimulated Raman mechanism. Model calculations show that the oscillatory absorption signal that arises from this ground-state coherence is maximized for a limited range of pulse lengths and that there is a complex relationship between the probe wavelength and the strength of the spectral oscillations. The generalized time-dependent linear susceptibility of the nonstationary system created by the impulsive pump pulse is defined and used to discuss the strong dependence of the measured signals on the properties of the probe pulse. Finally, calculations are presented to analyze the high-frequency oscillations ({approximately}20-fs period) recently observed in the transient absorption spectra of light-adapted bacteriorhodopsin (BR{sub 568}) following excitation with a 12-fs optical pulse. At the probe wavelengths used in this experiment, the contribution of stimulated emission is negligible at long times because of the extremely rapid excited-state isomerization; as a result, the spectral oscillations observed after this time are due to the impulsive excitation of coherent vibrations in the ground state. The transient response observed for BR{sub 568} is calculated using a 29-mode harmonic potential surface derived from a prior resonance Raman intensity analysis. Both the oscillatory signals and their dependence on the probe wavelength are satisfactorily reproduced. 68 refs., 11 figs.

  7. Resonance Raman Spectra of Five-Coordinate Heme-Nitrosyl Cytochromes c': Effect of the Proximal Heme-NO Environment.

    PubMed

    Servid, Amy E; McKay, Alison L; Davis, Cherry A; Garton, Elizabeth M; Manole, Andreea; Dobbin, Paul S; Hough, Michael A; Andrew, Colin R

    2015-06-01

    Five-coordinate heme nitrosyl complexes (5cNO) underpin biological heme-NO signal transduction. Bacterial cytochromes c' are some of the few structurally characterized 5cNO proteins, exhibiting a distal to proximal 5cNO transition of relevance to NO sensing. Establishing how 5cNO coordination (distal vs proximal) depends on the heme environment is important for understanding this process. Recent 5cNO crystal structures of Alcaligenes xylosoxidans cytochrome c' (AXCP) and Shewanella frigidimarina cytochrome c' (SFCP) show a basic residue (Arg124 and Lys126, respectively) near the proximal NO binding sites. Using resonance Raman (RR) spectroscopy, we show that structurally characterized 5cNO complexes of AXCP variants and SFCP exhibit a range of ν(NO) (1651-1671 cm(-1)) and ν(FeNO) (519-536 cm(-1)) vibrational frequencies, depending on the nature of the proximal heme pocket and the sample temperature. While the AXCP Arg124 residue appears to have little impact on 5cNO vibrations, the ν(NO) and ν(FeNO) frequencies of the R124K variant are consistent with (electrostatically) enhanced Fe(II) → (NO)π* backbonding. Notably, RR frequencies for SFCP and R124A AXCP are significantly displaced from the backbonding trendline, which in light of recent crystallographic data and density functional theory modeling may reflect changes in the Fe-N-O angle and/or extent of σ-donation from the NO(π*) to the Fe(II) (dz(2)) orbital. For R124A AXCP, correlation of vibrational and crystallographic data is complicated by distal and proximal 5cNO populations. Overall, this study highlights the complex structure-vibrational relationships of 5cNO proteins that allow RR spectra to distinguish 5cNO coordination in certain electrostatic and steric environments. PMID:25961377

  8. Soluble guanylate cyclase is activated differently by excess NO and by YC-1: Resonance Raman spectroscopic evidence†

    PubMed Central

    Ibrahim, Mohammed; Derbyshire, Emily R.; Soldatova, Alexandra V.; Marletta, Michael A.; Spiro, Thomas G.

    2010-01-01

    Modulation of soluble guanylate cyclase (sGC) activity by nitric oxide (NO) involves two distinct steps. Low level activation of sGC is achieved by the stoichiometric binding of NO (1-NO) to the heme cofactor, while much higher activation is achieved by the binding of additional NO (xsNO) at a non-heme site. Addition of the allosteric activator YC-1 to the 1-NO form leads to activity comparable to xsNO state. In this study the mechanisms of sGC activation were investigated using electronic absorption and resonance Raman (RR) spectroscopic methods. RR spectroscopy confirmed that the 1-NO form contains 5-coordinate NO-heme and showed that the addition of NO to the 1-NO form has no significant effect on the spectrum. In contrast, addition of YC-1 to either the 1-NO or xsNO forms alters the RR spectrum significantly, indicating a protein-induced change in the heme geometry. This change in the heme geometry was also observed when BAY 41-2272 was added to the xsNO form. Bands assigned to bending and stretching motions of the vinyl and propionate substituents change intensity in a pattern suggesting altered tilting of the pyrrole rings to which they are attached. In addition, the N-O stretching frequency increases, with no change in the Fe-NO frequency, an effect modeled via DFT calculations as resulting from a small opening of the Fe-N-O angle. These spectral differences demonstrate different mechanisms of activation by synthetic activators, such as YC-1 and BAY 41-2272, and excess NO. PMID:20459051

  9. Interaction of anthranilic acid with silver nanoparticles: A Raman, surface-enhanced Raman scattering and density functional theoretical study

    NASA Astrophysics Data System (ADS)

    Chadha, Ridhima; Maiti, Nandita; Kapoor, Sudhir

    2014-11-01

    Raman and surface-enhanced Raman scattering (SERS) studies of anthranilic acid have been investigated in solid, aqueous solution and on silver colloid. Anthranilic acid plays a key role in the brain in the production of quinolinic acid which is a powerful excitant and convulsant substance. Due to its medicinal importance, the surface adsorption properties of anthranilic acid have been studied. The experimental Raman and SERS data is supported with DFT calculations using B3LYP functional with aug-cc-pvdz and LANL2DZ basis sets. The comparison of experimental and theoretical results infers that anthranilate is chemisorbed to the silver surface directly through the carboxylate group with a perpendicular orientation. The time-dependent SERS spectrum of anthranilate showed no observable change indicating no structural transformation with time. The SERS spectrum recorded at different excitation wavelengths helped in understanding the origin of the SERS mechanism.

  10. Raman study of thermochromic phase transition in tungsten trioxide nanowires

    NASA Astrophysics Data System (ADS)

    Lu, Dong Yu; Chen, Jian; Chen, Huan Jun; Gong, Li; Deng, Shao Zhi; Xu, Ning Sheng; Liu, Yu Long

    2007-01-01

    Tungsten trioxide (WO3) nanowires were synthesized by thermal evaporation of tungsten powder in two steps: tungsten suboxide (WO3-x) nanowires were synthesized, and then oxidized in O2 ambient and transformed into WO3 nanowires. Raman spectroscopy was applied to study the thermochromic phase transition of one-dimensional WO3 nanowires. From the temperature dependence of the characteristic mode at 33cm-1 in WO3, the phase transition temperature was determined. It was found that the phase transition of WO3 nanowires was reversible and the phase transition temperatures were even lower than that of WO3 nanopowder.

  11. [IR and Raman spectra studies of Rotundine based on DFT].

    PubMed

    Li, Jun-Ping; Zhou, Guang-Ming; Zhang, Li-Jun; Cheng, Hong-Mei; Qin, Hong-Ying

    2014-11-01

    Infrared spectroscopy (IR), the normal Raman spectroscopy (NRS) and the surface enhanced Raman spectroscopy (SERS) in new Ag/Cu nanomaterial of Rotundine were studied in the present paper. The IR and the NRS of Rotundine were calculated by the density functional theory (DFT) using B3LYP/6-311+G(d, p), then the spectral intensity graph of Rotundine were given. The vibrational peaks were assigned comprehensively by the visualization software of Gauss view 5. 0. Rotundine has obvious infrared and Raman vibrational peak in the wave number range of 3 300-2500 and 1 800-600 cm(-1). SnCl2 and PVP was used as capping agent for the silver nanoparticles in SERS of Rotundine. Finally, by using the method of cyclic immersion well dispersed silver nanoparticles was obtained and achieved good enhancement effect. This molecule acquired strong selective enhancement vibration peak, In the wave number ranges of 1 500-1 400 and 1 000-700 cm(-1) the enhancement effect is most obvious. After analyzed, the methylene of this molecule is adsorbed on the silver nanoparticles surface and the angle between the benzene ring and the silver substrate is close to 90 degrees. The theoretically calculated spectra of Rotundine are consistent with the obtained experimental spectra. There are some differences may be due to the interaction forces between molecules and so on. The visualization software displayed the structure characteristics and molecular group vibration of this molecular visually and provided important basis for assigning the vibrational peaks. Rotundine is an important traditional Chinese medicine agent contained in many kinds of sedative drugs. The study provides a strong basis for the rapid, feature and trace identification of Rotundine and also supplies important reference for the biological role of central inhibition of analgesic drugs. PMID:25752044

  12. Silver Nanoparticle-Enhanced Resonance Raman Sensor of Chromium(III) in Seawater Samples

    PubMed Central

    Ly, Nguyễn Hoàng; Joo, Sang-Woo

    2015-01-01

    Tris(hydroxymethyl)aminomethane ethylenediaminetetraacetic acid (Tris-EDTA), upon binding Cr(III) in aqueous solutions at pH 8.0 on silver nanoparticles (AgNPs), was found to provide a sensitive and selective Raman marker band at ~563 cm−1, which can be ascribed to the metal-N band. UV-Vis absorption spectra also supported the aggregation and structural change of EDTA upon binding Cr(III). Only for Cr(III) concentrations above 500 nM, the band at ~563 cm−1 become strongly intensified in the surface-enhanced Raman scattering spectra. This band, due to the metal-EDTA complex, was not observed in the case of 50 μM of K+, Cd2+, Mg2+, Ca2+, Mn2+, Co2+, Na+, Cu2+, NH4+, Hg2+, Ni2+, Fe3+, Pb2+, Fe2+, and Zn2+ ions. Seawater samples containing K, Mg, Ca, and Na ion concentrations higher than 8 mM also showed the characteristic Raman band at ~563 cm−1 above 500 nM, validating our method. Our approach may be useful in detecting real water samples by means of AgNPs and Raman spectroscopy. PMID:25938200

  13. Cutaneous lycopene and beta-carotene levels measured by resonance Raman spectroscopy: high reliability and sensitivity to oral lactolycopene deprivation and supplementation.

    PubMed

    Blume-Peytavi, Ulrike; Rolland, Anne; Darvin, Maxim E; Constable, Anne; Pineau, Isabelle; Voit, Christiane; Zappel, Kristina; Schäfer-Hesterberg, Gregor; Meinke, Martina; Clavez, Roger L; Sterry, Wolfram; Lademann, Jürgen

    2009-09-01

    Carotenoids, naturally occurring lipophilic micronutrients, possess an antioxidant activity associated with protection from damage induced by free radicals. The present study investigated an innovative non-invasive method to measure cutaneous levels of lycopene and beta-carotene and to monitor the distribution of orally administered lactolycopene in human skin and plasma. A double-blind placebo-controlled randomized study was performed in 25 volunteers, who were under a lycopene-deprived diet (4 weeks prior to study until end of the study) and orally received either lactolycopene or placebo for 12 weeks. Skin and plasma levels of lycopene and beta-carotene were monitored monthly using Raman spectroscopy and HPLC, respectively. Cutaneous levels of lycopene and beta-carotene monitored by resonance Raman spectroscopy showed high reliability. Irrespective of the investigated area, cutaneous levels were sensitive to lycopene deprivation and to oral supplementation; the forehead showed the closest correlation to lycopene variation in plasma. Plasma and skin levels of lycopene were both sensitive to oral intake of lactolycopene and, interestingly, also skin levels of beta-carotene. Thus, oral supplementation with lycopene led to an enrichment of beta-carotene in human skin, possibly due to the fact that carotenoids act in the skin as protection chains, with a natural protection against free radicals. PMID:19442725

  14. Indentation device for in situ Raman spectroscopic and optical studies

    NASA Astrophysics Data System (ADS)

    Gerbig, Y. B.; Michaels, C. A.; Forster, A. M.; Hettenhouser, J. W.; Byrd, W. E.; Morris, D. J.; Cook, R. F.

    2012-12-01

    Instrumented indentation is a widely used technique to study the mechanical behavior of materials at small length scales. Mechanical tests of bulk materials, microscopic, and spectroscopic studies may be conducted to complement indentation and enable the determination of the kinetics and physics involved in the mechanical deformation of materials at the crystallographic and molecular level, e.g., strain build-up in crystal lattices, phase transformations, and changes in crystallinity or orientation. However, many of these phenomena occurring during indentation can only be observed in their entirety and analyzed in depth under in situ conditions. This paper describes the design, calibration, and operation of an indentation device that is coupled with a Raman microscope to conduct in situ spectroscopic and optical analysis of mechanically deformed regions of Raman-active, transparent bulk material, thin films or fibers under contact loading. The capabilities of the presented device are demonstrated by in situ studies of the indentation-induced phase transformations of Si thin films and modifications of molecular conformations in high density polyethylene films.

  15. Raman microprobe spectroscopic studies of solid DNA-CTMA films

    NASA Astrophysics Data System (ADS)

    Yaney, Perry P.; Ahmad, Faizan; Grote, James G.

    2008-08-01

    Extensive studies have been carried out on developing the new biopolymer, deoxyribonucleic acid (DNA) derived from salmon, that has been complexed with a surfactant to make it water insoluble for application to bioelectronic and biophotonic devices. One of the key issues associated with the properties and behavior of solid films of this material is the extreme size of the >8 MDa molecular weight of the virgin, as-received material. Reduction of this molecular weight by factors of up to 40 is achieved by high power sonication. To support the various measurements that have been made to confirm that the sonicated material is still double strand DNA and to look for other effects of sonication, Raman studies were carried out to compare the spectra over a wide range of molecular weights and to develop baseline data that can be used in intercolation studies where various dopants are added to change the electrical, mechanical or optical properties. Raman microprobe spectra from solid, dry thin films of DNA with molecular weights ranging from 200 kDa to >8 MDa complexed with cetyltrimethyl-ammonium chloride (CTMA) are reported and compared to the as-received spectrum and to published DNA spectra in aqueous solutions. In addition, microscopy and measurements on macro-molecular structures of DNA-CTMA are reported.

  16. A Study of Olivine Alteration to Iddingsite Using Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Kuebler, K. E.; Wang, Alian; Haskin, L. A.; Jolliff, B. L.

    2003-01-01

    A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.

  17. A theoretical simulation of the resonant Raman spectroscopy of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes

    NASA Astrophysics Data System (ADS)

    Franklin-Mergarejo, Ricardo; Rubayo-Soneira, Jesús; Halberstadt, Nadine; Janda, Kenneth C.; Apkarian, V. Ara

    2016-02-01

    The resonant Raman spectra of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes have been studied in the framework of a 2-dimensional model previously used in the simulation of their UV-visible absorption spectra using time-dependent techniques. In addition to the vibrational progression along the dihalogen mode, a progression is observed along the intermolecular mode and its combination with the intramolecular one. The relative intensity of the inter to intramolecular vibrational progressions is about 15% for H2O⋯Cl2 and 33% for H2O⋯Br2. These results make resonant Raman spectra a potential tool for detecting the presence of halogen bonded complexes in condensed phase media such as clathrates and ice.

  18. Shifting of infrared radiation using rotational raman resonances in diatomic molecular gases

    DOEpatents

    Kurnit, Norman A.

    1980-01-01

    A device for shifting the frequency of infrared radiation from a CO.sub.2 laser by stimulated Raman scattering in either H.sub.2 or D.sub.2. The device of the preferred embodiment comprises an H.sub.2 Raman laser having dichroic mirrors which are reflective for 16 .mu.m radiation and transmittive for 10 .mu.m, disposed at opposite ends of an interaction cell. The interaction cell contains a diatomic molecular gas, e.g., H.sub.2, D.sub.2, T.sub.2, HD, HT, DT and a capillary waveguide disposed within the cell. A liquid nitrogen jacket is provided around the capillary waveguide for the purpose of cooling. In another embodiment the input CO.sub.2 radiation is circularly polarized using a Fresnel rhomb .lambda./4 plate and applied to an interaction cell of much longer length for single pass operation.

  19. Multiple relaxation and inhomogeneous broadening in resonance enhanced Raman scattering - Application to tunable infrared generation

    NASA Technical Reports Server (NTRS)

    Ryan, J. C.; Lawandy, N. M.

    1989-01-01

    The solutions for the imaginary susceptibility of the Raman field transition with arbitrary relaxation rates and field strengths are examined for differing sets of relaxation rates with emphasis on alkali metal vapors which have spontaneous emission dominated relaxation. The model is further expanded to include Doppler broadening and used to predict the peak gain as a function of detuning for a frequency doubled alexandrite laser-pumped cesium vapor gain cell.

  20. Remote Raman and fluorescence studies of mineral samples.

    PubMed

    Bozlee, Brian J; Misra, Anupam K; Sharma, Shiv K; Ingram, Melissa

    2005-08-01

    In the present study, we investigated remote laser-induced fluorescence (LIF), at a distance of 4.8 m, of a variety of natural minerals and rocks, and Hawaiian Ti (Cordyline terminalis) plant leaves. These minerals included calcite cleavage, calcite onex and calcite travertine, gypsum, fluorapatite, Dover flint and chalk, chalcedony and nephelene syenite, and rubies containing rock. Pulsed laser excitation of the samples at 355 and 266 nm often resulted in strong fluorescence. The LIF bands in the violet-blue region at approximately 413 and approximately 437 nm were observed only in the spectrum of calcite cleavage. The green LIF bands with band maxima in the narrow range of approximately 501-504 nm were observed in the spectra of all the minerals with the exception of the nephelene syenite and ruby rocks. The LIF red bands were observed in the range approximately 685-711 nm in all samples. Excitation with 532 nm wavelength laser gave broad but relatively low fluorescence background in the low-frequency region of the Raman spectra of these minerals. One microsecond signal gating was effective in removing nearly all background fluorescence (with peak at approximately 610 nm) from calcite cleavage Raman spectra, indicating that the fluorescence was probably from long-lifetime inorganic phosphorescence. PMID:16029855

  1. Raman Spectroscopy Applied to Mars Water Cycle Studies

    NASA Astrophysics Data System (ADS)

    Nikolakakos, G.; Whiteway, J. A.

    2014-12-01

    One of the key findings during the Phoenix and Mars Science Laboratory landed Mars missions has been the detection of perchlorate, a highly deliquescent salt. Perchlorates are of great interest on Mars due to their high affinity for water vapour as well as their ability to greatly depress the freezing point of water when in solution. This has intriguing biological implications as resulting brines could potentially provide a habitable environment for living organisms. Additionally, it has been speculated that these salts may play a significant role in influencing the hydrological cycle on Mars. In order to experimentally study brine formation on Mars and assess the feasibility of a future landed detection tool, a stand-off Raman spectroscopy instrument and environmental simulation chamber have been developed at York University. A sample of magnesium perchlorate has been subjected to the water vapour pressure, background pressure and temperatures found at polar Martian latitudes. Results indicate that at a water vapour pressure of ~20 Pa, Raman spectroscopy is able to detect the onset of brine formation and provide an estimate of the quantity of water taken up by the sample. At the lower water vapour pressures typically found on Mars ( ~1 Pa), it appears that slower dynamics inhibit the onset of water uptake over relevant time scales. The experimental setup and current results will be presented.

  2. Structure, IR and Raman spectra of phosphotrihydrazide studied by DFT

    NASA Astrophysics Data System (ADS)

    Furer, V. L.; Vandyukov, A. E.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2016-09-01

    The FTIR and FT Raman measurements of the phosphotrihydrazide (S)P[N(Me)-NH2]3 have been performed. This compound is a zero generation dendrimer G0 with terminal amine groups. Structural optimization and normal mode analysis were obtained for G0 by the density functional theory (DFT). Optimized geometric bond length and angles obtained by DFT show good agreement with experiment. The amine terminal groups are characterized by the well-defined bands at 3321, 3238, 1614 cm- 1 in the experimental IR spectrum and by bands at 3327, 3241 cm- 1 in the Raman spectrum of G0. The experimental frequencies of asymmetric and symmetric NH2 stretching vibrations of amine group are lower than theoretical values due to intramolecular Nsbnd H ⋯ S hydrogen bond. This hydrogen bond is also responsible for higher experimental infrared intensity of these bands as compared with theoretical values. Relying on DFT calculations a complete vibrational assignment is proposed for the studied dendrimer.

  3. Raman study of radiation-damaged zircon under hydrostatic compression

    NASA Astrophysics Data System (ADS)

    Nasdala, Lutz; Miletich, Ronald; Ruschel, Katja; Váczi, Tamás

    2008-12-01

    Pressure-induced changes of Raman band parameters of four natural, gem-quality zircon samples with different degrees of self-irradiation damage, and synthetic ZrSiO4 without radiation damage, have been studied under hydrostatic compression in a diamond anvil cell up to ~10 GPa. Radiation-damaged zircon shows similar up-shifts of internal SiO4 stretching modes at elevated pressures as non-damaged ZrSiO4. Only minor changes of band-widths were observed in all cases. This makes it possible to estimate the degree of radiation damage from the width of the ν3(SiO4) band of zircon inclusions in situ, almost independent from potential “fossilized pressures” or compressive strain acting on the inclusions. An application is the non-destructive analysis of gemstones such as corundum or spinel: broadened Raman bands are a reliable indicator of self-irradiation damage in zircon inclusions, whose presence allows one to exclude artificial color enhancement by high-temperature treatment of the specimen.

  4. Structure, IR and Raman spectra of phosphotrihydrazide studied by DFT.

    PubMed

    Furer, V L; Vandyukov, A E; Majoral, J P; Caminade, A M; Kovalenko, V I

    2016-09-01

    The FTIR and FT Raman measurements of the phosphotrihydrazide (S)P[N(Me)-NH2]3 have been performed. This compound is a zero generation dendrimer G0 with terminal amine groups. Structural optimization and normal mode analysis were obtained for G0 by the density functional theory (DFT). Optimized geometric bond length and angles obtained by DFT show good agreement with experiment. The amine terminal groups are characterized by the well-defined bands at 3321, 3238, 1614cm(-1) in the experimental IR spectrum and by bands at 3327, 3241cm(-1) in the Raman spectrum of G0. The experimental frequencies of asymmetric and symmetric NH2 stretching vibrations of amine group are lower than theoretical values due to intramolecular NH⋯S hydrogen bond. This hydrogen bond is also responsible for higher experimental infrared intensity of these bands as compared with theoretical values. Relying on DFT calculations a complete vibrational assignment is proposed for the studied dendrimer. PMID:27179692

  5. Water - Based TiO2 Suspensions: A Raman Study

    NASA Astrophysics Data System (ADS)

    Rangel, Roberto; Chipara, Dorina; Yust, Brian; Padilla, Desiree; Chipara, Mircea

    The antibacterial features of TiO2 are under scrutiny due to the UV radiation, which contributes to the generation of reactive oxygen species, mainly in water environments. A study of TiO2 suspensions in water and broth is reported. TiO2 has a low solubility in water. TiO2 (anatase), with average diameter of 15 nm from Nanostructured & Amorphous Materials, Inc. has been added to the fluid (water, broth) and the mixture was stirred for 1-10 h, followed by a 10-60 minutes sonication. The suspension was left to sediment for 1 day before measurements. Quasistable suspensions of TiO2 in water and broth were investigated by Raman spectroscopy using a Renishaw InVia spectrometer operating at 532 and 785 nm. The spectra of the nanofiller have been simulated by a collection of Breit-Wigner Fano line shapes and the effect of the preparation conditions (stirring and sonication time) on the parameters of Raman lines are reported. The differences are explained by observing that the sonication destroys the agglomerates of anatase resulting in a better dispersion of nanoparticles and consequently a longer sedimentation time. Sample preparation/storage have been done both under dark and UV light conditions.

  6. Comparative studies by IR, Raman, and surface-enhanced Raman spectroscopy of azodicarbonamide, biurea and semicarbazide hydrochloride

    NASA Astrophysics Data System (ADS)

    Xie, Yunfei; Li, Pei; Zhang, Jin; Wang, Heya; Qian, He; Yao, Weirong

    2013-10-01

    Azodicarbonamide is widely applied in the food industry as a new flour gluten fortifier in China, Canada, the United States, and some other countries, whose metabolites of biurea and semicarbazide hydrochloride are reaction products during baking. In this study, IR, Raman and surface-enhanced Raman scattering (SERS) spectra of azodicarbonamide, biurea, and semicarbazide hydrochloride have been studied, and vibrational bands have been assigned on the basis of density functional theory (DFT) calculations. The calculated Raman spectra were in good agreement with experimental Raman spectra. The SERS method coupled with active gold substrates has also been applied for detection of the three chemicals with pure water as solvent, with the limit of detection of this method being as low as 10 μg/mL (less than 45 μg/mL). These results showed that azodicarbonamide and its metabolites could be detected by the vibrational spectra technique, which might be applied as a powerful tool for the rapid detection on these species derived from agents added to flour.

  7. Observation of structural relaxation during exciton self-trapping via excited-state resonant impulsive stimulated Raman spectroscopy

    SciTech Connect

    Mance, J. G.; Felver, J. J.; Dexheimer, S. L.

    2015-02-28

    We detect the change in vibrational frequency associated with the transition from a delocalized to a localized electronic state using femtosecond vibrational wavepacket techniques. The experiments are carried out in the mixed-valence linear chain material [Pt(en){sub 2}][Pt(en){sub 2}Cl{sub 2}]⋅(ClO{sub 4}){sub 4} (en = ethylenediamine, C{sub 2}H{sub 8}N{sub 2}), a quasi-one-dimensional system with strong electron-phonon coupling. Vibrational spectroscopy of the equilibrated self-trapped exciton is carried out using a multiple pulse excitation technique: an initial pump pulse creates a population of delocalized excitons that self-trap and equilibrate, and a time-delayed second pump pulse tuned to the red-shifted absorption band of the self-trapped exciton impulsively excites vibrational wavepacket oscillations at the characteristic vibrational frequencies of the equilibrated self-trapped exciton state by the resonant impulsive stimulated Raman mechanism, acting on the excited state. The measurements yield oscillations at a frequency of 160 cm{sup −1} corresponding to a Raman-active mode of the equilibrated self-trapped exciton with Pt-Cl stretching character. The 160 cm{sup −1} frequency is shifted from the previously observed wavepacket frequency of 185 cm{sup −1} associated with the initially generated exciton and from the 312 cm{sup −1} Raman-active symmetric stretching mode of the ground electronic state. We relate the frequency shifts to the changes in charge distribution and local structure that create the potential that stabilizes the self-trapped state.

  8. Observation of structural relaxation during exciton self-trapping via excited-state resonant impulsive stimulated Raman spectroscopy.

    PubMed

    Mance, J G; Felver, J J; Dexheimer, S L

    2015-02-28

    We detect the change in vibrational frequency associated with the transition from a delocalized to a localized electronic state using femtosecond vibrational wavepacket techniques. The experiments are carried out in the mixed-valence linear chain material [Pt(en)2][Pt(en)2Cl2]⋅(ClO4)4 (en = ethylenediamine, C2H8N2), a quasi-one-dimensional system with strong electron-phonon coupling. Vibrational spectroscopy of the equilibrated self-trapped exciton is carried out using a multiple pulse excitation technique: an initial pump pulse creates a population of delocalized excitons that self-trap and equilibrate, and a time-delayed second pump pulse tuned to the red-shifted absorption band of the self-trapped exciton impulsively excites vibrational wavepacket oscillations at the characteristic vibrational frequencies of the equilibrated self-trapped exciton state by the resonant impulsive stimulated Raman mechanism, acting on the excited state. The measurements yield oscillations at a frequency of 160 cm(-1) corresponding to a Raman-active mode of the equilibrated self-trapped exciton with Pt-Cl stretching character. The 160 cm(-1) frequency is shifted from the previously observed wavepacket frequency of 185 cm(-1) associated with the initially generated exciton and from the 312 cm(-1) Raman-active symmetric stretching mode of the ground electronic state. We relate the frequency shifts to the changes in charge distribution and local structure that create the potential that stabilizes the self-trapped state. PMID:25725733

  9. Raman spectroscopy: an evolving technique for live cell studies.

    PubMed

    Smith, Rachael; Wright, Karen L; Ashton, Lorna

    2016-06-21

    One of the most exciting developments in Raman spectroscopy in the last decade has been its application to cells and tissues for diagnostic and pharmaceutical applications, and in particular its use in the analysis of cellular dynamics. Raman spectroscopy is rapidly advancing as a cell imaging method that overcomes many of the limitations of current techniques and is earning its place as a routine tool in cell biology. In this review we focus on important developments in Raman spectroscopy that have evolved into the exciting technique of live-cell Raman microscopy and highlight some of the most recent and significant applications to cell biology. PMID:27072718

  10. Raman spectrometric studies of selected lanthanide tribromides and trichlorides

    SciTech Connect

    Daniel, J.F.

    1988-03-01

    Laser Raman spectroscopy was used to identify the crystal structures of lanthanide and actinide compounds. The phonon Raman spectrum is characteristic of the particular crystal structure. GdCl/sub 3/ exhibits two crystal structures, the UCl/sub 3/-type hexagonal and the PuBr/sub 3/-type orthorhombic. In the literature it is reported that the low temperature form is orthorhombic; results of experiments here suggest that it is hexagonal. Interconversion between these two forms can be accomplished with temperature andor pressure. In the present work laser Raman spectrometry was used to monitor crystal structure changes in GdCl/sub 3/ as a function of temperature or pressure to determine the temperature or pressure at which the hexagonal-to-orthorhombic transformation occurs. Raman spectroscopy was also used to determine the symmetry assignments for the Raman-active bands of a single crystal. Raman spectra of polycrystalline NdBr/sub 3/ have been recorded at room temperature and pressure and at approximately 100/degree/K. In addition, polarized Raman spectra of a single crystal NdBr/sub 3/ have been measured. Based on these polarization measurements, symmetry assignments of eight Raman-active modes were made. These assignments are useful in interpreting the phonon Raman spectrum of any compound exhibiting the PuBr/sub 3/-type orthorhombic structure. 24 figs., 5 tabs.

  11. Investigation of magnetic field enriched surface enhanced resonance Raman scattering performance using Fe3O4@Ag nanoparticles for malaria diagnosis

    NASA Astrophysics Data System (ADS)

    Yuen, Clement; Liu, Quan

    2014-03-01

    Recently, we have demonstrated the magnetic field-enriched surface-enhanced resonance Raman spectroscopy (SERRS) of β-hematin by using nanoparticles with iron oxide core and silver shell (Fe3O4@Ag) for the potential application in the early malaria diagnosis. In this study, we investigate the dependence of the magnetic field-enriched SERRS performance of β-hematin on the different core and shell sizes of the Fe3O4@Ag nanoparticles. We note that the core and shell parameters are critical in the realization of the optimal magnetic field-enrich SERRS β-hematin signal. These results are consistent with our simulations that will guide the optimization of the magnetic SERRS performance for the potential early diagnosis in the malaria disease.

  12. A new combined nuclear magnetic resonance and Raman spectroscopic probe applied to in situ investigations of catalysts and catalytic processes

    SciTech Connect

    Camp, Jules C. J.; Mantle, Michael D.; York, Andrew P. E.; McGregor, James

    2014-06-15

    Both Raman and nuclear magnetic resonance (NMR) spectroscopies are valuable analytical techniques capable of providing mechanistic information and thereby providing insights into chemical processes, including catalytic reactions. Since both techniques are chemically sensitive, they yield not only structural information but also quantitative analysis. In this work, for the first time, the combination of the two techniques in a single experimental apparatus is reported. This entailed the design of a new experimental probe capable of recording simultaneous measurements on the same sample and/or system of interest. The individual datasets acquired by each spectroscopic method are compared to their unmodified, stand-alone equivalents on a single sample as a means to benchmark this novel piece of equipment. The application towards monitoring reaction progress is demonstrated through the evolution of the homogeneous catalysed metathesis of 1‑hexene, with both experimental techniques able to detect reactant consumption and product evolution. This is extended by inclusion of magic angle spinning (MAS) NMR capabilities with a custom made MAS 7 mm rotor capable of spinning speeds up to 1600 Hz, quantified by analysis of the spinning sidebands of a sample of KBr. The value of this is demonstrated through an application involving heterogeneous catalysis, namely the metathesis of 2-pentene and ethene. This provides the added benefit of being able to monitor both the reaction progress (by NMR spectroscopy) and also the structure of the catalyst (by Raman spectroscopy) on the very same sample, facilitating the development of structure-performance relationships.

  13. Guided-mode-resonance-coupled plasmonic-active SiO2 nanotubes for surface enhanced Raman spectroscopy

    PubMed Central

    Xu, Xiaobin; Hasan, Dihan; Wang, Lei; Chakravarty, Swapnajit; Chen, Ray T.; Fan, D. L.; Wang, Alan X.

    2012-01-01

    We demonstrate a surface enhanced Raman scattering (SERS) substrate by integrating plasmonic-active SiO2 nanotubes into Si3N4 gratings. First, the dielectric grating that is working under guided mode resonance (GMR) provides enhanced electric field for localized surface plasmon polaritons on the surface of metallic nanoparticles. Second, we use SiO2 nanotubes with densely assembled silver nanoparticles to provide a large amount of “hot spots” without significantly damping the GMR mode of the grating. Experimental measurement on Rhodamine-6G shows a constant enhancement factor of 8 ∼ 10 in addition to the existing SERS effect across the entire surface of the SiO2 nanotubes. PMID:22685345

  14. The first detection of the 3A g- state in carotenoids using resonance-Raman excitation profiles

    NASA Astrophysics Data System (ADS)

    Furuichi, Kentaro; Sashima, Tokutake; Koyama, Yasushi

    2002-04-01

    The singlet 3A g- state that had been theoretically predicted in shorter polyenes [P. Tavan and K. Schulten J. Chem. Phys. 85 (1986) 6602; Phys. Rev. B 36 (1987) 4337] was first identified in bacterial carotenoids by measurements of resonance-Raman excitation profiles. It is almost overlapped with the 1B u+ state in spheroidene (the number of conjugated double bonds, n=10), and located in-between the 1B u+ and 1B u- states in lycopene, anhydrorhodovibrin and spirilloxanthin ( n=11-13). The slopes when the 2A g--, 1B u-- and 3A g--state energies were expressed as linear functions of 1/(2 n+1) exhibited the ratio of 2:3.1:3.8 in excellent agreement with that theoretically predicted, 2:3.1:3.7.

  15. Guided-Mode Resonance Grating with Self-Assembled Silver Nanoparticles for Surface-Enhanced Raman Scattering Spectroscopy

    PubMed Central

    Chong, Xinyuan; Fan, Donglei; Chakravarty, Swapnajit; Wang, Zheng; Chen, Ray T.; Wang, Alan X.

    2016-01-01

    We designed and fabricated guided-mode resonance (GMR) gratings on indium-tin-oxide (ITO) thin film to generate a significantly enhanced local electric field for surface-enhanced Raman scattering (SERS) spectroscopy. Ag nanoparticles (NPs) were self-assembled onto the surface of the grating, which can provide a large amount of “hot-spots” for SERS sensing. The ITO gratings also exhibit excellent tolerance to fabrication deviations due to the large refractive index contrast of the ITO grating. Quantitative experimental results of 5,5’-dithiobis(2-nitrobenzoic acid) (DTNB) demonstrate the best enhancement factor of ~14× on ITO gratings when compared with Ag NPs on a flat ITO film, and the limit of detection (LOD) of DTNB is as low as 10 pM. PMID:26958546

  16. Excitation dependent Raman studies of self-seeded grown InN nanoparticles with different carrier concentration.

    PubMed

    Madapu, Kishore K; Polaki, S R; Dhara, Sandip

    2016-07-21

    High quality InN nanoparticles are grown using an atmospheric chemical vapour deposition technique via a self-seeded catalytic approach in the temperature range of 580-650 °C. In this temperature region, the nucleation barrier of InN is overcome by seeding low density In nanoparticles prior to introduction of reactive NH3. Samples with increasing carrier densities are grown, with the help of increasing growth temperature, to understand the role of carrier density in the optical phonon structure. Near-resonance Raman spectra show completely different phonon pictures compared to those for the off-resonance spectra. A Raman forbidden mode of B1(high), because of the possible breakdown of selection rules in the near-resonance conditions, is invoked for the first time. The intensity and frequency of this mode strongly depend on the carrier concentration in the sample. In off-resonance conditions, the A1(LO) mode for the sample with higher carrier concentration is dominated by Fano interference rather than plasmon-phonon coupling. Variation of the intensity of the B1(high) mode is correlated with a band filling effect, which is substantiated by the luminescence studies of the InN samples with different carrier concentrations. PMID:27345503

  17. Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

    NASA Astrophysics Data System (ADS)

    Suzuki, Atsushi; Oku, Takeo

    2016-02-01

    Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of 13C, 14N and 1H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in 13C, 14N and 1H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

  18. Structural analysis of molybdo-zinc-phosphate glasses: Neutron scattering, FTIR, Raman scattering, MAS NMR studies

    NASA Astrophysics Data System (ADS)

    Renuka, C.; Shinde, A. B.; Krishna, P. S. R.; Reddy, C. Narayana

    2016-08-01

    Vitreous samples were prepared in the xMoO3-17ZnO-(83-x) NaPO3 with 35 ≥ x ≥ 55 glass forming system by energy efficient microwave heating method. Structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), Raman scattering, Magic Angle Spin Nuclear magnetic resonance (MAS NMR) and Neutron scattering. Addition of MoO3 to the ZnO-NaPO3 glass leads to a pronounced increase in glass transition temperature (Tg) suggesting a significant increase in network connectivity and strength. In order to analyze FTIR and Raman scattering, a simple structural model is presented to rationalize the experimental observations. A number of structural units are formed due to network modification, and the resulting glass may be characterized by a network polyhedral with different numbers of unshared corners. 31P MAS NMR confirms a clear distinction between structural species having 3, 2, 1, 0 bridging oxygens (BOs). Further, Neutron scattering studies were used to probe the structure of these glasses. The result suggests that all the investigated glasses have structures based on chains of four coordinated phosphate and six coordinated molybdate units, besides, two different lengths of P-O bonds in tetrahedral phosphate units that are assigned to bonds of the P-atom with terminal and bridging oxygen atoms.

  19. High pressure Raman scattering study on the phase stability of LuVO{sub 4}

    SciTech Connect

    Rao, Rekha; Garg, Alka B.; Sakuntala, T.; Achary, S.N.; Tyagi, A.K.

    2009-07-15

    High pressure Raman spectroscopic investigations have been carried out on rare earth orthovanadate LuVO{sub 4} upto 26 GPa. Changes in the Raman spectrum around 8 GPa across the reported zircon to scheelite transition are investigated in detail and compared with those observed in other vanadates. Co-existence of the zircon and scheelite phases is observed over a pressure range of about 8-13 GPa. The zircon to scheelite transition is irreversible upon pressure release. Subtle changes are observed in the Raman spectrum above 16 GPa which could be related to scheelite reversible fergusonite transition. Pressure dependencies of the Raman active modes in the zircon and the scheelite phases are reported. - Graphical abstract: Study of scheelite-fergusonite transition in RVO{sub 4} by Raman spectroscopy is rare. Here we report Raman spectroscopic investigations of LuVO{sub 4} at high pressure to obtain insight into nature of post-scheelite phases.

  20. Vibrational properties of epitaxial Bi4Te3 films as studied by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Xu, Hao; Song, Yuxin; Pan, Wenwu; Chen, Qimiao; Wu, Xiaoyan; Lu, Pengfei; Gong, Qian; Wang, Shumin

    2015-08-01

    Bi4Te3, as one of the phases of the binary Bi-Te system, shares many similarities with Bi2Te3, which is known as a topological insulator and thermoelectric material. We report the micro-Raman spectroscopy study of 50 nm Bi4Te3 films on Si substrates prepared by molecular beam epitaxy. Raman spectra of Bi4Te3 films completely resolve the six predicted Raman-active phonon modes for the first time. Structural features and Raman tensors of Bi4Te3 films are introduced. According to the wavenumbers and assignments of the six eigenpeaks in the Raman spectra of Bi4Te3 films, it is found that the Raman-active phonon oscillations in Bi4Te3 films exhibit the vibrational properties of those in both Bi and Bi2Te3 films.

  1. Two-dimensional stimulated resonance Raman spectroscopy of molecules with broadband x-ray pulses

    PubMed Central

    Biggs, Jason D.; Zhang, Yu; Healion, Daniel; Mukamel, Shaul

    2012-01-01

    Expressions for the two-dimensional stimulated x-ray Raman spectroscopy (2D-SXRS) signal obtained using attosecond x-ray pulses are derived. The 1D- and 2D-SXRS signals are calculated for trans-N-methyl acetamide (NMA) with broad bandwidth (181 as, 14.2 eV FWHM) pulses tuned to the oxygen and nitrogen K-edges. Crosspeaks in 2D signals reveal electronic Franck-Condon overlaps between valence orbitals and relaxed orbitals in the presence of the core-hole. PMID:22583220

  2. Hydrogen bonding of sulfur ligands in blue copper and iron-sulfur proteins: detection by resonance raman spectroscopy

    SciTech Connect

    Mino, Y.; Loehr, T.M.; Wada, K.; Matsubara, H.; Sanders-Loehr, J.

    1987-12-15

    The resonance Raman spectrum of the blue copper protein azurin from Alcaligenes denitrificans exhibits nine vibrational modes between 330 and 460 cm/sup -1/, seven of which shift 0.4-3.0 cm/sup -1/ to lower energy after incubation of the protein in D/sub 2/O. These deuterium-dependent shifts have been previously ascribed to exchangeable protons on imidazole ligands or to exchangeable protons on amide groups which are hydrogen bonded to the cysteine thiolate ligands (a feature common to all blue copper proteins of known structure). In order to distinguish between these two possibilities, a systematic investigation of Fe/sub 2/S/sub 2/(Cys)/sub 4/-containing proteins was undertaken. Extensive hydrogen bonding between sulfur ligands and the polypeptide backbone had been observed in the crystal structure of ferredoxin from Spirulina platensis. The resonance Raman spectrum of this protein is typical of a chloroplast-type ferredoxin and exhibits deuterium-dependent shifts of -0.3 to -0.5 cm/sup -1/ in the Fe-S modes at 283, 367, and 394 cm/sup -1/ and -0.6 to -0.8 cm/sup -1/ in the Fe-S modes at 328 and 341 cm/sup -1/. Considerably greater deuterium sensitivity is observed in the Raman spectra of spinach ferredoxin and bovine adrenodoxin, particularly for the symmetric stretching vibration of the Fe/sub 2/S/sub 2/ moiety at approx. 390 cm/sup -1/. This feature decreases of 9.8 and 1.1 cm/sup -1/, respectively, for the two oxidized proteins in D/sub 2/O and by 1.8 cm/sup -1/ for reduced adrenodoxin in D/sub 2/O. These results suggest that the bridging sulfido groups may be more extensively hydrogen bonded in spinach ferredoxin and adrenodoxin than in S. platensis ferredoxin, with a further increase in hydrogen-bond strength in the reduced form of adrenodoxin.

  3. A computational study on surface-enhanced Raman spectroscopy of para-substituted Benzenethiol derivatives adsorbed on gold nanoclusters.

    PubMed

    You, Tingting; Liang, Xiu; Gao, Yukun; Yin, Penggang; Guo, Lin; Yang, Shihe

    2016-01-01

    We presented a computational study on para-substituted Benzenethiol (x-BT, x=H, F, Cl, Br, OH, SH, SeH, NH2, CH3) derivatives interacting with gold cluster for chemical effects related to surface-enhanced Raman spectroscopy (SERS). Density functional theory (DFT) calculations were performed on a series of bridge-type and vertex type x-BT/Au13 complexes for geometric, electronic and excitation properties to determine the key factor in spectral enhancement. Results indicated that off-resonance enhancement factors of bridge-type and vertex-type complexes exhibited different dependency on substitutions, which was greatly influenced by molecule-cluster transitions instead of properties such as interaction energy and charge transfer due to same origination for off-resonance and resonance chemical enhancement. PMID:26231778

  4. A computational study on surface-enhanced Raman spectroscopy of para-substituted Benzenethiol derivatives adsorbed on gold nanoclusters

    NASA Astrophysics Data System (ADS)

    You, Tingting; Liang, Xiu; Gao, Yukun; Yin, Penggang; Guo, Lin; Yang, Shihe

    2016-01-01

    We presented a computational study on para-substituted Benzenethiol (x-BT, x = H, F, Cl, Br, OH, SH, SeH, NH2, CH3) derivatives interacting with gold cluster for chemical effects related to surface-enhanced Raman spectroscopy (SERS). Density functional theory (DFT) calculations were performed on a series of bridge-type and vertex type x-BT/Au13 complexes for geometric, electronic and excitation properties to determine the key factor in spectral enhancement. Results indicated that off-resonance enhancement factors of bridge-type and vertex-type complexes exhibited different dependency on substitutions, which was greatly influenced by molecule-cluster transitions instead of properties such as interaction energy and charge transfer due to same origination for off-resonance and resonance chemical enhancement.

  5. Rhombohedral Multilayer Graphene: A Magneto-Raman Scattering Study.

    PubMed

    Henni, Younes; Ojeda Collado, Hector Pablo; Nogajewski, Karol; Molas, Maciej R; Usaj, Gonzalo; Balseiro, Carlos A; Orlita, Milan; Potemski, Marek; Faugeras, Clement

    2016-06-01

    Graphene layers are known to stack in two stable configurations, namely, ABA or ABC stacking, with drastically distinct electronic properties. Unlike the ABA stacking, little has been done to experimentally investigate the electronic properties of ABC graphene multilayers. Here, we report on the first magneto optical study of a large ABC domain in a graphene multilayer flake, with ABC sequences exceeding 17 graphene sheets. ABC-stacked multilayers can be fingerprinted with a characteristic electronic Raman scattering response, which persists even at room temperatures. Tracing the magnetic field evolution of the inter Landau level excitations from this domain gives strong evidence for the existence of a dispersionless electronic band near the Fermi level, characteristic of such stacking. Our findings present a simple yet powerful approach to probe ABC stacking in graphene multilayer flakes, where this highly degenerated band appears as an appealing candidate to host strongly correlated states. PMID:27164265

  6. Enhanced Raman spectroscopic study of rotational isomers on metal surfaces

    NASA Technical Reports Server (NTRS)

    Loo, B. H.; Lee, Y. G.; Frazier, D. O.

    1986-01-01

    Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

  7. A Raman Spectroscopic Study of Kernite to 25 GPa

    NASA Astrophysics Data System (ADS)

    Silva, M. E.; O'Bannon, E. F., III; Williams, Q. C.

    2015-12-01

    A Raman spectroscopic study of kernite to 25 GPaMarcus Silva, Earl O'Bannon III, and Quentin Williams Department of Earth & Planetary Sciences, University of California Santa Cruz The Raman spectrum of kernite (Na2B4O6(OH)2·3(H2O)) has been characterized up to ~25 GPa in order to explore pressure-induced changes in a structurally novel mineral that contains mixed coordination borate groups (three- and four-fold), and both hydroxyl units and water. During compression, all of the ~30 modes monitored shift positively and monotonically until ~2.2 GPa where a few low frequency modes disappear and tetrahedral borate modes merge. The low frequency modes that disappear at ~2.2 GPa are likely associated with Na vibrations, and their disappearance suggests that dramatic changes occur in the Na sites at ~2.2 GPa. The merging of the boron bending and stretching modes at ~2.2 GPa suggests that the local symmetry of the BO4 tetrahedra changes at this pressure, and likely becomes more symmetric. The remaining modes shift positively up to ~7.4 GPa where a second notable change occurs. All but 5 modes (with initial frequencies of 150, 166, 289, 307, and 525 cm-1) disappear at ~7.4 GPa. This indicates that a second phase transition has occurred which affects both the BO3H and BO4­ groups: based on the loss of modes, this transition may be associated with disordering of the crystal. These 5 modes persist and shift monotonically up to ~25 GPa. On decompression, the 5 modes shift smoothly down to ~2.0 GPa where a few new modes appear in the spectrum. When fully decompressed to room pressure, the Raman spectrum of the recovered sample is significantly different from the ambient spectrum of the initial sample. Thus, our results are suggest a phase transition occurring at 2.2 GPa with changes in the Na and tetrahedral boron sites, followed by an additional transition at 7.4 GPa that may involve disordering of the crystal. In the latter transition, at least the BO3H groups appear to be

  8. Interference effects in Auger resonant Raman spectra of CO via selective vibrational excitations across the O 1s{yields}2{pi} resonance

    SciTech Connect

    Tanaka, T.; Shindo, H.; Kitajima, M.; Tanaka, H.; Makochekanwa, C.; De Fanis, A.; Tamenori, Y.; Okada, K.; Feifel, R.; Sorensen, S.; Kukk, E.; Ueda, K.

    2005-08-15

    The Auger resonant Raman spectra of CO, arising from the transitions to the X and A final electronic states of CO{sup +}, have been recorded at photon energies corresponding to the vibrational excitations v{sup '}=3,5, and 8 in the O 1s{yields}2{pi} resonance. The spectra are simulated within the model that takes into account both the lifetime-vibrational interference (LVI) and interference with the nonresonant photoemission. The spectroscopic parameters, {omega}{sub e}, {omega}{sub e}x{sub e}, {gamma} and r{sub e}, of the O 1s{sup -1}2{pi} core-excited state, necessary for the simulation, have been derived by fitting the Franck-Condon simulation to the total ion yield spectrum, assuming a Morse potential for the O 1s{sup -1}2{pi} state. Not only the LVI but also the interference with the nonresonant photoemission turn out to be significant.

  9. Natural and synthetic gas hydrates studied by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Savy, Jean-Philippe; Bigalke, Nikolaus; Aloisi, Giovanni; Kossel, Elke; Pansegrau, Moritz; Haeckel, Matthias

    2010-05-01

    Over the past decade, the interest in using CH4-hydrates as an energy resource and CO2-hydrates as a storage option for anthropogenic CO2 has grown in the scientific community as well as in the oil and gas industry. Among all the techniques used to characterize gas hydrates, the non-destructive, non-invasive Raman spectroscopy provides significant insights into the structure and composition of hydrates. In this study, we compare gas hydrates synthetically produced in the laboratory with natural hydrate samples collected from marine sediments. CO2 and CH4 gas hydrates were investigated with a high-resolution Raman microscope at in-situ p-T conditions. A water-filled glass capillary (inner diameter: 1.7 mm) was placed in a stainless steel cell, which was sealed, cooled down to 3.6 ° C and pressurized to 60 bar with liquid CO2. Video images taken after 1 h revealed droplets (~10 μm in diameter) trapped in the ice-like solid. The two Fermi dyads of CO2 in the liquid and hydrate phase at 1274 & 1381 cm1 and 1280 & 1384 cm-1, respectively, confirm the presence of liquid CO2 droplets trapped in a CO2-hydrate matrix. Equivalent experiments were conducted with CH4 gas at 1 ° C and 90 bar. The nucleation of CH4-hydrate was followed in the Raman spectral region of the C-H stretching mode. At the early stage of the nucleation, the peak at 2915 cm-1 (CH4 in small cages) was stronger than the one at 2904 cm-1 (CH4 in large cages) indicating that methane starts to populate the small 512 cages of the s-I hydrate structure first and then, as nucleation continues, the large cages are stabilized leading to a quickly growing peak at 2904 cm-1 until a final peak intensity ratio of 3.7 is established. In contrast to other studies, intermediate stabilization of the s-II structure was not observed. Video images confirmed the absence of gas inclusions. The hydrate density, 1.1 & 0.9 for CO2-hydrate and CH4-hydrate respectively, compared to the one of water may explain the formation of

  10. Aggregation-Induced Resonance Raman Optical Activity (AIRROA) and Time-Dependent Helicity Switching of Astaxanthin Supramolecular Assemblies.

    PubMed

    Dudek, Monika; Zajac, Grzegorz; Kaczor, Agnieszka; Baranska, Malgorzata

    2016-08-18

    New methods for enhancing the Raman optical activity (ROA) signal are desirable due to the low efficiency of ROA, demanding otherwise high sample concentrations, high laser powers, and/or long acquisition times. Previously, we have demonstrated a new phenomenon, aggregation-induced resonance ROA (AIRROA), that produces significant enhancement of the ROA signal provided that the excitation wavelength coincides with the absorption of the measured species and that the electronic circular dichroism (ECD) signal in the range of this absorption is nonzero. In this work, analyzing three very different supramolecular astaxanthin aggregates (H1, H2, and J), we confirm the phenomenon and demonstrate that aggregation itself is not enough to enhance the ROA signal and that the above-mentioned conditions are necessary for induction of the resonance ROA effect. Additionally, by analyzing the changes in the ECD spectra of the H1 assembly, we demonstrate that the supramolecular helicity sign switches with time, which is dependent on the prevalence of kinetic or thermodynamic stabilization of the obtained aggregates. PMID:27438433

  11. Solvent Effects on the Coexistence of Localized and Delocalized 4,4′-Dinitrotolane Radical Anion by Resonance Raman Spectroscopy

    SciTech Connect

    Zink, J.I.; Wu, Q.; Hoekstra, R.M.; Telo, J.P.; Stephenson, R.M.; Nelsen, S.F.

    2010-07-07

    The resonance Raman spectrum of the simple alkyne bridge in 4,4{prime}-dinitrotolane radical anion shows two distinct bands, providing proof of the solvent-dependent coexistence of charge-localized and -delocalized species. The Raman spectra of normal modes primarily involving the charge-bearing ?PhNO{sub 2} units also support the coexistence of two solvent-dependent electronic species. The temperature dependence of the spectra of the bridging unit shows an inverse relationship between the solvent reorganization energy ({lambda}{sub s}) and the temperature.

  12. Observation of x-ray resonant Raman scattering: The early days

    SciTech Connect

    Sparks, C.J.

    1995-12-31

    My early observation of Raman scattering came as a serendipitous by-product of our efforts to achieve the best possible signal for x-ray fluorescent analysis. We were also investigating the x-ray spectrum produced by a monochromatic x-ray beam striking metal targets which might contribute to the inelastic background. This background could contaminate the very weak diffusively distributed elastically scattered radiation associated with defects in the perfect periodicity of crystals. Energy analysis of the x-ray spectra created by monochromatic Cu K{sub {alpha}} and Mo K{sub {alpha}} radiation impinging on highly pure metal targets showed an inelastically scattered intensity related to the energy difference between the exciting radiation and the nearest bound state. Confirmation of these observations and availability of synchrotron radiation has led to wide application of this new x-ray spectroscopy in atomic physics including its use as a probe of the unoccupied density of states.

  13. Dissecting X-Ray Raman Resonances Using Four-Wave Mixing

    SciTech Connect

    Biggs, Jason D.; Zhang, Yu; Healion, Daniel; Govind, Niranjan; Shaul, Mukamel; Chergui, M.; Taylor, A.; Cundiff, S.; de Vivie-Riedle, R.; Yamagouchi, K.

    2013-01-01

    The stimulated x-ray Raman signal has been calculated for the amino acid cysteine using broadband (FWHM ≃14.2eV, 128 as) pulses tuned to the nitrogen K-edge. Peaks correspond to those valence excited states and reveal electronic Frank-Condon overlaps between canonical valence orbitals and relaxed orbitals in the presence of the core hole. The coupling between excited states with valence- and core-holes is further explored using a coherent, wave-vector matched photon echo technique, where it is possible to eliminate stimulated emission and excited-state absorption by taking the waiting time to be longer the lifetime of the core hole (~ 7:1 fs for nitrogen).

  14. Alpha resonant scattering for astrophysical reaction studies

    NASA Astrophysics Data System (ADS)

    Yamaguchi, H.; Kahl, D.; Nakao, T.; Wakabayashi, Y.; Kubano, S.; Hashimoto, T.; Hayakawa, S.; Kawabata, T.; Iwasa, N.; Teranishi, T.; Kwon, Y. K.; Binh, D. N.; Khiem, L. H.; Duy, N. G.

    2014-05-01

    Several alpha-induced astrophysical reactions have been studied at CRIB (CNS Radioactive Ion Beam separator), which is a low-energy RI beam separator at Center for Nuclear Study (CNS) of the University of Tokyo. One of the methods to study them is the α resonant scattering using the thick-target method in inverse kinematics. Among the recent studies at CRIB, the measurement of 7Be+α resonant scattering is discussed. Based on the result of the experiment, we evaluated the contributions of high-lying resonances for the 7Be(α,γ) reaction, and proposed a new cluster band in 11C.

  15. Alpha resonant scattering for astrophysical reaction studies

    SciTech Connect

    Yamaguchi, H.; Kahl, D.; Nakao, T.; Wakabayashi, Y.; Kubano, S.; Hashimoto, T.; Hayakawa, S.; Kawabata, T.; Iwasa, N.; Teranishi, T.; Kwon, Y. K.; Binh, D. N.; Khiem, L. H.; Duy, N. G.

    2014-05-02

    Several alpha-induced astrophysical reactions have been studied at CRIB (CNS Radioactive Ion Beam separator), which is a low-energy RI beam separator at Center for Nuclear Study (CNS) of the University of Tokyo. One of the methods to study them is the α resonant scattering using the thick-target method in inverse kinematics. Among the recent studies at CRIB, the measurement of {sup 7}Be+α resonant scattering is discussed. Based on the result of the experiment, we evaluated the contributions of high-lying resonances for the {sup 7}Be(α,γ) reaction, and proposed a new cluster band in {sup 11}C.

  16. Micro-Raman spectroscopy study of ALVAC virus infected chicken embryo cells

    NASA Astrophysics Data System (ADS)

    Misra, Anupam K.; Kamemoto, Lori E.; Hu, Ningjie; Dykes, Ava C.; Yu, Qigui; Zinin, Pavel V.; Sharma, Shiv K.

    2011-05-01

    Micro- Raman spectroscopic investigation of ALVAC virus and of normal chicken embryo fibroblast cells and the cells infected with ALVAC virus labeled with green fluorescence protein (GFP) were performed with a 785 nm laser. Good quality Micro-Raman spectra of the Alvac II virus were obtained. These spectra show that the ALVAC II virus contains buried tyrosine residues and the coat protein of the virus has α-helical structure. A comparison of Raman spectra of normal and virus infected chicken embryo fibroblast cells revealed that the virus infected cells show additional bands at 535, 928, and 1091 cm-1, respectively, corresponding to δ(C-O-C) glycosidic ring, protein α-helix, and DNA (O-P-O) modes. In addition, the tyrosine resonance double (833 and 855 cm-1) shows reversal in the intensity of the higher-frequency band as compared to the normal cells that can be used to identify the infected cells. In the C-H stretching region, the infected cells show bands with higher intensity as compared to that of the corresponding bands in the normal cells. We also found that the presence of GFP does not affect the Raman spectra of samples when using a 785 nm micro-Raman system because the green fluorescence wavelength of GFP is well below the Stokes-Raman shifted spectral region.

  17. Molecular vibrational dynamics in water studied by femtosecond coherent anti-Stokes Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhao, Yang; Zhang, Sheng; Zhou, Boyang; Dong, Zhiwei; Chen, Deying; Zhang, Zhonghua; Xia, Yuanqin

    2014-10-01

    We utilized femtosecond time-resolved coherent anti-Stokes Raman spectroscopy (CARS) to study the ultrafast vibrational dynamics in distilled water at room temperature. The CARS signals from the broad OH-stretching modes between 3100 cm-1 and 3700 cm-1 were obtained and analyzed. The dephasing times of four Raman modes in water were detected and compared.

  18. Studies of Minerals, Organic and Biogenic Materials through Time-Resolved Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Garcia, Christopher S.; Abedin, M. Nurul; Ismail, Syed; Sharma, Shiv K.; Misra, Anupam K.; Nyugen, Trac; Elsayed-Ali, hani

    2009-01-01

    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.

  19. The pH dependent Raman spectroscopic study of caffeine

    NASA Astrophysics Data System (ADS)

    Kang, Jian; Gu, Huaimin; Zhong, Liang; Hu, Yongjun; Liu, Fang

    2011-02-01

    First of all the surface enhanced Raman spectroscopy (SERS) and normal Raman spectra of caffeine aqueous solution were obtained at different pH values. In order to obtain the detailed vibrational assignments of the Raman spectroscopy, the geometry of caffeine molecule was optimized by density functional theory (DFT) calculation. By comparing the SERS of caffeine with its normal spectra at different pH values; it is concluded that pH value can dramatically affect the SERS of caffeine, but barely affect the normal Raman spectrum of caffeine aqueous solution. It can essentially affect the reorientation of caffeine molecule to the Ag colloid surface, but cannot impact the vibration of functional groups and chemical bonds in caffeine molecule.

  20. Raman scattering studies and charge transport in polyfluorenes

    NASA Astrophysics Data System (ADS)

    Arif, Mohammad Ali Iftekhar

    Organic semiconductors, such as short-chain oligomers and long-chain polymers, are now a core constituent in numerous organic and organic-inorganic hybrid technologies. Blue-emitting polyfluorenes (PFs) have emerged as especially attractive pi conjugated polymers (CP) due to their high luminescence efficiency and excellent electronic properties and thus great prospects for device applications. The performance of devices based on these polymers depends on side chain conformations, overall crystalline structure, and charge transport processes at the microscopic level. This project entails detailed Raman scattering studies and charge transport properties of two side chain substituted PFs: Poly(2,7-[9,9'-bis(2-ethylhexyl)] fluorene) (PF2/6) and Poly(9,9-(di-n,n-octyl) fluorene) (PF8). The structural properties of PFs are extremely sensitive to the choice of functionalizing side chains. PF8 adopts metastable structures that depend upon the thermal history and choice of solvents used in film forming conditions. Raman scattering techniques as a function of thermal cycling are used to monitor the changes in the backbone and side chain morphology of PF8. These studies establish a correlation between the conformational isomers and the side and main chain morphology. Theoretical modeling of the vibrational spectra of single chain oligomers in conjunction with the experimental results demonstrate the incompatibility of the beta phase, a low energy emitting chromophore, with the overall crystalline phase in PF8. Further, electroluminescence and photoluminescence measurements from PF-based light-emitting diodes (LEDs) are presented and discussed in terms of the crystalline phases and chain morphologies in the PFs. Charge carrier injection and transport properties of PF-based LEDs are presented using current-voltage (I--V) characteristic which is modeled by a space-charge-limited conduction (SCLC) for discrete and continuous traps. PF2/6 with a high level of molecular disorder is